D 1368 cr radiation-curable primary coating for optical fibre

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.

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Cross-reference to related application

[0001] This patent application claims the priority of provisional patent application U.S. serial No. 60/874719, "radiation-Curable primary coating CR for optical fiber", filed December 14, 2006.

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 coated with the aforementioned coating optical fibers, and methods of producing optical fibers with the floor.

The level of technology

[0003] Optical fibers typically cover two or more radiation-curable coatings. These coatings are usually applied to the optical fiber in liquid form, and then exposed to radiation to effect the curing. The type of radiation that can be used for curing coatings, must be such as to be able to initiate the polymerization of one or more radiation-curable components such coatings. Radiation suitable for curing such coatings are well known and include ultraviolet radiation ("UV") and electron beam ("E"). The preferred type of radiation for curing coatings used in the preparation of optical fibers with the floor, JW is aetsa UV.

[0004] Coating that is in contact directly with optical fiber, called primary coating, and a coating that covers the primary coating, referred to as the secondary coating. In the field of radiation curable coatings for optical fibers is known that the primary coatings are softer than the secondary coating. One of the benefits of this composition, is the increased resistance to microshell.

[0005] the Previously described radiation-curable coating suitable for use as a primary coating for optical fibers, include the following.

[0006] In published patent application China No. CN16515331, "Radiation Solidification Paint and Its Application", assigned Shanghai Feikai Photoelectric, inventors Jibing Lin and Jinshan Zhang, described and claimed radiation curable coating containing oligomer, an active diluent, photoinitiator, thermo stabilizer, selective adhesion promoter, in which the content of the oligomer is between 20% and 70% (mass, hereinafter), the content of other components is between 30% and 80%; the oligomer chosen from (meth)acelerando polyurethane oligomer or a mixture of (meth)acelerando polyurethane oligomer and (meth)acelerando epoxy oligomer; mentioned (meth)atilirovanie polyurethane ol the Homer is obtained using at least one of the following substances:

[0007] (1) one of the polyols selected from poliuretanovye, primidolol, simple polyetherpolyols, complex polyetherpolyols, polycarbonatediol, hydrocarbon polyol, polysiloxane, a mixture of two or more identical or different types of polyols;

[0008] (2) a mixture of two or more diisocyanates or polyisocyanates;

[0009] (3) (meth)acelerando compound containing one hydroxyl, capable to react with isocyanate.

[0010] Example 3 of the published application for a patent of China No. CN16515331 is the only example in the published 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.

[0011] In the article "UV-CURABLE 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, Polim. Tworz. Wielk, Vol.41, Nos.7/8, p.448-55, 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 fibers. For the synthesis used made in Poland oligotherapy, diethylenglycol the ü, 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 UV light 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).

[0012] In the article "properties of UV-CURABLE POLYURETHANE-ACRYLATES" ("PROPERTIES OF ULTRAVIOLET CURABLE POLYURETHANE-ACRYLATES") authors M.Koshiba; K.K.S. Hwang; S.K.Foley.; DJ. Yarusso; and S.L.Cooper published in J.Mat. Sci., 17, No. 5, may 1982, str-58; NDN-131-0063-1179-2 described the investigation of the dependence between the chemical structure and physical properties of the hardened UV polyurethane-acrylate-based isophorondiisocyanate and colordistance (TDI). These two systems were obtained with different molecular weight soft segme the TA 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. As more recent Twithpolyol shifted to lower temperatures. Increase using either N-vinylpyrrolidone (NVP), or polietilenglikolsuktsinata (PEGDA) was caused by the increase of young's modulus and tensile strength. Cross stitching NVP increased the fracture toughness of two-phase materials and moved the high temperature peak of the Twithfor higher temperatures, a PEGDA did not give these effects. Tensile properties of the two systems were generally similar.

[0013] Typically, in the production of radiation curable coatings for use on optical fiber in order to obtain urethane oligomers using isocyanates. In many references, including U.S. patent No. 7135229, "radiation-CURABLE COATING COMPOSITION" ("RADIATION-CURABLE COATING COMPOSITION"), issued on November 14, 2006, assigned to the patentee DSM IP Assets B.V., column 7, lines 10-32 provided the following information as a guide for specialists in the synthesis of the urethane oligomer: "the Polyisocyanates suitable for use in preparation of the compositions of the present invention can be aliphatic, cycloaliphatic or aromatic and include diazo ianity, such as 2,4-colorvision, 2,6-colorvision, 1,3-xylylenediisocyanate, 1,4-xylylenediisocyanate, 1,5-naphthalenedisulfonate, m-delete the entry, the n-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 particularly preferred diisocyanates are 2,4-colorvision, isophorondiisocyanate, xylylenediisocyanate and Methylenebis(4-cyclohexylidene). These diisocyanate compounds are used either individually or in combination of two or more".

EP-A-1408017 team aims to 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. Therefore, this document does not cover radiation-curable composition of the primary coating.

US--6714712 is directed to radiation-curable composition for coating optical fibers. Obtaining oligomers polyester and/or alkyd (meth)acrylate, specified in this document does not imply the use of isocyanates, not to mention the combination of aliphatic and aromatic isocyanates.

WO-A-02/42236 relates to a special method of drying coatings of optical fibers to increase the adhesion between the coating and the fiber. US-B-7135229 describes radiation-curable composition coating based on alkyd without solvent that can be used as compositions of primary and secondary coatings. 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. US-A-2004/0048946 relates to radiation-curable coating composition without solvent containing a radiation-curable urethane-(meth)acrylate oligomer containing alkyd main chain. US-A-5616630 aimed at hybrid oligomer of ester/urethane-acrylate, which can be used in the compositions of the coating. Article Podkoscielny et al, Applied Macromolecular Chemistry and Physics, 1996, 242, 123-138 aimed at optimizing the urethane-acrylates curable by radiation of the composition is. None of these documents discloses the use of combinations of aromatic and aliphatic isocyanates to obtain the same oligomer.

