D 1364 bt secondary coatings on optical fibre

FIELD: chemistry.

SUBSTANCE: radiation curable secondary coating composition contains an alpha-oligomer which does not contain urethane, obtained by reacting the following components: (a) an acrylate compound selected from an alcohol-containing acrylate or alcohol-containing methacrylate compound, (b) an anhydride compound, (c) an expoxide-containing compound, (d) an optional chain extending compound, and (e) an optional catalyst. Said composition additionally contains a beta-oligomer, said beta-oligomer being different from said alpha-oligomer, said beta-oligomer obtained by reacting 1) hydroxyethyl acrylate; 2) one or more diisocyanates; 3) a glycol selected from a group consisting of polyether polyols and polyester polyols. The polyester polyols are obtained by reacting a polyatomic alcohol with a polybasic acid, wherein the polyether polyols are selected from a group consisting of polyethylene glycol, polypropylene glycol, a copolymer of polypropylene glycol and ethylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol and polydecamethylene glycol; and 4) a catalyst. The invention also relates to a wire and an optical fibre having a secondary coating made from said composition.

EFFECT: high rate of curing the coating while ensuring desirable coating properties, such as modulus of elasticity, impact viscosity and elongation.

8 cl, 5 tbl

 

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This patent application claims priority based on provisional patent application U.S. serial No. 60/874723 "radiation Curable secondary coating D for optical fiber", filed December 14, 2006, provisional application for U.S. patent No. 60/874720 "radiation Curable secondary coating R for optical fiber", filed December 14, 2006, and provisional application for U.S. patent No. 60/874730 "Superority for optical fiber", filed December 14, 2006.

The technical FIELD TO WHICH the INVENTION RELATES

[0002] the Present invention in General relates to radiation curable secondary coating is suitable for use in optical fibers. More specifically, the present invention relates to compositions of secondary coatings for optical fibers that include not containing urethane oligomer, and optical fibers coated with such secondary compositions.

The LEVEL of TECHNOLOGY

[0003] Optical fibers often cover two or more layered on each other radiation-curable coatings immediately after the fiber is manufactured by drawing. The coating, which is in direct contact with the optical fiber, is called "the inner primary coating and the overlying p is a covering is called "outer primary coating". In some sources the inner primary coating is also called simply "the primary coating and an outer primary coating called "secondary coating". Inner primary coatings are softer than the secondary coating.

[0004] a Relatively soft inner primary coating provides resistance to microshell that occur in weakening the ability of the coated optical fiber to transmit the signal and therefore undesirable. Microengine are sharp, but microscopic curvature in the optical fiber involving local axial displacement on a few micrometers and spatial wavelengths of a few millimeters. Microengine can be caused by thermal stress and/or mechanical shearing forces. Coatings can provide protection from shear forces, which protects the optical fiber from microthiol, but with decreasing diameter of the coating is reduced and the degree of protection. The relationship between coverage and protection from side voltage, which leads to microshell, is discussed, for example, in articles D. Gloge, “Optical-fiber packaging and its influence on fiber straightness and loss”,Bell System Technical Journalvol. 54, № 2, 245 (1975); W.B. Gardner, “Microbending Loss in Optical Fibers”, Bell System Technical Journal, vol. 54, No. 2, p. 457 (1975); T. Yabuta, “Structural Analysis of Jacketed Optical Fibers Under Lateral Pressure”,J. LightwaveTech ., vol. LT-1, No. 4, p. 529 (1983); L.L. Blyler, “Polymer Coatings for Optical Fibers”,Chemtech., R. 682 (1987); J. Baldauf, “Relationship of Mechanical Characteristics of Dual Coated Single Mode Optical Fibers and Microbending Loss”,IEICE Trans. Commun., vol. E, No. 4, p. 352 (1993); and K. Kobayashi, “a Study of Microbending Loss in Thin Coated Fibers and Fiber Ribbons”, IWCS, R. 386 (1993). More hard outer primary coating, that is, the secondary coating provides resistance to loads encountered when handling the fiber, so what occur when covered with fiber together in the tape and/or cable.

[0005] the Composition of the secondary coating for optical fibers in General include before curing the mixture of compounds with ethylene unsaturation, often consisting of one or more oligomers which are dissolved or dispersed in a liquid solvent with ethylene unsaturation, and photoinitiators. The coating composition is typically applied to the optical fiber in a liquid form and then exposed to actinic radiation to effect the cure.

[0006] In many of these compositions use a urethane oligomer having reactive end groups and a polymer frame. Further, the composition in General include reactive diluents, photoinitiators to make compositions curable by ultraviolet (UV), and other suitable additives.

[0007] Published PCT patent application WO 2005/026228 A1, opublikowany what I 24.03.2005 some,, “Curable Liquid Resin Composition”, with the named inventors Sugimoto, Kamo, Shigemoto, Komiya and Steeman describes and claims curable liquid polymer composition suitable for use as a secondary coating on the optical fiber, comprising: (A) a urethane(meth)acrylate having a structure derived from the polyol, and srednecenovogo molecular weight of 800 g/mol or more, but less than 6000 g/mol, and (B) a urethane(meth)acrylate having a structure derived from the polyol, and srednecenovogo molecular weight 6000 g/mol or more but less than 20000 g/mol, and the total amount of the component (a) and component (b) is 20-95 wt.% from the curable liquid polymer composition, and the content of component (C) is 0.1-30 wt.% from the amount of the component (a) and component (B).

[0008] Many materials have been proposed for use as a polymer frame for urethane oligomer. For example, the urethane oligomers were applied polyols, such as hydrocarbon polyols, simple polyether polyols, polycarbonate polyols and complex polyether polyols. Complex polyether polyols are particularly attractive due to their commercial availability, resistance to oxidation and versatility in terms of exact matching characteristics of the coating by the fixture frame. The use of complex polyether polyols as frame n is limera in urethane-acrylate the oligomer described, for example, in U.S. patents№№ 5146531, 6023547, 6584263, 6707977, 6775451 and 6862392, as well as the European patent 539030 A.

[0009] the problems associated with the cost, use and processing of urethane precursors led to the use in the compositions of the coating not containing urethane oligomers. For example, do not contain urethane complex preferability oligomers were used in the radiation curable compositions of coatings for optical glass fibers. Japanese patent 57-092552 (firm Nitto Electric) discloses a coating material for optical glass fiber comprising a complex polyester di(meth)acrylate, where the skeleton is a complex polyester has an average molecular weight of 300 or more. Patent application Germany 04 12 68 60 A1 (Bayer) discloses a matrix material for tricholimnas tape, consisting of a complex of the polyester-acrylate oligomer, 2-(N-butylcarbamoyl)acrylate as a reactive diluent and 2-hydroxy-2-methyl-1-phenylpropane-1-it as photoinitiator. The patent application of Japan No. 10-243227 (publication No. 2000-072821) discloses a liquid curable polymer composition comprising a complex of the polyester-acrylate oligomer, which consists of a complex polyetherdiol blocked on the two ends of the chain dicarboxylic acids or anhydrides containing terminal fragment hydroxyethylacrylate is. U.S. patent 6714712 B2 discloses radiation-curable coating composition comprising a complex of the polyester and/or alkyd (meth)acrylate oligomer comprising polycarboxylic the remainder or its anhydride, optional reactive diluent, and optionally photoinitiator. In addition, the authors Mark D. Soucek and Aaron H. Johnson present application hexahydrophthalic acid to impart hydrolytic stability in the article “New Intramolecular Effect Observed for Polyesters: An Anomeric Effect”,JCT Researchvol. 1, No. 2, p. 111 (April 2004).

[0010] US-A-2004/0048946 discloses radiation-curable coating composition without solvent containing a radiation-curable urethane-(meth)acrylate oligomer containing alkyd main chain. US-A-5616630 aimed at hybrid oligomer of ester/urethane-acrylate, which can be used in the compositions of the coating. Article Podkoscielnyet al., Applied Macromolecular Chemistry and Physics, 1996,242, 123-138 focused on the optimization of a urethane acrylate radiation-curable compositions. None of these documents discloses oligomer containing no urethane.

[0011] EP-A-1408017 team aims to tape containing a plurality of optical fibers coated. JP-A-2004-210979 is directed to a composition suitable for pereodevaniy processed glue paper and containing at least one curable emission the m component. US-B-6630242 and US-A-2002/0057881 describe radiation-curable coating composition for optical fibers to the primary or secondary coating that is painted. US-B-7135229 describes radiation-curable coating composition without solvent for optical fibres, containing radiation-curable urethane-(meth)acrylate oligomer. US-B-6714712 is directed to radiation-curable composition for coating optical fibers. WO-A-02/42236 relates to a special method of drying coatings of optical fibers to increase the adhesion between the coating and the fiber. WO 98-A-98/57902 is directed to radiation curable coating composition that can be used as primary or secondary coatings for optical fibers. None of these documents discloses the oligomer which is the reaction product of alcohol-containing (meth)acrylate, anhydrite connection and epoxydodecane connection.

[0012] EP-A-1647585 describes radiation-curable composition that can be used as a top coating, for example, on glass substrates. JP-A-2004-051905 describes a polymer composition for coating optical fibers. These documents do not disclose the composition of the secondary coating containing oligomeric mixture of two different oligomers, alpha and beta, as indicated in paragraph 1 of the formula image is etenia.

[0013] Despite the efforts made in the prior art to develop coating compositions, including not containing urethane oligomers, there remains a need in the secondary coverages that are cost-effective, at the same time satisfying many different desirable requirements, such as improved curing and high speed curing, and versatile in application, however, while still providing desirable physical characteristics of different applied coatings.

The INVENTION

[0014] the First aspect of the claimed invention now is a radiation-curable composition of the secondary coating containing not containing urethane alpha oligomer obtained by the reaction of the following:

(a) acrylate compounds selected from alcohol-containing acrylate or alcohol-containing methacrylate compound,

(b) anhydrite connection

(C) epoxydodecane connection

(d) optional connection-chain extension, and

(e) optional catalyst

in fact the composition further comprises a beta oligomer, and mentioned a beta oligomer is different from the aforementioned alpha oligomer,

these beta oligomer obtained by the reaction of

1) hydroxyethylacrylate;

2) one or more diisocyanates;

3) a glycol selected from the group consisting of simple polyether polyols and complex polyether polyols;

the complex polyether polyols obtained by reacting a polyhydric alcohol with a polybasic acid;

this simple polyether polyols selected from the group consisting of polyethylene glycol, polypropyleneglycol, copolymer polypropylenglycol and ethylene glycol, polytetramethylene, polietilenglikolja, polyphthalocyanines and politicalideological; and

4) catalyst.

[0015] the Second aspect of the claimed invention now is the above-mentioned radiation-curable composition of the secondary coating, optionally containing gamma oligomer.

[0016] a Third aspect of the claimed invention now is the above-mentioned radiation-curable composition of the secondary coating, and said composition further comprises an antioxidant; the first photoinitiator; second photoinitiator and, optionally, a single improves the slip additive or a blend of improving slip additives;

these beta oligomer obtained by the reaction of

β1) hydroxyethylacrylate;

(2) one or more diisocyanates;

β3) polyol; and

these polyol is a simple polyetherpolyols selected from the group consisting of polyethylene glycol, p is dipropyleneglycol, copolymer polypropylenglycol and ethylene glycol, polytetramethylene, polietilenglikolja, polyphthalocyanines and politicalideological; and

these polyol preferably is polytetramethylene with srednetsenovoj molecular weight of about 600 to 700, preferably about 625-675; and

β4) catalyst;

when this catalyst beta oligomer selected from the group consisting of dilaurate dibutylamine; carboxylates of metals; sulfonic acids; catalysts based on amines or organic bases; alkoxides (alcoholate) of zirconium and titanium and ionic liquid phosphonium salts, imidazole and pyridinium; and

these gamma oligomer is epoxidized.

[0017] the Fourth aspect of the claimed invention now is an optical fiber covered with a radiation-curable primary coating and a radiation-curable composition of the secondary coating, characterized in any of the above first to third aspects.

[0018] the Fifth aspect of the claimed now of the invention is a method of coating an optical fiber, including:

a) operation of the column extraction of glass to obtain a glass optical fiber; and

b) coating the aforementioned glass optical fiber curing emission is m the composition of the primary coating;

C) optionally contacting the mentioned radiation-curable composition of the primary coating with radiation for curing of the coating;

d) coating the aforementioned glass optical fiber radiation-curable composition of the secondary coating, characterized in any of the above first to third aspects;

(e) contacting mentioned radiation-curable composition of the secondary coating to radiation to cure the coating.

The sixth aspect of the claimed now of the invention is the method according to the fifth aspect, the operation of the mentioned columns extraction of glass is performed with a linear speed between 750 meters/minute and 2100 meters/minute.

The seventh aspect of the claimed invention now is wire covered with the first and second layer, the first layer is utverjdenie radiation curable primary coating that is in contact with the outer surface of the wire, and the second layer is utverjdenie radiation curable secondary coating described in any of the above first to third aspects, in contact with the outer surface of the primary coating,

this utverjdenie secondary coating on the wire has the following properties after initial hotwired the Deposit and one month aging at 85°C and 85%relative humidity:

A) a % RAU of from 80% to 98%, and "% RAU" denotes the degree of cure, expressed as a percentage reacted acrylate unsaturation;

C) in-situ modulus of between 0,60 GPA 1.90 GPA; and

C) Tctubes from 50°C to 80°C.

[0019] the Eighth aspect of the claimed invention now is an optical fiber coated with the first and second layer, the first layer is utverjdenie radiation curable primary coating that is in contact with the outer surface of the optical fiber and the second layer is utverjdenie radiation curable secondary coating described in any of the above first to third aspects, in contact with the outer surface of the primary coating,

this utverjdenie secondary coating on the optical fiber has the following properties after initial cure and after one month aging at 85°C and 85%relative humidity:

A) a % RAU of from 80% to 98%, and "% RAU" denotes the degree of cure, expressed as a percentage reacted acrylate unsaturation;

C) in-situ modulus of between 0,60 GPA 1.90 GPA; and

C) Tctubes from 50°C to 80°C.

DETAILED description of the INVENTION

[0020] throughout this patent application the following terms have the indicated meanings:

ReductionValue
EIT2,6-di-tert-butyl-4-METHYLPHENOL manufactured by Fitz Chem.
CN-120ZEpoxidized, manufactured by Sartomer company.
DABCO1,4-diazabicyclo[2.2.2]octane, manufactured by Air Products.
DBTDLDilaurate dibutylamine manufactured by OMG Americas.
HEAHydroxyethylacrylate, produced by BASF.
HHPAHexahydrophthalic anhydride, manufactured by Milliken Chemical.
Irgacure 1841-Hydroxycyclohexane, manufactured by Ciba Geigy.
Irganox 1035Thiodiethyl-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), manufactured by Ciba Geigy.
SR-506Isobutylacetate, manufactured by Sartomer company.
Photomer 4066The ethoxylated nonylphenolic produced by the company Cognis.
Pluracol 1010Polypropyleneglycol (MW=1000)manufactured by BASF
SR-306HPDiacrylate tripropyleneglycol (TPGDA), produced by Sartomer company.
SR-349Diacrylate ethoxylated bisphenol a, manufactured by Sartomer company.
TDIA mixture of 2,4 - and 2,6-isomers colordistance in relation to 80/20, produced by BASF
IPDIIsophorondiisocyanate produced by Bayer
TPOPhotoinitiator type 2,4,6-trimethylbenzenesulfonamide manufactured by Chitech.
CAS indicates the registration number of refereed journal Chemical Abstracts

[0021] Coating for optical fibers typically are radiation-curable compositions that include, before curing, one or more radiation-curable oligomers or monomers having at least one functional group capable of polymerization when exposed to actinic radiation. This application discloses an improved radiation-curable oligomer (alpha oligomer), which is not what keeps urethane and is derived from the anhydride, which is applicable in the composition of the secondary coating for optical fibers.

[0022] In addition to the alpha oligomer composition of the secondary coating for optical fiber according to the invention includes a beta oligomer, and preferably includes one or more additional oligomers (e.g., gamma oligomer and at least one reactive diluent, which has at least one functional group capable of polymerization when exposed to actinic radiation. The composition of the secondary coating for optical fiber according to the invention optionally include additional components, as described herein, including one or more antioxidants, photoinitiators improving slip additives and the like.

[0023] Examples of suitable radiation-curable compositions of the secondary coating, which can be used in a variety of ways to form coating compositions, described, for example, in U.S. patents№№ 4624994, 4682851, 4782129, 4794133, 4806574, 4849462, 5219896 and 5336563. New alpha oligomer used in the composition of the secondary coating of the present invention, can be applied in such coatings to reduce the overall content of the urethane secondary coating and to improve its physical and/or chemical properties.

Alpha oligomer

[0024] the composition of the secondary is rite according to the invention includes the alpha oligomer, which is derived from the anhydride. Alpha oligomer formed by the reaction:

[0025] (a) hydroxyl-containing (meth)acrylate (also referred to here as the "acrylate");

[0026] (b) anhydride;

[0027] (C) mono - or multifunctional epoxydodecane connection;

[0028] (d) optional chain extension; and

[0029] (e) optionally one or more catalysts.

[0030] the Reaction can also be carried out in the presence of antioxidants. In some embodiments, the implementation of the oligomer is obtained by reacting (a) a hydroxyl-containing (meth)acrylate and (b) anhydride and reacting the reaction product of these acrylate anhydride and (C) epoxidation connection. Thus obtained oligomer will include the rest of the acrylate, the remainder of the complex diapir derived from anhydrous compounds, a residue with a secondary alcohol derived from epoxydodecane compounds, and, optionally, the remainder of the chain extension. In General, the acrylates are preferred before methacrylates, since there can be obtained a composition having a higher speed curing.

