JP4682544B2 - RESIN COMPOSITION FOR PHOTOCURABLE COATING AND PROCESS FOR PRODUCING THE SAME - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a photocurable coating resin composition optimal for optical fiber coating, a method for producing the same, and an optical fiber core, a colored core, a unit, or an overcoat core coated with the resin composition. The present invention relates to a photocurable coating resin composition capable of reducing normal stress during shearing.

  The resin composition for photocurable coating is conventionally used in various uses. Specific examples include optical fiber coating materials, tape surface protective coatings, hard coating materials for wires, glass products, and wood protective coatings.

  Various resin compositions for photo-curable coatings are known and are provided for various uses according to properties such as film-forming properties, adhesive properties, and thick-film forming properties. In particular, a resin composition for a photocurable coating containing a polyurethane structure often exhibits excellent properties in terms of film-forming properties, abrasion resistance, optical properties, etc., and is used in a wide range of applications. It is attracting attention as.

  An optical fiber is usually provided with a coating layer composed of a flexible primary coating layer and a rigid secondary coating layer. Also, a form of a colored optical fiber having a colored layer (colored core) on an optical fiber (core) provided with a coating layer, and a form of an optical fiber unit (unit) in which a plurality of colored cores are integrated and integrated. There are also forms (overcoat core wires) in which an overcoat layer is provided on the core wires or colored core wires (including tape units in which the core wires are gathered in a tape shape in parallel), and these colored layers, unit materials, and overcoats. As the layer, a photocurable coating resin composition is used.

The following performance is required for a resin composition for a photocurable coating for a core wire, a colored core wire, a unit, and an overcoat core wire (hereinafter collectively referred to as “core wire”). .
(High-speed workability): It is liquid and has excellent workability during coating.
(Storage stability): Viscosity does not change during storage at low or high temperatures, and excellent long-term stability.
(Curability): The curing speed is fast and the material can be processed at high speed.
(Toughness): Hardened | cured material has sufficient tensile fracture modulus and tensile fracture elongation, and the core wire coat | covered with cured | curing material has sufficient mechanical strength.
(Temperature dependence): The cured product has a small change in physical properties due to a wide range of temperature changes, and the temperature change of the optical signal transmission characteristics of the coated core covered with the cured product is small.
(Environmental resistance): Hardened product has excellent heat resistance, hydrolysis resistance, acid resistance, alkali resistance, oil resistance, light yellowing resistance, heat yellowing resistance, and UV resistance, and the coated core wire is environmentally resistant. To be excellent.

  In addition, in order to increase mass productivity in response to the growing demand for optical fibers in recent years, among the performance of resin compositions for photo-curable coatings, optical fibers that can obtain good normal stress during high-speed shearing are obtained. Therefore, there is a demand for a photocurable coating resin composition suitable for coating.

  In order to satisfy the above required performance, various ultraviolet curable compositions for core wires have already been proposed. For example, a bifunctional (diethylenic) polymerizable polyurethane based on diisocyanate (Patent Document 1), a tetrafunctional polymerizable polyurethane reacted with a polyhydroxy functional amine having an amino hydrogen atom (Patent Document 2), 3 Polyfunctional polymerizable polyurethane based on a functional or higher core (Patent Document 3, Patent Document 4), tetrafunctional polymerizable polyurethane reacted with diacrylate of trishydroxyalkylisocyanurate (Patent Document 5), Containing a trifunctional polymerizable polyurethane obtained by a reaction of a polymerizable unsaturated group and a hydroxyl group-containing isocyanuric acid derivative, a polyisocyanate, and a compound having a polymerizable unsaturated group and a hydroxyl group at the terminal (Patent Document 6) , Having two or more radical polymerizable groups at one end and one radical polymerizable group at the other end An optical fiber coating resin composition comprising an asymmetric polymeric linear polyurethane compound (Patent Document 7) have been proposed.

JP 59-170155 A Japanese Patent Laid-Open No. 62-12640 Japanese Unexamined Patent Publication No. 62-21734 JP-A-62-106918 JP-A 61-227947 JP-A-5-271619 JP 2001-199748 A

  However, the conventional ultraviolet curable composition for a core wire satisfies the above-described requirements for a core wire and does not sufficiently satisfy the requirements for normal stress during high-speed shearing.

The resin composition for a photocurable coating of the present invention satisfies the above-described requirements for a core wire, and can obtain a good normal stress during high-speed shearing. Therefore, by using the present invention, an excellent core wire that satisfies the above-described requirements for the core wire can be efficiently produced in a short time.
In addition, according to the method for producing a resin composition for a photocurable coating of the present invention, the photocurable coating that satisfies the above-described requirements for a core wire and that can obtain a normal stress during high-speed shearing is obtained. A resin composition can be provided.

  The present invention has been made in view of the above problems, and provides a resin composition for a photocurable coating that satisfies the requirements for a core wire and that provides a normal stress during high-speed shearing. For the purpose.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have obtained a reaction between an organic diisocyanate, a radical polymerizable group-containing monool compound, and a radical polymerizable group-free monool compound. By using the resin composition for photocurable coating containing the first polyurethane compound (A) having a low molecular weight polymer having a radical polymerizable group in the normal line during high-speed shearing as shown in the examples described later. The present inventors have found that the stress can be reduced and a normal stress at the time of good high-speed shearing can be obtained, and the present invention has been completed.

That is, in order to solve the above problems, the resin composition for photocurable coating of the present invention is obtained by reacting an organic diisocyanate, a radical polymerizable group-containing monool compound, and a radical polymerizable group-free monool compound. The low-molecular-polymerizable first polyurethane compound (A) having a radically polymerizable group at one end is contained.
By using such a photocurable coating resin composition, a resin composition for photocurable coating that satisfies the requirements for a core wire and has a normal stress during high-speed shearing is obtained. Is possible.

In addition, the above-mentioned resin composition for photocurable coating is obtained by reacting an organic diisocyanate and a radical polymerizable group-containing monool compound, and a low molecular polymerizable second polyurethane having radical polymerizable groups at both ends. The compound (B) can further be contained.
By setting it as such a photocurable coating resin composition, as shown in the examples described later, the high-temperature Young's modulus retention ratio is improved, and the photocurable coating resin is more preferable as a core wire. It becomes a composition.

