Radiation curable primary coatings d1363 bt on optical fibre

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

 

Cross references to related applications

[0001] This patent application claims priority based on provisional patent application U.S. serial No. 60/874719 "radiation-Curable primary coating CR for optical fiber", filed December 14, 2006; provisional patent application U.S. serial No. 60/874722 "radiation-Curable primary coating P on the optical fiber", filed December 14, 2006; provisional patent application U.S. serial No. 60/874721 "radiation Curable primary coating of SA for optical fiber", filed December 14, 2006; provisional patent application U.S. serial No. 60/874730 "Superority for optical fiber", filed December 14, 2006; and provisional patent application U.S. serial No. 60/974631 "radiation-Curable primary coating P on the optical fiber", filed September 24, 2007.

The technical field to which the invention relates.

[0002] the Present invention relates to radiation curable coatings for use as a primary coating for optical fibers, optical fibers coated with the aforementioned coating, and methods of producing coated optical fibers.

The level of technology

[0003] Optical fibers typically cover two or more radiation-curable coatings. These coatings about what a rule is applied on the optical fiber in liquid form, and then exposed to radiation (irradiation), to cause solidification. The type of radiation that can be used for curing coatings, should be the same, which is capable of initiating the polymerization of one or more radiation-curable components such coatings. Radiation suitable for curing such coatings are well known and include ultraviolet light ("UV") and electron beam ("E"). The preferred type of radiation for curing coatings applied when obtaining covered optical fiber is UV radiation.

[0004] Coating, which is in direct contact with the optical fiber, called primary coating, and a coating that covers the primary coating, referred to as the secondary coating. In the art radiation-curable coatings for optical fibers is known that the primary coatings are softer than the secondary coating. One advantage resulting from this composition represents an increased resistance to microshell.

[0005] 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 Ter the practical voltage and/or mechanical shearing forces. When they are present, microengine impede the ability of the coated optical fiber to transmit the signal. Weakening is an undesirable decrease of the signal transmitted on the optical fiber. Relatively soft primary coating provides resistance optical fiber to the emergence of microthiol, thereby minimizing signal attenuation.

[0006] Published information about radiation-curable coatings, suitable for use as a primary coating for optical fibers, includes the following:

[0007] Published patent application China No. CN16515331 "Radiation Solidification Paint and Its Application", assigned to the firm Shanghai Feikai Photoelectric, inventors: Jibing Lin and Jinshan Zhang, describes and claims radiation-curable coating comprising the oligomer, an active diluent, photoinitiator, thermo stabilizer, selective adhesion promoter, in which the content of the oligomer is between 20% and 70% by weight, later the same thing), the content of the remaining components is between 30% and 80%; the oligomer is selected from (meth)acelerando polyurethane oligomer or a mixture of (meth)acelerando polyurethane oligomer and a (meth)acelerando epoxy oligomer; mentioned (meth)atilirovanie polyurethane oligomer is obtained using at least the trail is related substances:

[0008] (1) one of the polyols selected from polyurethane polyol, polyamide polyol, a simple polyester polyol, a complex of the polyester polyol, polycarbonate polyol, hydrocarbon polyol, polysiloxane polyol, a mixture of two or more identical or different types of polyol(s);

[0009] (2) a mixture of two or more diisocyanates or polyisocyanates;

[0010] (3) (meth)acelerando compounds containing one hydroxyl group capable of reacting with isocyanate.

[0011] Example 3 in published patent application China No. CN16515331 is the only example in this published patent application, which describes the synthesis of radiation-curable coating suitable for use as radiation-curable primary coating. Floor, synthesized in example 3, has a modulus of elasticity of 1.6 MPa.

[0012] the Article "UV-CURED POLYURETHANE-ACRYLIC COMPOSITION as a SOLID OUTER LAYERS two-layer PROTECTIVE COATINGS FOR OPTICAL FIBERS" ("UV-CURED POLYURETHANE-ACRYLIC COMPOSITIONS AS HARD EXTERNAL LAYERS OF TWO-LAYER PROTECTIVE COATINGS FOR OPTICAL FIBRES"), authors W. Podkoscielny and B. Tarasiuk, journal Polim.Tworz.Wielk, volume 41, No. 7/8, str-455, 1996, NDN - 131-0123-9398-2, describes an optimization study of the synthesis of UV-hardened urethane-acrylic oligomers and their use as hard protective coatings for optical the x fibers. For the synthesis used made in Poland oligomeric oligotherapy, diethylene glycol, colorvision (Izocyn T-80) and isophorondiisocyanate, in addition to hydroxyethyl - and hydroxypropylmethacrylate. Active diluents (butyl acrylate, 2-ethyl hexyl acrylate and 1,4-batangyagit or mixtures thereof) and 2,2-dimethoxy-2-phenylacetophenone as photoinitiator was added to the urethane-acrylic oligomer, which had a polymerization-active double bond. The composition was irradiated with ultraviolet light (UV) in an oxygen-free atmosphere. I recorded the IR spectra of these compositions was determined by some physical, chemical and mechanical properties before and after curing (density, molecular weight, viscosity as a function of temperature, the refractive index, the content of the gel, the glass transition temperature, shore hardness, young's modulus, tensile strength, elongation at break, heat resistance and the diffusion coefficient of water vapor).

[0013] the Article "properties of UV-CURABLE POLYURETHANE-ACRYLATES" ("PROPERTIES OF ULTRAVIOLET CURABLE POLYURETHANE-ACRYLATES"), authors M. Koshiba, K.K.S.Hwang, S.K.Foley, D.J.Yarusso and S.L.Cooper, published in the journal J.Mat.Sci., volume 17, No. 5, may 1982, str-1458; NDN-131-0063-1179-2, describes the investigation of the relationship between the chemical structure and physical properties of UV-hardened polyurethane-acrylate based from oranisational and colordistance (TDI). These two systems were obtained with variations of the molecular weight of the soft segment and the content of the crosslinking agent. The results of dynamic mechanical tests showed that it was possible to get one - or two-phase materials, depending on the molecular weight of the soft segment. Increases past the glass transition temperature (Twith) polyol shifted to lower temperatures. The increased use either N-vinylpyrrolidone (NVP), or polietilenglikolsuktsinata (PEGDA) caused increase in the young's modulus and ultimate tensile strength. The stitching with the use of NVP increased impact strength of two-phase materials and moved the high temperature peak of the Twithfor higher temperatures, but PEGDA did not give such effects. Properties when stretching the two systems were similar.

[0014] Typically, in the production of radiation curable coatings for use on optical fiber in order to obtain urethane oligomers using isocyanates. In many sources, including U.S. patent No. 7135229 "radiation-CURABLE COATING COMPOSITION" ("RADIATION-CURABLE COATING COMPOSITION"), issued November 14, 2006, assigned to the patentee DSM IP Assets B.V., in column 7, line 10-32 presents the following information as a guide for professionals on the synthesis of urethane oligomer: "the Polyisocyanates, when adnie for use in preparation of the compositions according to the present invention, can be aliphatic, cycloaliphatic or aromatic and include diisocyanates, such as 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'-dimethylphenylsilane, 4,4'-biphenylenediisocyanate, 1,6-hexadienal, isophorondiisocyanate, Methylenebis(4-cyclohexyl)isocyanate, 2,2,4-trimethylhexamethylenediamine, bis(2-isocyanatomethyl)fumarate, 6-isopropyl-1,3-phenyldiazonium, 4-diphenylmethanediisocyanate, liaindizecign, hydrogenated diphenylmethanediisocyanate, hydrogenated xylylenediisocyanate, tetramethylethylenediamine and 2,5 (or 6)-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane. Among these diisocyanates are particularly preferred 2,4-colorvision, isophorondiisocyanate, xylylenediisocyanate and Methylenebis(4-cyclohexyl)isocyanate. These diisocyanate compounds are used either individually or in combination of two or more".

[0015] EP-A-1408017 team describes a tape containing a plurality of optical fibers coated. The objective of this document is to provide radiation-curable paint composition, which has a high adhesion to the outer primary coating. Traces of the tion, this document does not cover radiation-curable composition of the primary coating.

[0016] Article Podkoscielny et al, International Polymer Science and Technology, 1994, 21(3), T-103 is a study of UV-hardened polyurethane-acrylic compositions as protective coatings for optical waveguides. This document says nothing about the use of branched or cyclic aliphatic isocyanates.

[0017] WO-A-01/27181 directed to radiation-curable composition for optical fiber. Article Podkoscielny et al, Applied Macromolecular Chemistry and Physics, 1996, 242, 123-138 focused on the optimization of a urethane acrylate radiation-curable compositions. US-A-2006/0084756 describes radiation-curable coating composition for receiving layer coating with a low refractive index and with desirable properties. EP-A-1647585 describes radiation-curable composition that can be used as a top coating, for example, on glass substrates. 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 does not disclose and does not involve the combination of colordistance and branched or cyclic aliphatic isocyanate to obtain the same oligomer.

[0018] Although the currently available range of the primary coating, it is advisable to offer new primary coatings that have superior technological and/or operational characteristics in comparison with existing coatings.

The invention

[0019] the First aspect of the claimed invention now is a radiation-curable primary coating composition containing at least one urethane(meth)acrylate functional oligomer and photoinitiator,

this urethane-(meth)acrylate functional oligomer is a reaction product of hydroxyethylacrylate, mixtures of 2,4-colordistance and 2,6-colordistance, isophorondiisocyanate and simple polyetherpolyols in the presence of catalyst and inhibitor,

this urethane-(meth)acrylate functional oligomer contains (meth)acrylate groups, at least one polyol as one main chain and a urethane group,

15% or more urethane groups are derived from one of 2,4 - and 2,6-colordistance or both of them,

at least 15% of the urethane groups are derived from isophorondiisocyanate, and

these urethane(meth)acrylate functional oligomer has srednecenovogo molecular weight of at least 4000 g/mol to less than or equal to 15000 g/mol; and

when the cured film of the radiation curable compositions is AI primary coating has an equilibrium modulus, less than or equal to 1.2 MPa.

[0020] Preferably, the storage modulus shear, G', a liquid radiation-curable composition of the primary coating is less than or equal to 0.8 PA, as measured at G=100 PA.

Preferably, the cured film of the radiation curable primary coating composition has an equilibrium modulus, measured as described less than or equal to 1.0 MPa.

Preferably, the composition has a refractive index of 1.48 or higher.

Preferably, the viscosity, measured as described, is about 2 PA·s to 8 PA·s at 10 rad/s and at 20°C.

Preferably, 40% or more urethane groups are derived from isophorondiisocyanate.

Preferably, 15% or more urethane groups are derived from both 2,4 - and 2,6-colordistance through the use of a mixture of colordistance with 10 wt.% or more 2,6-colordistance and 50 wt.% or more of 2,4-colordistance.

Preferably, the said mixture of 2,4-colordistance and 2,6-colordistance is a mixture of 80/20.

Preferably, the said catalyst is selected from the group comprising dilaurate dibutylamine, carboxylates of metals, sulfonic acid catalysts based on amines or organic bases, alcoholate of titanium and zirconium, and ion is idgie salt of phosphonium, imidazole and pyridinium.

Preferably, the said catalyst is dilaurate dibutylamine or vimalaramsi catalyst.

[0021] the Second aspect of the claimed now of the invention is a method of coating a glass optical fiber radiation-curable primary coating, including:

(a) operation of the column extraction of glass to obtain a glass optical fiber preferably at a linear speed between 750 m/min and 2100 m/min;

(b) applying a radiation-curable primary coating composition according to the claimed invention now on the surface of the optical fiber;

(c) optional irradiation with radiation to effect the curing of the mentioned radiation-curable composition of the primary coating.

[0022] the Third aspect of the claimed invention now is a wire covered with the first and second layers, the first layer is utverjdenie radiation curable primary coating of the above-mentioned radiation-curable primary coating composition according to the claimed invention now, which is in contact with the outer surface of the wire, and the second layer is utverjdenie radiation curable secondary coating in contact with the outer surface of the primary is on the cover,

[0023] utverjdenie primary 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 84% to 99%;

B) in-situ modulus of between 0.15 MPa and 0,60 MPa; and

C) Twithtube from -25°C to -55°C.

[0024] a Fourth aspect of the claimed invention now is an optical fiber coated with the first and second layers, the first layer is utverjdenie radiation curable primary coating of the above-mentioned radiation-curable primary coating composition according to the claimed invention now, which is in contact with the outer surface of the optical fiber and the second layer is utverjdenie radiation curable secondary coating in contact with the outer surface of the primary coating,

[0025] utverjdenie primary 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 84% to 99%;

B) in-situ modulus of between 0.15 MPa and 0,60 MPa; and

C) Twithtube from -25°C to -55°C.