[0031] Preferably the molar ratio of the balance of the acrylate to the residue complex diapir in the alpha oligomer according to the invention is essentially equal to one. For example, the molar ratio of the balance of the acrylate to the residue complex diapir in the oligomer desire is entrusted is from 0.8:1 to 1:0.8 to. Preferably, the remains acrylate, complex diapir and secondary alcohol inside the oligomer linked so that the rest of the acrylate is connected to the remainder of the complex diapir, which is connected to the remainder of the secondary alcohol. More preferably, the residues of acrylate (A), complex diapir (B)secondary alcohol (C) and optional chain extension (D) inside the oligomer linked together essentially as follows:

-A-b-C-b-A or a-b-C-b-D-b-C-B-A-.

[0032] the hydroxyl-containing (meth)acrylate can be any compound comprising acrylate or (meth)acrylate group and an alcohol group. Typically the acrylate is selected from the group consisting of hydroxyethylacrylate (NEA), monoacrylate 1,4-butyleneglycol, monoacrylate tripropyleneglycol (TPGMA), monoacrylate polyethylene glycol, monoacrylate of polypropylenglycol (RRA), dimethacrylate of ethylene glycol, diacrylate 1,3-butyleneglycol, diacrylate 1,4-butyleneglycol, diacrylate neopentyl glycol, diacrylate 1,6-hexaglycine, dimethacrylate 1,6-hexaglycine, diacrylate of polyethylene glycol, polyethylene glycol dimethacrylate, diacrylate of polypropylenglycol, dimethacrylate of polypropylenglycol, 2,2-bis(4-aryloxyphenoxy)propane, diacrylate tripropyleneglycol (TPGDA), 2,2-bis(4-aryloxyphenoxy)propane, 2,2-bis(4-methacryloxyethyl)propane, 2,2-bis(4-methacryloxyethyl)about the Ana, triacrylate of trimethylolpropane (e.g., SR-351), trimethacrylate of trimethylolpropane, triacrylate tetranitromethane, triacrylate pentaerythritol (e.g., SR-444), complex polyester-acrylate oligomer, polymetacrylate, monoacrylate complex polyester acrylates of caprolactone, such as acrylates of caprolactone TONETMsold by the company Dow Chemical, and polycaprolactones alcohol SR-495, sold by Sartomer company, epoxyacrylate, diacrylate derived diglycidylether ether of bisphenol a, epoxidized on the basis of bisphenol a (for example, CN-120 or CN-120Z) or combinations thereof. Preferably the acrylate is selected from the NEA, RRA, acrylates of caprolactone, TPGMA, triacrylate pentaerythritol (e.g., SR-444), diacrylate derived diglycidylether ether of bisphenol a, epoxidized on the basis of bisphenol a (for example, CN-120), and combinations thereof. More preferably, the acrylate is a NEA.

[0033] the Anhydride is any anhydride of a saturated or unsaturated polybasic acid. Typically saturated or unsaturated polybasic acid is a polyfunctional carboxylic acid. For example, the polybasic acid is an aromatic or aliphatic dibasic carboxylic acid selected from the group consisting of phthalic acid, isophthalic acid, terete the eve acid, maleic acid, fumaric acid, basis of itaconic acid, adipic acid, glutaric acid, azelaic acid, sabatinovka acid, citric acid, trimellitic acid, pyromellitic acid, dodecadienol acid, dodecandioic acid, cyclohexanedicarboxylic acid, tetrahydrophthalic acid, methylenetetrahydrofolic acid, hexahydrophthalic acid, succinic acid, or their lower alilovic esters and combinations thereof. Preferably the anhydride is selected from the group consisting of hexahydrophthalic anhydride (NRA), methylhexahydrophthalic anhydride (MNRE), succinic anhydride (SA), phthalic anhydride (PA), maleic anhydride (MA), dodecanesian anhydride (DDSA), aktanyshskogo anhydride (OSA), tetrahydrophthalic anhydride, trimellitic anhydride and combinations thereof.

[0034] Epoxydodecane compound is any compound or polymer containing one or more epoxy groups per molecule, preferably two epoxypropyl molecule. For example, epoxydodecane connection may be aromatic or cycloaliphatic compound or polymer comprising one or more epoxy groups per molecule. Preferably epoxydodecane compound is an aromatic epoxydodecane connection. Sentence on the nye epoxydodecane compounds include diglycidyl ethers, such as diglycidyl simple ether of bisphenol a (for example, EPON Resins sold by Hexion Specialty Chemicals, including unmodified epoxy liquid resin based on bisphenol a and epichlorohydrin, MW=700, sold under the trade name EPON 825 and EPON 828 (CAS # 25068-38-6); YD-126, epoxy resin based on bisphenol a and epichlorohydrin, sold by TRInternational), cyclohexanone, stimulated, aminoacridine resin-based pilgramage ether, diglycidylether, diglycidylether, diglycerol simple ether, glycidyloxy simple ether of butanediol, glycidyloxy simple ether of propylene glycol, 2-glycidylmethacrylate a simple ether, diglycidyl simple ether of resorcinol, glycidyloxy simple ether of alkylphenol, phenylglycidyl simple ether, butespecially simple ether, glycidyloxy simple ether of cresol, glycodelin, glycidaldehyde, polyepoxide based on hydrogenated bisphenol a, glycidyloxy ethers of bisphenol a, polyepoxide on the basis of phenolic Novolac resins and epoxydecane of polybutadienes, diepoxyoctane cycloaliphatic liquid epoxy resin, such as isopropylidene[4,4'-bis(2,3-epoxypropoxy)cyclohexane], monoglycerol a simple ester of the acid number of “Versatic” (branched carboxylic acid with a tertiary carbon atom) (VAME) and the like. Predpochtitel is about, epoxydodecane compound is an epoxy resin based on bisphenol a, such as EPON 825 or EPON 828 sold by Hexion Specialty Chemicals, and the like.

[0035] As discussed above, to obtain the oligomer may be optionally used in the chain extension. The chain extension is a polyol, a complex polyester, polyalkyl, fatty acid, oil or their derivatives. Moreover, the chain extension can have any suitable molecular weight. When the chain extension is a polyol, the polyol can have any suitable number of alcohol groups, for example, the polyol can have 2-10 alcohol groups, preferably 2-4 alcohol group, or may be a simple polyetherpolyols, such as aliphatic simple polyetherpolyols or cyclic simple polyetherpolyols. Preferably the use of alcohols which are substituted in the β-position so that there is no β-hydrogen atoms, which could lead to hydrolytic instability.

[0036] Suitable diols include, for example, 1,2-propandiol, 1,3-propandiol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropyleneglycol, polypropyleneglycol, neopentylglycol, 2-methyl-1,3-propandiol, 2,2-dimethyl-1,3-propandiol, 2-ethyl-1,3-disappear to the diol, 2,2-diethyl-1,3-propandiol, 2-propyl-2-methyl-1,3-propandiol, 2-propyl-2-ethyl-1,3-propandiol, 2-butyl-2-ethyl-1,3-propandiol (BEPD), hydroxyjulolidine (NRNR), 2-cyclohexyl-2-methyl-1,3-propandiol, 2-phenyl-2-methyl-1,3-propandiol, 1,4-cyclohexanediol, 2,4-diethyl-1,5-pentanediol or alkoxysilane derivatives of all the above-mentioned diols, such as preferably ethoxylated and propoxycarbonyl their derivatives. Also suitable With36-diols, such as diol Pripol 2033 (supplied by the company Uniqema) and diol Speziol C36/2 (supplied by the company Cognis). These diol components can be used in a mixture. Suitable diols for use as chain extenders further described in U.S. patent 6023547. Preferred dialami, which can be used as chain extenders, are ethoxylated bisphenol a, propoxycarbonyl bisphenol a, neopentylglycol (NPG), 2-butyl-2-ethyl-1,3-propandiol (BEPD), 2-methyl-1,3-propandiol (MPD), hydroxyjulolidine (NRNR), hydrogenated analogs of dimeric acids, 2,4-diethyl-1,5-pentanediol, or a mixture thereof.

[0037] other suitable polyols include, for example, triola, such as glycerin, trimethylated (i.e. 1,1,1-Tris(hydroxymethyl)ethane), and trimethylolpropane (i.e. 1,1,1-Tris(hydroxymethyl)propane); tetraol, such as pentaerythritol; pentaly, such as glucose; gaxiola, such as dipentaerythritol and the orbits; or alkoxysilane derivatives of all the above-mentioned polyhydric alcohols, preferably such as ethoxylated and propoxycarbonyl their derivatives, ethoxylated bisphenol a having 2-12 ethylenoxide structural units, propoxycarbonyl bisphenol a, having 2-12 propylenoxide structural units, sugar, halogenated sugars such as trichloropropane sucrose (Sucralose), glycerine and the like. In some embodiments, the implementation of the polyol is preferably a diol. The advantage of diols is their relatively non-polar nature, low ester content fragments in the resulting oligomer and low Tc.

[0038] Suitable aliphatic simple polyether polyols include polyethylene glycol, polypropyleneglycol, polytetramethylene, polietilenglikol, poliatilenglikol, politicalideological, simple polyetherpolyols obtained by copolymerization with opening cycle of two or more suitable for ionic polymerization of cyclic compounds, and the like. Examples of suitable ionic polymerization of cyclic compounds, including cyclic ethers, such as ethylene oxide, propylene oxide, 1,2-butylenes, butene-1-oxide, isobutoxide, 3,3-bis-chloromethyloxirane, tetrahydrofuran, 2-methyltetra hydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexanone, stimulated, epichlorohydrin, glycidylmethacrylate, allylglycidylether simple ether, allylglycidylether, butadience, isoprenoid, vinylacetal, vinyltetrahydrofuran, vinylcyclohexane, phenylglycidyl simple ether, butespecially simple ether and glycidylester. Moreover, there can be used a simple polyether polyols obtained by the copolymerization of disclosure cycle suitable for the above-mentioned ionic polymerization of cyclic compounds with monomers such as cyclic Minami, such as ethylenimine, lactones as cyclic derivatives of acids such as propiolactone and lactide and glycolic acid, and dimethylcyclohexylamine. As examples of specific combinations of two or more suitable for ionic polymerization of cyclic compounds can be called a combination of tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and of ethylene oxide, butene-1-oxide and ethylene oxide, a ternary copolymer of tetrahydrofuran, butene-1-oxide and ethylene oxide, and the like. Obtained with the disclosure of the loop these copolymers suitable for ionic polymerization of cyclic connected to the second can be either a statistical copolymer, or a block copolymer.

[0039] Suitable cyclic simple polyether polyols include diol product join accelerated to bisphenol a, diol product join accelerated to the bisphenol F, hydrogenated bisphenol a, hydrogenated bisphenol F, diol product join accelerated to gidrirovannogo the bisphenol a, the diol product join accelerated to gidrirovannogo the bisphenol F, diol product join accelerated to hydroquinone, diol product join accelerated to naphthohydroquinone, diol product join accelerated to anthrahydroquinone, 1,4-cyclohexanediol and diol product join accelerated to him, tricyclodecane, tricyclopentadiene, mentalcapacity, pentasaccharideindependent and the like. Of them are preferred diol product join accelerated to bisphenol a, tricyclopentadiene and the like. Among the above-mentioned simple polyether polyols are preferred at least one simple polyetherpolyols selected from the group consisting of polypropylenglycol, copolymer of 1,2-butilenica and ethylene oxide and a copolymer of propylene oxide and ethylene oxide.

[0040] In some embodiments, the implementation of the polyol is preferably selected from the group consisting of the complex is rificolona or simple polyether polyols. Some simple examples of polyether polyols include, for example, polyethylene glycol, polypropyleneglycol, a copolymer of polypropylenglycol and glycol, polytetramethylene, polietilenglikol, poliatilenglikol, politicalideological and simple polyetherdiol obtained by copolymerization with opening cycle of two or more suitable for ionic polymerization of cyclic compounds (e.g. ethylene oxide, propylene oxide, isobutoxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, phenylglycidyl simple ether or butespecially simple ether). Suitable polypropylenglycol include polypropyleneglycol having a molecular weight of from 300 g/mol to 5000 g/mol, for example, PPG400 (MW=400 g/mol), PPG1000 (MW=1000 g/mol), PPG2000 (MW=2000 g/mol), PPG3000 (MW=3000 g/mol), and EXCENOL 720 (MW=700 g/mol), EXCENOL 1020 (MW=1000 g/mol) and EXCENOL 2020 (MW=2000 g/mol) (manufactured by Asahi Glass Urethane Co., Ltd.). Suitable polyols further include polyols and copolymers of 1,2-butilenica and ethylene oxide having a molecular weight of from 300 g/mol to 5000 g/mol, for example SW/WO (MW=500 g/mol), SW/WO (MW=1000 g/mol), SW/WO (MW=2000 g/mol), SW/WO (MW=3000 g/mol), SW/WO (MW=4000 g/mol) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0041] Suitable polyols also include complex polyether polyols obtained by the reaction of a polyhydric alcohol (e.g. ethylene glycol, polyethylene is glycole, propylene glycol, polypropyleneglycol, tetraethyleneglycol, polytetramethylene, 1,6-hexandiol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonanediol and 2-methyl-1,8-octanediol) with a polybasic acid (e.g. phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid and sabatinovka acid), such as commercially available under the trade names MPD/IPA500 (MW=500 g/mol), MPD/IPA1000 (MW=1000 g/mol), MPD/IPA2000 (MW=2000 g/mol), MPD/TPA500 (MW=500 g/mol), MPD/TPA1000 (MW=1000 g/mol), MPD/TPA2000 (MW=2000 g/mol), Kurapol A-1010 (MW=1000 g/mol)And 2010 (MW=2000 g/mol), PNA-2000 (MW=2000 g/mol), PNOA-1010 (MW=1000 g/mol) and PNOA-2010 (MW=2000 g/mol) (manufactured by Kuraray Co., Ltd.). Commercially available polycarbonate polyols include DN-980 (MW=2000 g/mol) and DN-981 (MW=1000 g/mol) (manufactured by Nippon Polyurethane Industry Co., Ltd.), diarizonae complex polyether polyols based on fatty acids, such as Priplast 3196 (MW=3000 g/mol), Priplast 3190 (MW=2000 g/mol) and Priplast 2033 (MW=570 g/mol) (manufactured by Uniqema), poly(alkalescent)glycols, which are statistical copolymers of 1.9 nonmaterial and 2-meteoclimatologia, such as PNOC-2000 and PNOC-1000 (manufactured by Kuraray Co., Ltd.), polycaprolactone diols, such as PLACCEL CD220 (MW=2000 g/mol), CD210 (MW=1000 g/mol), CD208 (MW=830 g/mol), CD205 (MW=500 g/mol) (manufactured by Daicel Chemical Industies, Ltd.), and simple politicaleconomy diols, such as PC-THF-CD (MW=1000 g/mol and 2000 g/mol) (manufactured by BASF).

[0042] Other examples of suitable complex polyether polyols represented in the published patent application U.S. 2004/0209994 A1 (Terwillegar). These polyols can be used either individually or in combination of two or more. In addition, the above-described polyols, individually or in combination, can react on each end with anhydride (examples of which are described above) with the formation of dicarboxylic acids, which can serve the invention as chain extension. Such dicarboxylic acids may be further used for synthesis of the extension chain-based polyesters.

[0043] the Dimeric acids (and their esters) are well known, commercially available class of dicarboxylic acids (or esters). Typically they are obtained by dimerization of unsaturated long-chain aliphatic monocarboxylic acids, typically containing from 13 to 22 carbon atoms, or their esters (for example, alilovic esters). From the point of view of the technologists, the reaction proceeds according to a possible mechanism, which involves the reaction of Diels-alder reaction with a free radical or carbocationic mechanisms. Dimer acid will typically contain from 26 to 44 carbon atoms. Preferably d is measured acid (or esters) are derived from unsaturated monocarboxylic 18- and22acids (or esters), which will respectively form a dimer With36- and44-acids (or esters). Dimeric acid, formed from unsaturated With18acids, which include such acids as linoleic acid and linolenic acid, in particular the well-known (forming a dimer With36-acid). Dimeric acid as products usually contain also some of the trimeric acids (for example, C54acids, when source has been used With a18-acid), possibly even higher oligomers and also small amounts of Monomeric acids. Several different grades of dimer acid available from commercial sources, and they differ from each other mainly by the number of fractions monocarboxylic and trimeric acids and degree of unsaturation.

[0044] Typically dimeric acids (or esters) being initially formed products are unsaturated, possibly, could be a disadvantage in terms of their resistance to oxidation due to the presence of reactive sites for crosslinking or decomposition, thereby causing changes in the physical properties of the films of the coating over time. Therefore, it is preferable (although not required) to use the resulting dimeric acids, which have been subjected to hydrogenation Claudine greater part of the unreacted double bonds. Here, the term "dimer acid" is used to refer to as the dicarboxylic acid and its ester derivatives, such as esters with lower alkyl groups, which would act as an acid component in the synthesis of polyesters, and includes any trimer or monomer, if present.