Furthermore, the resin composition for photocurable coating described above is obtained by reacting an organic diisocyanate, a radically polymerizable group-containing monol compound, and a polycarbonate diol having a side chain alkyl group, with radically polymerizable groups at both ends. The polymer-containing third polyurethane compound (C) may further be contained.
By using such a resin composition for photo-curing coating, as shown in the examples described later, it satisfies the requirements for the core wire, and has a good normal stress during high-speed shearing, A photocurable coating resin composition having a good high temperature Young's modulus retention and more preferable for a core wire can be obtained.

In addition, the photocurable coating resin composition has a gel permeation ratio of the first polyurethane compound (A), the second polyurethane compound (B), and the third polyurethane compound (C). It is desirable that {(A) + (B)} :( C) = 20: 80 to 60:40 in the peak area ratio of the association chromatography.
By making such a resin composition for photocurable coating, the effect of improving the normal stress at the time of high-speed shear obtained by containing the first polyurethane compound (A), and the second polyurethane compound (B) Furthermore, the improvement effect of the high temperature Young's modulus retention obtained by containing can be obtained very effectively, and the resin composition for photo-curable coating is more preferable for the core wire.

Moreover, the manufacturing method of said resin composition for photocurable coatings which solves the said subject is as follows.
(A) reacting an organic diisocyanate with a radical polymerizable group-free monool compound and a radical polymerizable group-containing monool compound;
Obtaining a mixture of a low-molecular polymerizable first polyurethane compound (A) having a radical polymerizable group at one end and a low-molecular polymerizable second polyurethane compound (B) having a radical polymerizable group at both ends; ,
(B) An organic diisocyanate, a radically polymerizable group-containing monool compound, and a polycarbonate diol having a side chain alkyl group are reacted in an atmosphere containing an isocyanate group and a hydroxyl group to have radically polymerizable groups at both ends. Obtaining a polymer-polymerizable third polyurethane compound (C);
(C) mixing a mixture of the first polyurethane compound (A) and the second polyurethane compound (B) and the third polyurethane compound (C);
It is characterized by having at least.
By using such a method for producing a photocurable coating resin composition, as shown in the examples described later, it satisfies the requirements for a core wire and has good normal stress during high-speed shearing. And the resin composition for photocurable coatings with a favorable high temperature Young's modulus retention rate is obtained.

Moreover, the manufacturing method of said resin composition for photocurable coatings which solves the said subject is as follows.
(D) High reaction with radically polymerizable groups at both ends by reacting an organic diisocyanate, a radically polymerizable group-containing monool compound and a polycarbonate diol having a side chain alkyl group in an atmosphere containing an isocyanate group and a hydroxyl group. Obtaining a molecularly polymerizable third polyurethane compound (C);
(E) In the presence of the third polyurethane compound (C), an organic diisocyanate, a radical polymerizable group-free monool compound and a radical polymerizable group-containing monool compound are reacted to form a radical polymerizable group at one end. A step of obtaining a low molecular weight polymerizable first polyurethane compound (A) having a low molecular weight polymerizable second polyurethane compound (B) having radical polymerizable groups at both ends;
It is characterized by having at least.
Also by the method for producing such a photocurable coating resin composition, as shown in the examples described later, satisfy the requirements for the core wire, and has a normal stress at the time of good high-speed shearing, And the resin composition for photocurable coatings with a favorable high temperature Young's modulus retention rate is obtained.

Moreover, in order to solve the said subject, the optical fiber core wire, the colored core wire, the unit, or the overcoat core by which the glass fiber was coat | covered with the hardened | cured material of the resin composition for photocurable coatings in any one of the above. It may be a line.
By using such a core wire, an excellent core wire that can be efficiently produced in a short time and satisfies the above-described requirements for the core wire can be obtained.

The first polyurethane compound (A), which is a low molecular weight polymerizable polyurethane compound having a radical polymerizable group at one end constituting the resin composition for photocurable coating of the present invention, is an organic diisocyanate, a radical polymerizable group-containing monool. It is obtained by reacting a compound and a radical polymerizable group-free monool compound.
Moreover, the 2nd polyurethane compound (B) which is a low molecular-polymerizable polyurethane compound which has a radically polymerizable group in both terminals is obtained by making organic diisocyanate and a radically polymerizable group containing monool compound react.
The third polyurethane compound (C), which is a polymer polymerizable polyurethane compound having radical polymerizable groups at both ends, is composed of an organic diisocyanate, a radical polymerizable group-containing monol compound, and a polycarbonate diol having a side chain alkyl group. Obtained by reaction.

  Here, as the organic diisocyanate used in the first, second and third polyurethane compounds (A), (B) and (C), tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 2,4,4- Or 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl -2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4-bis (isocyanate methyl) cyclohexane, 1,3-bis (isocyanate methyl) silane Rhohexane, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,2'- or 2,4'-diphenylmethane Diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, dianidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 1,3- or 1,4-xylylene diisocyanate, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene, m-xylene diisocyanate, lysine diisocyanate methyl ester, isophorone diiso Cyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-phenylene diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, 2,5-bis ( Isocyanatomethyl) -bicyclo [2.2.1] heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3 -Phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated xylylene diisocyanate, tolidine diisocyanate, transcyclohexane-1,4-diisocyanate, tetra Chill xylene diisocyanate, hydrogenated dimer acid diisocyanate, a norbornene diisocyanate. These may be used alone or in combination of two or more.

  In the present invention, in consideration of high-temperature properties and toughness in the cured film of the photocurable coating resin composition, 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, Organic diisocyanates having a ring structure such as xylylene diisocyanate and methylene bis (4-cyclohexyl isocyanate) are preferred, with 2,4- or 2,6-tolylene diisocyanate being most preferred.