[0026] the Present invention provides advantages relative to existing primary coatings used when getting wholesale the ical fibers coated.

[0027] One such advantage is the provision of opportunities in various aspects of the invention use relatively inexpensive material, aromatic diisocyanate, which is colorvision (TDI), in combination with aliphatic diisocyanate, which is isophorondiisocyanate (IPDI), upon receipt of various oligomers without excessive deterioration of inelastic viscosity characteristics of the composition at low shear rates. Indeed, the curable composition preferably are essentially characteristics of the Newtonian flow at shear rates less than 100-1(20°C) unlike curable coatings, which exclusively contain oligomers, obtained using only aromatic isocyanates (for example, 2,4 - and 2,6-TDI), hereinafter referred to as fully aromatic oligomers.

A detailed description of the preferred embodiments

[0028] throughout this patent application the following abbreviations have the indicated meanings:

CAS
A-189γ-mercaptopropionylglycine manufactured by the General Electric
EIT2,6-di-tert-butyl-para-cresol, manufactured by Fitz Chem
indicates the registration number of refereed journal Chemical Abstracts
DBTDLdilaurate dibutylamine manufactured by OMG Americas
SR 504 Dethoxylated Nonylphenol, manufactured by Sartomer company
HEAhydroxyethylacrylate, produced by BASF
Irganox 1035thiodiethyl-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), manufactured by Ciba
P2010polypropylenglycol (2000 MM), manufactured by BASF
IPDIisophorondiisocyanate produced by Bayer
TDIa mixture of 80% 2,4-colordistance and 20% 2,6-colordistance produced by Bayer
TDS100%2,4-colorvision, solid
Photomer 4066the ethoxylated nonylphenolic, manufactured by Cognis
Irgacure 819phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide pressed into IMY firm Ciba
SR306diacrylate tripropyleneglycol, manufactured by Sartomer company

[0029] the First aspect of the claimed invention now is a radiation-curable composition of the primary coating containing at least one urethane(meth)acrylate functional oligomer and photoinitiator,

this urethane-(meth)acrylate functional oligomer contains (meth)acrylate groups, at least one polyol as one main chain and a urethane group,

15% or more urethane groups are derived from one of 2,4 - and 2,6-colordistance or both of them,

at least 15% of the urethane groups are derived from a cyclic or branched aliphatic isocyanate (isophoronediisocyanate),

these urethane(meth)acrylate functional oligomer has srednecenovogo molecular weight of at least 4000 g/mol to less than or equal to 15000 g/mol; and

when the cured film of the radiation curable primary coating composition has an equilibrium modulus of elasticity less than or equal to 1.2 MPa.

[0030] the Oligomers that are applicable in a variety of aspects of the present invention will be described in the following sections. In General, the oligomers are urethane-(meth)acrylat the e oligomers, containing (meth)acrylate group, urethane group and the main chain (the term "(meth)acrylate" includes acrylate and methacrylate functional groups). The primary circuit is derived from the applied polyol which is reacted with an aromatic diisocyanate and aliphatic diisocyanate and hydroxyalkyl(meth)acrylate, preferably hydroxyethylacrylate.

[0031] it has been Unexpectedly discovered that is predominant rather the use of a mixture of 2,4 - and 2,6-isomers colordistance in the 80/20 ratio than the use of the TDS, which represents 100%of 2,4-isomer colordistance.

Oligomer And

[0032] the Oligomer preferably be obtained by reaction of an acrylate (e.g., NEA) with aromatic isocyanate (e.g., TDI); aliphatic isocyanate (e.g., IPDI), polyol (for example, R); a catalyst (for example, DBTDL); and an inhibitor (e.g., BHT).

[0033] the Aromatic and aliphatic isocyanates are well known and are commercially available. Preferred aromatic isocyanate is TDI, while the preferred aliphatic isocyanate is isophorondiisocyanate.

[0034] Upon receipt of the oligomer And the isocyanate component may be added to the oligomer reaction mixture in quantities of 1 to 25 wt.%, preferably from 1.5 to 20 wt.%, and preferably from 2 to 15 wt.%, all based on the mass percentage of oligomeric mixture.

[0035] Preferably, the isocyanate should include more aliphatic isocyanate than aromatic isocyanate. More preferably, the ratio of aliphatic to aromatic isocyanate may range from 6:1, preferably from 4:1, and most preferably from 3:1.

[0036] To obtain the oligomer can be used many polyols. Examples of suitable polyols are simple polyester polyols, complex, polyester polyols, polycarbonate polyols, polycaprolactone polyols, acrylic polyols, and the like. These polyols can be used either individually or in combination of two or more. There are no particular restrictions on the method of polymerization of the structural units in these polyols; apply any statistical polymerization, block polymerization or graft polymerization. Preferably used R (BASF).

[0037] Upon receipt of the oligomer And polyol as one component can be added to the oligomer reaction mixture in any suitable amount, preferably comprising in the range from 20 to 99 wt.%, more preferably from 40 to 97 wt.%, and preferably from 60 to 95 wt.%, all based on the mass percentage of oligomeric mixture.

[0038] Brednikova molecular weight polyols suitable for use in the floor of the attachment of the oligomer, can vary from 500 to 8000, preferably from 750 to 6000, and preferably from 1000 to 4000.

[0039] Acrylate component, applicable upon receipt of the oligomer And may be of any suitable type, but preferably it is hydroxyalkyl(meth)acrylate, preferably hydroxyethylacrylate (NEA). Upon receipt of the oligomer And acrylate component may be added to the oligomer reaction mixture in any suitable amount, preferably from 1 to 20 wt.%, more preferably from 1.5 to 10 wt.%, and preferably from 2 to 4 wt.%, all calculated on the weight of the oligomeric mixture of the reactants.

[0040] In the reaction, which gives the oligomer And may be used in the catalyst oreanization. Suitable catalysts are well known in the art and can be one or more selected from the group consisting of dilaurate dibutylamine; carboxylates of metals, including but not limited to those: vismutorganicheskikh catalysts, such as neodecanoic bismuth, CAS 34364-26-6; neodecanoate zinc CAS 27253-29-8; neodecanoate zirconium CAS 39049-04-2; 2-zinc ethylhexanoate, CAS 136-53-8; sulfonic acids, including but not limited to such, dodecylbenzenesulfonic acid, CAS 27176-87-0; methansulfonate acid, CAS 75-75-2; catalysts based on amines or organic bases, including but not limited to so: 1,2-dimetil Idasa, CAS 1739-84-0 (very weak base) and diazabicyclo (AKA DABCO), CAS 280-57-9 (strong base); triphenylphosphine (TPP); the alcoholate of zirconium and titanium, including, but not limited to such, butyl zirconium (tetramethylsilane), CAS 1071-76-7, and butyl titanium (tetrabutyltin)CAS 5593-70-4; and ionic liquid phosphonium salts of, Cyphosil 101 (chloride, tetradecyl(trihexy)phosphonium). The preferred catalyst is DBTDL.

[0041] the Catalysts can be used in a free, soluble and homogeneous condition, or they may be associated with inert agents such as silica gel, or macrostate resins with divinely cross, and applied in a heterogeneous able to be filtered by the completion of the synthesis of the oligomer.

[0042] Upon receipt of the oligomer And catalyst component can be added to the oligomer reaction mixture in any suitable amount, preferably from 0.01 to 1.0 wt.%, more preferably from 0.01 to 0.5 wt.%, and preferably from 0.01 to 0.05 wt.%, all calculated on the weight of the oligomeric mixture of the reactants.

[0043] Upon receipt of the oligomer And is also used inhibitor. This component helps to prevent polymerization of the acrylate during synthesis and storage of the oligomer. In the art there are many inhibitors that can be applied upon receipt of the oligomer. Preferred is entrusted inhibitor is an EIT.

[0044] Upon receipt of the oligomer And the inhibitory component may be added to the oligomer reaction mixture in any suitable amount, preferably from 0.01 to 2 wt.%, more preferably from 0.01 to 1.0 wt.%, and preferably from 0.05 to 0.50 wt.%, all calculated on the weight of the oligomeric mixture of the reactants.

[0045] the Variant of implementation of the claimed invention now relates to the oligomer And that has srednecenovogo molecular weight less than or equal to 11000 g/mol. The option of implementing the claimed invention now relates to the oligomer And that has srednecenovogo molecular weight less than or equal to 10000 g/mol. The option of implementing the claimed invention now relates to the oligomer And that has srednecenovogo molecular weight less than or equal to 9000 g/mol.

[0046] Also here disclosed radiation-curable primary coating composition for use as a primary coating on an optical fiber, preferably glass optical fiber. Curing radiation, the coating composition contains:

A) oligomer P;

B) a first monomer-diluent;

C) a second monomer-diluent;

D) photoinitiator;

(E) an antioxidant; and

F) an adhesion promoter;

these oligomer R represents the reaction product of: (i) hydroxyethylacrylate; (ii) aromatizes the CSOs isocyanate; (iii) aliphatic isocyanate; (iv) a polyol; (v) catalyst; (vi) inhibitor;

these oligomer has srednecenovogo molecular weight of at least 4000 g/mol to less than or equal to 15000 g/mol; and

when this cured film mentioned radiation-curable primary coating composition has a peak tan Delta Twithfrom -25°C to -45°C and the modulus of elasticity of from 0.50 MPa to 1.2 MPa.

Oligomer P

[0047] the Oligomer R preferably be obtained by reaction of acrylate (NEA) with aromatic isocyanate (e.g., TDI); aliphatic isocyanate (e.g., IPDI), polyol (for example, R); a catalyst (for example, DBTDL); and an inhibitor (e.g., BHT).

[0048] the Aromatic and aliphatic isocyanates are well known and are commercially available. Preferred aromatic isocyanate is TDI, while the preferred aliphatic isocyanate is isophorondiisocyanate.

[0049] Upon receipt of the oligomer P isocyanate component may be added to the oligomer reaction mixture in quantities of 1 to 25 wt.%, preferably from 1.5 to 20 wt.%, and preferably from 2 to 15 wt.%, all based on the mass percentage of oligomeric mixture.

[0050] Preferably, the isocyanate should include more aliphatic isocyanate than aromatic isocyanate. More preferably, the ratio of the aliphatic isocya the ATA to aromatic can be from 2 to 7:1, preferably from 3-6:1, and most preferably from 3 to 5:1.

[0051] To obtain the oligomer R can be used many polyols, as described in connection with the oligomer A. Preferably used Pluracol R, polypropylenglycol (BASF) MM 2000.

[0052] Upon receipt of the oligomer R polyol as one component can be added to the oligomer reaction mixture in any suitable amount, preferably comprising in the range from 20 to 99 wt.%, more preferably from 40 to 97 wt.%, and preferably from 60 to 95 wt.%, all based on the mass percentage of oligomeric mixture.

[0053] the Molecular mass (MM) of polyols suitable for use in obtaining the oligomer R, can vary from 500 to 8000, preferably from 750 to 6000, and preferably from 1000 to 4000.

[0054] Acrylate component used to obtain the oligomer R represents the NEA. Upon receipt of this oligomer acrylate component may be added to the oligomer reaction mixture in any suitable amount, preferably from 1.0 to 20 wt.%, more preferably from 1.5 to 10 wt.%, and preferably from 2 to 4 wt.%, all calculated on the weight of the oligomeric mixture of the reactants.

[0055] In the reaction, which gives the oligomer R, can be used catalyst oreanization. Suitable catalysts are well known in the art and can be one or more, described in St. the zi with the oligomer A. The preferred catalysts are DBTDL and Coscat 83.

[0056] the Catalysts can be used in a free, soluble and homogeneous condition, 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] Upon receipt of the oligomer R catalyst component can be added to the oligomer reaction mixture in any suitable amount, preferably from 0.01 to 0.5 wt.%, and more preferably from 0.01 to 0.05 wt.%, all calculated on the weight of the oligomeric mixture of the reactants.

[0058] Upon receipt of the oligomer R is also used inhibitor. This component helps to prevent polymerization of the acrylate during synthesis and storage of the oligomer. In the art there are many inhibitors, which are described in connection with the oligomer A. Preferably the inhibitor is an EIT.