[0045] Another class of compounds suitable as chain extenders, are alcidi. Alcide, or alkyd resin is a complex type polyester having one or more ester groups located along the main polymer chain ester ligaments. Alkyd resins can be obtained by condensation reactions of polyols, polyfunctional carboxylic acids (hereinafter referred to as the polyacid and oils or fatty acids derived from oils. The oil may be a natural oil, which consists of a complex ether, for example complex Trevira glycerol and fatty acids. For example, a mixture of the polyol/fatty acid may be prepared in situ by alcoholysis of oils of natural origin or direct esterification of the polyol with the use of long-chain fatty acids of natural origin. The resulting product of both of these reactions can then be polymerized with other polyols and policestate (for example, dialami and dicarboxylic acids is), as usual polyesterification. More preferably Alcide is obtained by alcoholysis of oils of natural origin, preferably oil with a low degree of unsaturation. Side of the ester group in Alcide can be entered by using a monofunctional carboxylic acid (monocellate) together with the conventional components used to obtain a complex of the polyester. Monocellate used to obtain the main part, can be any monocarboxylic acid having from 4 to 28 carbon atoms. Preferably monocellate is a fatty acid, more preferably a long monocellate. Long monocerata, or long-chain fatty acid, is characterized as having from 12 to 28 carbon atoms in their chain; more preferably between 12 and 24 carbon atoms. Most fatty acids have 18 carbon atoms in its chain, but in the oils of natural origin may also be a higher number of carbon atoms. For example, in some varieties of rapeseed oil was found With22-acid, erucic acid (docosanoate acid). Preferably the fatty acids or oils of natural origin, or oil derivatives which are fatty acids, known as qualified specialists in this field of technology are fat is acid or oil, originating from plant or animal sources.

[0046] Other classes of suitable chain extenders, are closely associated with Alcide represent the fatty acids and oils. Fatty acids or oils suitable as frameworks for alkido of the present invention, can be saturated or unsaturated. Preferably the fatty acid or oil have a low degree of unsaturation, as defined below. Examples of unsaturated oils or fatty acids derived from oils include castor oil, corn oil, cottonseed oil, rapeseed oil, rapeseed oil, low erucic acid, hemp oil, oil from seeds Kapka, linseed oil, wild mustard, Oiticica oil (licania), olive oil, palm oil, peanut oil, perillae oil, poppy oil, tobacco oil, Argentine canola oil, the oil from the seeds of the rubber, safflower oil, sesame oil, soybean oil, sugar cane, sunflower oil, tall oil, Camellia oil, Tung oil, black walnut or mixtures thereof and the like. Examples of fatty acids/oils having low unsaturation include coconut oil, babassu oil, Chinese tallow oil, ouricuri, stone fruits, palm oil, Caprylic acid, Caproic acid, capric acid is, coconut fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like or a mixture thereof, fatty acids derived from oils, as well as gidrirovannoe the form of unsaturated oils and fatty acids derived from oils, such as castor oil, corn oil, cottonseed oil, rapeseed oil, low erucic acid, hemp oil, oil from seeds Kapka, linseed oil, wild mustard, Oiticica oil (licania), olive oil, palm oil, peanut oil, perillae oil, poppy oil, tobacco oil Argentine canola oil, the oil from the seeds of the rubber, safflower oil, sesame oil, soybean oil, sugar cane, sunflower oil, tall oil, Camellia oil, Tung oil, black walnut or mixtures thereof and the like.

[0047] the alpha oligomer can be obtained using any suitable method. For example, the alpha oligomer can be obtained according to the one-step method, in which the acrylate, anhydride, epoxydodecane connection and, optionally, the connection extension chain together loaded into the reactor. The reaction can be conducted at a temperature of from 80°to 150°C., typically from 90°C to 130°C, preferably from 100°C to 140°C, more preferably from 110°C to 130°C, when ATM is sphere or reduced pressure.

[0048] Preferably, the alpha oligomer receive under the two-step method of synthesis. During the first stage of the two-stage process alpha oligomer is obtained by combining acrylate, anhydride and, optionally, connection-chain extension and reacting these components at a temperature in the range from 90°C to 130°C, preferably from 100°C to 120°C, more preferably from 105°C. to 115°C. Preferably this step is carried out in air atmosphere, more preferably in an atmosphere of dry air. Without the intention to go into any specific theory, it appears that during this stage the alcohol group in the acrylate and/or connection-chain extension, if present, reacts with the anhydride, which is accompanied by disclosure of the cycle anhydride with the formation of ester bonds and carboxylic acid groups. In the second stage of the two-stage process carried out response epoxydodecane connection with the product of the first stage. In particular, a free acid group in the reaction product of the first stage (the free acid formed from the anhydride) is reacted with the epoxy group with the formation of the secondary alcohol group. The second stage is preferably carried out in the same reaction conditions, such as temperature and duration of reaction, as described for the above one is staged process. Due to the exothermic nature of the reaction disclosure anhydrite cycle, in some embodiments, the implementation preferably initially introduced into the reaction anhydrous connection with only part of the acrylate, until it reaches the desired reaction temperature. After the reaction the temperature of the support by adding the rest of the acrylate with controlled velocity, or by adding dropwise. If necessary, the reaction mixture can be heated to maintain the desired reaction temperature. A typical reaction in the first stage is carried out in a period of about 2-4 hours, and the reaction in the second stage of the methodology carried out for 8-15 hours.

[0049] For inhibition of polymerization of the acrylate in the reaction time may be added inhibitor or inhibiting polymerization. Examples of suitable inhibitors include bottled hydroxytoluene (BHT), hydroquinone, hydroquinone derivatives, such as methyl simple ether of hydroquinone, 2,5-dibutylamine (DBH), 3,5-di-tert-butyl-4-hydroxytoluene; methyl-di-tert-butylphenol; 2,6-di-tert-butyl-para-cresol and the like, nitrobenzol, phenothiazines, and the like. Among them, preferred BHT and DBH, as they provide relatively weak fading end of the oligomer.

[0050] To facilitate the reaction epoxydodecane connection at the time of receipt of the alpha oligomer can be used catalyst. Suitable catalysts include, for example, triarylphosphine catalysts such as triphenylphosphine (TPP) and trichlorfon, phosphonium salts of tertiary amines, such as triethylenediamine catalysts such as 1,4-diazabicyclo[2.2.2]octane (DABCO), and metal-containing catalysts, such as chromium acetate(III), metal salts of carboxylic acids, tin catalysts, such as alcoholate of divalent tin or acrylates of divalent tin and titanium catalysts, many of which are known in the art. The catalysts can be used individually or in combination. In a preferred embodiment, TPP and DABCO used in combination in order to provide the possibility of carrying out the reaction at a low temperature (for example, 110°C). The concentration of catalyst in the reaction mixture in General is between 0.1 and 1.0 wt.%, preferably between 0.1 and 0.7 wt.%, more preferably between 0.1 and 0.5 wt.%, and even more preferably between 0.1 and 0.3 wt.% (based on the total weight of the reaction mixture).

[0051] the alpha oligomer preferably has a low acid number and has a high hydrolytic stability. Acid number is a measure of the content of free carboxylic acid in the resin and is expressed as the number of milligrams of potassium hydroxide required to neutralize the free is the breaking of carboxylic acids in one gram of resin. Thus, the acid number reflects the amount of acid, such as the number of carboxylic acid remaining in the oligomer. Acid number can be determined by dissolving a weighed amount of resin in a solvent such as toluene or tetrahydrofuran (THF), together with neutralized ethyl alcohol or a mixture of isopropyl alcohol and acetone in the ratio of 50/50, and titration of the resulting solution does not contain carbonates decinormal potassium hydroxide solution to the equivalence point by phenolphthalein. It is also possible the determination of the acid number method potentiometry, as described further below in the section test methods. Acid value ("AV") in mg KOH/g resin" can be expressed by the formula:

AV=(56,1)(ml KOH)(normality)/(weight of resin (g)).

[0052] In some embodiments the invention, the acid number is preferably 20 mg KOH/g resin or less, preferably 15 mg KOH/g resin or less, more preferably 10 mg KOH/g resin or less, and still more preferably 5 mg KOH/g resin or less. In some cases, the resin is essentially neutral, so that the acid number is 1 mg KOH/g resin or less. If desirable, the oligomer may be washed and/or neutralized after synthesis, to further remove excess acid.

[0053] Brednikova molecule the full weight of the alpha oligomer is preferably 400 g/mol or more, but equal to or less than 6000 g/mol, preferably equal to or less than 5000 g/mol, more preferably equal to or less than 4000 g/mol. When the alpha oligomer used in the composition of the secondary coating, Brednikova molecular weight is preferably 2000 g/mol or less, more preferably 1500 g/mol or less and 500 g/mol or more, more preferably 800 g/mol or more. Brednikova molecular weight alpha oligomer can be precisely adjusted in part by the selection of a connection-chain extension with an appropriate molecular weight.

[0054] After preparation of the alpha oligomer percentage of urethane linkages in the oligomer can be calculated by multiplying the number of urethane linkages in theoretical structure on the molecular weight of the urethane links (42 g/mol) and dividing by the molecular weight of theoretical structure of the oligomer.

Beta oligomer

[0055] the Composition of the secondary coating according to the invention additionally comprises a second oligomer (beta oligomer) in addition to the alpha oligomer. The presence of beta-oligomer in addition, the alpha oligomer gives a more balanced composition with a coating properties, such as improved utverzhdennuyu surface with a low adhesive force and a low friction coefficient after curing. One advantage of this is is to create utverzhdenii composition of the coating with a lower modulus of elasticity, at the same time maintaining a high Twithor tan δmax. In some embodiments, the implementation is desirable that the beta oligomer had a different molecular weight than the alpha oligomer. Beta oligomer is orlandomiami oligomer, for example orlandomiami oligomer obtained in accordance with the instructions of the publication of International patent application no WO 2005/026228 A1 or U.S. patents 5527835, 6298189, 6584263, 6661959, 6775451 or 6872760. Preferably beta-oligomer has a low Twithand high elongation, if cures by itself and not as part of the secondary coating.

[0056] the Beta oligomer obtained by reaction of complex polyetherpolyols or simple polyetherpolyols with srednetsenovoj molecular weight in the range from 300 g/mol to 10,000 g/mol, one or more diisocyanates, hydroxyethylacrylate and catalyst. For example, a urethane-acrylate oligomer suitable for use as a beta oligomer may be obtained by the reaction of isocyanate groups of the diisocyanate respectively with the hydroxyl group of the polyol and a hydroxyl group hydroxyethylacrylate. This reaction can be conducted in several ways as follows: (a) loading polyol, diisocyanate and hydroxyethylacrylate and reacting them with each other; (b) reacting the polyol and diisocyanate, and reacting the obtained product with hydroxic what lacrimation; (C) reacting the diisocyanate and hydroxyethylacrylate and reacting the resulting product with the polyol or (d) reacting the diisocyanate and hydroxyethylacrylate, reacting the resulting product with the polyol, and further reacting the obtained product with hydroxyethylacrylate. The reaction typically is carried out in the presence of a catalyst of Aryanization.

Catalysts in the synthesis of oligomers based urethanes for use in radiation-curable coatings for optical fibers known in the field. Suitable catalysts are described here for the beta oligomer can be selected from the group consisting of dilaurate dibutyrate (DBTDL); carboxylates of metals, including, but not limited to, vismutorganicheskikh catalysts, such as neodecanoic bismuth CAS 34364-26-6; neodecanoate zinc CAS 27253-29-8; neodecanoate zirconium CAS 39049-04-2 and 2-zinc ethylhexanoate, CAS 136-53-8; sulfonic acids, including but not limited to, dodecylbenzenesulfonic acid, CAS 27176-87-0 and methansulfonate acid, CAS 75-75-2; catalysts based on amines or organic bases, including, but not limited to, 1,2-dimethylimidazole CAS 1739-84-0 (very weak base) and diazabicyclo[2.2.2]octane (DABCO), CAS 280-57-9 (strong base) and triphenylphosphine (TPP); alkoxides of zirconium and titanium, including, but not limit the category of them, butyl zirconium (tetramethylsilane) CAS 1071-76-7 and butyl titanium (tetrabutyltin) CAS 5593-70-4; and ionic liquid phosphonium salts, imidazole and pyridinium, such as, but not limited to, hexaflurophosphate trihexy(tetradecyl)phosphonium CAS No. 374683-44-0; acetate 1-butyl-3-methylimidazole CAS No. 284049-75-8 and chloride N-butyl-4-methylpyridine CAS No. 125652-55-3; and tetradecyl chloride(trihexy)phosphonium available on the market under the trade name Cyphosil 101.

All these catalysts are commercially available. It is now known that all of these catalysts can be used in a free, soluble and homogeneous state, or they may be associated with inert agents such as silica gel, or macrostate resins with divinely cross and applied in heterogeneous able to be filtered by the completion of the synthesis of the oligomer.

[0057] To obtain a beta oligomer use one or more diisocyanates. These diisocyanates may be selected from the group consisting of aromatic diisocyanates and aliphatic diisocyanates, such as, but not limited to, 2,4-colorvision, 2,6-colorvision, 1,3-xylylenediisocyanate, 1,4-xylylenediisocyanate, 1,5-naphthalenedisulfonate, meta-delete the entry, para-delete the entry, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, 4,4'-diphenylmethanediisocyanate, 3,3'-dimethylanilines the cyanate, 4,4'-biphenylenediisocyanate, 1,6-hexadienal, isophorondiisocyanate, Methylenebis(4-cyclohexyl)isocyanate, 2,2,4-trimethylhexamethylenediamine, bis(2-isocyanatomethyl)fumarate, 6-isopropyl-1,3-delete the entry, 4-diphenylmethanediisocyanate, liaindizecign, hydrogenated diphenylmethanediisocyanate, hydrogenated xylylenediisocyanate, tetramethylethylenediamine and 2,5(or 6)-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane. In one embodiment, the preferred isophorondiisocyanate, colorvision. In one embodiment, the preferred colorvision used by itself.

[0058] the Polyol used to obtain beta-oligomer, is a complex polyetherpolyols or simple polyetherpolyols, for example a simple polyetherpolyols selected from the group consisting of polypropylenglycol, copolymer of 1,2-butilenica and ethylene oxide and a copolymer of propylene oxide and ethylene oxide. Brednikova molecular weight polyol as one extension of the chain is in the range of from 300 g/mol to 10,000 g/mol. Preferably the chain extension is polypropylenglycol with srednecenovogo molecular weight of about 1000 g/mol.

[0059] In some embodiments, the implementation of both the alpha oligomer, and a beta oligomer include the remainder of the polyol as one chain extension, with a polyol, use isoamyl to get the alpha oligomer, different from the polyol used to obtain beta-oligomer, at least with respect to molecular weight. The polyol used in the alpha oligomer, may also differ in chemical structure from the polyol used in the beta oligomer. For example, the polyol used to obtain the alpha oligomer, may be a copolymer of 1,2-butilenica and ethylene oxide, whereas the polyol used to obtain beta-oligomer may be polypropylenglycol. In addition, the polyol used to obtain the alpha oligomer, can be a difficult polyetherpolyols, while polyol as one connection is used to obtain a beta oligomer, is a simple polyetherpolyols.

[0060] Brednikova molecular weight beta oligomer is preferably from 3000 g/mol to 10,000 g/mol, more preferably from 7000 g/mol to 9,000 g/mol. For this purpose, the chain extension applied for a beta oligomer, choose accordingly molecular weight. Suitable polyol as one connection extension chain include complex polyether polyols and simple polyether polyols, for example commercially available PREMINOL PML S-X4008 (MW=8000 g/mol), PML S-4011 (MW=10000 g/mol), PML S-X3008 (MW=8000 g/mol), PML S-3011 (MW=10000 g/mol), PML 7001 (MW=6000 g/mol), PML 7003 (MW=6200 g/mol) and PML 7012 (MW=10000 g/mol) (manufactured by Asahi Glass Co., Ltd.), and Perminol P1010 (MW=1000 g/mo is ü) (produced by BASF).

[0061] the Proportion of the polyol, diisocyanate and hydroxyethylacrylate preferably determined so that those present in the diisocyanate isocyanate groups and being present in hydroxyethylacrylate hydroxyl groups are, respectively, 1.1 to 3 equivalents, and 0.2-1.5 equivalent per one equivalent of hydroxyl groups present in the polyol.

[0062] the Total number of alpha-and beta oligomer-oligomer included in the radiation-curable coating composition for optical fibers according to the present invention is usually from 30 to 95 wt.%, preferably from 35 to 95 wt.%, more preferably from 40 to 80 wt.%, and most preferably from 50 to 80 wt.%, calculated on the total weight of the composition. Beta oligomer preferably present in the composition in an amount of from 0.1 to 30 wt.%, preferably from 1 to 25 wt.%, and more preferably from 3 to 20 wt.% of the total number of alpha-and beta oligomer-oligomer present in the composition.

[0063] When used in the composition of the secondary coating of the alpha oligomer in accordance with one aspect of the present invention in combination with writersdigest a beta oligomer, in particular an oligomer described in WO 2005/026228 A1, it is desirable to achieve a cured coating having a relatively low modulus of elasticity, at the same time maintaining a high Twith. As submitted the Xia, this is due to microphase separation within the final coating. The modulus of elasticity of the cured coating is less than 1500 MPa, preferably less than 1000 MPa, whereas Twiththe cured coating is 70°C or higher. In this preferred embodiment, radiation-curable composition comprises alpha oligomer and urethane-acrylate beta oligomer having a structure derived from the polyol, and having srednecenovogo molecular weight of 4000 g/mol or more, but less than 16000 g/mol, the composition comprises from 30 to 95 wt.% alpha and beta oligomer-oligomer, and a beta oligomer is from 0.1 to 30 wt.% of the total number of alpha-and beta oligomer-oligomer present in the composition.