[0014] Although the currently available number of primary coatings, it is desirable to provide new primary coatings that have superior technological and/or operational characteristics in comparison with existing coatings.

The invention

[0015] the First aspect of the claimed invention now is a radiation-curable primary coating composition containing:

A)oligomer;

B) the monomer-diluent;

C) photoinitiator;

D) an antioxidant; and

(E) an adhesion promoter;

moreover, the said oligomer is the reaction product of:

i) hydroxyethylacrylate;

ii) an aromatic isocyanate;

(iii) aliphatic isocyanate;

iv) a polyol;

v) a 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

these catalyst selected from the group consisting of dilauryl dibutylamine, carboxylates of metals, sulfonic acid catalysts based on amines or organic bases, alkoxides of zirconium and titanium and ionic liquid phosphonium salts of imidazole and pyridinium; and

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

The second aspect of the claimed now of the invention is a method of coating an optical fiber, including:

a) column extraction of glass with receiving optical fiber; and

b) coating the aforementioned optical fiber radiation-curable primary coating composition according to the claimed invention now.

The third aspect of the claimed now of the invention is a method of coating an optical fiber, including:

a) column extraction of glass with a linear speed between 750 meters/minute and 2100 meters/minute, receiving the optical fiber; and

b) coating the aforementioned optical fiber radiation-curable primary coating composition according to the claimed invention now.

[0016] the Fourth aspect of the claimed invention now is wire covered with the first and second layer and the first layer is utverjdenie radiation-curable primary coating according to the claimed invention now 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 hotwired the TES primary coating on the wire has the following properties after initial cure and after one month aging at 85°C and a relative humidity of 85%:

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.

The fifth aspect of the claimed invention now is an optical fiber coated with the first and second layer and the first layer is utverjdenie radiation-curable primary coating according to the claimed invention now 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 the initial cure and after one month aging at 85°C and a relative humidity of 85%:

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.

A detailed description of the preferred embodiments

[0017] throughout this patent application the following abbreviations have the following meanings:

A-189γ-mercaptopropionylglycine supplied by General Electric
EIT2,6-di-tert-butyl-p-cresol, supplied Fitz Chem
CASmeans the registration number of the Chemical Abstracts
DBTDLdilaurate dibutylamine supplied OMG Americas
Chivacure TPO2,4,6-trimethylbenzenesulfonamide supplied Chitech
HEAhydroxyethylacrylate supplied by BASF
Irganox 1035thiodiethyl-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), supplied by Ciba
P2010polypropylenglycol (2000 MM), supplied by BASF
IPDIisophorondiisocyanate supplied by Bayer
TDIa mixture of 80% 2,4-colordistance and 20% 2,6-colordistance supplied by Bayer
Photomer 4066the acrylate of ethoxylated Nonylphenol, supplied by Cognis

In the present invention proposed radiation-curable primary coating composition containing:

A) oligomer;

B) the monomer-diluent;

C) photoinitiator;

D)an antioxidant; and

(E) an adhesion promoter;

moreover, the above-mentioned oligomer is a product of Rea is tion:

i) hydroxyethylacrylate;

ii) an aromatic isocyanate;

(iii) aliphatic isocyanate;

iv) a polyol;

v) a 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

these catalyst selected from the group comprising dilaurate dibutylamine; carboxylates of metals, including, but not limited to: vismutorganicheskikh catalysts, such as neodecanoic bismuth, CAS 34364-26-6; neodecanoate zinc CAS 27253-29-8; neodecanoate zirconium CAS 39049-04-2; and 2-zinc ethylhexanoate, CAS 136-53-8; sulfonic acids, including but not limited to, dodecylbenzenesulfonic acid, CAS 27176-87-0; and methansulfonate acid, CAS 75-75-2; catalysts based on amines or organic bases, including, but not limited to: 1,2-dimethylimidazole, CAS 1739-84-0; and diazabicyclo[2.2.2]octane (DABCO), CAS 280-57-9 (strong base); and triphenylphosphine; alkoxides of zirconium and titanium, including, but not limited to, piperonyl zirconium (tetramethylsilane) AS 1071-76-7; and piperonyl titanium (tetrabutyltin) CAS 5593-70-4; and ionic liquid phosphonium salts of imidazole and pyridinium, such as, but not limited to, hexaflurophosphate trihexy(tetradecyl)phosphonium, CAS No. 374683-44-0; acetate 1-butyl-3-methylimidazole, CAS No. 284049-75-8; and chloride N-butyl-4-meth pyridine, CAS No. 125652-55-3; and tetradecyl(trihexy)phosphonium; 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.

[0018] the Oligomer, part of the radiation-curable primary coating composition of the present invention is a urethane-acrylate oligomer containing acrylate group, urethane group and the main chain. The primary circuit is derived from used polyol which is reacted with the diisocyanate and hydroxyethylacrylate.

[0019] the Oligomer is produced by interaction of hydroxyethylacrylate (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).

[0020] the Aromatic and aliphatic isocyanates are well known and are commercially available. Preferred aromatic isocyanate is a mixture of 80% 2,4-colordistance and 20% 2,6-colordistance, TDI, and preferred aliphatic isocyanate is isophorondiisocyanate, IPDI.

[0021] Upon receipt of the isocyanate oligomer component may be added to the oligomer reaction mixture in quantities of 1 to 15 wt.%, preferably from 1.5 to 20 wt.%, and prefer is Ino from 2 to 15 wt.%, all based on the mass percentage of oligomeric mixture (and NOT the mass percentage of the radiation-curable coating).

[0022] Preferably, the isocyanate should include more aliphatic isocyanate than aromatic isocyanate. More preferably, the ratio of aliphatic to aromatic isocyanates can vary from 6:1, preferably from 4:1, and most preferably from 3:1.