[0059] Upon receipt of the oligomer R inhibitor component may be added to the oligomer reaction mixture in any suitable amount, preferably from 0.01 to 1.0 wt.% and more preferably from 0.05 to 0.50 wt.%, all calculated on the weight of the oligomeric mixture of the reactants.

[0060] the Variant of implementation of the claimed invention now relates to the oligomer R that is no srednecenovogo molecular weight of at least 5000 g/mol. The option of implementing the claimed invention now relates to the oligomer R, which has srednecenovogo molecular weight of at least 6000 g/mol. The option of implementing the claimed invention now relates to the oligomer R, which has srednecenovogo molecular weight of at least 7,000 g/mol.

[0061] the Variant of implementation of the claimed invention now relates to the oligomer R, which has srednecenovogo molecular weight less than or equal to 10000 g/mol. The option of implementing the claimed invention now relates to the oligomer R, which has srednecenovogo molecular weight less than or equal to 9000 g/mol. The option of implementing the claimed invention now relates to the oligomer R, which has srednecenovogo molecular weight less than or equal to 8000 g/mol.

[0062] Also here disclosed radiation-curable primary coating composition for use as a primary coating on an optical fiber, preferably glass optical fiber. Curing radiation, the coating composition contains:

A) oligomer CA/CR;

B) the monomer-diluent;

C) photoinitiator;

D)an antioxidant; and

(E) an adhesion promoter;

these oligomer CA/CR is a reaction product of: (i) hydroxyethylacrylate; (ii) an aromatic isocyanate;and (iii) aliphatic isocyanate; iv) a polyol; (v) catalyst; and (vi) inhibitor;

these oligomer has srednecenovogo molecular weight of at least 4000 g/mol to less than or equal to 15000 g/mol; and

when this cured film mentioned radiation-curable primary coating composition has a peak tan Delta Twithfrom -30°C to -40°C. and a modulus of elasticity of from 0.65 MPa to 1 MPa.

Oligomer CA/CR

[0063] the Oligomer CA/CR is desirable to obtain the reaction of acrylate (NEA) with aromatic isocyanate (e.g., TDI); aliphatic isocyanate (e.g., IPDI), polyol (for example, R); a catalyst (for example, Coscat 83 or DBTDL); and an inhibitor (e.g., BHT).

[0064] the Aromatic and aliphatic isocyanates are well known and are commercially available. Preferred aromatic isocyanate is TDI, while the preferred aliphatic isocyanate is isophorondiisocyanate.

[0065] Upon receipt of the oligomer CA/CR isocyanate component may be added to the oligomer reaction mixture in quantities of 1 to 25 wt.%, preferably from 1.5 to 20 wt.%, and preferably from 2 to 15 wt.%, all based on the mass percentage of oligomeric mixture.

[0066] Preferably, the isocyanate should include more aliphatic isocyanate than aromatic isocyanate. More preferably, the ratio of aliphatic isocyanate to aromatize what anyone may vary from 6:1, preferably from 4:1, and most preferably from 3:1.

[0067] To obtain oligomer CA/CR can be used many polyols, as described in connection with the oligomer A. Preferably used R (BASF).

[0068] Upon receipt of the oligomer CA/CR polyol as one component can be added to the oligomer reaction mixture in any suitable amount, preferably comprising in the range from 20 to 99 wt.%, more preferably from 40 to 97 wt.%, and preferably from 60 to 95 wt.%, all based on the mass percentage of oligomeric mixture.

[0069] the Molecular mass (MM) of polyols suitable for use in obtaining oligomer CA/CR, can vary from 500 to 8000, preferably from 750 to 6000, and preferably from 1000 to 4000.

[0070] Acrylate component used to obtain the oligomer CA/CR is a NEA. Upon receipt of the acrylate oligomer component may be added to the oligomer reaction mixture in any suitable amount, preferably from 1 to 20 wt.%, more preferably from 1.5 to 10 wt.%, and preferably from 2 to 4 wt.%, all calculated on the weight of the oligomeric mixture of the reactants.

[0071] In the reaction, which gives the oligomer CA/CR, can be used catalyst oreanization. Suitable catalysts are well known in the art and described in connection with the oligomer A. the Preferred catalyst is a vis organicheskoi catalyst, for example Coscat 83.

[0072] the Catalysts can be used in a free, soluble and homogeneous condition, 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.

[0073] Upon receipt of the oligomer CA/CR catalyst component can be added to the oligomer reaction mixture in any suitable amount, preferably from 0.01 to 1.0 wt.%, more preferably from 0.01 to 0.5 wt.%, and preferably from 0.01 to 0.05 wt.%, all calculated on the weight of the oligomeric mixture.

[0074] Upon receipt of the oligomer CA/CR can also be used inhibitor. This component helps to prevent polymerization of the acrylate during synthesis and storage of the oligomer. In the art there are many inhibitors, which are described in connection with the oligomer A. Preferably the inhibitor is an EIT.

[0075] Upon receipt of the oligomer CA/CR inhibitor component may be added to the oligomer reaction mixture in any suitable amount, preferably from 0.01 to 2.0 wt.%, more preferably from 0.01 to 1.0 wt.%, and preferably from 0.05 to 0.50 wt.%, all based on the mass percentage of oligomeric mixture.

[0076] the Present invention further is cured of the doctrine of the composition of the primary coating. This coating composition contains at least one urethane(meth)acrylate functional oligomer N and photoinitiator, with a urethane(meth)acrylate oligomer N includes (meth)acrylate groups, at least one polyol as one main chain and a urethane group, and 15% or more urethane groups are derived from one of 2,4 - and 2,6-colordistance or both, and at least 15% of the urethane groups are derived from a cyclic or branched aliphatic isocyanate,

these oligomer has srednecenovogo molecular weight of at least 4000 g/mol to less than or equal to 11000 g/mol;

when the storage modulus (G') - curable coating is less than or equal to 0.8 PA, as measured at G=100 PA.

[0077] Obtaining the above-described oligomers can be performed in any suitable way, but preferably occurs by mixing the components of the isocyanate, polyol and an inhibitor, then the addition of the catalyst. The mixture can then be heated and left to react to completion. It is desirable then to add acrylate (for example, NEA), and the mixture is heated until the reaction is complete. This is a preferred method of producing oligomers of P and CA/CR.

[0078] it is also Possible first to introduce the reaction of isocyanate component (relatedentities or branched aliphatic polyisocyanate) acrylate (for example, NEA), preferably in the presence of the inhibitor and catalyst. The resulting product can then be introduced into the reaction with the polyol with the formation of the oligomer. When to obtain oligomer use of aromatic and aliphatic isocyanates, you can enter one type of isocyanate (e.g., aliphatic) reaction with acrylate (for example, NEA), preferably in the presence of the inhibitor and catalyst, and the resulting product is reacted with the polyol and the second type isocyanate (for example, aromatic).

[0079] In the above reactions used to produce oligomers, the reaction is preferably carried out at temperatures from 10°C to 90°C, and more preferably from 30°C. to 85°C.

Curing radiation coating composition

[0080] After receiving the oligomers can be prepared radiation-curable coating composition in accordance with various aspects of the present invention.

Curing radiation coating And

[0081] the Amount of the oligomer And curing of the composition may vary depending on the desired properties, but preferably will be from 20 to 80 wt.%, more preferably from 30 to 70 wt.%, and preferably from 40 to 60 wt.%, in the calculation of the mass percentage of the radiation-curable composition.

[0082] To the curable composition can also be added one or more of the reaction is posebnih monomer-solvent; such diluents are well known in the art. Various diluents known in the art and can be used to produce oligomers, including, without limitation, acrylate alkoxysilanes alkyl substituted phenol, such as acrylate of ethoxylated Nonylphenol (ENPA), the acrylate propoxyethanol of Nonylphenol (PNPA), vinyl monomers, such as vinylcaprolactam (nVC), isodecyladipate (IDA), (2-)hexyl acrylate (S), diethylene glycol hexyl acrylate (DEGEHA), isobutylacetate (IBOA), diacrylate tripropyleneglycol (TPGDA), diacrylate of hexandiol (HDDA), triacrylate of trimethylolpropane (TMRCA), triacrylate alkoxysilanes of trimethylolpropane and diacrylate alkoxysilanes bisphenol a, such as diacrylate ethoxylated bisphenol A (EO-BPADA). Preferably, the diluent used Photomer 4066. The total amount of diluent in the curable composition may vary depending on the desired properties, but will preferably be from 20 to 80 wt.%, more preferably from 30 to 70 wt.%, and preferably from 40 to 60 wt.%, in the calculation of the mass percentage of the radiation-curable composition.

[0083] the Curable composition also includes one or more photoinitiators. Such components are well known in the art. Photoinitiator can be included in the number of the function, components from 0.5 wt.% up to 3 wt.% from the curable composition, and preferably from 1 wt.% up to 2 wt.%. The preferred photoinitiator is Chivacure TPO.

[0084] Another component that may be used in the curable composition is an antioxidant. Such components are well known in the art. If present, the antioxidant component can be included in amounts comprising from 0.2 to 1 wt.% from the curable composition. Preferably, the antioxidant is Irganox 1035.

[0085] Another component, preferably included in the composition of the curable composition is an adhesion promoter, which means his name, enhances the adhesion of the cured coating to the optical fiber. Such components are well known in the art. If present, the adhesion promoter may be included in the composition in amounts comprising from 0.5 wt.% up to 2 wt.% from the curable composition. Preferably, the adhesion promoter is an A-189.

[0086] the Above components may be mixed with each other to provide radiation-curable coatings. Preferably, the oligomer, the monomer-diluent, photoinitiator and antioxidant are mixed and heated at 70°C for 1 hour to dissolve all of the powder material. ZAT is m the temperature is reduced to not more than 55°C, add an adhesion promoter and mix the components for 30 minutes.

[0087] In a preferred aspect of the present invention, the oligomer may be obtained from the following components (based on the mass percentage of the components used to obtain oligomer):

Acrylate (for example, NEA): from 1 to 3 wt.%;

Aromatic isocyanate (e.g., TDA): from 1 to 2 wt.%;

Aliphatic isocyanate (e.g., IPDI): from 4 to 6 wt.%;

Polyol (for example, R): from 40 to 60 wt.%;

The catalyst (for example, DBTDL): from 0.01 to 0.05 wt.%;

Inhibitor (e.g., BHT): from 0.05 to 0.10 wt.%.

[0088] In a preferred aspect of the present invention, in addition to from 40 to 60 wt.% oligomer A, the components of the curable composition may include (based on the mass percentage of the curable composition):

The monomer-diluent (e.g., Photomer 4066): 35 to 45 wt.%;

Photoinitiator (for example, Chivacure TPO): from 1.00 to 2.00 wt.%;

Antioxidant (for example, Irganox 1035): 0.25 to 0.75 wt.%;

An adhesion promoter (e.g., A-189): from 0.8 to 1.0 wt.%

(each of the above percentages is selected to achieve 100 wt.% the entire composition as a whole).

[0089] a More preferred implementation of the present invention can be executed as follows:

The oligomer And perving the cover Wt.%
Hydroxyethylacrylate (NEA)2,11
Aromatic isocyanate (TDI)1,59
Aliphatic isocyanate (IPDI)5,31
Polyol(R)46,9
Inhibitor (BHT)0,08
The catalyst (DBTDL)0,03
Curing radiation coating compositionWt.%
The oligomer And the primary coating56,0
The monomer-diluent (Photomer 4066)of 40.9
Photoinitiator (Chivacure TPO)1,70
Antioxidant (Irganox 1035)0,50
The adhesion promoter (A-189)0,90

[0090] the Above-described primary coating is designated as the primary coating CR.

[0091] the radiation-Curable coating R

[0092] the Amount of the oligomer P-curable composition may vary depending on gelatin the different properties, but will preferably be from 20 to 80 wt.%, more preferably from 30 to 70 wt.%, and preferably from 40 to 60 wt.%, in the calculation of the mass percentage of the radiation-curable composition.

[0093] Diverse reactive monomer diluent may also be added to the curable composition; such diluents known in the art. A variety of diluents known in the art and can be used to obtain an oligomer, including, without limitation, acrylate alkoxysilanes alkyl substituted phenol, such as acrylate of ethoxylated Nonylphenol (ENPA), the acrylate propoxyethanol of Nonylphenol (PNPA), vinyl monomers, such as vinylcaprolactam (nVC), isodecyladipate (IDA), (2-)hexyl acrylate (S), diethylene glycol hexyl acrylate (DEGEHA), isobutylacetate (IBOA), diacrylate tripropyleneglycol (TPGDA), diacrylate of hexandiol (HDDA), triacrylate of trimethylolpropane (TMRCA), triacrylate alkoxysilanes of trimethylolpropane and diacrylate alkoxysilanes bisphenol a, such as diacrylate ethoxylated bisphenol A (EO-BPADA), Photomer 4066, SR 504D and SR 306. Preferably, as a component of the diluent is a mixture of SR 504D and/or Photomer 4066 (first solvent) and SR 306 (second solvent).