  The radical polymerizable group-containing monol compound used in the first, second and third polyurethane compounds (A), (B) and (C) includes a (meth) acryloyl compound having a hydroxyl group and an allyl having a hydroxyl group. Compounds, vinyl ether compounds having a hydroxyl group, vinyl compounds having a hydroxyl group, acrylamide compounds having a hydroxyl group, and the like.

  Specifically, as the (meth) acryloyl compound having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1,4-butanediol mono (Meth) acrylate, neopentyl glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-alkyloxypropyl (meth) ) Acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ε-caprolactone) mono {2- (meth) acrylate Rokishiechiru} esters, ethylene oxide-modified phthalic acid (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate. Examples of the allyl compound having a hydroxyl group include 2-propen-1-ol and 4-hydroxybutyl allyl ether. Examples of the vinyl ether compound having a hydroxyl group include ethylene glycol monovinyl ether, butanediol monovinyl ether, cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, and hexanediol monovinyl ether. Examples of the vinyl compound having a hydroxyl group include both-end alcoholic polyisoprene TL-20 [manufactured by Kuraray Co., Ltd.], both-end alcoholic polybutadiene R-15HT, R-45HT [manufactured by Idemitsu Petrochemical Co., Ltd.], and the like. Esterification reaction of unsaturated group-containing polyvalent carboxylic acids such as acid, linolenic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic anhydride, and polyhydric alcohols such as 1,6-hexanediol There are unsaturated polyesters containing alcohol groups at both ends or at one end, cinnamyl alcohol, and the like. Examples of the (meth) acrylamide compound having a hydroxyl group include N-methylol (meth) acrylamide. These may be used alone or in combination of two or more.

  When used as a coating resin for optical fibers, the loss of light increases if the coating has crystallinity. Further, considering the efficiency (reactivity) of the coating / curing process, a hydroxyalkylene acrylate compound comprising acrylic acid and a side chain alkyl group-containing glycol is preferable, and specifically, 2-hydroxypropyl acrylate, neopentyl glycol. Monoacrylate and the like, and 2-hydroxypropyl acrylate is most preferable.

  Examples of the radical polymerizable group-free monool compound used in the first polyurethane compound (A) include monoalcohols such as methanol, ethanol, isopropyl alcohol, octanol, 2-ethyl-hexanol, dodecanol, stearyl alcohol, benzyl alcohol, Polyether monools added with alkylene oxide using the above monoalcohol or phenol as an initiator, polyester monools added with a cyclic ester such as ε-caprolactone using the above monoalcohol or phenol as an initiator, etc. It is done.

  In this invention, what has a bulky group which destroys the crystallinity of a film is preferable, and especially isopropyl alcohol, 2-ethyl-hexanol, and benzyl alcohol are the most preferable.

  The polycarbonate polyol having a side chain alkyl group used in the third polyurethane compound (C) is obtained by reacting a low molecular glycol having a side chain alkyl group with a low molecular carbonate compound or phosgene. The polycarbonate polyol having a side chain alkyl group has a number average molecular weight of preferably from 500 to 5,000, particularly preferably from 1,000 to 3,000, in view of flexibility and toughness required for the coating. Here, as the low molecular glycol having a side chain alkyl group, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2-methyl- 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol and the like can be mentioned. Moreover, as a low molecular carbonate compound, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. are mentioned.

  The side chain alkyl group has an effect of preventing crystallization of the resin at low temperature and lowering the viscosity of the coating composition. Resin crystallization causes light loss. The carbonate skeleton contributes to improving the durability of the resin. The third polyurethane compound (C) based on the polycarbonate polyol having a side chain alkyl group used in the present invention has a small loss of light and is excellent in coating property and durability.

  Examples of the additive used in the present invention include a reactive diluent, a polymerization inhibitor, a urethanization catalyst, and a photopolymerization initiator.

Examples of reactive diluents that can be used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, Heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, Dodecyl (meth) acrylate, isododecyl (meth) acrylate, tridecyl (meth) acrylate, isotridecyl (meth) acrylate, pentadecyl (meth) acrylate, isopentadecyl (meth) a Relate, isomyristyl (meth) acrylate, isovalmityl (meth) acrylate, isostearyl (meth) acrylate, nenyl (meth) acrylate, nerolidyl (meth) acrylate, farnesyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) Hydrocarbon monofunctional (meth) acrylates such as acrylate, behenyl (meth) acrylate, trans-2-hexene (meth) acrylate; alkyl group-substituted polyalkylene such as carbitol (meth) acrylate and butoxyethyl (meth) acrylate Glycol monofunctional (meth) acrylates;

  Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, bicycloheptyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentanyl di (meth) acrylate, tricyclodecyl (meth) acrylate, bicyclo Monofunctional (meth) acrylates with alicyclic structures such as pentenyl (meth) acrylate, norbornenyl (meth) acrylate, bicyclooctanyl (meth) acrylate, tricycloheptanyl (meth) acrylate, and cholesteroid skeleton-substituted (meth) acrylate Benzyl (meth) acrylate; alkyl-substituted (or unsubstituted) phenoxypolyalkylene glycol (meth) acrylates such as phenoxyethyl (meth) acrylate; Acrylic acid benzoate ester of ruxylene glycol; allyl (meth) acrylate, methallyl (meth) acrylate; glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Hydroxyl group-containing (meth) acrylates such as meth) acrylate and 3-chloro-2-hydroxyethyl (meth) acrylate; amino group-containing groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and acryloylmorpholine ( (Meth) acrylates;

  Acid group-containing (meth) acrylates such as (meth) acrylic acid; ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1, Alkylene glycol di (meth) acrylates such as 2-butylene glycol di (meth) acrylate and poly (1,2-butylene glycol) di (meth) acrylate; 1,3-butylene glycol di (meth) acrylate, 1,4 -Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9- Nonanediol di ( 1) acrylate, 1,10-decanediol di (meth) acrylate hydrocarbon diol di (meth) acrylates; 1 mol or more of ethylene oxide and / or propylene oxide and / or butylene oxide per 1 mol of neopentyl glycol Di (meth) acrylate of diol obtained by addition; pivalate ester neopentyl glycol diacrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol diacrylate;