[0023] To obtain the oligomer can be used in many different polyols. Examples of suitable polyols are simple polyether polyols complex polyether polyols, polycarbonate polyols, polycaprolactone polyols, acrylic polyols and the like. Such polyols can be used either individually or in combination of two or more. There are no particular limitations on the method of polymerization of the structural units in such polyols; apply any statistical polymerization, block polymerization or graft polymerization. Preferably used R (BASF).

[0024] Upon receipt of the oligomer polyol as one component can be added to the oligomer reaction mixture in any suitable amount, preferably comprising 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 (and NOT the mass percentage of curing the th radiation coverage).

[0025] Brednikova molecular weight polyols suitable for use in obtaining the oligomer can vary from 500 to 8000, preferably from 750 to 6000, and preferably from 1000 to 4000.

[0026] the Acrylate component is hydroxyethylacrylate (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 reagents (and NOT the mass percentage of the radiation-curable coating).

[0027] In the reaction, which gives the oligomer may be used catalyst oreanization, which is selected from the group comprising dilaurate dibutyrate (DBTDL); carboxylates of metals, including, but not limited to: vismutorganicheskikh catalysts, such as neodecanoic bismuth, CAS 34364-26-6; neodecanoate zinc CAS 27253-29-8; neodecanoate zirconium CAS 39049-04-2; and 2-zinc ethylhexanoate, CAS 136-53-8; sulfonic acids, including but not limited to, dodecylbenzenesulfonic acid, CAS 27176-87-0; and methansulfonate acid, CAS 75-75-2; catalysts based on amines or organic bases, including, but not limited to: 1,2-dimethylimidazole, CAS 1739-84-0 (very weak base); and diazabicyclo[2.2.2]octane (DABCO), CAS 280-57-9 (strong base); and t is Ivanishin (TRR); alkoxides (alcoholate) of zirconium and titanium, including, but not limited to, piperonyl zirconium (tetramethylsilane) CAS 1071-76-7; and piperonyl titanium (tetrabutyltin) CAS 5593-70-4; and ionic liquid phosphonium salts of imidazole and pyridinium, such as, but not limited to, hexaflurophosphate trihexy(tetradecyl)phosphonium, CAS No. 374683-44-0; acetate 1-butyl-3-methylimidazole, CAS No. 284049-75-8; and chloride N-butyl-4-methylpyridine, CAS No. 125652-55-3; and chloride, tetradecyl(trihexy)of phosphonium, commercially available as Cyphosil 101.

[0028] 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 crosslinked divinyl macrostate resin, and used in heterogeneous able to be filtered by the completion of the synthesis of the oligomer.

[0029] Upon receipt of the oligomer catalyst component can be added to the oligomer reaction mixture in any suitable amount, preferably from 0.01 to 3.0 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 reagents (and NOT the mass percentage of the radiation-curable coating).

[0030] Upon receipt of the oligomer also use the inhibitor. This component helps to prevent polymerization of the acrylate during the synthesis of the oligomer hraneniya. Many different inhibitors known in the art and can be used to obtain the oligomer. In one embodiment, the claimed invention now inhibitor is EIT.

[0031] Upon receipt of the inhibitory oligomer component may be added to the oligomer reaction mixture in any suitable amount. In one embodiment, the inhibitor is present in the oligomeric mixture of reagents in quantities of from 0.01 to 2.0 wt.%. In another embodiment, the inhibitor is present in the oligomeric mixture of reagents in quantities of from 0.01 to 1.0 wt.%. In yet another embodiment, the inhibitor is present in the oligomeric mixture of reagents in quantities of from 0.05 to 0.50 wt.%, all calculated on the weight of the oligomeric mixture of reagents (and NOT the mass percentage of the radiation-curable coating).

[0032] obtaining the oligomer may be made in any suitable way, but preferably occurs by mixing the components of the isocyanate, polyol and inhibitor followed by the addition thereto of a catalyst. Then the mixture can be heated and left to react to completion. Can then be added to the acrylate (NEA) and the mixture heated until then, until the reaction. Usually oligomeric reaction is carried out at a temperature from 10°C to 90°C, and preferably from 30°C. to 85°C.

[0033] This ol whom Homer has srednecenovogo molecular weight of at least 4000 g/mol to less than or equal to 15000 g/mol. In one embodiment, the claimed invention now has the oligomer, which has srednecenovogo molecular weight of at least 5000 g/mol. In one embodiment, the claimed invention now has the oligomer, which has srednecenovogo molecular weight of at least 6000 g/mol.

[0034] In one embodiment, the claimed invention now has the oligomer, which has srednecenovogo molecular weight less than or equal to 10000 g/mol. In one embodiment, the claimed invention now has the oligomer, which has srednecenovogo molecular weight less than or equal to 9000 g/mol.

[0035] After receiving the oligomer can be obtained radiation-curable composition. The amount of oligomer in this 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.

[0036] To this curable composition also add one or more reactive monomer diluents, such diluents are well known in the art. Many different diluents known in the art and may be used upon receipt the 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), di-ethylene glycol-ethyl hexyl acrylate (DEGEHA), isobutylacetate (IBOA), tri-propylene glycol-diacrylate (TPGDA), hexanediol-diacrylate (HDDA), trimethylolpropane-triacrylate (TMRCA), triacrylate alkoxysilanes of trimethylolpropane and diacrylate alkoxysilanes bisphenol a, such as ethoxylated diacrylate bisphenol A (EO-BPADA). Preferably, the diluent used Photomer 4066 (acrylate of ethoxylated Nonylphenol, ENPA), which is commercially available from Cognis.

[0037] the 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.

[0038] 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 to the AC.% up to 2 wt.%.

The preferred photoinitiator is Chivacure TPO.

[0039] Another component used in the curable composition is an antioxidant. Such components are well known in the art. The antioxidant may be included in the composition in an amount of 0.2 to 1 wt.% from the curable composition. Preferably, the antioxidant is Irganox 1035.