[0094] the Total amount of diluent in the curable composition may vary dependent on the STI from the desired properties, but will preferably be from 20 to 80 wt.%, more preferably from 30 to 70 wt.%, and preferably from 40 to 60 wt.% in the calculation of the mass percentage of the radiation-curable composition. Component of the diluent preferably includes an excess of the first diluent relative to the second diluent in the ratio of 20-80:1 (from 20 to 80 parts of the first diluent to 1 part of the second diluent), and preferably 40-60:1 (from 40 to 60 parts of the first diluent to 1 part of the second diluent).

[0095] the Curable composition also includes one or more photoinitiators. Such components are well known in the art. Photoinitiator can be included in the composition in amounts comprising from 0.2 wt.% up to 5 wt.% from the curable composition, and preferably from 0.5 wt.% up to 3 wt.%. The preferred photoinitiator is Irgacure 819.

[0096] Another component that may be used in the curable composition is antioksidantnye components well known in the art. If present, the antioxidant component can be included in the composition in amounts comprising from 0.1 to 2 wt.% and preferably from 0.25 to 0.75 wt.% from the curable composition. Preferably, the antioxidant is Irganox 1035.

[0097] Another component, preferably included in the composition of the curable composition is an adhesion promoter, which means his name, enhances the adhesion of the cured coating to the optical fiber. Such components are well known in the art. If present, the adhesion promoter may be included in the composition in amounts comprising from 0.2 wt.% up to 2 wt.%, preferably from 0.8 to 1.0 wt.% from the curable composition. Preferably, the adhesion promoter is an A-189.

[0098] the Above components may be mixed with each other to provide radiation-curable coatings. Preferably, the oligomer, the monomer-diluent, photoinitiator and antioxidant are mixed and heated at 70°C for 1 hour to dissolve all of the powder material. The temperature was then reduced to not more than 55°C, add an adhesion promoter and mix the components for 30 minutes.

[0099] the Following examples are presented as illustrating the curable coating composition according to the invention.

Example 1Example 2Example 3
Oligomer P primary cover
Acrylate (NEA) 1,411,611,54
Aromatic isocyanate (TDI)1,051,201,15
Aliphatic isocyanate (IPDI)4,71to 4.685,13
Polyol (R)42,2442,4046,07
The catalyst (Coscat 83)0,030,030,03
Inhibitor (BHT)0,080,080,08
49,5050,0054,00
Curing radiation, the composition coating
The first diluent (Photomer 4066)47,0046,4041,90
The second diluent (SR 306)1,00 0,801,00
Photoinitiator (Chivacure TPO)1,101,401,70
Antioxidant (Irgacure 1035)0,500,500,50
The adhesion promoter (A-189)0,900,900,90
100,00100,00100,00
Example 4Example 5Example 6
Oligomer P primary cover
Acrylate (NEA)1,841,481,54
Aromatic isocyanate (TDI)1,381,111,15
Aliphatic isocyanate (IPDI)5,284,94 5,13
Polyol (R)47,4044,3846,07
The catalyst (DBTDL)0,030,030,03
Inhibitor (BHT)0,080,080,08
56,0052,0054,00
Curing radiation, the composition coating
The first diluent (Photomer 4066)40,9044,5041,90
The second diluent (SR 306)0,951,001,00
Photoinitiator (Chivacure TPO)1,701,401,70
Photoinitiator (Irgacure 819)-1,10-
Antioxidant (Irgacure 1035)0,500,500,50
The adhesion promoter (A-189)0,900,900,90
100,00100,00100,00

[0100] the Above-described primary coating is designated as the primary coating R.

[0101] the radiation-Curable coating CA/CR

[0102] the Amount of the oligomer CA/CR in the curable composition may vary depending on the desired properties, but will preferably be from 20 to 80 wt.%, more preferably from 30 to 70 wt.%, and preferably from 40 to 60 wt.% in the calculation of the mass percentage of the radiation-curable composition.

[0103] One or more reactive monomer-diluent may also be added to the curable composition; such diluents are well known in the art. A variety of diluents known in the art and can be used to obtain an oligomer, including, without limitation, acrylate alkoxysilanes alkyl substituted phenol, such as acrylate of ethoxylated Nonylphenol (ENPA), the acrylate propoxyethanol of Nonylphenol (PNPA), vinyl monomers such as vinylcaprolactam (nVC), isodecyladipate (IDA), (2-)hexyl acrylate (S), diethylene glycol hexyl acrylate (DEGEHA), isobutylacetate (IBOA), diacrylate tripropyleneglycol (TPGDA), diacrylate of hexandiol (HDDA), triacrylate of trimethylolpropane (TMRCA), triacrylate alkoxysilanes of trimethylolpropane and diacrylate alkoxysilanes bisphenol a, such as diacrylate ethoxylated bisphenol A (EO-BPADA). Preferably, the diluent used Photomer 4066. The total amount of diluent in the curable composition may vary depending on the desired properties, but will preferably be from 20 to 80 wt.%, more preferably from 30 to 70 wt.%, and preferably from 40 to 60 wt.% in the calculation of the mass percentage of the radiation-curable composition.

[0104] the Curable composition also includes one or more photoinitiators. Such components are well known in the art. Photoinitiator can be included in the composition in amounts comprising from 0.5 wt.% up to 3 wt.% from the curable composition, and preferably from 1 wt.% up to 2 wt.%. The preferred photoinitiator is Chivacure TPO.

[0105] Another component that may be used in the curable composition is antioksidantnye components well known in the art. If present, the antioxidant component which may be included in the composition in amounts components from 0.2 to 1 wt.% from the curable composition. Preferably, the antioxidant is Irganox 1035.

[0106] Another component, preferably included in the composition of the curable composition is an adhesion promoter, which means his name, enhances the adhesion of the cured coating to the optical fiber. Such components are well known in the art. If present, the adhesion promoter may be included in the composition in amounts comprising from 0.5 wt.% up to 2 wt.% from the curable composition. Preferably, the adhesion promoter is an A-189.

[0107] the Above components may be mixed with each other to provide radiation-curable coatings. Preferably, the oligomer, the monomer-diluent, photoinitiator and antioxidant are mixed and heated at 70°C for 1 hour to dissolve all of the powder material. The temperature was then reduced to not more than 55°C, add an adhesion promoter and mix the components for 30 minutes.

[0108] In a preferred aspect of the present invention, the oligomer CA/CR can be obtained from the following components (based on the mass percentage of the components used to obtain oligomer):

Acrylate (for example, NEA): from 1 to 3 wt.%;

Aromatic isocyanate (e.g., TDI): from 1 to 2 wt.%;

Alipac the ical isocyanate (for example, IPDI): from 4 to 6 wt.%;

Polyol (for example, R): from 40 to 60 wt.%;

The catalyst (for example, Coscat 83): from 0.01 to 0.05 wt.%;

Inhibitor (e.g., BHT): from 0.05 to 0.10 wt.%.

[0109] In a preferred aspect of the present invention, in addition to from 40 to 60 wt.% the oligomer, the components of the curable composition may include (based on the mass percentage of the curable composition):

The monomer-diluent (e.g., Photomer 4066): 35 to 45 wt.%;

Photoinitiator (for example, Chivacure TPO): from 1.00 to 2.00 wt.%;

Antioxidant (for example, Irganox 1035): 0.25 to 0.75 wt.%;

An adhesion promoter (e.g., A-189): from 0.8 to 1.0 wt.% (can be adjusted to achieve 100 wt.%).

[0110] a More preferred implementation of this aspect of the present invention can be executed as follows:

Oligomer CA/CR primary coverageWt.%
Hydroxyethylacrylate (NEA)1,84
Aromatic isocyanate (TDI)1,38
Aliphatic isocyanate (IPDI)5,28
Polyol (R)47,40
Inhibitor (BHT) 0,08
The catalyst (DBTDL or Coscat 83)0,03
Curing radiation coating compositionWt.%
Oligomer CA/CR primary coating56,01
The monomer-diluent (Photomer 4066)of 40.9
Photoinitiator (Chivacure TPO)1,70
Antioxidant (Irganox 1035)0,50
The adhesion promoter (A-189)0,90

[0111] the Above-described primary coating designated as primary coverage CA/CR.

Oligomer N and radiation-curable coating N

[0112] the Present illustrates the composition of the oligomer N and radiation-curable coatings N, which includes the Oligomer N and other ingredients.

[0113] the Following illustration presents the uncured primary coating containing oligomer corresponding to the parameters of the oligomer N.

[0114] the radiation-Curable primary coating H

Trade nameThe Mac.%
% of oligomer55,00%
The composition of the oligomer NHydroxyethylacrylateNOPE1,82%
IsocyanateTDI2,73%
IsocyanateIPDI3,49%
PolyolR BASF PPG46,85%
CatalystDBTDL0,03%
InhibitorEIT0,08%
The monomerSR 504D36,25%
The monomerSR395D3,00%
The monomerSR3062,50%
PhotoinitiatorChivacure TPO1,50%
AntioxidantIrganox 1035 0,60%
StabilizerLowilite 200,15%
The adhesion promoterA-1891,00%

[0115] Preferably, the illustrative radiation-curable coating N may include: 15-98 wt.% at least oligomer H having a molecular weight of 500 or more, preferably 20-80 wt.%, and more preferably 30-70 wt.%; 0-85 wt.% one or more reactive diluents, preferably 5-70 wt.%, more preferably 10-60 wt.%, and most preferably 15-60 wt.%; 0.1 to 20 wt.% one or more photoinitiators, preferably 0.5 to 15 wt.%, more preferably 1-10 wt.%, and most preferably 2-8 wt.%; and 0-5 wt.% additives.

[0116] One or more coloring substances can also be incorporated into any of the uncured coating, if desired. The dye may be a pigment or dye, but preferably is a dye.

[0117] Methods of curing are described here uncured coatings are well known in the art and include electron beam (E) and ultraviolet (UV) svetel for curing coatings using UV light.

[0118] Described C is the return of the primary coating typically will be applied on the optical fiber immediately after pulling the fiber, followed by curing. Utverjdenie primary coating can then be covered with a secondary coating, which also preferably is cured by radiation. Suitable secondary coatings are commercially available. Curable by radiation of the secondary coating can be any commercially available radiation curable secondary coating for optical fibers. Such commercially available radiation curable secondary coating are made by the company DSM Desotech Inc., and others, including, but without limitation, Hexion, Luvantix and PhiChem. As a secondary coating in the present invention can be used, for example, coating, described in documents EP 2091883 B1, EP 2089334 A1, EP 2091884 A1, WO 2010/053532 (Specialty High Temperature Resistant Secondary Coating), US 6534557 and US 6306924.

[0119] If desired, the coated optical fiber can be applied colorful material to make fibers visible in the fiber Assembly. Fiber Assembly typically includes cables, which may contain loose tube fiber, or ribbon, or both. Tape in General is made by connecting multiple coated optical fibers in a matrix material.

[0120] the Cured primary coating described herein preferably have properties, which are described in the following paragraphs.

[0121] the Viscosity at zero shear at 23°C is described ZV is camping uncured coating is preferably 1 PA·s or higher, more preferably 2 PA·s or higher, and still more preferably 3 PA·s or higher. This viscosity is preferably 20 PA·s or less, more preferably 12 PA·s or less, even more preferably 9 PA·s or lower, and most preferably 7 PA·s or below.

[0122] the refractive Index of the coatings described here is preferably of 1.48 or higher, and more preferably is 1.51 or higher.

[0123] the Elongation at break solidified primary coating is preferably more than 50%, preferably more than 60%, more preferably at least 100%, but preferably not higher than 400%. This elongation can be measured at a speed of stretching 5 mm/min 50 mm/min and 500 mm/min, respectively, and preferably at 50 mm/min

[0124] the Equilibrium modulus, as tested on utverzhdenii the film composition of the primary coating according to the present invention, is 1.2 MPa or less, more preferably 1.0 MPa or less, and most preferably 0.8 MPa or less. Preferably, this value is 0.1 MPa or higher, and more preferably 0.3 MPa or higher.