  For example, di (meth) acrylates of modified alkylene oxides of bisphenols such as bisphenol A, F, and S, di (meth) acrylates of hydrogenated bisphenols such as bisphenol A, F, and S, bisphenol A, F, and S, etc. Di (meth) acrylates of alkylene oxide modified products of hydrogenated bisphenols, di (meth) acrylates of alkylene oxide modified products of trisphenols, di (meth) acrylates of hydrogenated trisphenols, hydrogenated trisphenols Di (meth) acrylate modified with alkylene oxide, di (meth) acrylate modified with alkylene oxide of p, p'-biphenol, di (meth) acrylate of hydrogenated p, p'-biphenol, hydrogenated biphenol Di (meta) of a modified alkylene oxide of Acrylate, di (meth) acrylate of p, p'-dihydroxybenzophenone modified alkylene oxide, dicyclopentane di (meth) acrylate such as Kayrad R684 (manufactured by Nippon Kayaku Co., Ltd.), tricyclodecane dimethylol di ( Methacrylic acid such as meth) acrylate, bisphenol fluorenedioxyhydroxy (meth) acrylate, cycloalkylene ring such as phenylene ring, cyclohexane ring, cyclodecane ring, bicycloalkylene ring such as dicyclopentane ring, dicyclopentene ring, tricyclo such as tricyclodecane ring Alkylene ring, furan ring, condensed furan ring, thiophene ring, condensed thiophene ring, pyrrole ring, condensed pyrrole ring, pyran ring, pyrone ring, quinoline ring, isoquinoline ring, azole ring, naphthalene ring, fluorene ring, triazine ring Azine ring, a 1,3-dioxolane ring, 1,3-dioxane ring, 1,4-dioxane ring, a polyfunctional (meth) acrylate compounds having spirane ring, a cyclic structure, such as a triazolone ring;

  Mono (meth) acrylate or poly (meth) acrylate of trimethylolpropane, mono (meth) acrylate or poly (meth) acrylate of glycerin, mono (meth) acrylate or poly (meth) acrylate of pentaerythritol, mono of ditrimethylolpropane (Meth) acrylate or poly (meth) acrylate, dipentaerythritol mono (meth) acrylate or poly (meth) acrylate and other triols, tetraol and hexaol mono (meth) acrylate or poly (meta ) Acrylates;

  Mono, di or tri of triol obtained by adding 1 mol or more of cyclic ether compound such as ethylene oxide and / or propylene oxide and / or butylene oxide or cyclic lactone compound such as ε-caprolactone to 1 mol of trimethylolpropane. A mono-, di- or triol obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide and / or propylene oxide and / or butylene oxide or a cyclic lactone compound such as ε-caprolactone to 1 mol of meth) acrylate or glycerin. Tri (meth) acrylate, 1 mol or more of cyclic ether compound such as ethylene oxide and / or propylene oxide and / or butylene oxide per 1 mol of pentaerythritol, or ε-caprolactone Triol mono-, di-, tri- or tetra (meth) acrylate obtained by adding a cyclic lactone compound, 1 mol or more of cyclic ether compound such as ethylene oxide and / or propylene oxide and / or butylene oxide per 1 mol of ditrimethylolpropane Or a triol mono, di, tri or tetra (meth) acrylate obtained by adding a cyclic lactone compound such as ε-caprolactone, 1 mol or more of ethylene oxide and / or propylene oxide and / or butylene per 1 mol of dipentaerythritol Triols obtained by adding cyclic ether compounds such as oxides or cyclic lactone compounds such as ε-caprolactone, or polyalcohols such as triols such as poly (meth) acrylate, tetraols, hexaols, etc. Mono (meth) acrylates or poly (meth) acrylates; 2,3-dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate, ethylene oxide modified tribromophenyl (meth) acrylate, ethylene oxide modified tetrabromo (Meth) acrylates having a bromine atom such as bisphenol A di (meth) acrylate;

  Trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, hexadecafluorononyl (meth) acrylate, hexa Fluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) Acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) ) (Meth) acrylates having a fluorine atom such as acrylate, 3- (perfluoro-8-methyldecyl) -2-hydroxypropyl (meth) acrylate; (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (Meth) acrylamides such as alkyl ether compounds of hydroxymethyl (meth) acrylamide; maleimides such as N-methylmaleimide, N-phenylmaleimide, N, N′-m-phenylenebismaleimide;

  Maleic acid esters such as dimethyl maleate, diethyl maleate, diisopropyl maleate, dibutyl maleate, di (2-ethylhexyl) maleate, monomethyl maleate, monobutyl maleate, mono (2-ethylhexyl) maleate; dimethyl fumarate , Diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, diisobutyl fumarate, disec-butyl fumarate, di (2-ethylhexyl) fumarate, etc .; dimethyl itaconate, dibutyl itaconate, di (2- Ethyl hexyl) itaconate, monomethyl itaconate, monobutyl itaconate, etc .; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether Ter, 2-ethylhexyl vinyl ether, octyl vinyl ether, nonyl vinyl ether, dodecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, butoxyethyl vinyl ether, cetyl vinyl ether, phenoxyethyl vinyl ether, allyl vinyl ether, methallyl vinyl ether, glycidyl vinyl ether, 2-chloroethyl vinyl ether, Monovinyl ethers such as cyclohexyl vinyl ether, ethylene glycol monovinyl ether or divinyl ether, triethylene glycol divinyl ether “RAPYCURE DVE-3 manufactured by ISP”, polyethylene glycol monovinyl ether or divinyl ether, propylene glycol monovinyl ether or divinyl ether , Polypropylene glycol monovinyl ether or divinyl ether, 1,3-butylene glycol monovinyl ether or divinyl ether, tetramethylene glycol monovinyl ether or divinyl ether, hexamethylene glycol monovinyl ether or divinyl ether, neopentyl glycol monovinyl ether or divinyl ether, trimethylol Propane monovinyl ether, divinyl ether or trivinyl ether, glycerin monovinyl ether, divinyl ether or trivinyl ether, pentaerythritol monovinyl ether, divinyl ether or trivinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol divinyl ether “I.S. . P. "Rapicure CHVE" manufactured by the company, 1 mol or more of ethylene oxide and / or propylene oxide and / or butylene oxide adduct monovinyl ether or divinyl ether per 1 mol of neopentyl glycol, 1 mol or more of ethylene oxide per 1 mol of trimethyl propane And / or monovinyl ether, divinyl ether or trivinyl ether of propylene oxide and / or butylene oxide adduct, 1 mol or more of ethylene oxide and / or propylene oxide and / or butylene oxide adduct monovinyl ether, divinyl ether per mol of bisphenol A Vinyl ethers such as