[0040] Another component included in the curable composition is an adhesion promoter, which, as follows from its name, improves the adhesion of the cured coating to the optical fiber. Such components are well known in the art. The adhesion promoter may be included in the composition in amounts comprising from 0.2 wt.% up to 2 wt.% from the curable composition, for example, in amounts comprising from 0.5 wt.% up to 2 wt.%, preferably from 0.8 to 1.0 wt.%, from the curable composition. Preferably, the adhesion promoter is A-189.

[0041] the above components may be mixed together 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 to mix the components for 30 minutes.

[0042] In a preferred aspect of the present invention, the oligomer can be obtained from the following components (based on the mass percentage of the components used to produce the oligomer):

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

Aromatic isocyanate (e.g., TDI): 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.%.

[0043] In a preferred aspect of the present invention, in addition to 50 wt.% up 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.%

(these percentages are selected to achieve a total of 100 wt.% composition).

[0044] Exemplary embodiments of the claimed invention now presented below:

Oligomer primary coatingwt.%wt.%wt.%
Hydro is similarit (NEA) 2,111,152,49
Aromatic isocyanate (TDI)1,581,371,87
Aliphatic isocyanate (IPDI)5,314,84,50
Polyol(R)46,940,049,0
Inhibitor (BHT)0,070,060,10
The catalyst (DBTDL)0,030,020,04

The composition is radiation curable coatingwt.%wt.%wt.%
Oligomer primary coating56,050,058,0
The monomer-diluent (Photomer 4066)of 40.947,0 39,9
Photoinitiator (Chivacure TPO)1,701,501,90
Antioxidant (Irganox 1035)0,500,750,45
The adhesion promoter (A-189)0,900,750,55

[0045] the Primary coating according to the claimed invention now designated here as the PRIMARY COATING CR.

After receiving an initial application it can be applied directly to the surface of the optical fiber. The pulling is done using the mode or "wet on dry"or "wet on wet". Mode "wet on dry" means that the liquid primary coating is applied wet, and then exposed radiation (irradiated) for curing the liquid primary coating to a hard layer on the wire. After the primary coating overiden cause secondary coating and then also utverjdayut. Mode "wet on wet" means that the liquid primary coating is applied wet, then wet cause secondary floor, and then both primary and secondary coating utverjdayut. As a secondary coating in the present invention can be used too, for example, the coating described in the documents EP 2091883 B1, EP 2089334 A1, EP 2091884 Al, WO 2010/053532 (Specialty High Temperature Resistant Secondary Coating), US 6534557 and US 6306924.

[0046] the Preferred radiation, which act to effect the curing is ultraviolet.

[0047] After overiden secondary coating may be applied layer of the paint coating. Then covered and coated optical fiber is placed along the other covered and coated optical fiber in the "consolidated tape" and use radiation-curable matrix coating for holding the optical fibers in the desired position in this team the tape.

Examples

Test method tensile strength, elongation and modulus of elasticity

[0048] the Properties in tension (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 75-micrometer film of material using a UV processor Fusion. Samples utverjdayut at 1.0 j/cm2in nitrogen atmosphere. Test samples having a width of 1.27 cm (0.5 inch) and a length of 12.7 cm (5 inches), cut from the film. The exact thickness of each sample is measured with a micrometer.

[0049] For relatively soft coatings (for example, with mo is ul of elasticity less than 10 MPa), the coating is applied and utverjdayut on a glass plate and the individual samples are cut with this glass plate with a scalpel. In the Instron device using a torque sensor 0.9 kg (2 lb) and calculate the modulus of elasticity of the 2.5%wage elongation with fitting by method of least squares graph of stress-strain. Before the test cured film can stand under conditions of temperature 23,0±0.1°C and a relative humidity of 50.0±0,5% for 16 to 24 hours.

[0050] For a relatively hard surface coating applied to the film of Mylar (Mylar) and cut samples 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%wage elongation by clipping at this point. Before the test cured film can stand under conditions of temperature 23,0±0.1°C and a relative humidity of 50.0±0,5% for 16 to 24 hours.

[0051] To test samples of the base length is 5.1 cm (2 inches), and the speed of the RAM is 2.54 cm/minute (1.00 inch/minute). 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

[0052] Dynamic Mechanical Analysis (DMA) wire the t on the test samples with the use of the device RSA-II production Rheometric Scientific Inc. Free sample film (usually 36 mm long, 12 mm wide and 0.075 mm thick) is inserted into the clamping device and the temperature is initially adjusted to 80°C and kept at it for five minutes. During the last period of exposure at 80°C the sample stretch of 2.5% of its original length. Also during this time, identification information about the sample, its size and specific test methods introduced in the software (RSI Orchestrator)installed on the connected PC.

[0053] All tests are performed at a frequency of 1.0 radian dynamic method step change of temperature with steps of 2°C, the cooling-off period of 5-10 seconds, the initial deformation of about 0,001 (DELTA.L/L), in one embodiment, L=22,4 mm, when activated options autonation and avtodetali. Autonation establish in order to ensure that the sample remains under the action of tensile forces throughout the entire test cycle, and autodermal set in order to allow deformation as the sample passes through the glass transition and softens. After 5 minutes of exposure, the temperature in a heating Cabinet for samples reduce the speed to 20°C before reaching the initial temperature, usually -80°C or -60°C. the Final temperature of the test cycle is introduced into programme the e provision before the start of the test cycle to data about the sample ranged from the region of the vitreous state through the transition region and far in the area of high elasticity.

[0054] Test cycle start and allow you to go to completion. After completion of the test cycle on the computer screen shows a plot of storage modulus tensile = E', loss modulus tensile = E" and tan Delta, all depending on the temperature. The experimental data for each curve smooth out with use of the program software. In this graph, identify three points, representing the transition:

[0055] 1) the Temperature at which E'=1000 MPa;

[0056] 2) the Temperature at which E'=100 MPa;

[0057] 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 obtained from this graph represents the minimum value for E' in the field of high elasticity. This value is recorded as the equilibrium modulus E0.