[0125] the glass transition Temperature Twiththe cured primary coating (defined as the peak of tangent Delta (tan δ) curve dynamic mechanical analysis (DMA)) is preferably 0°C. or below, more gellately is about -15°C or below, and most preferably -25°C. or lower at Twithpreferably component also -55°C or higher.

[0126] the Viscosity and elasticity of the coatings can be measured, as explained below.

[0127] with the viscosity at zero shear (η0) elasticity in the steady state (Je) largely determines the flow characteristics of the uncured composition coating. While the viscosity at zero shear is a measure of the viscous behavior of the fluid, the elasticity in the steady state is a measure of the elasticity of the fluid. Super-elastic fluids are undesirable due to the mentioned problems when dealing with them. For detailed descriptions of these rheological parameters and their interdependence should refer to pages 109-133 books "Rheology: principles, measurements and applications" ("Rheology: principles, measurements and applications") of the author C.W. Macosko (published by VCH Publishers, 1994). Although both parameters are determined at low shear rate, they determine the rheological curve in General for a wide range of shear rates.

[0128] In the experiment difficult to accurately determine the elasticity in the steady state, because it requires measurements of the elastic fluid at very low shear rates and/or frequencies (when performing dynamic measurements). In good approximation, the UE shall post fluid can be measured (using a dynamic mechanical measurements on liquid uncured coating) from the values of storage modulus shear G' at a fixed low value of the loss modulus G" (for example, 100 PA). A higher value of G' corresponds to a more elastic fluid. It was found that the uncured coating modulus shear G' is lower than 0.8 PA, the unit loss (G" 100 PA are easy to handle. In this case, it is preferable that G' at G"=100 PA was less than 0.6 PA, even more preferably less than 0.5 PA, and most preferably less than 0.4 PA.

[0129] as an example, a simple polyester urethane-acrylate oligomer CA/CR, including 2,6-colorvision, when measured in composition, consisting of 68.5 wt.% the oligomer, of 28.5 wt.% nonylphenolethoxylates (SR 504) monomer-diluent and 3 wt.% photoinitiator Irgacure 184, shows G' at G"=100 PA, 0.8 PA or less.

[0130] In a good approximation to the viscosity at zero shear was found that it is possible to use dynamic viscosity at 20°C and at an angular frequency of 10 rad/s as a measure of the viscosity of the uncured liquid. The viscosity in this respect is preferably 1 PA·s or higher, more preferably 2 PA·s or higher, and still more preferably 3 PA·s or higher. Preferably, this viscosity can be up to 100 PA·s or lower, more preferably 20 PA·s or lower, and most preferably 8 PA·s or below.

[0131] the Following examples further illustrate the invention but, of course, should not be construed as in any way limiting agoraki.

EXAMPLES

The first set of test methods for liquid coatings and hardened films

Test methods tensile strength tensile, elongation and modulus of elasticity

[0132] Mechanical tensile properties (ultimate tensile strength, percentage elongation at break and modulus of elasticity) of solidified samples was determined using a universal measuring device Instron model 4201. Samples are prepared for testing by curing the film material with a thickness of 75 μm using a UV processor Fusion. Samples utverjdayut at 1.0 j/cm2in nitrogen atmosphere. Film cut test samples having a width of 1.27 cm (0.5 inch) and a length of 12.7 cm (5 inches). The exact thickness of each sample is measured with a micrometer.

[0133] For relatively soft coatings (for example, with modulus less than 10 MPa) coating is applied and utverjdayut on a glass plate, and the individual samples are cut with a glass plate with a scalpel. In the Instron device using a torque sensor 0.9 kg (2 lb) and calculate the module at a 2.5%elongation with the fitting by method of least squares graph of stress-strain. Before testing solidified film is conditioned at a temperature 23,0±0.1°C and a relative humidity of 50.0±0.5% for at least one hour.

[0134] For relatively b is more solid film coating applied to the film of Mylar, and samples cut of 1.27-cm (0.5-inch) precision blade sampler Thwing Albert. In the Instron device using a torque sensor to 9.1 kg (20 pounds) and calculate the modulus of elasticity of the 2.5%elongation at intersecting at this point. Before testing solidified film is conditioned at a temperature 23,0±0.1°C and a relative humidity of 50.0±0.5% in a period of sixteen hours.

[0135] For the test samples, the working length is 5.1 cm (2 inches), and the speed of the RAM is 2.54 cm/min (1.00 inch/min). All testing is carried out at a temperature 23,0±0.1°C and a relative humidity of 50.0±0,5%. All measurements determined from the average of at least 6 test specimens.

Test method DMA

[0136] Dynamic mechanical analysis (DMA) is performed on the test samples with the use of the device RSA-II manufactured by Rheometric Scientific Inc. Free sample film (typically with a length of about 36 mm, a width of 12 mm and a thickness of 0.075 mm) is placed in the clamps of the device, and the temperature is initially adjusted to 80°C and maintained at this level for about five minutes. During the last period of pre-heating at a temperature of 80°With the sample stretch approximately 2.5% of its original length. Also during this period, the identification information about the sample, its size and specific IU the ode test is administered in a computer program (RSI Orchestrator), installed on a connected personal computer.

[0137] All tests are performed at a frequency of 1.0 radian on the dynamic method step change temperature using steps 2°C, the exposure time from 5 to 10 seconds, the initial deflection of 0.001 (.DELTA.L/L) and activated options autonation and auto deformation. Autonation establish in order to ensure that the sample remains under the action of tensile forces throughout the test cycle, and autodermal set in order to allow deformation as the sample passes through the glass transition and becomes softer. After a five-minute exposure temperature in a heating Cabinet reduce speed to 20°C before reaching the initial temperature, typically leading to a -80°C or -60°C. the Final temperature of the test cycle is introduced into a computer program before starting the test cycle so that the data about the sample ranged from the region of the vitreous state through the transition region and deep into the area of high elasticity.

[0138] Test cycle start and allow you to go to completion. Upon completion of the test cycle on the computer screen displayed a graph of temperature dependence of several parameters: E'=storage modulus tensile E"=modulater tensile and tan Delta. Using computer programs to smooth the experimental point on each curve. In this graph, identify three points, representing the transition:

[0139] (1) the Temperature at which the storage modulus tensile=E'=1000 MPa;

[0140] (2) the Temperature at which the storage modulus tensile=E'=100 MPa;

[0141] (3) the Temperature peak on the curve of tan Delta. If the curve is tangent Delta contains more than one peak, measure the temperature of each peak. One additional value that is obtained from this graph represents a minimum value for the storage modulus tensile=E E' in the field of high elasticity. This value is registered as the equilibrium modulus, E0.

Measurement of adhesion in dry and wet conditions

[0142] Determination of adhesion in dry and wet conditions is performed by using a universal measuring device Instron model 4201. On a polished glass plate for thin-layer chromatography (TLC) cause a film thickness of 75 microns and utverjdayut using a UV processor Fusion. Samples utverjdayut at 1.0 j/cm2in an atmosphere of nitrogen.

[0143] the Sample is conditioned at a temperature 23,0±0.1°C and a relative humidity of 50.0±0.5% in the period of 7 days. After conditioning cut off with a scalpel eight samples with a length of 15.2 cm (6 d is imov) and a width of 2.54 cm (1 inch) in the direction of extrusion. Four sample apply a thin layer of talc. First of 2.54 cm (first inch) of each sample prepare the chin from the glass. The glass is fixed in a horizontal holder on the Instron instrument with a fixed end of the sample next to the pulley attached to the holder and located directly below the slider. To the end of the debonded sample attach the wire, pass it along the sample and then transferred through the pulley in the direction perpendicular to the sample. The free end of the wire is clamped in the upper jaw of the Instron instrument, which then lead to action. The test continued until until the average force in grams-force/2.54 cm (gram-force/inch) becomes relatively constant. The speed of the RAM is 25.4 cm/min (10 in/min). The importance of adhesion in the dry state is the average of four samples.

[0144] the Other four sample is then conditioned at a temperature 23,0±0.1°C and a relative humidity 95,0±0.5% in 24 hours. On the sample surface a thin layer of slurry of polyethylene in water. Then conduct the same test as in the previous paragraph. The importance of adhesion in the wet state is the average of four samples.

Sensitivity to water

[0145] Utverjdayut layer composition to obtain test strips UV-cured coating with dimensions of 3.8 cm × 3.8 cm × 15 μm (1,5 guy is and 1.5 inches by 0.6 mil). The test strip is weighed and placed in a bottle containing demineralized water, which is then stored for 3 weeks at 23°C. at periodic intervals, e.g., 30 minutes, 1 hour, 2 hours, 3 hours, 6 hours, 1 day, 2 days, 3 days, 7 days, 14 days and 21 days, the test strip is removed from the vial and gently wipe dry with a paper towel and weighed again. The percentage of water absorption register as 100×(weight after immersion - weight before immersion)/(weight before immersion). The peak absorption of water represents the highest value of water absorption reached a 3-week period of immersion. At the end of 3-week period of the test strip is dried in an oven at 60°C for 1 hour, cooled in a desiccator for 15 minutes and re-weighed. The percentage of recoverable water is expressed as 100×(weight before immersion - weight after drying)/(weight before immersion). Sensitivity to water are classified as |peak absorption of water|+|recoverable water|. To improve the accuracy of the tests have three test strips.

The refractive index of

[0146] the refractive Index of the hardened compositions determined by the method of strips Becke, which is based on the agreement of the refractive index thinly sliced strips utverzhdenii composition with immersion liquids with known properties of refraction. Ispy is the W is performed under a microscope at 23°C and with light, having a wavelength of 589 nm.

Viscosity

[0147] the Viscosity is measured using a Physica viscometer MS. Test samples are examined and, if there is an excessive amount of bubbles, take measures to remove most of the bubbles. At this stage it is not necessary to remove all the bubbles, since the loading of the sample introduces some amount of bubbles.

[0148] the Device set up on the ordinary system of Z3, which is used. Samples are loaded into a disposable aluminum cups using a syringe for measuring 17 cm3. The sample in the glass are examined, and if it contains an excessive amount of bubbles, remove them by a direct method, such as centrifugation, or leave for a time sufficient to allow the bubbles to leave the volume of liquid. Bubbles on the upper surface of the liquid is acceptable.

[0149] Carefully immerse the pendulum in the liquid in the measuring Cup, and a glass with a pendulum set in the device. Allow the sample temperature to be balanced with the temperature of the circulating fluid, after waiting for five minutes. Then the rotational speed is set at the desired value, which gives the desired shear rate. The desired shear rate is easily determined by the average person skilled in the technical field expected is the range of viscosity of the sample. Typical shear rate of 50 sec-1or 100 sec-1.

[0150] Read the reading values of the viscosity on the instrument panel, and if the viscosity varies only slightly (less than 2% relative deviation) for 15 seconds, complete the measurement. If not, then it is possible that the temperature has not reached the equilibrium state, or that the material is changed because of the shift. In the latter case you will need further testing at different shear rates to determine the rheological properties of the sample. The recorded results are average values of viscosity for the three test samples. Results expressed or centipoise (SP)or millipascals (MPa·s), which is equivalent.

[0151] a sample of the radiation-curable primary coating N synthesized according to the following formula.

[0152] the Following illustration presents the uncured primary coating N-containing oligomer, the characteristics of the oligomer N.

[0153] the radiation-Curable primary coating

The composition of the oligomerTrade nameThe Mac.%
HydroxyethylacrylateNOPE 1,82%
IsocyanateTDI2,73%
IsocyanateIPDI3,49%
PolyolR BASF PPG46,85%
CatalystDBTDL0,03%
InhibitorEIT0,08%
Wt.% the oligomer in the radiation-curable primary coating N55,00%
The monomerSR 504D36,25%
The monomerSR 395D3,00%
The monomerSR3062,50%
PhotoinitiatorChivacure TPO1,50%
AntioxidantIrganox 10350,60%
Stabilizer Lowilite 200,15%
The adhesion promoterA-1891,00%
Only100,00

[0154] the Primary coating N test for viscosity, mechanical tensile properties and characteristics of dynamic mechanical analysis (DMA), respectively, the above test methods. The results are shown here.