  Allyl compounds such as diallyl phthalate and triallyl cyanurate; styrene, chlorostyrene, α-methylstyrene, divinylbenzene; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octylate, vinyl caprate, vinyl laurate, vinyl myristate , Vinyl stearates, vinyl adipates, vinyl (meth) acrylates, vinyl crotonates, vinyl sorbates, vinyl benzoates, vinyl cinnamates, etc .; acrylonitrile; limonene, cyclohexene; 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, N-vinyl pyrrolidone; reaction product of 1 mol of 2-hydroxyethyl (meth) acrylate and 1 mol of phenyl isocyanate, 1 mol of 2-hydroxyethyl (meth) acrylate and n- There are reaction products of chill isocyanate mole.

  In the present invention, isobornyl acrylate (IBA) and N-vinyl pyrrolidone (N-VP), which are fast-curing and have a low shrinkage, are particularly preferable among the reactive diluents described above.

  Examples of the polymerization inhibitor used in the present invention include paramethoxyphenol (MQ), hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,5-di-tert-butyl-p-benzoquinone, nitrosobenzene, tert- Examples thereof include butyl hydroquinone, pyrogallol, phenothiazine, N, N-di-sec-butyl-p-phenylenediamine, N-nitrosophenylhydroxyamine ammonium salt, tris (N-nitroso-N-phenylhydroxyamine), and aluminum salt.

  Examples of the urethanization catalyst used in the present invention include dioctyltin dilaurate (DOTDL), triethylamine, N, N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethyl-p-toluidine. , Β- (dimethylamino) propionitrile, N-methylpyrrolidone, N, N-dicyclohexylmethylamine, dimethylaminoethanol, dimethylaminoethoxyethanol, triethylenediamine, N, N, N′-trimethylaminoethylethanolamine, N , N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane-1,3-diamine, N, N, N ′, N′-tetramethylhexane-1,6 -Diamine, bis (N, N-dimethylaminoethyl) Ether, N'-cyclohexyl-N, N-dimethylformamidine, N, N'-dimethylpiperazine, trimethylpiperazine, 1,2-piperidinoethane, bis (aminopropyl) piperazine, N- (N, N'-dimethylaminoethyl ) Morpholine, bis (morpholinoethyl) ether, 1,2-dimethylimidazole, N-methylimidazole, 1,4-diamidine, diazabicyclo- [2.2.2] -octane (DABCO), 1,4-diazabicyclo [3] .3.0] -Oct-4-ene (DBN), 1,8-diazabicyclo- [4.3.0] -non-5-ene (DBN), 1,8-diazabicyclo- [5.4.0]. ] -Undec-7-ene (DBU) and its salts such as phenol salts, octylates, N, N, N ', N "-penta Methyldiethylenetriamine, N, N, N ′, N ″ -pentamethyldipropylenetriamine, tetramethylguanidine, N-cyclohexyl-N ′, N ′, N ″, N ″ -tetramethylguanidine, N-methyl-N ′ -(2-dimethylaminoethyl) piperazine, 1,5,7-triazabicyclo- [4.4.0] -dec-5-ene, 1,4,7,0,10-hexamethyltriethylenetetramine 1,3,5-tris (N, N-dimethylpropyl) -hexahydro-1,3,5-triazine, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate , Dibutyltin dimaleate, dioctyltin mercaptide, dioctyltin thiocarboxylate, 2-ethyl Sun lead, tetraalkyl titanates, and the like such as tetrabutyl titanate (TBT).

  As a photopolymerization initiator used in the present invention, a bond is cleaved in a molecule by light, and an intramolecular bond cleavage type initiator that generates an active species for polymerization initiation (radical active species) reacts between molecules. There is an intermolecular hydrogen abstraction type initiator that generates an active species for polymerization initiation (radical active species).

  Examples of the intramolecular bond cleavage type initiator include, for example, diethoxyacetophenone (FIRSTCURE DEAP manufactured by First Chemical Co., USA), 1- {4- (2-hydroxyethoxy) phenyl} -2-hydroxydi-2-methyl-1- Propan-1-one {Irgacure 2959 manufactured by Ciba Specialty Chemicals (hereinafter abbreviated as CSC), 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one (Irgacure 907 manufactured by CSC) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by CSC Irgacure 369), 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by CSC) Darocur 1173), 1-hydroxycyclohexyl phenyl ketone (CS Irgacure 184), 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Darocur 1116, CSC), benzyldimethyl ketal (Irgacure 651, CSC), 1-hydroxycyclohexyl A mixture of phenylketone and benzophenone (Irgacure 500 manufactured by CSC), 4- (2-acryloyl-oxyethoxy) phenyl-2-hydroxy-2-propylketone (ZLI3331 manufactured by CSC), oligo {2-hydroxy-2- Acetophenone series such as methyl-1- “4- (1-methylvinyl) phenyl” propanone, molecular weight 2000 or less} (Esacure KIP100 manufactured by Ramberty)

  Benzoin, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole, benzoin isopropyl ether, benzoin isobutyl ether, and other benzoin series, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF) (Lucirin TPO, LR8953), 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (Lucirin TPO-L manufactured by BASF), bisacylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropane-1- Mixture with ON (CGI 1700 manufactured by CSC), Irgacure 819 manufactured by CSC, CGI403 manufactured by CSC, acyl phosphine oxides, benzyl, methylphenylglyoxyester, 3,3 ′, 4,4 - there is tetra (t-butyl peroxy carbonyl) benzophenone (manufactured by NOF Corporation BTTB), and the like.