Measurement of adhesion in dry and wet conditions

[0058] Determination of adhesion in dry and wet condition, make use of a universal measuring device Instron model 4201. The film thickness of 75 μm is applied on a polished glass plate for tokelaun the th chromatography (TLC) and utverjdayut using a UV processor Fusion. Samples utverjdayut at 1.0 j/cm2in an atmosphere of nitrogen.

[0059] the Samples incubated under conditions of temperature 23,0±0.1°C and a relative humidity of 50.0±0.5% in 7 days. After keeping under these conditions, the scalpel cut the eight samples with a length of 15.2 cm (6 inches) and a width of 2.54 cm (1 inch) in the direction of drawing. Four of these samples 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 an Instron 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 passed through a pulley in the direction perpendicular to the sample. The free end of the wire is fixed in the upper clamp of the Instron, which then activate. 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.

[0060] the Remaining four sample is then incubated under conditions of 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 polyethylene/water. ZAT is m the tests, as described in the previous paragraph. The importance of adhesion in the wet state is the average of four samples.

Sensitivity to water

[0061] the Layer of the composition utverjdayut with getting the test strips of the cured UV coating 3.8 cm × 3.8 cm × 15-mm (1.5 inch × 1.5 inch and 0.6 mil). The test strip is weighed and placed in a bottle containing deionized water, which is then stored for 3 weeks at 23°C. at periodic intervals of time, for example 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 re-weighed. The percentage of water absorption is recorded as 100 × (weight after immersion - weight before immersion)/(weight before immersion). The peak absorption of water represents the highest value of water absorption reached 3 weeks of immersion. After a 3-week period of the test strip is dried in a heating Cabinet at 60°C for 1 hour, cooled in a desiccator for 15 minutes and re-weighed. The percentage of recoverable water is recorded as 100 × (weight before immersion - weight after drying)/(weight before immersion). Sensitivity to water log |peak absorption of water| + |recoverable water|. Experience three test strips to improve the accuracy of the test.

Display the spruce refraction

[0062] the refractive Index of the hardened compositions determined by the method of strips Becke, which entails matching the refractive index of thinly sliced strips utverzhdenii composition with immersion liquids with known properties of refraction. The test is carried out under a microscope at 23°C and using light with a wavelength of 589 nm.

Viscosity

[0063] 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. No need to remove all the bubbles at this stage, because the loading of the sample introduces some amount of bubbles.

[0064] the Device set up on the ordinary system of Z3, which is used. Samples are loaded into a disposable aluminum glass syringe for measuring 17 cm3. The sample in the Cup investigate and, if it contains an excessive amount of bubbles, remove them by a direct method, such as centrifugation, or leave it for sufficient to enter the time in order to allow the bubbles to exit the fluid volume. Bubbles on the upper surface of the liquid is acceptable.

[0065] the Pendulum gently immersed in the liquid in a measuring Cup, and a glass with a pendulum set in the device. The temperature of the treatment is zza give the opportunity to be balanced with the temperature of the circulating fluid, after waiting five minutes. Then the rotational speed is set at the desired value, which gives the desired shear rate. The desired value of the shear rate is easily determined by the average expert in the art based on the expected interval of the sample viscosity. The shear rate is usually 50 sec-1or 100 sec-1.

[0066] the Panel reads the value of the viscosity and, if the viscosity varies slightly (less than 2% relative change) within 15 seconds, the measurement is complete. If not, then it is possible that the temperature has not reached the equilibrium value or that the material is changed because of the shift. In the latter case, further testing under different shear rates to determine properties of the sample viscosity. The recorded results are average values of viscosity for the three test specimens. Results are recorded either in centipoise (SDR), or in millipascal seconds (MPa·s).

[0067]

The cured film of the radiation curable primary coating according to the claimed invention now has a peak tan Delta Twithfrom -25°C to -45°C. In one embodiment, the cured film of the radiation curable primary coating according to the claimed invention now has a peak tan Delta Twithfrom -3°C to -40°C.

The cured film of the radiation curable primary coating according to the claimed invention now has a modulus of elasticity of from 0.50 MPa to 1.2 MPa. In one embodiment, the cured film of the radiation curable primary coating according to the claimed invention now has a modulus of elasticity of from 0.6 MPa to 1.0 MPa.

[0068] In the early years of the development of coatings of optical fibers all newly developed primary and secondary coatings were first tested on the properties of their utverzhdenii film, 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, at most 30% of them felt on the extraction column because of the high cost 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.

[0069] In the technology of radiation hardened coatings for optical fibers, it is known that when either the primary coating, a secondary coating applied to the glass, its properties often differ from the properties of flat utverzhdenii film of the same coating. I believe that this is due to the fact that the coating on the fiber and flat film coatings have differences in R is smeru sample, geometry, the 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.

[0070] in order to make possible the development of more reliable coverage and reduce the period of implementation in production, we developed equipment that would support curing, similar to the conditions existing at manufacturers of fiber. This type of alternative equipment for applying and curing should be easy to use, require low maintenance and give reproducible process parameters. The name of this equipment - simulator extraction columns", hereinafter abbreviated designated as "CPI". Simulators exhaust columns are designed according to customer order and are based on a detailed study of the structural elements of the real pillars of glass fiber drawing. All measurements (position lamps, the distance between the rungs of the coating, the gaps between the steps of coating and UV lamps etc.) duplicated with columns of glass fiber drawing. This helps to simulate process conditions used in the industrial equipment of pulling the fiber.

[0071] One of the known CPI has five lamps Fusion F600 - a twelve top step coverage and three on the bottom. The second lamp at each stage can be rotated at different angles between 15-135°, allowing a more detailed study of the curing profile.