[0064] the alpha oligomer may be mixed with a beta oligomer (with formation of a mixture of oligomers of the secondary coating in the coating composition in any suitable way and in any relative amount. The overall percentage of urethane linkages in the resulting coating composition may be determined based on the molar amount used in the reaction of isocyanate compounds as follows.

% urethane=[(wt.% used isocyanate/MW isocyanate)×(MW urethane)]/weight of coating

[0065] the Reactive functional end group of the alpha oligomer preferably is active when it is exposed to actinic radiation. Preferably radiation-curable reactive functional end group includes ethylene unsaturation, which can be depolimerization by radical polymerization or cationic polymerization. Specific examples of suitable ethylene unsaturation are group containing acrylate, methacrylate, styrene, simple vinyl ether complex vinyl ether, N-substituted acrylamide, N-vinylamide, esters of maleic acid and esters of fumaric acid. Preferably the ethylene unsaturation is provided by a group containing acrylate, methacrylate, N-vinyl or styrene functional group, most preferably acrylate functional fragment. The oligomer is effective for curing the ultraviolet (UV) coating compositions for optical fibers.

Gamma oligomer

[0066] In a preferred embodiment of the invention the composition of the secondary coating includes a third oligomer (gamma oligomer). Gamma oligomer can be derived from the anhydride, i.e. not contain urethane, or, alternatively, may be orlandomiami oligomer. Typical gamma oligomer is epoxidization and does not contain a urethane component. Preferred epoxidized is a CN-120 or CN-12Z, epoxidized based on bisphenol A. Gamma oligomer preferably has srednecenovogo molecular weight of 500 g/mol or less, and extension, if cures by itself and not as part of a radiation curable secondary coating.

[0067] the alpha oligomer may be mixed with a beta oligomer and gamma oligomer, if present, with formation of a mixture of oligomers of the secondary coating in the coating composition in any suitable way and in any relative amount.

Reactive diluents

[0068] the radiation-Curable coating composition according to the invention optionally further include at least one reactive diluent, which can be used to regulate the viscosity of the compositions. Reactive diluents can be a monomer with low viscosity, having at least one functional group capable of polymerization when exposed to actinic radiation. This functional group may have the same nature, as used in radiation-curable alpha oligomer or beta oligomer. Preferably the functional group present in the reactive diluent capable of copolymerization with the radiation-curable functional group being in the alpha oligomer or without the a-oligomer. More preferably, the radiation-curable functional group forms free radicals during curing, which can react with the free radicals formed on the surface of the optical fiber with the processed surface.

[0069] for Example, the reactive diluent can be a monomer or mixture of monomers having the functional fragment of the acrylate or simple vinyl ether and4-C20is an alkyl or easy polyester fragment. Specific examples of such reactive diluents include hexylaniline, 2-ethyl hexyl acrylate, isobutylacetate, dellaquila, laurelcrest, stearylamine, 2-ethoxyacetylene, Laurelville simple ether, 2-ethylhexylacrylate simple ether, isodecyladipate, isooctadecyl, N-vinylcaprolactam, N-vinyl pyrrolidone, the acrylate of tripropyleneglycol, acrylamide and alkoxysilane derivatives, such as the ethoxylated laurelcrest, the ethoxylated isodecyladipate and the like.

[0070] Another type of reactive diluent that can be used is a compound having an aromatic group. Specific examples of reactive diluents having an aromatic group include acrylate simple phenyl ether of ethylene glycol, AKP is lat simple phenyl ether of polyethylene glycol, acrylate simple phenyl ester polypropylenglycol and alkyl substituted phenyl derivatives of the above monomers, such as acrylate simple nonylphenylether ether of polyethylene glycol. Suitable ethoxylated nonylphenolic.

[0071] the Reactive diluent may also include a diluent having two or more functional groups capable of polymerization. Specific examples of such diluents include diacrylate diols with2-C18-hydrocarbon fragments, simple divinelvie esters with C4-C18-hydrocarbon fragments, triacrylate with3-C18-hydrocarbon fragments and their simple polyether analogues and the like, such as diacrylate 1,6-hexandiol, triacrylate of trimethylolpropane, simple divinely ether hexandiol, diacrylate triethylene glycol, triacrylate pentaerythritol, diacrylate ethoxylated bisphenol a, diacrylate tripropyleneglycol and triacrylate Tris-2-hydroxyethylmethacrylate (SR-368).

Antioxidant

[0072] the Antioxidant is a spatial shortness of phenolic compounds such as 2,6-di-tert-butyl-4-METHYLPHENOL, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, and such commercially available compounds, as thiodiethyl-bis(3,5-di-tert-is util-4-hydroxy)hydrocinnamate, octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,6-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) and tetrakis(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))methane, all commercially available under the trade names Irganox 1035, 1076, 259 and 1010, respectively, of the company Ciba Geigy. Other examples of spatial difficult phenolic compounds suitable here include 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and 4,4'-methylene-bis(2,6-di-tert-butylphenol), available on the market as Ethyl 330 and 702, respectively, of the company Ethyl Corporation. Preferably the antioxidant is thiodiethyl-bis(3,5-di-tert-butyl-4-hydroxyl)hydrocinnamate (for example, Irganox 1035).

Photoinitiator

[0073] the coating Composition according to the invention optionally further includes photoinitiator or a mixture of photoinitiators to promote curing of the compositions during exposure of the active radiation and to provide a satisfactory speed curing. Illustrative examples of photoinitiators applicable in the coating composition of the present invention, are isobutyl simple benzoin ether; 2,4,6-trimethylbenzoyl-diphenylphosphine; bis(2,4,6-trimethylbenzoyl)phenylphosphine (sold under the trade name Irgacure 819)and 1-hydroxycyclohexane; 2-benzyl-2-dimethylamino-1-(4-morph linopril)butane-1-he; 2,2-dimethoxy-2-phenylacetophenone; perfluorinated diphenylethanone; 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone; 2-hydroxy-2-methyl-1-phenylpropane-1-he; 4-(2-hydroxyethoxy)phenyl-2-hydroxy-2-propylketone, dimethoxyphenylacetone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-he; 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-he; 4-(2-hydroxyethoxy)phenyl-2-(2-hydroxy-2-propyl)ketone; detoxification; a mixture of (2,6-dimethoxybenzoyl)-2,4,4-trimethylindolenine and 2-hydroxy-2-methyl-1-phenylpropane-1-it; benzophenone; 2-methyl-1-(4-(methylthio)phenyl)-2-(4-morpholinyl)-1-propanone, and mixtures thereof.

[0074] the radiation-Curable coating composition of the present invention optionally contains one or two photoinitiator phosphinoxide type, such as photoinitiator type 2,4,6-trimethylbenzenesulfonamide (SRW) or type besatisfied (VARO), and/or photoinitiator α-hydroxyketone type (for example, Irgacure 184 (i.e. 1-hydroxycyclohexane, manufactured by Ciba Geigy) or Darocur 1173 (i.e. 2-hydroxy-2-methyl-1-phenylpropane-1-he, manufactured by Ciba Geigy)). Even more preferred mixture of besatisfied (VARO), Lucirin TPO (i.e. 2,4,6 - trimethylbenzenesulfonamide, manufactured by BASF Corporation), Irgacure 184, Darocur 1173 and Irgacure 907 (i.e. 2-methyl-1-[4(methylthio)phenyl]-2-morpholinopropan-1-it is manufactured by Ciba Geigy).

P is ocie supplements

[0075] other additives that may be used in the coating composition include, but are not limited to, catalysts, lubricants, improving slip additives, wetting means, amplifiers adhesion and stabilizers. Selection and use of such additives is within the competence of a qualified specialist in this field of technology.

[0076] In a preferred embodiment of the invention the composition of the secondary coating includes one or more improves the slip additives. Preferred improves slip additives include DC-190, DC-57. It is most preferable to use a mixture of DC-190, DC-57. DC-57 is a siloxane derivative dimethyl-methyl(propyl(poly(ethylene oxide))acetate; registration number CAS 70914-12-4. DC-190 is a mixture of (a) from 40.0 to 70.0 wt.% siloxane derivative dimethyl-methyl(propyl(poly(ethylene oxide)(propylene oxide))acetate; registration number CAS 68037-64-9; (b) from 30.0 to 60.0 wt.% monoallelic simple ester of poly(ethylene oxide-propylene oxide)acetate; registration number CAS 56090-69-8; (C) less than 9,0 wt.% acetate simple polyetherpolyols, registration number CAS 39362-51-1. DC-57, DC-190 manufactured by the company Dow Corning.

[0077] In a preferred embodiment, the composition of the secondary coating according to the invention the mass percentage of each of the component of radiation curable secondary coating is as follows:

Alpha oligomer
Anhydridefrom 5 to 7 wt.%
Hydroxyl-containing (meth)acrylatefrom 3 to 5 wt.%
Epoxidefrom 5 to 9 wt.%
The first catalyst0.005 to 0.25 wt.%
The second catalystfrom 0.01 to 0.05 wt.%
Inhibitor of polymerizationfrom 0.01 to 0.05 wt.%

Beta oligomer
Hydroxyethylacrylatefrom 3 to 5 wt.%
Diisocyanatefrom 4 to 6 wt.%
Simple polyetherpolyolsfrom 13 to 17 wt.%
Inhibitor of polymerization (e.g., BHT)from 0,010 and 0.125 wt.%
Catalyst0.005 to 0.025 wt.%

Gamma oligomer
Epoxidizedfrom 20 to 30 wt.%

Other additives
The first monomer-diluentfrom 5 to 7 wt.%
The second monomer-diluentfrom 20 to 25 wt.%
Antioxidantfrom 0.25 to 1.25 wt.%
First photoinitiatorfrom 1 to 4 wt.%

The second photoinitiatorfrom 0.25 to 0.95 wt.%
Improves slip additives (optional)from 0.35 to 0.75 wt.%

[0078] In a higher degree preferred variant implementation of the composition of the secondary coating according to the claimed invention now is the following:

Alpha oligomer47,94 wt.%
Anhydride (for example, NNRA) 6,86 wt.%
Hydroxyl-containing (meth)acrylate (for example, NEA)4.3 wt.%
Epoxide (for example, Epotec yd-126 or Epotec yd-128)to $ 7.91 wt.%
The first catalyst (e.g., DABCO)0.01 wt.%
The second catalyst (e.g., TPP)0.03 wt.%
Inhibitor of polymerization (e.g., BHT)0.03 wt.%

Beta oligomer24,87 wt.%
NOPE4.3 wt.%
Diisocyanate (e.g., TDI)5,12 wt.%
Simple polyetherpolyols (for example, R)15,44 wt.%
Inhibitor of polymerization (e.g., BHT)of 0.05 wt.%
The catalyst (for example, DBTDL)0.01 wt.%

Gamma oligomer
Epoxidized for example, CN120Z)23 wt.%

Other additivesto 4.52 wt.%
The first monomer-diluent (for example, isobutylacetate)6 wt.%
The second monomer-diluent (for example, diacrylate tripropyleneglycol)22.98mm wt.%
Antioxidant (for example, Irganox 1035)0.5 wt.%
First photoinitiator (for example, Irgacure 184)2.76 wt.%
The second photoinitiator (e.g., TPO)0,76 wt.%
0.5 wt.%
Improves slip additives (e.g., DC-57+DC-190)(to 0.17 wt.%+of 0.33 wt.%)
Just100,33 wt.%
*0,33 other ingredients are not present, and when present the optional mixture improves slip additives

[0079] Once found a commercially available primary coverage, it can be applied directly onto the surface shall be fiber optic. Curable by radiation of the primary coating can be any commercially available radiation curable primary coating for optical fibers. Such commercially available radiation curable primary coating produced by the firm DSM Desotech Inc. and others, including, but without limitation, Hexion, Luvantix and PhiChem. As the primary coating in the present invention can be used, for example, coating, described in documents EP 2089333 B1, WO 2010/053532, US 6534557 and US 6306924.

[0080] After the primary coating is applied, then the surface of the primary coating is applied to the secondary coating, produce radiation and utverjdayut secondary coating. When the secondary coating is declared now the invention, the preferred type of radiation is UV radiation.

[0081] the Stretching is carried out with the use of either "wet on dry"or "wet on wet". Mode "wet on dry" means that the liquid primary coating is applied wet, and then affect the radiation for curing the liquid primary coating to a hard layer on the wire. After curing the primary coating is applied to the secondary coating and then also utverjdayut. Mode "wet on wet" means that the liquid primary coating is applied wet, then the secondary coating is applied wet and then utverjdayut both coatings primary and secondary.

If the secondary coating is transparent and not colored, it may be covered with a layer of paint covering. If the second floor is painted, the layer of the coating of paint is usually not applied on the secondary floor. Regardless of whether applied paint coat, common practice is to place multiple covered with fibers parallel to each other in the team ribbon (bus), application of a radiation-curable matrix coatings for fixation of many fibers in his place in this team the tape.

[0082] After the secondary curing of the coating is typically applied layer of the coating of paint, and then covered and coated optical fiber fitted in parallel to other covered and coated optical fibers in the ribbon and cause radiation-curable matrix coating for fixing optical fibers in a desired position in the team the tape.

The properties of the secondary coating

[0083] the secondary coating obtained from the coating composition according to the invention, it is desirable to have properties, such as modulus of elasticity, impact strength and elongation, suitable for coating on the optical fiber. The secondary coating typically has an impact strength of more than 12 j/m3, the secant modulus of elasticity less than 1500 MPa and Twithhigher than 50°C. P is edocfile, the secondary coating has an impact strength of more than 14 j/m3, the secant modulus of elasticity of 200 MPa to 1200 MPa and Twithhigher than 60°C. More preferably, the secondary coating has an impact strength of more than 16 j/m3, the secant modulus of 400 MPa to 1000 MPa and Twithhigher than 70°C. the secondary coating preferably has an elongation of from 30% to 80%. In addition, preferably, the secondary coating shows the change in equilibrium modulus at 20% or less, when aged for 60 days at 85°C and 85%relative humidity.

[0084] the secondary coating obtained from the coating composition according to the invention, it is desirable to have the sensitivity to oil and/or sensitivity to water, suitable for coating on the optical fiber. Typically the secondary coating will have the sensitivity to oil 10% or less, and the sensitivity to water of 10% or less. Preferably the secondary coating will have the sensitivity to oil 5% or less, and the sensitivity to water of 5% or less.

[0085] the elastic Modulus, as is well known, represents the rate of change of deformation depending on the voltage. Graphically this is represented as the slope of the straight part of the chart depending on the "stress-strain". The module can be determined by use of any device suitable for receiving the Riva according to "stress-strain" pattern. Devices suitable for this analysis include manufactured by Instron, Inc. and including the Instron model 5564.

[0086] When determining the modulus of elasticity of hardened coating compositions in accordance with the invention, the sample radiation curable compositions stretch on the plate to create a thin film or, alternatively, is formed in the form of a rod using a cylindrical template. The sample is then exposed to radiation to effect the curing. One (or more, if desired average value) of the sample film cut from utverzhdenii film. Sample(sci) should be declared to be free(s) from major defects, such as holes, jagged edges, significant non-uniformity of thickness. The opposite ends of the sample is then clamped in the device. During the test the first end of the sample remains stationary while the device moves the second end away from the first end, which may be called by the speed slider. The speed of the RAM, which may be initially set at 2.54 cm/minute (1 inch/minute), can be changed, if it is unacceptable for a particular sample, for example, a film with high modulus is broken before a satisfactory curve "stress-strain". After completing the settings, then WA what is the test device, who gives a curve dependence of stress-strain, elastic modulus and other data.

[0087] it is Important to note that the impact strength can be measured in several ways. One path includes the modulus of tensile elasticity for toughness, which is based on the ability of a material to absorb energy up to the point of destruction, and which is determined by measuring the area under the curve "stress-strain". Another way of measuring toughness is the resistance to the development of cracks based on the tensile strength that requires to start the test with a predetermined very sharp crack of a certain length and to use the critical stress intensity factor caused by the resistance of a material to the propagation of cracks.

[0088] the Invention will be further elucidated with the following examples.