  Examples of intermolecular hydrogen abstraction initiators include benzophenone (Kayacure BP-100, manufactured by Nippon Kayaku Co., Ltd.), methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4 '-Methyl-diphenyl sulfide (Kayacure BMS manufactured by Nippon Kayaku Co., Ltd.), acrylated benzophenone (Ubekryl P36 manufactured by UCB), mixture of 2,4,6-trimethylbenzophenone and 4-methylnzophenone (Esacure TZT manufactured by Ramberty ) 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, benzophenone series such as 3,3′-dimethyl-4-methoxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioki Thioxanthones such as N, 2,4-dichlorothioxanthone, Michler's ketone, aminobenzophenones such as 4,4'-diethylaminobenzophenone, 10-butyl-2-chloroacridone, 2-ethylanthraquinone (Kayacure, Nippon Kayaku Co., Ltd.) 2-EAQ), 9,10-phenanthrenequinone, camphorquinone, and the like.

  In addition, solid photoinitiator is previously 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- “4- (1-methylvinyl)”. When mixed with a liquid photoinitiator such as “phenyl” propanone, molecular weight of 2000 or less}, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, benzophenone, etc., it is effective in improving workability.

  Moreover, in this invention, in order to improve sclerosis | hardenability, it is preferable to use a photosensitizer together with said photoinitiator. Examples of such a photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylaminobenzoate. There are amines such as isoamyl acid (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), ethyl (2-dimethylamino) benzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, etc. .

  In the present invention, among the above-mentioned photopolymerization initiators, acylphosphine oxides having high curability are preferable, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO) is particularly preferable.

  Other additives used in the present invention include saturated compounds having no unsaturated double bond, pigments / dyes, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, non-reactive compounds, chains Transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, adhesion improvers such as inorganic and organic fillers, coupling agents, thermal stabilizers, antibacterial and antifungal agents, flame retardants, matting agents, antifoaming agents Agent, leveling agent, wetting / dispersing agent, anti-settling agent, thickener / anti-sagging agent, anti-coloring agent, emulsifier, anti-slip / scratch agent, anti-skinning agent, drying agent, antifouling agent, antistatic agent Further, a conductive agent (electrostatic aid) or the like may be added. An organic solvent may be added as necessary. In this case, it is preferable to remove the organic solvent before curing with active energy rays. Further, a silicone compound may be added in order to increase the slipping property of the cured coating film.

  Saturated compounds having no unsaturated double bond include liquid or solid oligomers and resins having low or no radical reactivity, such as liquid polybutadiene, liquid polybutadiene derivatives, liquid chloroprene, liquid polypentadiene, dicyclohexane. Pentadiene derivative, saturated polyester oligomer, polyether oligomer, liquid polyamide, polyisocyanate oligomer, xylene resin, ketone resin, petroleum resin, fluorine-based oligomer / resin, silicon-based oligomer / resin, polysulfide-based oligomer / resin, nitrocellulose, benzylcellulose , Cellulose derivatives such as acetylcellulose and acetylbutylcellulose, vinyl chloride / vinyl acetate copolymer resins, other vinyl chloride copolymer resins, vinylidene chloride or its copolymer Resins, racks or copal resins, fatty acid-modified urethane resins, lacquers, oil-modified phenolic resins such as oxidative polymerization resins, alkyd resins, amino-alkyd resins, epoxy resins / fatty acid esters, epoxy resins, polyurethane resins, acrylic resins, acrylic resins・ There are polyurethane and vinyl resin. These non-reactive oligomers and resins may have functional groups such as halogen, epoxy group, amino group, hydroxyl group, thiol group, amide group, carboxyl group, phosphoric acid group, and sulfonic acid group.

  As pigments and dyes, oil-soluble dyes are suitable because of their excellent solubility, but any pigments and dyes may be used. After dispersing the pigment in the resin component, it is preferable to remove a large particle size with a filter. For secondary coatings, UV inks, and materials for coating outer layers, resin compositions that do not contain pigments with a particle size of 5 μm or more are effective without affecting the transmission loss of the coated optical fiber. is there.

  Antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, stearyl propionate-β- (3,5-di-t-butyl-4-hydroxyphenyl), n- Octadecyl-3- (4-hydroxy-3 ', 5'-di-t-butylphenyl) pyropionate, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzyl malonate, 2,4,6 -Tri-t-butylphenol, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'- Butylidene-bis (3-methyl-6-tert-butylphenol), NN-bis-3- (3 ′, 5 ′)-di-tert-butyl-4-hydroxyphenyl) propionyl Xamethylenediamine, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis- [3- (3-t-butyl-5- Methyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [1, 1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxyethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2 , 2'-ethylidene-bis- (2,4-di-t-butylphenol),

  1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl- 4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,1,3-tris- (2-methyl-4 -Hydroxy-5-t-butylphenylbutane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-di-t-butyl-4-hydroxybenzyl) benzene, tris (3 , 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ′, 5′-di-tert-butyl-4′-hydroxyhydro-cinnamoyloxyl) ethyl] isocyanurate, Lith- (4-t-butyl-2,6-di-methyl-3-hydroxybenzyl) isocyanurate, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxy- Phenyl) propionate] -phenolic antioxidants such as methane, sulfur antioxidants such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, triphenyl phosphite, phosphorus Diphenyl isdecyl acid, tris (nonylphenyl) phosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-tritridecyl) phosphite, cyclic neopentanetetrayl bisphosphate ( There are phosphorus antioxidants such as octadecyl, etc. Among them, phenolic antioxidants prevent decomposition at high temperatures. Since the strong use, it is particularly effective.

  Asahi Denka Co., Ltd. ADK STAB AO-50, AO-60, AO-75, AO-80, Ciba Specialty Chemicals Irganox 1222 are effective. The blending amount of the antioxidant is preferably 0.1 to 10% by mass in the resin composition of the present invention. If it is 0.1% by mass or less, the antioxidant function is weak, and if it is 10% by mass or more, the curability is greatly reduced.