[0072] 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 of different designs from different vendors. This configuration allows you to apply a coating on the optical fiber under conditions similar to those that take place at industrial enterprises.

[0073] the exhaust Simulator columns have been used to deepen the analysis of radiation-curable coatings for optical fiber. Method of measuring in-situ modulus of the primary coating, which can be used 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 Materials 52-th International Symposium cable-wire products (the Proceedings of the 52nd IWCS), p.246 (2003). In 2004 Steeman with 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. Zetelief, N. Cao and M. Bulters, Proceedings of the 53rd IWCS, p.532 (2004). Simulator extraction columns can be used to further study the properties of the primary and secondary coating on the optical fiber.

[0074] These test methods are applicable for the primary coating on the wire or coating on the optical fiber.

[0075] test Methods

[0076] the Percentage reacted acrylate unsaturation for the primary coating, abbreviated designated as test method % RAU primary coating.

[0077] 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 ratio of signal to noise ratio. Requires two spectra: one for the uncured liquid coating, which corresponds to the coating 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 the second adhesive to become tacky on it place a piece of optical fiber or wire. Place the sample under the optical microscope low power. The coating on the fiber or wire to cut glass using a sharp scalpel. Then cover the cut longitudinally to the upper side of the fiber or wire to about 1 centimeter, making sure that the cut is clean and that the external coating is 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 place where disclosed primary coverage.

[0078] Range of liquid coatings obtained after complete coverage of the diamond surface coating. The liquid must be from the same batch that was 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 set in the center of the diamond, and the axis of the fiber or wire parallel to the direction of the infrared beam. The back part of the sample should be accompanied by pressure to ensure good contact with the crystal. The spectrum should not contain any acquisitions from the contact the CSO glue. If you can see the peaks of 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.

[0079] 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 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.

[0080] the Ratio of the peak area of the acrylate to the square of the control peak defined as a liquid and cured samples. The degree of cure, expressed as a percentage reacted acrylate unsaturation (% RAU), calculated by the following equation:

where RLis the ratio of the square of the liquid sample, a RFis the ratio of the square of the cured primary coating.

In-situ modulus primary coating

[0081] In-situ modulus of perving the coating on the glass fiber or metal wire fiber with a double coating (soft primary coating and a solid secondary coverage) measured in this test method. A detailed discussion of this test can be found in Steeman, RAM, Slot, J.J.M., Melick, N.G.H. van, Ven, A.A.F. van de, Cao, H. & Johnson, R. (2003). Mechanical testing analysis in-situ modulus primary coating for optical fibers may be determined in accordance with methods described in the Materials 52-th International Symposium cable-wire products (IWCS, Philadelphia, USA, November 10-13,2003), article 41.

[0082] 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. Fiber cut, receiving 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 images, as schematically shown in Fig.6 in the article . Coated fiber is inserted into microtrace in the mounting bracket; microtube consisted of 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 homogeneous and significant deformation in the coating layer does not occur. Then clamping device with the fiber mounted on the device DMA (Dynamic m is a mechanical analysis): Rheometrics Solids Analyzer (RSA-II). Metal clamping device is clamped by the lower collet. The upper collet tightened, pressing on the upper part of the coated fiber to such an extent that it destroyed 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. Offset deformation correct by setting the axial pretensioning almost zero (-1 g ~ 1 g).

[0083] 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 the calculation using the standard geometry of the fiber, Rf=62.5 μm and Rp=92,5 μm. The sample length 8 mm (inserted parts) 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 radian/second. The shear deformation ε set at 0.05. Produce dynamic time base, get the 4 experimental point for the measured storage modulus shear G. Given the value of G is the average of all experimental points.

[0084] The measured shear modulus G is then further corrected according to the correction method described in the article . Correction is needed to account for the stretching of the glass in the inserted and nastavlenii parts. When making corrections, you must enter the modulus of elasticity tensile bare fiber (Ef). For optical fibers Ef=70 GPA. For the wire fibers, which used stainless steel wire S314, Ef=120 GPA. The adjusted value G next Ousterhout using the real values of Rfand Rp. For optical fibers of the fiber geometry, including the values of Rfand Rpmeasure using RC Fiber Geometry System. For the wire fibers Rfis 65 μm used for wires of stainless steel with a diameter of 130 μm; Rpmeasured under a microscope. Finally, in-situ modulus of elasticity E ' (storage modulus tensile) for the primary coating on the fiber is calculated according to the equation E=3G. Given the value of E is the average of three test specimens.

[0085] In-situ DMA to measure the Tcthe primary and secondary coating on the optical fiber

[0086] the glass transition Temperature (Twith) the primary and secondary coatings on glass or metal wire is cnom fiber (wire) with a double coating is measured by this method. These glass transition temperature denoted here as Twithtube".

[0087] To obtain a sample 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 N2for at least 10 seconds, and then removing the receiver cover fast movement, until the layers of coatings remain hard.

[0088] the Device DMA (Dynamic mechanical analysis): apply Rheometrics Solids Analyzer (RSA-II). In the case of RSA-II gap between the two clamps RSA-II can be extended up to 1 mm Gap initially set to the minimum level, adjusting the offset strain. A simple sample holder, made of metal plate, bent and hollow at the open end of the screw, are used for strong retention of the sample tube covering the bottom end. Shift the clamping device in the center of the lower clamp and tighten the clamp. Use tweezers to straighten the tube cover to the vertical position through the top clamp. Close and tighten the top clamp. Closed heat chamber and set 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 reached that the values, offset deformation correct up until the pre-tensioning was not in the range of 0 g to 0.3 g

[0089] When conducting dynamic tests DMA at step temperature change of the frequency of the test set at 1.0 radians/second; the deformation is 5E-3; a step change in temperature is 2°C, and the exposure time is 10 seconds.