EXAMPLES

[0089] the Abbreviations used in the following examples, have the following meanings:

• A-189 mean γ-mercaptopropionylglycine

• TDI means colorvision

• IPDI means isophorondiisocyanate

• NRA means hexahydrophthalic anhydride

• MNNR means methylhexahydrophthalic anhydride

• SA means succinic anhydride

• PA means phthalic anhydride

• MA means maleic anhydride

• DDSA means dodecanesulfonyl anhydride

• OSA means oktaviantrie anhydride

• EPON825 means bisphenol a/epichlorohydrin

• EPON828 means bisphenol a/epichlorohydrin

• YD-126 mean bisphenol a/epichlorohydrin

• SynFac 8015 means propoxycarbonyl bisphenol a (15 moles RO)

• Photomer 3016 means epoxyacrylate derived from diglycidylether simple ether of bisphenol a and acrylate (TPGDA, TMPTO or GPTA)

• Cadura E-10 means monolithically simple ether acid "versatic"

• VAME means monolithically simple ether acid "versatic"

• ON means 12-hydroxystearic acid

• TEG means triethylene glycol

• NEA means hydroxyethylacrylate

• RRA means monoacrylate of polypropylenglycol

• TPGMA means monoacrylate tripropyleneglycol

• TPGDA means diacrylate tripropyleneglycol

• SR-306 means diacrylate tripropyleneglycol

• SR-349 means diacrylate ethoxylated bisphenol

• SR-351 means triacrylate of trimethylolpropane

• SR-444 means triacrylate pentaerythritol

• SR-495 means the hydroxyl-containing polycaprolactones

• SR-504 means acrylate of ethoxylated Nonylphenol

• Photomer 4003 G means acrylate of ethoxylated Nonylphenol

• Photomer 4028 means diacrylate e is oksidirovannaja bisphenol

• Photomer 4061 means diacrylate tripropyleneglycol

• Photomer 4066 means acrylate of ethoxylated Nonylphenol

• Photomer 4006 means triacrylate of trimethylolpropane

• Photomer 4072 means triacrylate propoxyethanol of trimethylolpropane

• CN-120Z means epoxidized based on bisphenol

• Irgacure 819 means bis(2,4,6-trimethylbenzoyl)phenylphosphine

• Irganox 1035 means thiodiethyl-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)

• Irgacure 184 is 1-hydroxycyclohexane

• TRO means 2,4,6-trimethylbenzenesulfonamide

• TPP means triphenylphosphine

• DABCO means 1,4-diazabicyclo[2.2.2]octane

• DBTDL means dilaurate dibutylamine

• IPA means isophthalic acid

• Pripol 1006 means dimer dicarboxylic fatty acid

• EMPOL 1004 means gidrirovannoe a dimer acid obtained by the dimerization of fatty18acids

• BHT means of 2,6-di-tert-butyl-4-METHYLPHENOL

• Tereflex 85 mean complex polyester resin

• Uralac P5525 means a complex polyester containing carboxyl end groups

• Mr diol is 2-methyl-1,3-propandiol

• P710 means polypropyleneglycol (MW=700 g/mol)

• R means polypropyleneglycol (MW=1000 g/mol)

• R means polypropyleneglycol (MW=2000 g/mol)

• R means polypropyleneglycol (MW=4000 g/m is l)

[0090] the alpha oligomer can be obtained, for example, using hexahydrophthalic anhydride (NRA), which has a temperature of melting/solidification 35°C, so it can be heated in an oven to make liquid. Alpha oligomer can be obtained from a mixture of three monomers added in the following order: first, BHT (an inhibitor of polymerization of acrylate), the molten NRA and hydroxyethylacrylate (NEA) are combined and heated to achieve the desired temperature of 110°C. second, after about one hour, when the acid number of the mixture 205 mEq KOH, add epoxydodecane connection EPON 825 (EPON) together with the catalysts with triphenylphosphine and DABCO. Finally, after about 10-14 hours, when the acid number of the mixture is less than 5.0 mEq KOH, the product removed from the reaction chamber. The reaction product is represented with the following theoretical structure:

HEA-HHPA-EPON-HHPA-HEA.

[0091] the Acid value (AV) is measured as follows: approximately 2 grams of sample was diluted in 50 ml of acetone, mixed with 50 ml of isopropyl alcohol. The mixture potentiometrically titrated using 0.1 m solution of potassium hydroxide in methanol standard solution (KOH/Meon) after stirring for 5 minutes. Both acid number (AV1 for acids having PKand≤2, and AV2 for acids having PKand >2) automatically detect the device Brinkmann 751 Tirino Titrator.

[0092] Other alpha-oligomers can be obtained by using the extension chain for changes in molecular weight. For example, the acrylate (for example, NEA), anhydrous compound (for example, NNRA) and/or 12-hydroxystearate acid (ON) and/or polyol (for example, polypropylenglycol or “PPG”) can be mixed in the reactor together with BHT as an inhibitor of polymerization of the acrylate. The air used for purging to ensure the regeneration of BHT to maintain its activity as an inhibitor of polymerization. The reaction mixture is slowly heated to 80°C, and at this point begins slightly exothermic reaction with the disclosure of anhydrite cycle as a result of interaction with the hydroxyl group of the NEA or carboxylic acid group 12-hydroxystearate acid with the formation of derivatives with terminal acid groups. Then the progress of the reaction is controlled by cooling and heating until it reaches a temperature of 110°C. reaction Conditions constant support within one hour. When the mixture is present in the polyol, such as PPG, one mole of the anhydride of NRA will react with each terminal hydroxyl group of polypropylenglycol education pre-oligomer with terminal dicyclomine groups. Then to the mixture add polyfun the national epoxide.

[0093] In the case of a derived 12-hydroxystearate acid (ON) product preferably has a theoretical structure:

[HEA-HHPA]-EPON-[HHPA-12OH]-EPON-[HHPA-HEA].

In the case of a derived polypropyleneglycol (PPG) the product contains a mixture of theoretical structures:

[HEA-HHPA]-EPON-[HHPA-HEA]

[HEA-HHPA]-EPON-[HHPA-PPG-HHPA]-EPON-[HHPA-HEA].

[0094] In addition to using a diol as a chain extension glycidyloxy ester neodecanoic acid (Cardura E10 sold by Hexion Speciality Chemicals, also known as monoglycerol ester acid "versatic" or VAME) are used as chain extension can be enabled in the reaction mixture. This leads to the following derivative:

[HEA-HHPA-VAME-HHPA]-EPON-[HHPA-HEA]

and/or

[HEA-HHPA]-EPON-[HHPA-VAME-HHPA]-EPON-[HHPA-HEA].

[0095] table 1A lists the amount in wt.% anhydride, acrylate, epoxide 1, epoxide 2 (if present), chain extension (if present), catalyst 1, catalyst 2 and the polymerization inhibitor used to obtain a variety of alpha-oligomers (compounds A-W), suitable for use in the compositions of the secondary coating in accordance with the invention. In each case, the anhydride is NRA, the acrylate is an NEA, epoxide 1 is an EPON 825, catalyst 1 is a TPP, the catalyst 2 is a DABCO, and the inhibitor polymers the tion represents BHT, if not otherwise specified.

[0096] table 1b lists the amount in wt.% isocyanate, acrylate, connection-chain extension (if applicable), catalyst and polymerization inhibitor used to obtain a variety of traditional orlandersmith oligomeric compositions (formulations AA-AI), suitable as a beta oligomers for use in the compositions of the secondary coating. In each case, the diisocyanate is a TDI, the acrylate is an NEA, the catalyst is a DBTDL, and the polymerization inhibitor is a BHT, unless otherwise specified.

[0097]

TABLE 1b
The compositions of beta-oligomers for the compositions of the secondary coating
Ave. No.Isocyanate(wt.%)Acrylate 1(wt.%)Acrylate 2
(wt.%)
The chain extension(wt.%)Catalyst(wt.%)Inhibitor(wt.%)
AA30,824,7EPON 825/VAME 5,2/13,812OH
25,5
(DABCO) 0,010,00
AB(IPDI/TDI) 9,41/2,953,93---P2010
83,43
0,090,19
AU6,512,99---P1044
90,4
0,030,07
AD3,95was 2.76---PPG8000
93,25
0,020,02
AE4,291,33TPGMA*
50,0
P1044
44,43
0,0150,02
AF2,789(TPGDA) 30,0CN120Z
30,0
P1044
37,176
0,0150,02
AG4,39(TPGDA) 25,00SR-495
by 5.87
P55-28
64,705
0,0150,02
EN18,815,0SR-504
13,8
PTGL1000
43,7
TPO/DABCO 2,2/0,040,08
AI21,3314,22---P1010
64,35
0,0150,05
*includes some amount of reactive diluent TPGDA

[0098] the coating Composition comprising the above-described alpha-oligomers and beta oligomers prepared in accordance with the following examples. For the total number of parties in 50 g 25 g alpha oligomer composition And 7.5 g ratanawaraha beta oligomer composition of the AU and 15.5 g of diluent SR-306 (i.e. diacrylate tripropyleneglycol) is weighed and placed in the vessel 100, the Mixture is heated in a furnace with air supply at 80°C with periodic mixing manually, until the mixture becomes homogeneous. The mixture is allowed to cool down to a temperature below 70°C, and at this point, add the following powders: 1.5 g of photoinitiator Irgacure 184, 0.25 g photoinitiator Chivacure TPO and 0.25 stabilizer Irgacure 035. The resulting mixture was mechanically stirred for one hour at a speed of 275 rpm on a hot tile with controlled liquid temperature of 70°C. the Reaction mixture cover with aluminum foil for protection from ambient light.

[0099] table 2A lists the components of the comparative composition of the secondary coating (coating 1-14), including alpha oligomer in the absence of a beta oligomer or gamma oligomer. Alpha-oligomers are listed in Table 1A and received in accordance with the above method.

TABLE 2A
Compositions for secondary coatings
Floor No.Alpha oligomer(wt.%)Diluent 1(wt.%)Diluent 2(wt.%)Stabilizer(wt.%)Photoinitiator(wt.%)
1A
60
TPGDA
36
---Irg 1035
0,5
Irg 184/TPO
3/0,5
2In
60
TPGDA
31
Ph 4003g
5
Irg 1035
0,5
Irg 184/TPO
3/0,5
3With
60
TPGDA
31
Ph 4003g
5
Irg 1035
0,5
Irg 184/TPO
3/0,5
4D
60
TPGDA
33,5
Ph 3016
2,5
Irg 1035
0,5
Irg 184/TPO
3/0,5
5D
60
TPGDA
36
---Irg 1035
0,5
Irg 184/TPO
3/0,5
6E
60
TPGDA
33,5
Ph 3016
2,5
Irg 1035
0,5
Irg 184/TPO
3/0,5
7F
60
TPGDA
36
---Irg 1035
0,5
Irg 184/TPO
3/0,5
8G
60
TPGDA
36
---Irg 1035
0,5
Irg 184/TPO
3/0,5
9H
60
TPGDA
31
Ph 4003g
5
Irg 1035
0,5
Irg 184/TPO
3/0,5
10I
60
TPGDA
31
Ph 4003g
5
Irg 1035
0,5
Irg 184/TPO
3/0,5
11J
64
TPGDA
27
Ph 4003g
5
Irg 1035
0,5
Irg 184/TPO
3/0,5
12To
60
TPGDA
31
Ph 4003g
5
Irg 1035
0,5
Irg 184/TPO
3/0,5
13L
64
TPGDA
27
Ph 4003g
5
Irg 1035
0,5
Irg 184/TPO
3/0,5
14M
62,5
TPGDA
28,5
SR-351
5
Irg 1035
0,5
Irg 184/TPO
3/0,5

[0100] That is face 2b lists the components of the composition of the secondary coating (coating 15-23), comprising a mixture of alpha and beta oligomer-oligomer listed in Tables 1A and 1b and received in accordance with the above method.

Irg 184/TPO
3/0,5
TABLE 2b
Compositions for secondary coatings
Floor No.Alpha oligomer(wt.%)Beta oligomer(wt.%)Gamma oligomer(wt.%)Thinner(wt.%)Stabilizer(wt.%)Photoinitiator(wt.%)
15A
48
AB
20
---TPGDA
28,8
Irg 1035
0,4
Irg 184/TPO 2,4/0,4
16A
51
AB
15
---TPGDA
30
Irg 1035
0,5
Irg 184/TPO
3/0,5
17A
61,25
AB
14
---TPGDA
20,75
Irg 1035
0,5
18A
49,6
AC
15
---TPGDA
of 31.4
Irg 1035
0,5
Irg 184/TPO 0,3/0,5
19A
49,6
AD
15
---TPGDA
of 31.4
Irg 1035
0,5
Irg 184/TPO
3/0,5
20A
50,00
AC
30,0
---TPGDA
16,0
Irg 1035
0,5
Irg 184/TPO
3/0,5
21*A
42,11
AF
31,39
---TPGDA
22,5
Irg 1035
0,5
Irg 184/TPO
3/0,5
22*A
43,6
AG
of 17.5
CN-120Z
7,5
TPGDA
27,4
Irg 1035
0,5
Irg 184/TPO
3/0,5
23M
37,34
AI
23,91
CN-120Z
22,91
TPGDA
11,46
Irg 1035
0,5
Irg 184/TPO 2,75/0,76
* Comparative example

[0101] table 2C lists the components of the comparative composition of the secondary coating (coating 23-28), not containing alpha oligomer containing only traditional orlandomiami beta oligomer specified in Table 1b, or other components as specified.

TABLE 2C
Comparative compositions for secondary coatings
Floor No.Beta oligomer(wt.%)Diluent 1(wt.%)Diluent 2(wt.%)Stabilizer(wt.%)Photoinitiator(wt.%)
24 (comparative example)AA
60
TPGDA
36
---Irg 1035
0,5
Irg 184/TPO
3/0,5
25 (comparative example)ACB
55
Ph 4003g
42,5
---Irg 1035
0,5
A-189/Irg 819 0,9/1,1
26 (comparative example)---Ph 4028
77
Ph 3016
20
Irg 1035
0,5
Irg 184/Irg 819 1,5/1,5
27 (comparative example)SR-444
39,9
Ph 4028
37,1
Ph 3016
20
Irg 1035
0,5
Irg 184/Irg 819 1,5/1,5
28 (comparative example)AH
44
SR-349
56
---Irg 1035
1,2
Irg 184
a 4.9

[0102] Comparative examples 26 and 27, shown in Table 3, obtained respectively according to test coatings 1 and 10 presented in Table 1, column 20, U.S. patent 6707977 B2, which are obtained using commercially available materials. Comparative example 27 includes SR-444, which represents triacrylate pentaerythritol, sold by Sartomer Co. Comparative example 28 prepared with oligomer-based comparative example EN, which contains a set of materials for curing, as listed is Table 1A. The composition of the secondary coating, shown above in Tables 2A-2C, tested for various physical properties after curing, including modulus, tensile strength, elongation, modulus of tensile elasticity and sensitivity to oil and water.

[0103]Test methods

[0104]The modulus of Elasticity: The modulus of elasticity is determined using dynamic mechanical analysis (DMA). Storage modulus (E') of elasticity, loss modulus (E”) viscosity and tan Delta (E”/E') was measured by standard methods DMA. Cut out a free sample of the cured film of the material to size (approximately 35 mm in length), measure its width and thickness and mounted. The temperature in the artificial climate chamber containing the sample is brought to 80°C. the Sample stretch before scanning for temperature. The temperature decrease predetermined steps to the initial temperature. Start scanning by temperature and allowed to flow up the temperature scale to the exit of material from a range of vitrification and deep in the high region. The DMA device (Rheometrics Solids Analyzer RSA-II, equipped with a personal computer) displays on the computer display a graph with the data. From this graph to calculate the temperature at which E' is 1000 MPa, and E' is 100 MPa and tan δmax. Measure the minimum value of E', achieved in highly elastic region, and recorded in Table 3 as the equilibrium modulus of elasticity or modulus of viscoelasticity. Additional test samples prepared in the same manner, is subjected to aging in a controlled chamber supported at the temperature of 85°C and 85%relative humidity. After 60 days of aging under these conditions, the set of test samples is extracted and experience in accordance with the above procedure, dynamic mechanical analysis and determine the equilibrium modulus. This value is compared with the equilibrium modulus of elasticity to aging, and the result is fixed as a percentage loss of equilibrium modulus or change after 60 days of aging relative to their initial values.

[0105] the Data about the module of elasticity for hardened compositions of the secondary coating comprising only the alpha oligomer (cover 1-14), alpha oligomer in combination with a beta oligomer (cover 15-23) and comparative composition of the secondary coating including traditional urethane oligomers (cover 24-28), are shown in Table 3.

[0106]

[0107] the Results shown in Table 3, demonstrate that the composition of the coating prepared with the alpha oligomer, have Twithand percentage (%) change in equilibrium modulus pic is f aging, which are comparable to coating compositions containing urethane oligomers. All of the secondary coating according to the invention (coating 15-20 and 23) have shown Twithhigher than 50°C. These coatings also exhibit very good hydrolytic stability as compared with the comparative experiments, in terms of percentage change in equilibrium modulus after aging.

[0108]Test methods tensile strength, elongation and modulus of elasticity:

[0109] the Mechanical properties of tensile radiation curable secondary coating for optical fibers have on the films using a universal measuring device Instron Model 4201, equipped with suitable personal computer and software Instron, to obtain values of ultimate tensile strength, percentage elongation at break and hewer or segment of the modulus of elasticity. Torque sensors are designed for the load of 0.9 or 9.1 kg (2 or 20 pounds). For the preparation of samples for testing hood (utverzhdennuyu film) of each of the test material is produced on a glass plate and utverjdayut using a UV processor. Utverzhdennuyu film is conditioned at a temperature of 23±2°C and relative humidity of 50±5% for at least sixteen hours before the IP is Itanium. From utverzhdenii film cut at least eight test pieces having a width of 1.27±0,005 cm (0.5±0.002 inches) and a length of 12.7 cm (5 inches). To minimize the effect of small defects in the samples, the test samples cut parallel to the direction in which the prepared extracts utverzhdenii film. If the cured coating is sticky to the touch on the surface of the film causing a small amount of talc using an applicator with a tip made of cotton.

[0110] the Test samples are then separated from the substrate. Be careful not to stretch the test samples to their limit of elasticity at the time of separation. If the separation from the substrate is any noticeable change in the length of the sample, the test sample reject. If the top surface of the film coated with talcum powder to remove the stickiness, the small amount of talc is applied on the bottom surface of the test sample after removal from the substrate.