[0155] the test Results of the primary coating N

Test cycle12
Viscosity, MPa·s25°C54405671
34°C28602981
44°C15781642
52°C9931037
63°C599628
Test stretching the tion Ultimate tensile strength (MPa)0,580,59
Elongation(%)136137
The modulus of elasticity (MPa)0,920,89
DMAThe equilibrium modulus (MPa)0,880,91
Tan Delta maximum (°C)-36,5-36,6
Curing rate according to FTIR% RAU after 0,125 with exposure1312
% RAU after 0,250 with exposure4645
% RAU after 0,500 with exposure7574
% RAU after 2,000 with exposure9696

[0156] the Second set of test methods for liquid coatings and film coating

Determination of the dynamic viscosity at 20°C. and the storage modulus PR is the shift", also known as the elasticity of liquids = G' when the module losses when shift = G" = 100 PA

[0157] the Dynamic shear viscosity at 10 rad/s, η (10 rad/s, 20°C) and the elasticity of the fluid G' at G"=100 PA uncured compositions of the coating is determined using dynamic mechanical measurements. These dynamic mechanical measurements are performed by using a rheometer (ARES-LS company Rheometric Scientific (now TA instruments)equipped with a dual-band 200-2000 g·cm balanced by the torque Converter, system 25 mm parallel plates of Invar, oven with nitrogen atmosphere and a cooling device with liquid nitrogen.

[0158] At the beginning of the experiment, the polymer sample is placed between the parallel plates of the rheometer at room temperature. The distance between the plates set at 1.6 mm After closing of the furnace with an inert atmosphere, the sample is rinsed with gaseous nitrogen for approximately 5 minutes.

[0159] the Experiment is carried out by performing isothermal scans the frequency with angular frequencies between 100 and 0.1 rad/s (3 frequencies per decade, measured in declining order) at temperature intervals of 5°C, since the temperature of 20°C and lowering the temperature stepwise by 5°C until the sample becomes too viscous to measure the device (discussed examples of this limit typically occurs between the at about -20°C. and about -30°C). At the beginning of the scan frequency the amplitude of the deformation set at 2%. For the precise determination of viscosity and phase angle should be careful to ensure that the amplitude of the dynamic torque was higher than 0.5 g·see While reducing the measurement frequency, the torque will decrease. Therefore, after reaching the lower limit deformation increases to 5% and at the next stage, up to 20%in order to maintain the torque above the minimum allowable value of 0.5 g·see Typical dynamic viscosity at 20°C and 10 rad/s and the storage modulus shear G' when the module loss (G" 100 PA perform at 20%amplitude deformation.

[0160] the storage Modulus shear G', loss modulus G", the dynamic modulus G*=G'2+G”2)0,5dynamic viscosity η*=ω*G* and phase angle (δ) recorded as a function of angular frequency. Experimental points obtained with the dynamic torque of less than 0.5 g·cm, the results exclude.

[0161] the Dynamic viscosity at 10 rad/s is obtained from scanning frequency, measured at 20°C. G' at G"=100 PA output from the scanning frequency at the maximum temperature at which the value of G" is measured between 100 and 200 PA, by linear extrapolation of log G' relative to the log, G", of the two experimental points with the lowest frequency at G"=100 PA. In many cases the x this result can be obtained from scanning frequency when 10 or 0°C.

[0162] the Determination of the shear modulus G' (1 rad/s, 23°C.) of the cured coating

[0163] the Modulus of the cured coating was measured using dynamic mechanical analysis using a dynamic mechanical analyzer Rheometrics RDA-2. For this purpose, the layer of liquid coating thickness of 100 microns is placed between two parallel quartz plates with a diameter of 9.5 mm, as described in detail in the article Steeman C.S., Macromolecules, vol 37, No. 18, 2004, str-7007. The coating is completely utverjdayut by irradiation of UV light (25 mW/cm2within 60 seconds and see the growth module according to the method described in the link. After this curing conduct the measurement with the scanning frequency in the fully cured sample with the amplitude of deformation of 10%. This scanning frequency output value of the storage modulus shear G' at a frequency of 1 rad/s is the Modulus of tensile elasticity E of the cured coating are approximated by calculating three times this value of storage modulus shear G'.

[0164] DMA-dimension

[0165] the Equilibrium modulus of the coatings according to the present invention is measured by DMTA tensile according to ASTM D5026-95a Standard test method for measuring the dynamic mechanical properties of plastics in tension" under the following conditions.

[0166] smirenje when scanning temperature is conducted under the following test conditions:

Test samples:Rectangular strips
The distance between clamps:18-22 mm
Width:4 mm
Thickness:about 90 microns
Equipment:Tests are conducted on a DMTA machine from Rheometrics company type RSA2 (Rheometrics Solids Analyser II)
Frequency:1 rad/s
Initial deformation:0,15%
Temperature range:starting from -130°C heating up to 250°C
The rate of temperature change:5°C/min
Autonation:Tracking dynamic forces on static forces
Initial static force: 0,9 N
Static>Dynamic force 10%
Autodermice:The maximum applied Defoe is tion: 2%
Minimum effort: 0,05 N
(i) Maximum force: 1.4 N
Adjusting the strain: 10% (from the current deformation)
The dimensions of the test sample:Thickness: measured with a device for measuring the thickness of Heidenhain type MT 30V with a resolution of 1 micron.
Width: measured by a MITUTOYO microscope with a resolution of 1 micron.

[0167] All equipment is calibrated in accordance with ISO 9001.

[0168] IN the DMTA measurement, which is a dynamic measurement, measure the following modules: storage modulus shear E', loss modulus E" and the dynamic module in accordance with the following relation E*=(E'2+E2)1/2.

[0169] the Smallest value of the storage modulus shear e' on the DMTA curve in the temperature range between 10 and 100°C, measured at a frequency of 1 rad/s under the conditions described above, taking as the equilibrium modulus of the coating. The storage modulus shear E' at 23°C on DMTA curve is taken for E'23.

Examples I-VI and experiments A-D

[0170] table 1 shows examples and experiments in relation to viscosity and modules (uncured and solidified on the RITech).

[0171] Synthesis of urethane-acrylate oligomers perform in accordance with the synthesis inside-out (inside-out), as described above. Triablogue oligomers with 50% TDI and 50% of IPDI were obtained with TDI in the middle of the oligomer (T/1) and at the end (I/T); the latter showed a higher viscosity. The polyols used for the synthesis of the urethane-acrylate oligomers, had a molecular weight of about 2000, 4000 and 6000 g/mol, that was used by a number. Rooms (1), (2) and (3) in table 1 indicate the number of the polyol as one of the segments used to build the urethane-acrylate oligomer.

[0172] Preparation of coatings: 68.5 wt.% the oligomer, of 28.5 wt.% monomer-diluent ENPA (SR 504 from Sartomer company), 3 wt.% photoinitiator Irgacure 184 (from the company Ciba).

[0173] Prepared several oligomers, and tested them in model compounds, to show the effect on the viscoelastic characteristics and modulus of elasticity in the cured state.

Table 1

ExampleOligomerη*(10 rad/s, 20°C) [PA·s]G' at G"=100 PA [PA]G' at 23°C, utverjdenie [MPa]
ComparativeR(2)T13,0±0,71,2±0,1 0,6±0,05
Example a
An example of the invention IR(2)T/I 50/504,3±0,50,4±0,050,4±0,05
ComparativeR(3)T27±1,50,9±0,10,45±0,05
The example In
Example according to the invention IIR(3)T/I 50/5022±1,00,7±0,10,3±0,05
IIIR(3)I/T 50/5029,7±1,00,3±0,050,3±0,05
IVR(3)T/I 25/7521±1,00,2±0,050,5±0,05
ComparativeR(2)T17,0±1,00,9±0,10,35±0,04
Example
An example of the invention VR(2)T/I21,5±1,00,4±0,050,24±0,03
ComparativeR(1)T13,2±1,01,0±0,10,37±0,04
Example D
Example according to the invention VIR(1)T/I12,1±1,00,6±0,050,25±0,03

[0174] This table shows unexpectedly found the actual/the advantage of the elastic modulus in the dry state, which is lower when using mixed diisocyanate (TDA and IPDI) to obtain the same oligomer (examples according to the invention) in comparison with obtaining the same oligomer with only one isocyanate (TDI) (comparative examples are not examples according to the invention).

[0175] the Results show a decrease in the elastic properties of (in many cases also the fall in viscosity and decrease in the elastic modulus of the cured coating using the mixture of TDI technical purity and IPDI compared to using only the TDI.

Examples VII and VIII

[0176] Further, the coating composition was obtained according to the following table 2 (amounts in wt.%)

Table 2
ExampleVIIVIII
Oligomer
Hydroxyethylacrylate (NEA)2,111,41
First isocyanate (TDI)1,591,05
The second isocyanate (IPDI)5,314,71
Polyol (R) (PPG BASF)46,942,24
The catalyst (DBTDL)0,030,03
Inhibitor (BHT)0,080,08
Just oligomer5649,5
Other components
The monomer-diluent (an ethoxylated nonylphenolic)40,9047,0
The monomer-diluent (diacrylate tripropyleneglycol)-1,0
PhotoinitiatorChivacure TPO: 1,70Irgacure 819: 1,1
Antioxidant (Irganox 1035)0,500,50
The us is the amplifier adhesion (γ-mercaptopropionylglycine) 0,900,90

[0177] the Oligomers obtained according to the above method inside-out. The composition of the coating showed mainly the characteristics of the Newtonian flow.

[0178] the Viscosity is approximately 5.1 PA·s and 5.0 PA·s for the composition I and II at 25°C, respectively. The equilibrium elastic modulus (E') is about 1 MPa and 0.9 MPa, respectively. The glass transition temperature Twithmake -36°C and -33°C, respectively.

[0179] the exhaust Simulator columns

[0180] In the early years of the development of coatings of 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 was found that all of the coatings that were required to pull, no more than 30% of them felt a column of pulling the fiber due to the high costs and difficulties with schedule planning. The time from the moment when the surface was first drawn up, until the moment when it is applied to fiberglass, usually accounted for approximately 6 months, which has slowed down the development cycle of the product.

[0181] In the technology of radiation hardened coatings for optical fibers is known that, when either the primary coating, a secondary coating applied to glass the fiber, its 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, conditions inert atmosphere of nitrogen.

[0182] in order to provide more reliable ways of developing coatings and faster implementation period in production, we developed equipment that would support curing, similar to those with manufacturers of fiber. This type of alternative equipment for applying and curing should be easy to use, require less maintenance and give reproducible process parameters. The device has the name "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 glass fiber drawing. All measurements (position lamps, the distance between stages of the coating process, the intervals between stages of coating and UV lamps etc. are copied with Colo is n glass fiber drawing. This helps to simulate process conditions used in the industrial equipment of pulling the fiber.

[0183] One of the known CPI has 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.

[0184] 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 variety of designs from various suppliers. This arrangement allows the application of coatings to optical fiber under conditions similar to those occurring in industrial manufacturing plants.

[0185] 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 RAM Steeman, J.J.M. Slot, H.G.H. van Melick, A.A.F. v.d. Ven, H. Cao, and R. Johnson, in proceedings of the 52nd International Symposium cable-wire products (Proceedings of the 52ndIWCS), p is .246 (2003). In 2004 Steeman and co-authors reported how 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 RAM Steeman, W. Zoetelief, NSA and .Bulters, "Proceedings of the 53rdIWCS", str (2004). Simulator extraction columns can be used to further study the properties of the primary and secondary coating on the optical fiber.

[0186] These test methods are applicable for the primary coating on the wire or coating on the optical fiber.

[0187] test Methods

[0188] the Percentage reacted acrylate unsaturation for the primary coating, shortly denoted as test method % RAU primary coating.

[0189] the Degree of cure of the inner primary coating on an optical fiber or a metal wire 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-1and approximately 25%reduction in the default rate mirrors to improve the signal-to-noise ratio. Requires two spectra: one for the uncured liquid coating that corresponds to p is covered on the fiber or wire, and one for the inner primary coating on the fiber or wire. In the Central area of 2.54-cm (1-inch) square piece of Mylar film thickness of 76 microns (3 mil) smear a thin film of contact glue. After contact adhesive to become tacky, he placed a piece of optical fiber or wire. The sample is placed under a low-power optical microscope. The coating on the fiber or wire to cut glass with a sharp scalpel. Then cover the cut longitudinally to the upper side of the fiber or wire approximately 1 inch, making sure that the incision was clean and to the outer covering was not bent on the primary floor. Then cover turn on contact adhesive so that the primary floor next to the glass or wire disclosed as a flat film. Fiberglass or wire break in the area where disclosed primary coverage.