  Examples of ultraviolet absorbers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetradihydroxybenzophenone, Benzophenone-based UV absorbers such as 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone, 2 (2'-hydroxy -5-methylphenyl) Zotriazole, 2 (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2 (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2 (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy- 3 ', 5'-dibutylphenyl) -6-chlorobenzotriazole and other benzotriazole ultraviolet absorbers,

  Phenylsalicylate UV absorbers such as phenylsalicylate, para-t-butylphenylsalicylate, para-octylphenylsalicylate, ethyl-2-cyano-3,3-diphenylacrylate, methyl-2-carbomethoxy-3 Cyanoacrylate ultraviolet absorbers such as-(paramethoxy) -acrylate, nickel- [2,2'-thiobis- (4-t-octyl) -phenolate] -n-butylamine, nickel dibutyldithiocarbamate, cobalt dicyclohexyldithiophosphate Metal complex ultraviolet absorbers such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-octyloxyfunol, 2- (4 6-diphenyl) -1,3,5-triazine- -Yl) -5-hexyloxyphenol and other triazine UV absorbers, 2-ethoxy-2'-ethyl oxanilic acid bisanilide and other oxanilide UV absorbers, cerium oxide and other inorganic UV absorbers, resorcinol -Other UV absorbers such as monobenzoate, 2'-ethyl-hexyl-2-cyan, 3-phenylcinnamate.

  In particular, a benzotriazole type is preferable. Chinubin P, 234, 320, 326, 327, 328, 329, and 213 manufactured by Ciba Specialty Chemicals are effective. The addition amount of the ultraviolet absorber is 0.1 to 10 parts by mass, preferably 0.5 to 8 parts by mass in the resin composition of the present invention, since the curability is not lowered and the ultraviolet absorption effect is obtained. preferable.

  Examples of the light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidyl) separate, bis (2,2,6,6-tetramethyl-4-piperidyl) separate, 2- (3 , 5-di-t-butyl-4-hydroxybenzel) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), dimethyl succinate-1- (2 -Hydroxylethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine complex, poly [16- (1,1,3,3-tetramethylbutyl) imino-1.3.5- Triazine-2,4-diyl], [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] , 1- [2- [3- (3,5-di- -Butyl-4-hydroxyphenyl) propionyloxy) ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine (Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethyl -4-piperidyl / β, β, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecacy] diethyl] diethyl 1-1,2,3,4 -Hindered amine light stability such as butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate There is.

  Ciba Specialty Chemicals Tinuvin 144, 292, 622LD, LS770, Asahi Denka ADEKA STAB LA-52, LA-57, LA-62, LA-67, LA-63, LA-68, LA-77 are preferred. . One kind of hindered amine light stabilizer may be used, or two or more kinds may be used in combination. The blending amount of the light stabilizer is 0.1 to 10 parts by mass, preferably 0.5 to 8 parts by mass in the resin composition of the present invention, and the light stabilizing effect is obtained without deteriorating the curability. Therefore, it is preferable.

  Examples of plasticizers include adipic acid compounds such as di- (2-ethylhexyl) adipate and diisodecyl adipate, azelaic acid compounds such as azelaic acid di (2-ethylhexyl), diethyl phthalate, dibutyl phthalate, and phthalates Phthalic acid compounds such as dihexyl acid, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, di-n-heptyl phthalate, diisodecyl phthalate, butyl phthalyl butyl glycolate, dioctyl sebacate, etc. Sebacic acid compounds, trimellitic acid compounds such as trimellitic acid tris- (2-ethylhexyl), phosphoric acid compounds such as triphenyl phosphate and tricresyl phosphate, epoxidized soybean oil, medium molecular weight polyester, chlorinated There are paraffin and the like.

  Non-reactive compounds include n-docosane, 2,6,10,14-tetramethylpentadecane, eicosane, α-farnesene, squalane, squalene, n-dodecylcyclohexane, stearylcyclohexane, n-dodecylbenzene, o-terphenyl. And m-terphenyl.

  Examples of chain transfer agents include dodecyl mercaptan, ethyl mercaptoacetate, butanediol dithiopropionate, pentaerythritol tetrakis (β-thiopropionate), and triethylene glycol dimercaptan. The amount of the chain transfer agent in the resin composition of the present invention is in the range of 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, without lowering the curability and reducing the tensile modulus. Among chain transfer agents, mercapto-based silane coupling agents are required to have low tensile elastic modulus and high adhesion to glass because they have an adhesion strength with glass and a chain transfer function. It is effective when added to the resin composition for the primary coating material. As the mercapto silane coupling agent, A-189 and AZ-6129 manufactured by Nihon Unicar Company are preferable.

  As the thermal polymerization initiator, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4 ′ -Peroxides such as di (t-butylperoxy) valerate and dicumyl peroxide, azo compounds such as 7-azobisisobutylnitrile, tetramethylthiuram disulfide and the like. The compounding quantity of a thermal-polymerization initiator is 0.05-5 mass parts in the resin composition of this invention, Preferably it is 0.1-2 mass parts. Addition within this range is effective without causing a decrease in coating strength in the environmental test. If the amount is less than 0.1 parts by mass, the effect is not achieved. A thermal polymerization initiator having a half-life of 70 ° C. to 100 ° C. may be selected. If it is less than 70 ° C, the standing stability is poor, and if it is 100 ° C, the curability is poor. The thermal polymerization initiator is decomposed by infrared light simultaneously irradiated from the lamp when irradiated with ultraviolet rays to generate polymerization initiation radicals. Or it is good to take the process (for example, infrared irradiation process) of heating a coating film before ultraviolet irradiation or after irradiation, and to decompose and generate a polymerization initiation radical.