[0111] the Average film thickness of the test samples is determined using a micrometer. Spend at least five measurements of the film thickness in the tested area (from the top surface to the bottom), and calculations used the average value. If any of the measured values of the film thickness deviated from the average by more che is 10% relative, test sample reject. The width of the film is also measured. All samples originate from the same plate, and in General at least six strips are required for characterizing the strain. After calibration and standardization of each test sample experience by hanging it in the gap between the upper pneumatic clamps so that a test sample is positioned at the center in the transverse direction and is suspended vertically. Bar top clamp (only). The lower end of the test specimen gently pull it so that it is not sagging or deflection and positioned at the center in the transverse direction between the open bottom clamps. Holding the sample in this position, lock the lower clamp.

[0112] Information on the number of samples and the size of the sample is injected into the database, following the instructions that came with the software. Then using the Instron device performs the measurements of the characteristics of strain for the sample. This is repeated for additional samples. Measure temperature and humidity after it has been tested the last sample of this extract. The calculation of the characteristics of the stretching is performed automatically using software. Values of tensile strength at elongation, percent untinen and hewer of modulus of elasticity test to determine not rejected if any one of them from the middle enough to be an "outlier". If necessary, repeat procedure. The measure of toughness calculated based on the ability of a material to absorb energy up to the point of destruction, and it is determined by measuring the area under the curve "stress-strain".

[0113] the Mechanical characteristics tensile hardened secondary coatings have on the rods according to the method described in U.S. patent 6862392. The rods are prepared by filling an elastomeric transparent tube made of silicone rubber composition of the coating and the use of UV Fusion processor. Settings UV processor Fusion following:

Lamp:D
Intensity120 W/cm
Photometer to measure light intensityIL390
Doseof 1.0 j/cm2
AtmosphereNitrogen
Time conditioned at 50%humidity 16-24 hours
The compositions exhibiting the AI to one Joule of UV radiation from the lamp D nitrogen purging.

[0114] If the tubes are rotated 180°, then there is no need for curing tubes in aluminum foil. If the tube is not rotated 180°, the tube may be cured on aluminum foil.

[0115] the Rods are then removed from the tube by gently pulling the tube from one end of the rod and cut the empty part of the tube with a razor blade. The end of the rod then firmly grasp using surgical forceps, and the tube is slowly pulled away from the terminal.

[0116] the ultimate tensile strength, elongation, modulus of tensile elasticity Emaxand the viscosity of the compositions of the secondary coating comprising only the alpha oligomer (cover 1-14), alpha oligomer in combination with a beta oligomer (cover 15-23), and comparative compositions a secondary coating, including traditional urethane oligomers (cover 24-28), are given in Table 4.

TABLE 4
Characteristics tensile for the compositions of the secondary coating
Floor No.Tensile (MPa)Elongation (%)Modulus (MPa)Impact strength (j/m3)Emax
(%)
Viscosity (MPa·s)
1*63,337187218,845,25831
2*61,847,5147821of 58.96681
3*to 49.336,31127,313,6464624
4*4339,6105113,649,67423
5*51,1a 38.51212,315,52523182
6*44,239,81058,513,949,76393
7*62the 5.719052,5of 40.3NA
8*47,543124215,952,34873
9*38,935,2919,310,948,55727
10*41,338,4126013,148,14459
11*41,843128815,1507152
12*4536,4132513,7523522
13*42128815507152
14*4830119312397519
1545,2to 38.3111813,3of 60.59066
1643,739,7107313,7539421
1756,963,41093,723,572,47462
1858,759,31036,815,0776951
1943,5to 33.81103,6 11,8566465
2049,132,61232,513,052,19693
21*50,440,4113516,2498,26885
22*41,042,3101814,749,46942
2359,047,31047,221,056,36797
24*47,831,5120312,8346751
25*NANANANANA NA
26*66,519,81899,411,331,02531
27*87,68,32206,25,3the 11.61980
28*51,93894513,95800
* Comparative example

[0117] the Results shown in Table 4, demonstrate that the compositions of the coatings obtained with the alpha oligomer, have impact strength, secant modulus of elasticity and elongation, which is comparable to coating compositions comprising urethane oligomers. Almost all of the secondary coating according to the invention is shown having an impact strength of more than 12 j/m2, the secant modulus of elasticity less than 1500 MPa and elongation of between 30-80%.

[0118]The method of determining the dynamic sensitivity to oil UV-hardened materials

[0119] the Sensitivity to oil for each sample is determined with use of the requirement of ASTM D 570 standard test method for water absorption of plastics), which describes the method of determining the maximum absorption of grease and total recoverable oil material from UV-hardened coatings, as well as the procedure for determination of dimensional changes of UV-hardened coatings when they are exposed to oil. Samples are prepared by (1) preparation of one of the hoods on the tested material with a film thickness of 150 microns (6 mils); (2) curing the film at the exposure energy of 1.0 j/cm2using a Fusion lamp D and inert nitrogen atmosphere; (3) cut in utverzhdenii film three test specimens with dimensions of about 7.5 cm×3.8 cm using a one-sided razor blade; (4) cutting small slits approximately 2 mm×2 mm in one corner of each sample so that dimensional changes can be made on the same side throughout the experiment; (5) the premises of the glass plates containing three test sample in an oven to 60°C (for temperature 60°C±3°C) one hour; (6) extraction of the glass plates and the samples from the oven and placing them in a desiccator (providing for a relative humidity of ≤20%) for 15 minutes and (7) check the relative humidity in the desiccator. Sensitivity to oil each sample is determined by (1) premises 125 ml (4 oz) light light is the logo of mineral oil into each of three Petri dishes made of glass Pyrex (dimensions 100 mm×20 mm with cover lids from glass Pyrex), supported at a temperature of 23±2)°C; (2) measure the length and width of each of the samples with an accuracy of almost 0.1 mm using a ruler, graduated with divisions of 1 mm; (3) weighting each of the test samples with an accuracy of almost 0.1 mg on an analytical balance (accurate to 0.1 mg) using corrugated Teflon paper to prevent sticking; (4) the premises of each sample in one of the Petri dishes with cable gel; (5) after 30 minutes remove the samples one by one using surgical forceps (length approximately 15-20 cm) and blot them on a wiping cloth (filter - cloth, wiping with a low fiber content); (6) repeated measurements of the length and width of the samples; (7) re-weighting of samples and placing them back in their respective for them in Petri dishes. The stage of removal, measuring and weighing of samples, as described above in paragraphs 1, 3, 6, repeated after 24 hours, 7 days and 14 days. After 21 days, the samples were re-measured and re-weighed and placed on a glass plate and placed in an oven to 60°C for one hour. The samples are then removed from the furnace and placed in a desiccator for 15 minutes, after which time record relative humidity and measured and weighed samples as before. Determine the change in weight in percent and resizing procentah for each time interval, and each set of average values. Maximum absorption oil represents the highest average positive change of weight in percent. The percentage of recoverable oil components for each sample is determined by dividing the difference between the initial dry weight and dry weight after 21-day cycle at the initial dry weight and multiplying by 100. General sensitivity to oil represents the sum of the absolute values of the maximum absorption oil and the percentage of recovered components cable gel.

[0120]The method of determining the dynamic sensitivity to water, UV-hardened materials:

[0121] the Dynamic sensitivity to water for each sample determined using ASTM D 570-81 (standard test method for water absorption plastics), which describes the method of determining the maximum water absorption and total recoverable water material from UV hardened coating. Samples are prepared by (1) preparation of one of the hoods on the tested material with a film thickness of 150 microns (6 mils); (2) curing the film at the exposure energy of 1.0 j/cm2using a Fusion lamp D and inert nitrogen atmosphere; (3) cut in utverzhdenii film three test samples with dimensions of approximately 3 cm×3 cm with the use od otorongo razor blades; (4) the premises of the glass plates containing three test sample in an oven to 60°C (for temperature 60°C ±3°C) for one hour; (5) extraction of the glass plates and the samples from the oven and placing them in a desiccator (providing for a relative humidity of ≤20%) for 15 minutes, and (6) check relative humidity and temperature in a desiccator. Dynamic sensitivity to water of each sample is determined by (1) premises 125 ml (4 oz) demineralized or distilled water in glass bottles 125 ml (4 oz) with screw-caps, supported at a temperature of 23±2)°C; (2) weighting each test sample on an analytical balance (to provide the reading to 0.0001 g) using corrugated Teflon paper to prevent sticking and placing each sample into one of the vials of water; (3) after 30 minutes remove the samples one by one using surgical forceps (length approximately 15-20 cm) and blot them on a wiping cloth (filter - cloth, wiping with a low fiber content); (4) re-weighting samples, as described above, and placing them back in proper for them bottles; (5) repeating the stages of removal and re-weighing the samples after 1, 2, 6 and 24 hours and 7 and 14 days; (6)on the 21 day re-weighting samples, as described above, and placing them on a glass plate and placed in an oven to 60°C for one hour; (7) extract the samples from the oven and placing them in a desiccator for 15 minutes and (8) check relative humidity and temperature, and re-weighing the samples, as described above. Determine the percentage weight change for each time interval, and average values. The maximum water absorption represents the highest average positive change of weight in percent. The percentage of recoverable water components for each sample is determined by dividing the difference between the initial dry weight and dry weight after 21-day cycle at the initial dry weight and multiplying by 100. Overall sensitivity to water represents the sum of the absolute values of the maximum water absorption and percentage of recoverable water components.

[0122] Data on sensitivity to oil and water for a few hardened compositions of the secondary coating according to the invention (coating 18 and 23) and comparative coating compositions (coating 1, 2, 14, 28 and DS2002) shown in Table 5.

TABLE 5
The sensitivity to water and oil solidified the secondary coating
Floor No.Max. absorbed is e oil % recoverable oilGeneral sensitivity to oilMax. absorption of H2O% extract H2OGeneral sensitivity to H2O
1*0,9080,001420,9102,1340,07512,209
2*0,8980,2391,137from 2.4450,2762,720
14*1,6020,1211,7232,4560,3612,818
180,8461,672,5192,2461,7233,969
230,9070,05430,9612,72604901 3,217
28*1,0200,09461,1151,1070,6651,772
*to 0.9000,004880,9051,8080,02681.835 squa
* Comparative example

[0123]Simulator exhaust columns

[0124] In the early years of the development of coatings for optical fibers, all newly developed primary and secondary coatings were first tested on the hardened properties of their films and then sent for evaluation to the columns of pulling the fiber. It is estimated that all of the coatings that were required to pull, no more than 30% of them felt on the extraction column due to the high cost and difficulty planning graph. The time from the moment when the first floor was, until, when it was applied to a glass fiber, typically reached approximately 6 months, which significantly slowed down the development cycle of the product.

[0125] In the technology of radiation-curable coatings for optical fibers is known that, when l is Bo primary coating, or a secondary coating applied to the glass fiber, the properties often differ from the properties of flat utverzhdenii film of the same coating. This seems to be due to the fact that the coating on the fiber and flat film coatings vary in sample size, geometry, intensity of UV radiation, the total dose received UV radiation, speed of processing, the temperature of the substrate, the curing temperature and, possibly, an inert nitrogen atmosphere.

[0126] in order to make possible a more reliable way of developing coatings and reduce the period of implementation, we developed equipment that would support curing, similar to having manufacturers fiber. This type of alternative equipment for applying and curing should be easy to handle, require less maintenance and provide reproducible process parameters. The name of this equipment - simulator extraction columns", hereinafter abbreviated as "CPI". Simulators exhaust columns are designed according to customer order and are constructed on the basis of a detailed study of the structural elements of the real pillars of drawing glass fibers. All measurements (position lamps, the distance between stages of the coating process, the intervals between stages nanese the Oia coating and UV lamps etc. are copied from the columns of drawing glass fibers. This helps to simulate process conditions used in industrial equipment for pulling the fiber.

[0127] One well-known the CPI come five lamps Fusion F600 - two for the upper stage of coating and three for the bottom. The second lamp at each stage can be rotated at various angles between 15-135°, allowing a more detailed study of the curing profile.

[0128] the "Core"used in the known CPI, is a stainless steel wires with a diameter of 130,0±1,0 μm. To assess the available applicators for pulling the fiber varied designs from various suppliers. This arrangement allows the application of the coating on the optical fiber in conditions similar to having a place in industrial enterprises.

[0129] the Simulator exhaust column has already been used for more in-depth analysis of radiation-curable coatings for optical fiber. Method of measuring in-situ modulus primary coating that can be applied to determine the strength of the coating, the degree of curing and performance of fiber in different environments was presented in 2003 by the authors P.A.M. Steeman, J.J.M. Slot, H.G.H. van Melick, A.A.F. v.d. Ven, H. Cao, and R. Johnson in Materials 52-th International Symposium cable-wire products (Proceedings of the 52ndIWCS), page 246 (2003).IN 2004 Steeman and co-authors reported as the rheological profile of the coatings of the optical fibers at high shear rate can be used to predict the maintainability of the coatings at higher speeds stretching, see P.A.M. Steeman, W. Zoetelief, H. Cao and M. Bulters, “Proceedings of the 53rdIWCS,” p. 532 (2004). Simulator extraction columns can be used to further study the properties of the primary and secondary coating on the optical fiber.

[0130] These test methods are applicable for the secondary coating on the wire or coatings on optical fiber:

[0131]Test method % RAU secondary cover:

The degree of cure in the outer coating on the optical fiber is determined using infrared spectroscopy with Fourier transform (FTIR with diamond ATR snap. The parameters of the device FTIR include: 100 jointly imposed scans, resolution 4 cm-1, DTGS detector spectral range 4000-650 cm-1approximately 25%reduction in the default rate mirrors to improve the signal-to-noise ratio. Requires two spectra: one for the uncured liquid coating, which corresponds to the coating on the fiber, and one for the outer coating on the fiber. Range of liquid coatings are produced after the coating is completely occupy the surface of the diamond. The liquid must be from the same party who, which is used for coating on the fiber, but the minimum requirement is that it should have the same composition. The final format of the spectrum must be on the uptake.

[0132] the Fiber set on the diamond and attach to the fiber pressure sufficient to obtain a spectrum that is suitable for quantitative analysis. For maximum spectral intensity of the fiber should be placed on the center of the diamond parallel to the direction of the infrared beam. If a single fiber is obtained insufficient intensity, the diamond can be placed 2-3 fibers in parallel to each other and as close as possible to each other. The final format of the spectrum must be on the uptake.

[0133] for the liquid, and to the cured coating measure the peak area as the peak of the double bond of the acrylate at 810 cm-1and control the peak in the field of 750-780 cm-1. The peak area determined using the method of the baseline, where the baseline is chosen tangent to the minima of the absorption on both sides of the peak. Then determine the area under the peak and above the base line. The limits of integration for liquid and cured sample are not identical, but similar, especially for the control of the peak.

[0134] the ratio of the area acrylate peak to the area of control of the peak is defined as liquid, and the CTE is established sample. The degree of cure, expressed as a percentage reacted acrylate unsaturation (% RAU), calculated by the following equation:

where RLrepresents the ratio of the area of the liquid sample, and RFrepresents the ratio of the area of the cured coating.

[0135]Test method for in-situ modulus of the secondary coating:In-situ modulus of the secondary coating having a two-layer coating (soft primary coating and a hard secondary coating) glass fiber or the fiber of the metal wire is measured in this test method. For preparation of a sample removed from the fiber layers covering length ~2 cm in the form of a solid tube cover with one end covered with fiber, first immersing the end of the coated fibers together with the edging tool in liquid nitrogen (N2) for at least 10 seconds, and then removing the receiver cover fast movement, while the coatings are still hard. Device DMA (Dynamic Mechanical Analysis): to measure the elastic modulus of the secondary coating is used, the device Rheometrics Solids Analyzer (RSA-II). The fiber with double coating, the secondary coating has a much higher modulus of elasticity than primary coverage, so the contribution of the primary coating in the results of the dynamic IP the trial for stretch performed on-hook coverage, can be neglected. In the case of the device RSA-II, where the adjustable gap between the two clamps RSA-II limited sample tube cover may be shorter than the distance between the two clamps. A simple sample holder, made of metal plate, bent and pinched at the open end of the screw, is used for thorough fixation of the sample tube covering the bottom end. Shift the clamping device in the center of the lower clamp and tighten the clamp. Use tweezers to straighten the tube cover to the vertical position through the top clamp. Close and tighten the top clamp. Regulate the deformation displacement until the pre-tension will not be ~10,

[0136] the Test was performed at room temperature (~23°C). In the dynamic tensile test when the DMA frequency test set at 1.0 radians/second; the deformation is 5E-4. The geometry type choose cylindrical. The sample length equal to the length of the tube cover between the top edge of the metal clamping device and the lower clamp in the trial of 11 mm Diameter (D) being equal to 0.16 mm according to the following equation:

where Rsand Rpare the outer radii of the secondary and primary coating, respectively. To calculate use the Ute geometry standard fiber R s=122,5 μm and Rp=92,5 μm. Conduct dynamic scan time and register 5 experimental points of the storage modulus tensile means that the value E represents the average of all experimental points. This measured module E is then adjusted by multiplying by a correction factor, which takes into account the real geometry of the fiber. The correction factor is (122,52-92,52)/Rsactual-Rpactual). For glass fibers actual geometry of the fiber, including the values of Rsand Rpmeasure using PK2400 Fiber Geometry System. For the wire fibers values of Rsand Rpmeasured under a microscope. Given the value E represents the average of three test samples.

[0137]Test method for measuring in-situ Twiththe primary and secondary coatings: Glass transition temperature (Twith) the primary and secondary coatings on glass fiber or the fiber of the metal wire (the wire) with a double coating is measured by this method. These glass transition temperature is indicated as "Twithtube".