[0190] Range of liquid coatings are produced after all the diamond surface is completely occupied by the coating. The liquid must be from the same batch, which is used for coating the fiber or wire, but the minimum requirement is that it should have the same composition. The final format of the spectrum must be on the uptake. Open primary coating on the Mylar film is placed in the centre of al the Aza with the axis of the fiber or wire, parallel to the direction of the infrared beam. The back side of the sample should press down to ensure good contact with the crystal. The spectrum should not contain any peaks of absorption from contact glue. If there are absorption peaks contact adhesive, it is necessary to prepare a fresh sample. It is important to remove the range immediately after preparation of the sample, and not to cook any of numerous samples and remove spectra after all samples will be ready. The final format of the spectrum must be on the uptake.

[0191] 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.

[0192] the ratio of the area acrylate peak to the area of control of the peak is defined as liquid, and for the cured 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 primary coating.

In-situ modulus primary coating

[0193] In-situ modulus of the primary coating having a two-layer coating (soft primary coating and a hard secondary coating) glass fiber or metal wire portage measured in this test method. A detailed discussion of this test can be found in the work Steeman, RAM, Slot, J.J.M., Melick, N.G.H. van, Ven, A.A.F. van de, Cao, H. and Johnson, R. (2003). Mechanical analysis test in-situ modulus primary coating for optical fibers may be determined in accordance with methods described in the materials "Proceedings 52ndInternational Wire and Cable Symposium (IWCS, Philadelphia, USA, November 10-13, 2003), article 41.

[0194] For the preparation of the sample remove the coating layer short length (~2 mm) using a tool for removing insulation at a distance of ~2 cm from the end of the fiber. The fiber is cut so as to form the other end on the exact distance of 8 mm from the edge of the removed cover to the end of the fiber. Part 8-mm coated fiber is then inserted into a metal clamping device for sample. Coated fiber is inserted into microtrace in the mounting bracket; microtube is the C two semi-cylindrical recesses; its diameter is dimensioned approximately the same as the outer diameter (~245 µm) standard fiber. Fiber tightly clamp after tightening the screw, the clamping force on the surface of the secondary coating is uniform, and the coating layer is not significant deformation occurs. Clamping device with the fiber is then installed on the device DMA (dynamic mechanical analysis): Rheometric Solids Analyser (RSA-II). Metal clamping device is clamped by the lower clamp. Tighten the top clamp, pressing on the upper portion of the covered fibers against such a force, to destroy the coating layer. Clamping device and the fiber must be strictly vertical. You need to ensure that you have not inserted a portion of the fibers had a constant length for each sample: 6 mm in our tests. Regulate the deformation displacement, by setting the axial pretensioning almost zero (-1 g ~ 1 g).

[0195] To measure the shear modulus G of the primary coating selected geometric layout of the two-sided test on the shift. The width of the sample, W, in two-sided test shift introduced is equal to 0.24 mm, calculated according to the following equation:

where Rfand Rprepresent the outer radius of the bare fiber and the primary coating, respectively. For calculation use geometry mill is artego fiber, Rf=62.5 μm and Rp=92,5 μm. The sample length 8 mm (inserted length) and a thickness of 0.03 mm (the thickness of the primary coating) is injected into the geometry of two-sided tests on the shift. Testing was performed at room temperature (~23°C). Used frequency test is 1.0 rad/S. the shear Deformation ε set at 0.05. Produce dynamic time base, having 4 experimental point for the measured storage modulus shear G. Given G value represents average value for all experimental points.

[0196] The measured shear modulus G is then further corrected according to the method of correction. Correction needed to account for the stretching of the glass in the inserted and nastavlenii parts. In the correction procedure requires you to enter a modulus of tensile elasticity bare fiber (Ef). For glass fibers, the value of Ef=70 GPA. For the wire fibers, which used stainless steel wire S314, the value of Ef=120 GPA. The adjusted value G next Ousterhout using the real values of Rfand Rp. For the glass fibers of the fiber geometry, including the values of Rfand Rpmeasure using RC Fiber Geometry System. For the wire fibers is Rfis 65 µm for used wire stainless steel S314 diameter of 130 μm; Rp/sub> measured under a microscope. Finally, in-situ modulus of elasticity E ' (storage modulus shear and tensile) for the primary coating on the fiber is calculated according to the equation E=3G. Given the value E represents average value for the three test specimens.

In-situ DMA to measure THE primary and secondary coating on the optical fiber

[0197] This method measure the glass transition temperature (Twith) the primary and secondary coatings on glass fiber or metal wire fiber (wire) with double-layer coating. These glass transition temperature is indicated as "Twithtube".

[0198] For the preparation of samples with 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 coated fiber with a tool for removing insulation in liquid nitrogen (N2) for at least 10 seconds, and then removing the receiver cover fast movement, while the coatings are still hard.

[0199] the Device DMA (dynamic mechanical analysis): use Rheometrics Solids Analyzer (RSA-II). In the case of 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 metallicheskaya, bent and hollow at the open end of the screw, are used for tight fixing of the tubular sample 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 until the pre-tension will not be in the range from 0 g to 0.3 g

[0200] When conducting dynamic tests DMA at step temperature change of the frequency of the test set at 1.0 rad/s; the deformation is 5E-3; a step change in temperature is 2°C, and the exposure time is 10 seconds

[0201] the geometry Type choose 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 Rs and Rp are the outer radii of the secondary and primary coatings, respectively. For calculation use geometry standard fiber, Rs=122,5 μm and Rp=92,5 mm.

[0202] 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 tube cover.

Examples of simulator exhaust columns

[0203] Various compositions declared now the primary coating and a commercially available radiation curable secondary coating 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 m/min and 2100 m/min

[0204] the Stretching is carried out with the use of either "wet on dry"or "planota 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."Wet on wet" means that the liquid primary coating is applied wet, then wet cause secondary coating, and then utverjdayut both coverages, primary and secondary.

[0205] the properties of the primary coating and the secondary coating is measured and recorded for the following tests: % RAU, initial and after one month aging at 85°C and relative humidity (RH) of 85% under uncontrolled lighting. After the primary coating was overiden, then put the secondary coating.

[0206] Conduct multiple test cycles with different compositions of the primary coating P, primary coating SA, the primary coating CR, BJ primary coating and the primary coating N and a commercially available radiation curable secondary coating.

[0207] Utverjdenie primary coating on the wire have on the initial % RAU, the initial in-situ modulus and initial Cu tube. The covered wire is then subjected to aging for one month at 85°C and 85%relative humidity. Utverjdenie primary coating on the wire then p will gorhaut aging for one month and experience the % RAU, in-situ modulus and Twithtube in aged condition.

Tuning simulator exhaust columns:

- Use of the nozzle of Seidl: 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) Use 93 W/cm2(600 W/inch2) UV lamp D Fusion at 100% for 1°-governmental coatings.

- (3) Use 93 W/cm (600 watts/inch) UV lamp D Fusion at 100% for 2°-governmental coatings.

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

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

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

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

[0208] Utverjdenie radiation-curable primary coating P on the wire was found has the following properties:

[0209]

Linear speed (m/min)% RAU primary coating (primary)% RAU primary cover (1 month)
750 96-9992-96
120095-9992-95
150088-9392-96
180089-9389-93
210084-8888-92
Linear speed (m/min)In-situ modulus of the primary coating (MPa)In-situ modulus of the primary coating (MPa) (1 month)
7500,30-0,600.29 to 0.39
12000,25-0,350,25-0,35
15000,17-0,280,25-0,35
18000,15-0,250,20-0,30
21000,15-0,170,14-0,24
Linear speed (m/min)C is achene T withtube primary coating (°C) (initial)The values of Twithtube primary coating (°C) (1 month)
750from to -52 -47from -48 to -52
1200from -25 -51from -48 to -52
1500from -49 to -51from -46 to -50
1800from -47 to -51from -48 to -52
2100from -49 to -55from -48 to -52

[0210] Therefore, it is possible to describe and claim the wire covered with the first and second layers, the first layer is utverjdenie radiation-curable primary coating according to the claimed invention now, which is in contact with the outer surface of the wire, and the second layer is utverjdenie radiation curable secondary coating in contact with the outer surface of the primary coating,

this utverjdenie primary 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 84% to 99%;

B) in-situ modulus of between 0.15 MPa and 0,60 MPa; and

C) Twithtube from -25°C to -55°C.

[0211] using this information, it is also possible to describe and to declare an optical fiber covered with the first and second layers, the first layer is utverjdenie radiation-curable primary coating according to the claimed invention now, which is in contact with the outer surface of the optical fiber and the second layer is utverjdenie radiation curable secondary coating in contact with the outer surface of the primary coating,

this utverjdenie primary 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 84% to 99%;

B) in-situ modulus of between 0.15 MPa and 0,60 MPa; and

C) Twithtube from -25°C to -55°C.

[0212] the radiation Curable secondary coating may be any commercially available radiation curable secondary coating for optical fibers. Such commercially available radiation curable secondary coating are made by the company DSM Desotech Inc. and others, including, but without limitation, Hexion, Luvantix and PhiChem.

[0213] the Use of terms in the singular in the context of describing the invention (ESP the NGOs 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 those"), unless otherwise specified. Specifying ranges of values here is only intended to serve as a quick way to individually list 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 agreed otherwise or unless otherwise explicitly 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. One expression in the description should not be construed to indicate any undeclared element as essential to the practical implementation of the invention.

1. Curable by radiation of the primary coating composition containing at least one urethane(meth)acrylate functional oligomer, fotonica the torus,
this urethane-(meth)acrylate functional oligomer is a reaction product of hydroxyethylacrylate, mixtures of 2,4-colordistance and 2,6-colordistance, isophorondiisocyanate and simple polyetherpolyols in the presence of catalyst and inhibitor,
this urethane-(meth)acrylate functional oligomer contains (meth)acrylate groups, at least one polyol as one main chain and a urethane group,
15% or more urethane groups are derived from one of 2,4 - and 2,6-colordistance or both, with at least 15% of the urethane groups are derived from isophorondiisocyanate, and
these urethane(meth)acrylate functional oligomer has srednecenovogo molecular weight of at least 4000 g/mol to less than or equal to 15000 g/mol; and
when the cured film of the radiation curable primary coating composition has an equilibrium modulus, measured as described less than or equal to 1.2 MPa.

2. Curable by radiation of the primary coating composition according to claim 1, in which the storage modulus shear G' liquid radiation-curable composition of the primary coating is less than or equal to 0.8 PA, as measured at G=100 PA.

3. Curable by radiation of the primary coating composition according to claim 1, in which overide the full film of radiation-curable primary coating composition has an equilibrium modulus, measured as described less than or equal to 1.0 MPa.

4. Curable by radiation of the primary coating composition according to claim 1, in which the composition has a refractive index of 1.48 or higher.

5. Curable by radiation of the primary coating composition according to claim 1, in which the viscosity, measured as described, is about 2 PA·s to 8 PA·s at 10 rad/s and at 20°C.

6. Curable by radiation of the primary coating composition according to claim 1, in which 40% or more urethane groups are derived from isophorondiisocyanate.

7. Curable by radiation of the primary coating composition according to claim 1, in which 15% or more urethane groups are derived from both 2,4 - and 2,6-colordistance through the use of a mixture of colordistance with 10 wt.% or more 2,6-colordistance and 50 wt.% or more of 2,4-colordistance.

8. Curable by radiation of the primary coating composition according to claim 1, in which the said mixture of 2,4-colordistance and 2,6-colordistance is a mixture of 80/20.

9. Curable by radiation of the primary coating composition according to claim 1, in which the said catalyst is selected from the group comprising dilaurate dibutylamine, carboxylates of metals, sulfonic acid catalysts based on amines or organic bases, alcoholate of titanium and zirconium, and ionic liquid phosphonium salts of, midsole and pyridinium.

10. Curable by radiation of the primary coating composition according to claim 1, in which the said catalyst is dilaurate dibutylamine or vimalaramsi catalyst.

11. Method of coating glass optical fiber radiation-curable primary coating that includes
(a) operation of the column extraction of glass to obtain a glass optical fiber, preferably at a linear speed between 750 m/min and 2100 m/min;
(b) applying a radiation-curable primary coating composition according to claim 1 on the surface of the optical fiber; and
(c) optional irradiation with radiation to effect the curing of the mentioned radiation-curable primary coating composition according to claim 1.