[0090] the geometry Type of the selected cylindrical. Set geometry parameters were the same as used for testing in-situ modulus of the secondary coating. The sample length equal to the length of the tube cover between the top edge of the metal clamping device and the lower clamp 11 mm in this test. The diameter (D) was administered equal to 0.16 mm according to the following equation:

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

[0091] the Dynamic test at step temperature change is carried out from the initial temperature (in our test 100°C) to a temperature below Twithprimary coverage or -80°C. After the test cycle peaks on the curve tangent (tan δ log Twithprimary coverage (corresponding to a lower temperature) and the withthe 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 coatings on the fiber due to the shift of the tan δ due to the complicated structure of the tube cover.

Examples of simulators exhaust columns

[0092] 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 with five different linear velocity: 750 m/min, 1200 m/min to 1500 m/min, 1800 meters/minute and 2100 meters/minute.

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

The properties of the PE the primary coating and the secondary coating is measured and recorded for the following tests: % RAU, the start and after one month aging at 85°C/85%RH with uncontrolled light. After the primary coating was overiden, put the secondary coating.

Spend a lot of test cycles with different compositions declared now the primary coating and a commercially available radiation curable secondary coating. Utverjdenie primary coating on the fiber have initial % RAU, the initial in-situ modulus and the initial Twithof the tube. The wire coating is then subjected to aging for one month at 85°C and a relative humidity of 85%. Utverjdenie primary coating on the wire is then subjected to aging for one month and experience the % RAU, in-situ modulus and Twithtube after aging.

Tuning simulator exhaust columns:

- use the die Seidle (Zeidl): 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) 600 watt/inch2D Fusion UV lamp is used at 100% for 1°'s coatings;

- (3) 600 watts/inch2D Fusion UV lamp is used at 100% for 2°'s coatings;

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

- the level of carbon dioxide is 7 liters/min at each of filiere;

- the level of nitrogen is 20 liters/min to each lamp;

- pressure for 1°th coating is 1 bar at 25 m/min up to 3 bar at 1000 m/min;

- pressure for 2°th coating is 1 bar at 25 m/min and up to 4 bar at 1000 m/min

Utverjdenie radiation-curable primary coating on the wire has the following properties:

Linear speed (m/min)% RAU primary coating (Primary)% RAU primary cover (1 month)
75096-9992-96
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 (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)The values of Twithprimary tube (°C) (initial)The values of Twithprimary tube (°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

[0093] it is Therefore possible description of the diamonds and the making of the wire, covered with the first and second layers and the first layer is utverjdenie radiation-curable primary coating for now declared the invention, 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 a relative humidity of 85%:

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.

Therefore, it is possible to describe and to declare an optical fiber covered with the first and second layers and the first layer is utverjdenie radiation-curable primary coating for now declared the invention, 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 wire has the following properties after initial cure and after one month aging at 85°C and a relative humidity of 85%:

A) A % RAU of from 84% to 99%;

B) in-situ fashion is eh elasticity between 0.15 MPa and 0,60 MPa; and

C) Twithtube from -25°C to -55°C.

[0094] the radiation Curable secondary coating may be any commercially available radiation curable secondary coating for optical fibers. Such commercially available radiation curable secondary coating supplied by DSM Desotech Inc. and others, including, but not limited to, Hexion, Luvantix and PhiChem.

[0095] the original of the articles "a" and "an" and "the" and similar designations in the context of describing the invention (especially in the context of the following claims) should be considered as related to a single and plural, if there is not specified or expressly contrary to the context. The terms "comprising", "having", "including" and "comprising" should be considered as a non-limiting terms (i.e., meaning "including, but not limited to"), unless otherwise noted. Specifying ranges of values here is intended to serve as a quick way to individually list each separate value falling within this range, if this is not specified, and each separate value is incorporated into the description, as if it had been listed here individually. All methods described here can be performed in any suitable order, if this is not specified or otherwise contrary to what ntext. The use of any and all examples, or exemplary expressions (e.g., "such as")provided here is intended merely to better illuminate the invention and does not impose restrictions on the scope of the invention unless stated otherwise. No expressions in the description should not be construed to indicate any claimed element as essential to the practical implementation of the invention.

1. Curable by radiation of the primary coating composition containing:
A) oligomer;
B) the monomer-diluent;
C) photoinitiator;
D) an antioxidant; and
E) an adhesion promoter;
moreover, the said oligomer is the reaction product of:
i) hydroxyethylacrylate;
ii) an aromatic isocyanate;
(iii) aliphatic isocyanate;
iv) a polyol;
v) a 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
these catalyst selected from the group comprising dilaurate dibutylamine, carboxylates of metals, sulfonic acid catalysts based on amines or organic bases, alkoxides of zirconium and titanium, and ionic liquid phosphonium salts of imidazole and pyridinium; and
when this cured film mentioned radiation-curable primary coating composition has a peak Tang the NSA Delta T withmeasured as indicated in the description, from -25°C to -45°C and the modulus of elasticity of from 0.50 MPa to 1.2 MPa.

2. The composition according to claim 1, in which the said catalyst is dilaurate dibutylamine.

3. The method of coating an optical fiber, which includes:
a) column extraction of glass with receiving optical fiber; and
b) coating on said optical fiber radiation-curable primary coating composition according to claim 1.

4. The method according to claim 3, in which the work mentioned column extraction of glass is performed with a linear speed between 750 m/min and 2100 m/min

5. The wire is covered with the first and second layers and 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 a relative humidity of 85%:
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.

6. The optical fiber coated with the first and second layers and the first layer of the two who 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 a relative humidity of 85%:
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.



 

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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.

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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.

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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.

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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.

EFFECT: improved and valuable properties of covers.