[0138] For the preparation of the sample with the fiber peeling off layers of coating a length of ~2 cm in the form of a solid tube cover with one end covered with fiber, first immersing the end of the covered what about the fiber together with the edging tool in liquid nitrogen for at least 10 seconds, and then removing the receiver cover fast movement, while the coatings are still hard.

[0139] the Device DMA (Dynamic Mechanical Analysis): use the device Rheometrics Solids Analyzer (RSA-II). In the case of the device RSA-II gap between the two clamps RSA-II can be extended up to a maximum of 1 mm, the Gap initially set to the minimum level by adjusting the deformation displacement. A simple sample holder, made of metal plate, bent and pinched at the open end of the screw, is used for thorough fixation of the sample tube covering the bottom end. Shift the clamping device in the center of the lower clamp and tighten the clamp. Use tweezers to straighten the tube cover to the vertical position through the top clamp. Close and tighten the top clamp. Closed heat chamber and adjust the temperature of a heating Cabinet at a value higher than Twithsecondary coverage, or 100°C, using liquid nitrogen as a medium for temperature control. When the temperature of the heating Cabinet reaches this temperature, regulate the deformation displacement up until the pre-tensioning will not be in the range from 0 g to 0.3 g

[0140] When conducting dynamic tests DMA at step temperature change of the frequency of the test set at 1.0 radians/second; the deformation is 5E-3; step ISM is in temperature is 2°C, and the exposure time is 10 seconds. The geometry type of the selected cylindrical. Set geometry parameters were the same as used for testing in-situ modulus of the secondary coating. The sample length equal to the length of the tube cover between the top edge of the metal clamping device and the lower clamp in the trial of 11 mm Diameter (D) is equal to 0.16 mm according to the following equation:

where Rsand Rpare the outer radii of the secondary and primary coating, respectively. For calculation use geometry standard fiber Rs=122,5 μm and Rp=92,5 mm.

The dynamic test at step temperature change is carried out from the initial temperature (100°C in our test) to a temperature below Twithprimary coverage or -80°C. After the test cycle peaks on the curve of tan δ log Twithprimary coverage (corresponding to a lower temperature) and Twiththe secondary coating (corresponding to a higher temperature). It should be noted that the measured glass transition temperature, especially for the glass transition temperature of the primary coating should be considered as relative values of glass transition temperatures for the layers of the coating on the fiber due to the shift of the tan δ due to the complicated structure of the cutting coating.

Examples of simulator exhaust columns

[0141] Place a commercially available radiation curable primary coating. As disclosed previously, radiation-curable primary coating can be any commercially available radiation curable primary coating for optical fibers. Such commercially available radiation curable primary coating produced by the firm DSM Desotech Inc. and others, including, but without limitation, Hexion, Luvantix and PhiChem.

Commercially available primary coverage and a variety of options declared now the secondary coating is applied to the wire using a simulator exhaust column. The wire is passed in five different linear velocity: 750 m/min, 1200 m/min to 1500 m/min, 1800 meters/minute and 2100 meters/minute.

The pulling is done using the mode or "wet on dry"or "wet on wet". Mode "wet on dry" means that the liquid primary coating is applied wet, and then liquid primary coating utverjdayut to a hard layer on the wire. After curing the primary coating is applied to the secondary coating and then also utverjdayut. Mode "wet on wet" means that the liquid primary coating is applied wet, then the secondary coating is applied wet, and then utverjdayut both coatings, the primary and wtorek the second.

Conduct multiple test cycles with a commercially available radiation curable primary coating and compositions claimed now secondary coverage.

[0142] the tuning of the exhaust simulator columns:

- Use the die Sadly: S99 for 1° and S105 to 2°.

- Speed 750, 1000, 1200, 1500, 1800 and 2100 m/min

- Use the 5 lamps in the process of "wet on dry" and 3 lamps in the process of "wet on wet".

- (2) 93 W/cm2(600 W/inch2) UV lamp D Fusion is used at 100% for 1°'s coatings.

- (3) 93 W/cm2(600 W/inch2) UV lamp D Fusion is used at 100% for 2°'s coatings.

- Temperature for these two coatings is 30°C. the Die is also set to 30°C.

- The level of carbon dioxide is 7 liters/min at each filiere.

- The level of nitrogen is 20 liters/min on each lamp.

- Pressure for 1°th coating is 0.1 MPa (1 bar) at 25 m/min up to 0.3 MPa (3 bar) at 1000 m/min

- Pressure for 2°th coating is 0.1 MPa (1 bar) at 25 m/min up to 0.4 MPa (4 bar) at 1000 m/min

[0143] Utverjdenie secondary coating on the wire have on the initial % RAU, the initial in-situ modulus and the initial Twithof the tube. The covered wire is then subjected to aging for one month at a temperature of 85°C and 85%relative humidity. Atwere the military secondary coating on the wire then test on the % RAU, in-situ modulus and Twithtube.

[0144] Utverjdenie radiation curable secondary coating on the wire was found has the following properties:

Linear speed
(m/min)
% RAU secondary coating (primary)% RAU secondary coating
(1 month)
75090-9494-98
120086-9091-95
150082-8690-94
180083-8789-93
210080-8488-93

Linear speed
(m/min)
In-situ modulus secondary coating (HPa)In-situ modulus secondary coating (HPa)
(1 month)
7501,30-1,701,40-1,90
12001,00-1,40 1,50-1,70
15001,00-1,401,30-1,70
18001,00-1,401,10-1,50
21000,60-1,001,00-1,40

Linear speed
(m/min)
The values of Twithtube secondary coating (°f) (initial)The values of Twithtube secondary coating (°C) (1 month)
75068-8068-80
120065-6967-71
150060-6461-65
180061-6561-65
210050-5855-59

[0145] Therefore, it is possible to describe and claim the wire covered with the first and second layer, the first layer is utverjdenie radiation curable primary coating that is in contact with the outer surface of the completion of the wire, and the second layer is utverjdenie radiation curable secondary coating of the claimed invention now in contact with the outer surface of the primary coating,

this utverjdenie secondary coating on the wire has the following properties after initial cure and after one month aging at 85°C and 85%relative humidity:

A) a % RAU of from 80% to 98%;

C) in-situ modulus of between 0,60 GPA 1.90 GPA; and

C) Tctubes from 50°C to 80°C.

Using this information it is also possible to describe and to declare an optical fiber covered with the first and second layer, the first layer is utverjdenie radiation curable primary coating that is in contact with the outer surface of the optical fiber and the second layer is utverjdenie radiation curable secondary coating of the claimed invention now in contact with the outer surface of the primary coating,

this utverjdenie secondary coating on the optical fiber has the following properties after initial cure and after one month aging at 85°C and 85%relative humidity:

A) a % RAU of from 80% to 98%;

C) in-situ modulus of between 0,60 GPA 1.90 GPA; and

C) Tctubes from 50°C to 80°C.

[0146] the Use of terms in the singular in pin is XTE describing the invention (especially in the context of the following claims) should be considered as related to a single, and plural, if there is not specified or expressly contrary to the context. The terms "comprising", "having", "including" shall be construed as non-limiting terms (i.e. meaning "including, but not limited to,") unless otherwise stated. Specifying ranges of values here is only intended to serve as a quick way of individually specifying each separate value falling within the range, if this is not stipulated, and each separate value is incorporated into the description, as if it was individually listed here. All methods described here can be performed in any suitable order, here if not otherwise specified, or unless otherwise clearly contrary to the context. The use of any and all examples, or exemplary expressions (e.g., "such as")provided here are intended only to better illuminate the invention and does not limit the invention, unless stated otherwise. No expressions in the description should not be construed to indicate any undeclared element as essential to the practical implementation of the invention.

1. Curing radiation, the composition of the secondary coating containing not containing urethane alpha oligomer obtained by the reaction of the following:
(a) acrylate connect the tion, selected from alcohol-containing acrylate or alcohol-containing methacrylate compound,
(b) anhydrite connection
(c) epoxydodecane connection
(d) optional connection-chain extension, and
(e) optional catalyst
in fact the composition further comprises a beta oligomer, and mentioned a beta oligomer is different from the aforementioned alpha oligomer,
these beta oligomer obtained by the reaction of
1) hydroxyethylacrylate;
2) one or more diisocyanates;
3) a glycol selected from the group consisting of simple polyether polyols and complex polyether polyols;
the complex polyether polyols obtained by reacting a polyhydric alcohol with a polybasic acid;
this simple polyether polyols selected from the group consisting of polyethylene glycol, polypropyleneglycol, copolymer polypropylenglycol and ethylene glycol, polytetramethylene, polietilenglikolja, polyphthalocyanines and politicalideological; and
4) catalyst.

2. Curing radiation, the composition of the secondary coating according to claim 1, additionally containing gamma oligomer.

3. Curing radiation, the composition of the secondary coating according to claim 2, with said composition further comprises an antioxidant; the first photoinitiator; second photoinitiator; and n is necessarily only improves the slip additive or a blend of improving slip additives;
these beta oligomer obtained by the reaction of
β1) hydroxyethylacrylate;
(2) one or more diisocyanates;
β3) polyol;
these polyol is a simple polyetherpolyols selected from the group consisting of polyethylene glycol, polypropyleneglycol, copolymer polypropylenglycol and ethylene glycol, polytetramethylene, polietilenglikolja, polyphthalocyanines and politicalideological; and
these polyol preferably is polytetramethylene with srednetsenovoj molecular weight of about 600 to 700, preferably about 625-675; and
β4) catalyst;
when this catalyst beta oligomer selected from the group consisting of dilaurate dibutylamine; carboxylates of metals; sulfonic acids; catalysts based on amines or organic bases; alkoxides of zirconium and titanium; and ionic liquid phosphonium salts, imidazole and pyridinium; and
these gamma oligomer is epoxidized.

4. Optical fiber covered with a radiation-curable primary coating and a radiation-curable composition of the secondary coating according to any one of claims 1 to 3.

5. The method of coating an optical fiber, including:
a) operation of the column extraction of glass to obtain a glass optical fiber; the
b) coating the aforementioned glass optical fiber radiation-curable primary coating composition;
c) optionally contacting the mentioned radiation-curable composition of the primary coating with radiation for curing of the coating;
d) coating the aforementioned glass optical fiber radiation-curable composition of the secondary coating according to any one of claims 1-3;
(e) contacting mentioned radiation-curable composition of the secondary coating to radiation to cure the coating.

6. The method according to claim 5, the operation of the mentioned columns extraction of glass is performed with a linear speed between 750 m/min and 2100 m/min

7. The wire is covered with the first and second layer, the first layer is utverjdenie radiation curable primary coating that is in contact with the outer surface of the wire, and the second layer is utverjdenie radiation curable secondary coating according to any one of claims 1 to 3 in contact with the outer surface of the primary coating
this utverjdenie secondary coating on the wire has the following properties after initial cure and after one month aging at 85°C and 85%relative humidity:
A) A % RAU of from 80% to 98%, and "% RAU" denotes the degree of cure, expressed the AK percentage reacted acrylate unsaturation;
B) in-situ modulus of between 0,60 GPA 1.90 GPA; and
C) Twithtubes from 50°C to 80°C.

8. The optical fiber coated with the first and second layer, the first layer is utverjdenie radiation curable primary coating that is in contact with the outer surface of the optical fiber and the second layer is utverjdenie radiation curable secondary coating according to any one of claims 1 to 3 in contact with the outer surface of the primary coating
this utverjdenie secondary coating on the optical fiber has the following properties after initial cure and after one month aging at 85°C and 85%relative humidity:
A) A % RAU of from 80% to 98%, and "% RAU" denotes the degree of cure, expressed as a percentage reacted acrylate unsaturation;
B) in-situ modulus of between 0,60 GPA 1.90 GPA; and
C) Twithtubes from 50°C to 80°C.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: present invention relates to radiation-curable compositions, as well as a coating containing said composition for protecting metal substrates from corrosion. The composition consists of radiation-curable urethane(meth)acrylate with OH number ≥ 10 mg KOH/g, a monofunctional, radiation-curable reactive diluent, an acidic adhesion promoter, a photoinitiator, a multifunctional reactive diluent, radiation-curable resins and other inert additives. The adhesion booster used is phosphoric or phosphonic acid or products of their conversion with functionalised acrylates.

EFFECT: radiation-curable compositions, having good corrosion-protective properties for metal substrates, which are elastic and capable of being well moulded.

15 cl, 2 tbl, 5 ex

FIELD: construction.

SUBSTANCE: supercoating contains at least two layers, at the same time the first layer is a primary coating, which is in contact with the outer surface of optic fibre, and the second layer represents the secondary coating, which is in contact with the outer surface of the primary coating, at the same time the hardened primary coating on the optic fibre has the following properties after initial hardening and after one month of ageing at 85°C and 85% relative humidity: A) % RAU from 84% to 99%; B) in-situ elasticity module between 0.15 MPa and 0.60 MPa; and C) glass-transition temperature of the tube is from -25°C to -55°C. At the same time the hardened secondary coating on optic fibre has the following properties after initial hardening and after one month of ageing at 85°C and 85% relative humidity: A) % RAU from 80% to 98%; B) in-situ elasticity module between 0.60 GPa and 1.90 GPa; and C) glass-transition temperature of the tube is from 50°C to 80°C.

EFFECT: improved technological or operational characteristics.

12 cl

FIELD: construction.

SUBSTANCE: primary coating composition hardened by radiation contains oligomer; monomer-dissolvent; photoinitiator; antioxidant; and adhesion intensifier; besides, the specified oligomer represents a product of reaction: hydroxyethylacrylate; aromatic isocyanate; aliphatic isocyanate; polyol; catalyst; and inhibitor, at the same time the specified catalyst represents a bismuth organic catalyst; at the same time the specified oligomer has an number-average molecular weight from at least 4000 g/mole to less than or equal to 15000 g/mole; and at the same time the hardened film of the specified coating composition hardened by radiation has a peak of dielectric loss tangent of glass-transition temperature from -25°C to -45°C; and an elasticity module from 0.50 MPa to 1.2 MPa.

EFFECT: improved technological or operational characteristics.

5 cl

FIELD: chemistry.

SUBSTANCE: radiation-curable primary coating composition for optical fibre or wire contains A) an oligomer; B) a first diluent monomer; C) a second diluent monomer; D) a third diluent monomer; E) a first light stabiliser; F) a first photoinitiator; G) a second photoinitiator; H) an antioxidant; I) a second light stabiliser; J) an adhesion promoter; where said oligomer is a product of reaction of: i) hydroxyl-containing (meth)acrylate; ii) isocyanate; iii) polyether polyol; iv) a polymerisation inhibitor; v) a catalyst; vi) a diluent; where said oligomer has number-average molecular weight ranging from at least 4000 g/mol to less than or equal to 15000 g/mol; and where said catalyst is selected from a group consisting of copper naphthenate; cobalt naphthenate; zinc naphthenate; triethylamine; triethylene diamine; 2-methyl triethylene amine; dibutyl tin dilaurate, metal carboxylates, sulphonic acids, catalysts based on amines or organic bases, zirconium and titanium alcoholates, and ionic liquid salts of phosphonium, imidazolium and pyridinium, and where the hardened film of said radiation-curable primary coating composition has peak value tan δ Tc, measured as indicated in the description, ranging from 25°C to -55°C and modulus of elasticity from 0.85 MPa to 1.10 MPa.

EFFECT: improved production and operational characteristics of primary coatings.

5 cl

FIELD: chemistry.

SUBSTANCE: radiation curable secondary coating composition contains an Alpha-oligomer which does not contain urethane, obtained via reaction of (a) an acrylate compound selected from alcohol-containing acrylate or alcohol-containing methacrylate compound, (b) an anhydride compound, (c) an epoxide-containing compound, (d) an optional chain extender compound, and (e) an optional catalyst, where said composition additionally contains a Beta-oligomer, where said Beta-oligomer is different from said Alpha-oligomer, where said Beta-oligomer is obtained via reaction of (β1) hydroxyethyl acrylate; (β2) one or more diisocyanates; (β3) polyester polyol or polyether polyol with number-average molecular weight ranging from 300 g/mol to 10000 g/mol; and (β4) a catalyst. The secondary coating composition can additionally contain a Gamma-oligomer which is epoxy diacrylate. The invention also relates to a method coating an optical fibre involving a) using a glass drawing column to obtain optical glass fibre; and b) applying a radiation-curable primary coating composition onto said optical glass fibre; c) optional exposure of said radiation-curable primary coating composition to radiation in order to cure said coating; d) applying a radiation-curable secondary coating composition onto said optical glass fibre; e) and exposing said radiation-curable secondary coating composition to radiation in order to said coating. The invention also relates to a coated wire and a coated optical fibre. The radiation-curable secondary coating on the wire and optical fibre has the following properties after initial curing and after one month of ageing at 85°C and 85% relative humidity: A) % RAU from 80% to 98%; B) in-situ modulus of elasticity between 0.60 GPa and 1.90 GPa; and C) Tc of the tube from 50°C to 80°C.

EFFECT: improved coating properties.

8 cl, 5 tbl

FIELD: chemistry.