12. The wire is covered with the first and second layer, the first layer is utverjdenie radiation-curable primary coating according to claim 1, which is in contact with the outer surface of the wire, and the second layer is utverjdenie radiation curable secondary coating in contact with the outer surface of the primary coating
this utverjdenie primary 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 84% to 99%;
B) in-situ modulus of between 15 MPa and 0,60 MPa; and
C) Twithtube from -25°C to -55°C.

13. The optical fiber coated with the first and second layer, the first layer is utverjdenie radiation-curable primary coating according to claim 1, which is in contact with the outer surface of the optical fiber and the second layer is utverjdenie radiation curable secondary coating in contact with the outer surface of the primary coating
this utverjdenie primary 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 84% to 99%;
B) in-situ modulus of between 0.15 MPa and 0,60 MPa; and
C) Twithtube from -25°C to -55°C.



 

Same patents:

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 processing polyvinyl chloride through dispersion, particularly to production of highly filled adhesive plastisols used in making protective coatings in motor-car construction, as anticorrosion protection of inner surfaces of metal structures. The method of producing highly filled plastisol based on polyvinyl chloride involves successive addition and mixture in a mixer of di(2-ethylhexyl)phthalate, triethylene glycol dimethacrylate, isopropylbenzene hydroperoxide, half of the given amount of kaolin, calcium strearate, polyvinyl chloride and the remaining amount of kaolin. Hexafunctional oligourethane acrylate, diatomite and NGZ-4 phosphate hydraulic fluid are added before adding polyvinyl chloride, and after adding the remaining amount of kaolin, a polysulphide oligomer - liquid thiocol II with weight ratio of SH groups of 1.7-2.6% and molecular weight of 2100 is added.

EFFECT: high degree of restoration of the thixotropic structure, extrusion, fire resistance and tensile strength of the polyvinyl chloride plastisol and the hardened material.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to processing polyvinyl chloride through dispersion, particularly to production of highly filled adhesive plastisols used in making protective coatings in motor-car construction, as anticorrosion protection of inner surfaces of metal structures. The method of producing highly filled plastisol based on polyvinyl chloride involves successive addition and mixture in a mixer of di(2-ethylhexyl)phthalate, isopropylbenzene hydroperoxide, half of the given amount of kaolin, calcium strearate, polyvinyl chloride and the remaining amount of kaolin. Hexafunctional oligourethane acrylate, diatomite and NGZ-4 phosphate hydraulic fluid are added before adding polyvinyl chloride, and after adding the remaining amount of kaolin, a polysulphide oligomer - liquid thiocol II with weight ratio of SH groups of 1.7-2.6% and molecular weight of 2100 is added.

EFFECT: high degree of restoration of the thixotropic structure, extrusion, fire resistance and tensile strength of the polyvinyl chloride plastisol and the hardened material.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyurethanedi(met)acrylates applicable as binders for powder coatings applied on metal substrates, plastic parts, fiber-reinforced plastic parts. Polyurethanedi(met)acrylates are obtained by interaction of diisocyanate component, diol component and hydroxy-C2-C4-alkyl(met)acrylate at mol ratio of x:(x-1):2, where x takes any value from 2 to 5. 1,6-hexanediisocyanate comprises 50 to 80 mol % of diisocyanate component, and one or two diisocyanates selected out of defined diisocyanate group where mol content of respective diisocyanates amount to 100 mol % comprise(s) 20 to 50 mol %, so that each diisocyanate comprises at least 10 mol % of diisocyanate component. Diol component includes not more than four different diols, and at least one linear aliphatic alpha, omega-C2-C12-diol comprises 20 to 100 mol % of diol component, while at least one (cyclo)aliphatic diol different from linear aliphatic alpha, omega-C2-C12-diols comprises 0 to 80 mol %. Each diol of the diol component comprises at least 10 mol % of diol component, and mol content or respective diols amounts to 100 mol %. Due to the absence of solvent in polyurethanedi(met)acrylate production, further cleaning of end product is not required, thus increasing process product output.

EFFECT: higher acid resistance of coating films applied and solidified with the use of powder coatings containing claimed polyurethanedi(met)acrylates.

6 cl, 15 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: powdered coating agent contains solid particles of a resin-polyurathane binding substance with equivalent mass of olefinic double bonds ranging from 200 to 2000 and content of silicon bonded in alkoxy silane groups ranging from 1 to 10 mass % and a photoinitiator. In the method of obtaining a single layered or multilayered coating on substrates, in particular when obtaining multilayered coating for transportation equipment and their components (car body or car body components coating), at least one layer of this coating is deposited from a powdered coating agent. In that case, solidification of at least one layer of the above mentioned powdered coating is achieved through free-radical polymerisation of olefinic double bonds when irradiated with high energy radiation and through formation of siloxane atomic bridges under the effect of moisture.

EFFECT: obtaining a powdered coating, which is hard, has scratch resistance and good resistance to chemical effects.

8 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: aqueous composition for coatings has a rapid curing mechanism and allows cross-linking of poorly illuminated areas, the composition comprising (I) at least one polyisocyanate (A), (II) at least one polyurethane (B) containing from 0 to 0.53 mmole/g of active, according to Tserevitinov, hydrogen atoms and being a product of reaction of: (a) one or several polyisocyanates, (b1) one or more compounds with hydrophilising action having ion groups and/or groups transferable to ion groups, and/or non-ionic groups, (b2) one or more compounds capable of radical polymerisation and including unsaturated acrylate or methacrylate groups, (b3) if necessary, one or more polyols with an average molecular weight of 50-500 and a hydroxyl functionality more than or equal to 2 and less than or equal to 3, (b4) if necessary, one or more polyols with an average molecular weight of 500 to 13,000 g/mole and an average hydroxyl functionality of 1.5 to 2.5, and (b5) if necessary, one or more di- or polyamines, and (III) an initiator (C).

EFFECT: capable to cross-link poorly illuminated areas and to cause radical polymerisation.

8 cl, 15 ex, 8 tbl

FIELD: powder covers.

SUBSTANCE: invention relates to a powder cover composition and to a method for its preparing that forms cover with reduced luster after hardening. Composition comprises one or some cross-linked basic polymers: cross-linked polyester, cross-linked polyurethane, cross-linked acrylated polyether and their combinations, about from 5 to 60 wt.-%; cross-linked acrylic polymer with solidification point about from 40°C to 100°C, and about 0.1 to 10 wt.-% of one or some free-radical initiating agents. Additional reducing luster and improved smoothness can be obtained by addition spheroidal particles to the powder cover composition. Proposed compositions can be used for making covers on metallic backings, such as vehicle bodies and on nonmetallic backings, such as backings made of pressed wood materials with impregnation used for making table tops of different species.

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21 cl, 4 tbl

FIELD: polymers, covering compositions.

SUBSTANCE: invention relates to photoactivating aqueous-base covering composition. The proposed composition comprises the following components: a)(meth)acryloyl-functional polyurethane dispersion wherein this (meth)acryloyl-functional polyurethane comprises from 5 to 18 weight % of alkylene-oxide groups and (meth)acryloyl functionality represents a value in the range from 2 to 40, and b) UV-initiating agent. The presence of reactive diluting agent in the covering composition is preferable. (Meth)acryloyl-functional polyurethane can be prepared by carrying out the following interactions: a) at least one organic polyisocyanate; b) optionally, at least one organic compound comprising at least two isocyanate-reactive groups and having an average molecular mass in the range from 400 to 6000 Da; c) at least one isocyanate-reactive and/or isocyanate-functional compound comprising non-ionogenic dispersing groups; d) at least one isocyanate-reactive (meth)acryloyl-functional compound; e) optionally, at least one chain elongating agent comprising active hydrogen, and f) optionally, at least one compound comprising active hydrogen and ionic groups. Aqueous-base covering composition is useful especially for applying as a clear cover. Covers based on the proposed composition show resistance to water, solvents and scratches and flexibility and high adhesion also.

EFFECT: improved and valuable properties of composition.

15 cl, 12 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: composition for sports coatings contains oligobutadiene diol, plasticiser, mineral filler, trifunctional low molecular weight alcohol, polymethylene-polyphenylene polyisocyanate containing 29.5-31.0% isocyanate groups, organotin catalyst, 2,4,6-tri-tertbutylphenol, polyfluorinated alcohol, copper diacetate-di-ε-caprolactamate.

EFFECT: improved dynamic, physical and mechanical properties and light-resistance of the coatings.

2 tbl

FIELD: chemistry.

SUBSTANCE: composition for sports coatings contains oligobutadiene diol, plasticiser, mineral filler, trifunctional low molecular weight alcohol, polymethylene-polyphenylene polyisocyanate containing 29.5-31.0% isocyanate groups, organotin catalyst, 2,4,6-tri-tertbutylphenol, copper diacetate-di-ε-caprolactamate and a modifier - prepolymer - oligodiene diol ether of ε-aminocaproic acid oligomer.

EFFECT: improved dynamic, physical and mechanical properties, resistance to thermal-oxidative and light ageing of the coatings.

2 tbl

Coating composition // 2434918

FIELD: chemistry.

SUBSTANCE: coating composition contains a base in form of hydroxyl-containing polybutadiene rubber with a microstructure, %: 1,4-trans 10-15 and 1,2-links 85-90, molecular weight 1250-3200 and content of hydroxyl groups 0.82-2.36%; isocyanate curing agent - polyisocyanate, urethane-formation catalyst. The composition can additionally contain a low molecular weight trifunctional alcohol.

EFFECT: high coating strength.

2 cl, 1 tbl

Coating composition // 2434917

FIELD: chemistry.

SUBSTANCE: coating composition contains a base in form of hydroxyl-containing polybutadiene rubber with a microstructure, %: 1,4-trans 10-15 and 1,2-links 85-90, molecular weight 1250-3200 and content of hydroxyl groups 0.82-2.36%; plasticiser, filler, antiageing agent, isocyanate curing agent - polyisocyanate, urethane-formation catalyst and additionally 3,5-dimethylthio-toluylne diamine or 3,5-diethylthio-toluylene diamine.

EFFECT: high level of strength properties - strength, hardness and relative elongation.

4 cl, 2 tbl

Coating composition // 2434916

FIELD: chemistry.

SUBSTANCE: coating composition contains a base in form of hydroxyl-containing polybutadiene rubber with a microstructure, %: 1,4-trans 10-15 and 1,2-links 85-90, molecular weight 1250-3200 and content of hydroxyl groups 0.82-2.36%; plasticiser 40-140, filler, antiageing agent, isocyanate curing agent - polyisocyanate, urethane-formation catalyst. The composition can additionally contain a low molecular weight trifunctional alcohol.

EFFECT: high strength of the coatings.

5 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

Coating composition // 2434909

FIELD: chemistry.

SUBSTANCE: coating composition contains oligobutadiene diol, mineral filler, trifunctional low molecular weight alcohol, polyisocyanate, urethane-formation catalyst and 2,4,6-tri-tertbutylphenol. The mineral filler additionally contains multifunctional filler which is a mixture of chemically co-deposited calcium carbonate and magnesium hydroxide.

EFFECT: obtaining coatings with improved dynamic and physical and mechanical properties.

2 tbl

Coating composition // 2433155

FIELD: chemistry.

SUBSTANCE: coating composition as a base contains hydroxyl-containing polybutadiene rubber with a microstructure, %: 1,-4-trans 10-15 and 1,2-links 85-90, molecular weight 1250-3200 and content of hydroxyl groups 0.82-2.36%, isocyanate curing agent, polyisocyanate, urethane-formation catalyst and an additional mixture of isomers of 3,5-dimethylthio-2,4- toluylenediamine and 3,5-dimethylthio-2,6-toluylenediamine in ratio of 75.5-81:18-20 or a mixture of 3,5-diethyl-2,4-toluylenediamine and 3,5-diethyl-2,6-toluylenediamine in ratio of 75.5-81:18-20.

EFFECT: high strength of the coating.

1 tbl

FIELD: construction.

SUBSTANCE: composition for sporting surfaces includes oligobutadienediol, a plasticiser, a mineral filler, trifunctional low-molecular alcohol, polymethylene polyphenylene polyisocyanate with content of isocyanate groups 29.5-31.0%, tin-organic catalyst, 2,4,6-tri-tretbutylphenol, polysulfide oligomer, isocyanate prepolymer, aromatic diamine, which is a mixture of 2,4- and 2,6-isomers of 3,5-dimethyl thiotoluyelene diamine at the ratio of 80:20, diatomite and technical carbon P-803.

EFFECT: improved dynamic and physical-mechanical parameters of surfaces.

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

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