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

The invention relates to compositions based on emulsified resins, curable by ultraviolet radiation, which includes: unmodified oligomers as the basis of composition, which determines the final properties of the cured product; curing agents consisting of polyfunctional monomers; photoinitiator initiating polymerization; additives to make the product special properties

The invention relates to the field of coatings, curing under the action of radiation of low energy in the wavelength range of 400-700 nm and used in such fields as dentistry, electronics, printing

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: composition for sports coatings contains oligobutadiene diol, a plasticiser, mineral filler, trifunctional low-molecular alcohol, polymethylene polyphenylene polyisocyanate with 29.5-31.0% content of isocyanate groups, an organotin catalyst, 2,4,6-tri-tertbutylphenol, polysulphide oligomer, isocynate prepolymer, aromatic diamine which is a mixture of 2,4- and 2,6-isomers of 3,5-dimethylthiotoluylenediamine in ratio of 80:20 and diatomite, technical carbon P-803 and light ageing stabiliser 2-(3'-tertbutyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole.

EFFECT: improved dynamic and physical-mechanical properties of coatings.

2 tbl

FIELD: chemistry.

SUBSTANCE: composition for sports coatings contains oligobutadiene diol, a plasticiser, mineral filler, trifunctional low-molecular alcohol, polymethylene polyphenylene polyisocyanate with 29.5-31.0% content of isocyanate groups, an organotin catalyst, 2,4,6-tri-tertbutylphenol, polysulphide oligomer, isocynate prepolymer, aromatic diamine which is a mixture of 2,4- and 2,6-isomers of 3,5-dimethylthiotoluylenediamine in ratio of 80:20 and diatomite, technical carbon P-803 and light ageing stabiliser 2-(2'-hydroxy-3',5'-diisopentylphenyl)benzatriazole.

EFFECT: improved dynamic and physical-mechanical properties of coatings.

2 tbl

FIELD: chemistry.

SUBSTANCE: composition for sports coatings contains oligobutadiene diol, a plasticiser, mineral filler, trifunctional low-molecular alcohol, polymethylene polyphenylene polyisocyanate with 29.5-31.0% content of isocyanate groups, an organotin catalyst, 2,4,6-tri-tertbutylphenol, polysulphide oligomer, isocynate prepolymer, aromatic diamine which is a mixture of 2,4- and 2,6-isomers of 3,5-dimethylthiotoluylenediamine in ratio of 80:20 and diatomite.

EFFECT: improved dynamic and physical-mechanical properties of coatings.

2 tbl

FIELD: chemistry.

SUBSTANCE: composition contains the following in pts.wt: 100 - copolymer of butadiene and piperylene with molecular weight 1200-3200 and content of hydroxyl groups 0.8-1.1%, 20-polymethylene polyphenyl isocyanate with content of isocyanate groups 29-31%, 70-100 - rubber crumbs, and 25-20 - high-molecular polyethylene with molecular weight 30000-800000.

EFFECT: high dynamic and physical-mechanical properties of the composition based on the filled foamed polyurethane.

1 ex, 2 tbl

Polymer composition // 2421495

FIELD: chemistry.

SUBSTANCE: composition contains isocyanate hardener, urethane-formation catalyst, a rubber base and a mixture of 2,4 and 2,6-isomers of 3,5-dimethylthiotoluylene diamine. The rubber base contains low-molecular hydroxyl-containing rubber, a plasticiser, filler, an antiageing agent and a pigment. The isocynate hardener is a prepolymer obtained by reacting 4,4'-diphenylmethane diisocayanate and oligodiene diol with molecular weight 2000-2200, content of hydroxyl groups of 1.2-1.9% with the ratio of isocyanate to hydroxl groups equal to 2:1 with content of isocyanate groups in the prepolymer equal to 4-5%.

EFFECT: obtaining coatings with high strength, hardness and elasticity.

6 cl, 2 dwg, 2 tbl

Polymer composition // 2421494

FIELD: chemistry.

SUBSTANCE: composition contains an isocynate hardener, urethane-formation catalyst, a rubber base and glycerin. The rubber base contains low-molecular hydroxyl-containing rubber, a plasticiser, filler, an antiageing agent and a pigment. The isocynate hardener is a prepolymer obtained by reacting 4,4'-diphenylmethane diisocayanate and oligodiene diol with molecular weight 2000-2200, content of hydroxyl groups of 1.2-1.9% with the ratio of isocyanate to hydroxl groups equal to 2:1 with content of isocyanate groups in the prepolymer equal to 4-5%.

EFFECT: composition enables to obtain coatings with high strength, hardness and elasticity.

6 cl, 2 tbl

Coating composition // 2421493

FIELD: chemistry.

SUBSTANCE: coating composition contains an isocynate prepolymer obtained by reacting 4,4'-diphenylmethane diisocayanate and oligobutadiene diol with molecular weight 2800-3200, content of hydroxyl groups of 0.88-1.3% with ratio of isocynate to hydroxyl groups equal to 4:1, with content of isocyanate groups in the prepolymer equal to 8.0-9.7%, a base - rubber composition of low-molecular hydroxyl-containing rubber, a plasticiser, filler, an anti-ageing agent and a pigment, a urethane-formation catalyst and 3,3'-dichloro-4,4'-diaminodiphenyl methane.

EFFECT: high strength, hardness and relative elongation of coatings.

2 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to threads which can reinforce organic and/or inorganic materials. The threads are coated with a lubricating composition. The lubricating composition contains at least one bonding agent selected from silanes such as aminosilanes or epoxysilanes, and at least one additive capable of having an effect on the thread/matrix boundary surface(s) in order to improve fire resistance of the composite. The additive may be selected from the following: nitrates such as potassium nitrate (KNO3) and guanidine nitrate; alcohols selected from dipentaerythritol, tripentaerythritol, ethoxylated pentaerythritol, propoxylated pentaerythritol, ethoxylated/propoxylated pentaerythritol, sorbitol or derivatives thereof; phosphorus derivatives or derivatives of phosphoric acid, organophosphorus compounds, phosphates of cyclic esters, guanidine phosphate, 1,2,3-dioxaphosphorinane or ammonium pyrophosphate.

EFFECT: high fire resistance of the composite material.

15 cl

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