SUBSTANCE: radiation-curable secondary coating composition contains A) a mixture of secondary coating oligomers which is mixed with B) a first diluent; C) a second diluent; D) an antioxidant; E) a first photoinitiator; F) a second photoinitiator; G) an optional slide-enhancing additive or a mixture of slide-enhancing additives; where said mixture of secondary coating oligomers contains α) Alpha-oligomer; β) Beta-oligomer; γ) Gamma-oligomer; where said Alpha-oligomer is synthesised via reaction of αl) anhydride with α2) acrylate containing a hydroxyl group; and the reaction product of α1) and α2) then reacts with α3) epoxide; in the presence of α4) a first catalyst; α5) a second catalyst; and α6) a polymerisation inhibitor; to obtain an Alpha-oligomer; where said Beta-oligomer is synthesised via reaction of β1) acrylate containing a hydroxyl group; β2) diisocyanate; and β3) polyether polyol; in the presence of β4) a catalyst; where said catalyst is selected from a group containing copper naphthenate, cobalt naphthenate, zinc naphthenate, triethylamine, triethylene diamine, 2-methyltriethylene diamine, dibutyl tin dilaurate, metal carboxylates, sulphonic acids, catalysts based on amines or organic bases, zirconium and titanium alkoxides, and ionic liquid salts of phosphonium, imidazolium and pyridinium, and said Gamma-oligomer is epoxy diacrylate. The method of applying the coating onto an optical fibre involves a) using a glass drawing column to obtain optical glass fibre; and b) applying a radiation-curable primary coating composition onto said optical glass fibre; c) optional exposure of said radiation-curable primary coating composition to radiation in order to cure said coating; d) applying a radiation-curable secondary coating composition onto said optical glass fibre; e) and exposing said radiation-curable secondary coating composition to radiation in order to said coating.

EFFECT: improved technological or operational characteristics of secondary coating, particularly improved curing and high rate of curing.

5 cl

FIELD: chemistry.

SUBSTANCE: radiation curable primary coating composition contains at least one urethane-(meth)acrylate functional oligomer and a photoinitiator, wherein the urethane-(meth)acrylate functional oligomer is a product of reaction of hydroxyethyl acrylate, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, isophorone diisocyanate and polyether polyol in the presence of a catalyst and an inhibitor, where the urethane-(meth)acrylate functional oligomer contains (meth)acrylate groups, at least one polyol backbone chain and urethane groups, where 15% or more of the urethane groups are derivatives of one of 2,4- and 2,6-toluene diisocyanate or both, where at least 15% of the urethane groups are derivatives of isophorone diisocyanate, and where said urethane-(meth)acrylate functional oligomer has number-average molecular weight from at least 4000 g/mol to at least 15000 g/mol; and where the cured film of the radiation curable primary coating composition has equilibrium modulus of elasticity, measured as indicated in the description, which is equal to at least 1.2 MPa. The invention also relates to a method of coating glass optical fibre, involving (a) using a glass drawing column to obtain glass optical fibre, preferably at linear velocity between 750 m/min and 2100 m/min; (b) applying the radiation curable primary coating composition onto the surface of the optical fibre; and (c) optional exposure to radiation to cure said radiation curable primary coating composition. The cured primary coating composition on the optical fibre and conductor has the following properties after initial curing and after one month at 85°C and 85% relative humidity:A) % RAU from 84% to 99%; B) in-situ modulus of elasticity between 0.15 MPa and 0.60 MPa; and C) Tc of the tube -25°C to - 55°C.

EFFECT: improved coating characteristics.

13 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: radiation-curable secondary coating composition contains a mixture of secondary coating oligomers which is mixed with a first diluent monomer; a second diluent monomer; an optional third diluent monomer; an antioxidant; a first photoinitiator; a second photoinitiator; and, optionally, a slide-enhancing additive or a mixture of slide-enhancing additives; wherein said mixture of secondary coating oligomers contains: α) Omega-oligomer; and β) Upsilon-oligomer; wherein said Omega-oligomer is synthesised from reaction of α1) hydroxyl-containing (meth)acrylate; α2) isocynate; α3) polyether polyol; and α4) tripropylene glycol; in the presence of α5) a polymerisation inhibitor; and α6) a catalyst; to obtain an Omega-oligomer; wherein said catalyst is selected from a group comprising copper naphthenate, cobalt naphthenate, zinc naphthenate, triethylamine, triethylenediamine, 2-methyltriethylenediamine, dibutyl tin dilaurate, metal carboxylates, sulphonic acids, catalysts based on amines or organic bases, zirconium and titanium alkoxides and ionic liquid salts of phosphonium, imidazolium and pyridinium; and wherein said Upsilon-oligomer is epoxy diacrylate. The method of applying the coating onto an optical fibre involves operation of a glass drawing column to obtain optical glass fibre; applying a radiation-curable primary coating composition onto said optical glass fibre; optional exposure of said radiation-curable primary coating composition to radiation in order to cure said coating; applying a radiation-curable secondary coating composition in paragraph 1 onto said optical glass fibre; and exposing said radiation-curable secondary coating composition to radiation in order to said coating.

EFFECT: obtaining optical fibre and a conductor having a cured secondary coating.

6 cl

FIELD: chemistry.

SUBSTANCE: radiation-curable primary coating composition contains an oligomer, a diluent monomer; a photoinitiator; an antioxidant; and an adhesion promoter; wherein said oligomer is the reaction product of: a hydroxyethyl acrylate; an aromatic isocyanate; an aliphatic isocyanate; a polyol; a catalyst; and an inhibitor. Said oligomer has number-average molecular weight ranging from at least 4000 g/mol to less than or equal to 15000 g/mol; and wherein said catalyst is selected from a group comprising dibutyl tin dilaurate; metal carboxylates, sulphonic acids; catalysts based on amines or organic bases, zirconium and titanium alkoxides and ionic liquid salts of phosphonium, imidazolium and pyridinium.

EFFECT: obtaining a hardened film of said radiation-curable primary coating composition.

6 cl

FIELD: chemistry.

SUBSTANCE: invention relates to compositions for protective coating for window glass. The invention discloses a composition which contains a) one or more film-forming resins which contain acrylic and/or methacrylic functional fragments; b) one or more reactive diluents which contain an acrylate functional group; c) one or more compounds which promote adhesion of the composition to glass, which contain a product of a Michael reaction, having four or more siloxane groups, at least one acrylate group and a tertiary amine group; d) one or more filler substances, capable of endowing compositions with wear-resistance in solidified state; and e) one or more compounds which can react with a film-forming resin, which contain at least one acid fragment.

EFFECT: composition ensures high adhesion of the coating to adhesive substances on a structure in the absence of an undercoat.

16 cl, 5 dwg, 28 tbl, 38 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing self-curing polyurethane dispersions, use thereof as coating agents, coating agents containing these self-curing aqueous dispersions, a method of coating substrates, as well as substrates treated with coating agents. The method of producing self-curing aqueous polyurethane dispersions involves the following steps: I. reacting al) polyisocyanate with a mixture of, a2) 2,2-bis(hydroxymethyl)alkanecarboxylic acid as an anionic hydrophilisation agent containing a group which is reactive towards isocyanate and, a3) at least one polyol component with average OH-functionality >1, wherein any mixture from a2) and a3), or component a1) k) contains at least one catalyst selected from a group consisting of tertiary amines, tin, zinc or bismuth compounds; II obtaining an OH-functional polyurethane without NCO-groups from step I, which then; III. a4) is mixed with a reactive blocking agent for isocyanate groups, selected from a group consisting of butanone oxime, diisopropylamine or tert-butylbenzylamine, 3,5-dimethylpyrazole, triazole, respectively, mixture thereof; IV. subsequent reaction of that mixture from step III with a5) one or more polyisocyanates selected from group a1), wherein these polyisocyanates are the same as or are different from al), and subsequent V. obtaining a physical mixture of OH-functional polyurethane without NCO-groups and a blocked polyisocyanate from step IV, after which after either; VI. acid groups of OH-functional polyurethane a6) are completely or partially deprotonated by adding a neutralising agent; VII. and the polyurethane obtained at step VI id dispersed in water, or step VII is carried out before step VI.

EFFECT: obtaining self-curing aqueous polyurethane dispersions containing negligible amounts of cosolvent.

14 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing coating material. Disclosed is a method of producing coating material in form of powdered lacquer or a fluid resin, characterised by that one or more alcohols or polyols react with one or more silanes selected from a group consisting of (isocyanatomethyl)methyl-dimethoxysilane, 3-isocyanatopropyl-trimethoxysilane and 3-isocyanatopropyl-triethoxysilane, to form a covalent bond between the alcohol or polyol and the silane such that the reaction product is a high-molecular weight silane which is cured directly using a catalyst, wherein all alcohol or polyol organic functional groups participate in the reaction with the silane organic functional group. Coating material and use thereof are also disclosed.

EFFECT: disclosed method enables to obtain coating material which can be used to make scratch-resistant coatings.

12 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to rocket engineering, particularly to production of a protective-adhesive lacquer which is used as a primer for binding an inhibiting coating with the surface of the charge when inhibiting solid-propellant charge. The protective-adhesive lacquer contains 4,4',4"-triphenylmethane triisocyanate, dichloroethane, as an adhesive additive - a product of polycondensation of ethylene glycol, adipic acid and glycerine, with content of hydroxyl groups from 2.00 to 2.30 wt % and dibutyltin dilaurate as a curing agent.

EFFECT: obtaining lacquer with high capacity for protection from migration processes in the "fuel-inhibiting coating" system, which reduces smoke formation, increases adhesion strength between the inhibiting coating and the surface of the propellant charge, which contains polyformaldehyde derivative-based components, avoids use of an additional cellulose acetate-based primer, which ensures strong adhesion of solid-propellant charge pellets with the inhibiting coating for the guaranteed storage life of the charge and which enables to use readily available domestic raw materials.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to polymeric heat-reflecting coating compositions which are applied on inflatable structures, protective and rescue equipment (airstairs for civil aviation, floatation rafts, airships, pneumatic tents, heat-reflecting screens, shields for firefighters), consisting of airtight elastic material based on fabric (capron, nylon, lavsan, high-strength aramid fibre SVM). The polymeric heat-reflecting coating composition contains urethane rubber, a hardener, aluminium paste and ethyl acetate.

EFFECT: production of cold-curable polymeric heat-reflecting coating composition, having high resistance to thermal radiation (up to 29 kW/m2) and minimum weight gain (thickness).

3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to thermally solidificated covering substances based on aprotic solvents. Claimed is covering substance, which contains at least one compound (A), which contains hydroxyl groups, at least one compound (B) with free and/or blocked isocyanate groups, and at least one catalyst (D) for cross-linking silane groups, with one (i) or several components of covering substance containing hydrolysed silane groups and (ii) covering substance can be finally solidificated for covering, which has statistically distributed regions of lattice Si-O-Si. Obtained from covering substance solidificated coating has index of further cross-linking (PCI) lower than 2, with index of the further linking (PCI) being determined as coefficient from memory module E'(200) of finally solidificated coating, measured at 200°C, to minimum of memory module E'(min) of finally solidificated covering, measured at temperature higher than temperature of transition into glass-like state of Tg, and memory modules E'(200) and E'(min),as well as temperature of transition into glass-like state Tg are measured on free films with thickness of layer 40 mcm+/-10 mcm by means of dynamic mechanical thermal analysis (=DMTA) at rate of heating 2 K per minute and frequency 1 Hz and DMTA measurement on free films with thickness of layer 40 mcm+/-10 mcm, which are solidificated for 20 minutes at object temperature 140°C and after solidifying are kept for 8 days at 25°C, before carrying out DMTA measurements. Polyisocyanate (B) at least partially has one or several similar or different structural units of formula -X-Si-R"XG3-X, where G = identical or different hydrolysed groups, in particular alcoxy group, X=organic residue with from 1 to 20 carbon atoms, R" =alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be broken by non-adjacent oxygen groups, sulphur or NRa, with Ra=alkyl, cycloalkyl, aryl or aralkyl, x=0 to 2. Catalyst (D) is phosphorus-containing, and covering substance contains catalyst (D) from 0.1 to 10 wt % in terms of non-volatile components of covering substance. Also claimed are multi-step method of applying coating with application of claimed covering substance, as well as application of claimed method and versions of claimed coating application.

EFFECT: possibility to obtain transparent varnish coating with high resistance to atmospheric impact.

18 cl, 4 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to thermally solidificated covering substances based on aprotic solvent. Claimed is covering substance, which contains at least one compound (A), containing hydroxyl groups, at least one compound (B), containing isocyanate groups, and at least one phosphorus-containing catalyst (D) for cross-linking silane groups, with one or several components of covering substance containing between 2.5 and 97.5 mole %, counted for totality of structural units -N(X-SiR"x(OR')3-x)n(X'-SiR"y(OR')3-y)m (II) and -Z-(X-SiR"x(OR')3-x) (III), at least one structural unit of formula (II), where R'=hydrogen, alkyl or cycloalkyl, carbon chain can be interrupted by means of non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, X,X'=linear and/or branched alkylene pr cycloalkylene residue with from 1 to 20 carbon atoms, R" =alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by means of non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, preferably R"=alkyl residue, n=0 to 2, m=0 to 2, m+n=2, x,y=0 to 2; and between 2.5 and 97.5 mole %, counted per totality of structural units (II) and (III), at least one structural unit of formula (III), where Z=-NH-, -NR-, -O-, R=alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by means of non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, x=0 to 2, and X, R', R" have value, given above, and covering substance can be finally solidificated before covering, which has statistically distributed regions of lattice Si-O-Si. Also claimed are multi-step method of applying coating with application of claimed covering substance, as well as application of claimed method and versions of claimed coating application.

EFFECT: possibility to obtain transparent varnish coating with high resistance to formation of cracks under atmospheric impact and perfect resistance to scratching.

18 cl, 4 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to thermally solidificated covering substances based on aprotic solvent. Claimed is covering substance, which contains at least one compound (A), containing hydroxyl groups, and at least one compound (B), containing isocyanate groups, and one or several components of covering substance have between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (I), where R'=hydrogen, alkyl or cycloalkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, X,X'=linear and/or branched alkylene or cycloalkylene residue with from 1 to 20 carbon atoms; R"= alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, n=0 to 2, m=0 to 2, m+n=2, x,y=0 to 2; and between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (II), where Z=-NH-, -NR-, -O-; R=hydrogen, alkyl, cycloalkyl, aryl or aralkyl and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, x=0 to 2, and X, R', R" have value, given above; and polyol (A) contains at least one poly(meth)acrylate polyol. Also claimed are multi-step method of applying coating with application of said covering substance, method application and versions of coating application.

EFFECT: possibility of simple obtaining of transparent varnish coatings with high resistance to crack formation under atmospheric impact and perfect resistance to scratching, which do not cause any ecological problems.

15 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: polyurethane coating is made from a composition which contains refined castor oil, an ester, an antifoaming additive BYK-066 based on fluorine-modified polysiloxanes, aluminium oxide, titanium oxide, aerosil, a water adsorbent, an additive BYK-410 - urea in an organic solvent N-methylpyrrolidone, a curing agent isocyanate SUPRASEK 5025, which is 4,4'-diphenylmethane diisocyanate and additionally as filler - dolomite or zeolite or a mixture of dolomite and zeolite in ratio 3.25:1.

EFFECT: coating has high breaking strength and modulus of elasticity in tension, while providing sufficiently high deformation characteristics, particularly tensile elongation.

2 tbl

FIELD: construction.

SUBSTANCE: method to manufacture a coating includes preparation of a mixture by means of mixing of a filler from rubber crumb and a binder based on polyurethane. Simultaneously and separately from each other mixtures are produced for basic and upper layers, at the same time in the mixture for the basic layer they use a filler from rubber crumb with fraction of 2-12 mm, and in the mixture for the upper layer they use a filler from rubber crumb with fraction of 1-3 mm and a pigment dye. In process of mixture mixing for its upper layer it is compacted, afterwards the mixture for the upper layer is serially discharged into a die mould, then the mixture for the basic layer is discharged, and pressed under pressure with the help of a press, then maintained until full hardening, and the produced coating is discharged from the die mould.

EFFECT: high efficiency of coating manufacturing, higher reliability and durability of a coating, possibility to manufacture a double-layer coating with damping properties.

8 cl

FIELD: chemistry.

SUBSTANCE: formulation composition contains: A) 5-95 wt % at least one radiation-curable resin, B) 5-25 wt % silicic acid, C) 0.1-10 wt % at least one adhesion promoter, D) 5-90 wt % at least one radiation-curable reactive diluent, E) 0.5-5 wt % at least one dispersant. The adhesion promoter is selected form phosphoric acid and/or phosphonic acid and/or products of reaction thereof with functionalised acrylates. The composition can additionally contain photoinitiators, pigments and additives, selected from diffusion promoting agents, delustering agents and degassing agents. The compositions are used as a primer, an intermediate layer, coating varnish and/or clear varnish, as well as for making coatings via a coil coating technique.

EFFECT: coatings have flexibility, thereby providing excellent protection of metal substrates from corrosion.

18 cl, 2 tbl, 6 ex

FIELD: construction.

SUBSTANCE: supercoating contains at least two layers, at the same time the first layer is a primary coating, which is in contact with the outer surface of optic fibre, and the second layer represents the secondary coating, which is in contact with the outer surface of the primary coating, at the same time the hardened primary coating on the optic fibre has the following properties after initial hardening and after one month of ageing at 85°C and 85% relative humidity: A) % RAU from 84% to 99%; B) in-situ elasticity module between 0.15 MPa and 0.60 MPa; and C) glass-transition temperature of the tube is from -25°C to -55°C. At the same time the hardened secondary coating on optic fibre has the following properties after initial hardening and after one month of ageing at 85°C and 85% relative humidity: A) % RAU from 80% to 98%; B) in-situ elasticity module between 0.60 GPa and 1.90 GPa; and C) glass-transition temperature of the tube is from 50°C to 80°C.

EFFECT: improved technological or operational characteristics.

12 cl

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