  Examples of anaerobic polymerization initiators include cumene hydroperoxide and t-butyl hydroperoxide. Examples of the polymerization accelerator for anaerobic polymerization include dibenzenesulfonamide, tertiary amine, 1,2,3,4-tetrahydroquinoline and the like. The amount of the anaerobic polymerization initiator used is 0.05 to 5% by mass in the resin composition. Especially preferably, it is 0.1-3 mass%. The amount of the anaerobic polymerization accelerator used is 0.1 to 10% by mass in the resin composition. Most preferably, it is 0.5-5 mass%.

  Inorganic fillers and organic fillers are generally used to improve mechanical properties such as strength, cushioning properties, and slipperiness.

  Inorganic fillers include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, glass, mica, sulfuric acid There are barium, alumina white, zeolite, silica balloon, glass balloon and the like. By adding and reacting silane coupling agent, titanate coupling agent, aluminum coupling agent, zirconate coupling agent, etc. to inorganic filler, halogen group, epoxy group, amino group, hydroxyl group, thiol You may give functional groups, such as a group, an amide group, a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

  Organic fillers include benzoguanamine resin, melamine resin, benzoguanamine / melamine resin, urea resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, crosslinked polystyrene, polydivinylbenzene Styrene / divinylbenzene copolymer, acrylic copolymer, cross-linked acrylic resin, polymethyl methacrylate resin, vinylidene chloride resin, fluororesin, nylon 12, nylon 11, nylon 6/66, phenol resin, epoxy resin, urethane resin, There are polyimide resins and the like. The organic filler may have a functional group such as a halogen group, an epoxy group, an amino group, a hydroxyl group, a thiol group, an amide group, a carboxyl group, a phosphoric acid group, or a sulfonic acid group.

  When the inorganic filler / organic filler is added to the resin composition for the outermost layer, it is effective in improving workability such as slipperiness. When connecting an optical fiber in a state where a resin composition coating layer containing an inorganic filler and an organic filler is coated, the particle diameter of the inorganic filler and the organic filler contained is controlled to 10 μm or less, preferably 5 μm or less, It is important to be able to connect stably. When the optical fiber is connected in a state where the resin composition coating layer containing the inorganic filler and the organic filler is peeled off, a substantially smooth coated surface can be obtained if the particle diameter is smaller than the coating thickness related to the particle diameter. When it is desired to provide unevenness on the coated surface, an inorganic filler or an organic filler having a particle size larger than the coating thickness may be used.

  Coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-amino. Silane coupling agents having amino groups such as propyltrimethoxysilane and hexamethylsilazane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4 -Epoxycyclohexyl) silane coupling agent having an epoxy group such as ethyltriethoxysilane,

  Silane coupling agents having mercapto groups such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, and silane coupling agents having halogen groups such as γ-chloropropyltrimethoxysilane, γ-methacryloxypropyl Silane coupling agents having a methacryloxy group such as trimethoxysilane γ-methacryloxypropylmethyldimethoxysilane, silane coupling agents having an isocyanato group such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, etc. Silane coupling agent, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyldimethacrylisostearoyl titanate, Titanate couplings such as propyl diacrylic isostearoyl titanate, isopropyl triisostearoyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltricumylphenyl titanate Agents; aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate; and zirconium-based coupling agents such as acetylacetone / zirconium complex. In particular, a silane coupling agent is effective.

  In the resin composition of the present invention, the blending amount of the coupling agent is in the range of 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and has an effect of increasing the adhesion to the base. On the other hand, if the amount is large, the adhesion decreases. When a coupling agent is added, in addition to the effect of increasing the adhesion to glass, there is an effect of increasing the adhesion with the UV curable resin cured layer. Resin containing a silane coupling agent having an amino group, a silane coupling agent having an epoxy group, and a silane coupling agent having a mercapto group on a cured coating film irradiated with ultraviolet rays in an atmosphere having an oxygen concentration of 1000 ppm or more. When a coating film of the composition is formed, the adhesion is high. When a silane coupling agent having an isocyanato group is added, adhesion is high even for a coating film cured in an atmosphere having an oxygen concentration of 1000 ppm or less.

  Examples of the flame retardant include phosphate esters such as tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris phosphate (2 , 3-dibromopropyl), halogenated phosphates such as 2,3-dibromopropyl-2,3-chloropropyl phosphate, chlorinated paraffin, perchloropentacyclodecane, hexabromocyclododecane, hexabromobenzene, Low molecular weight halides such as tetrabromobisphenol A derivatives, decabromobisphenyl ether, high molecular weight halogens such as chlorinated polyethylene, brominated polycarbonate, brominated epoxy, brominated polystyrene, brominated polybenzyl acrylate, brominated polyphenylene oxide Chemicals Of brominated epoxy, brominated phenol, brominated phenyl (meth) acrylate, brominated styrene, tetrabromophthalic anhydride, brominated diallyl phthalate, chloroendoic acid and other reactive halides, phosphorus-containing polyols and phosphorus-containing polyols Polyurethanes, antimony trioxide, sodium antimonate, tin oxide, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, zinc borate, molybdenum, zinc stannate and other inorganic substances, melamine, urea, brominated There are nitrogen compounds such as guanamine and phosphazene compounds, silicone powder, expandable graphite and the like. Although it may be used alone, the effect increases when used in combination. Combinations of halogen and antimony, halogen and phosphorus, and phosphorus and nitrogen are effective.

  Moreover, when an additive is difficult to mix with the resin composition of this invention, a solvent is used as needed. Solvents used include aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol and isopropyl alcohol, esters such as ethyl acetate, ethicello, methicello and cellosolve acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. And the like. These solvents may be used alone or in combination of two or more.

  As the silicone compound, dimethylpolysiloxane (silicone) and modified silicone are effective. As dimethylpolysiloxane, a viscosity of 10 cSt to 1 million cSt of KF96 manufactured by Shin-Etsu Chemical Co., Ltd. is effective. As the modified silicone, those obtained by introducing an organic group other than a methyl group into the terminal and / or side chain of dimethylpolysiloxane (silicone) are preferable. As the organic group to be introduced, carboxyl group, (meth) acryl group, alkoxy (meth) acryl group, glycidyl group, mercapto group, polyether group, phenyl group, alkyl group, higher fatty acid ester group, alkoxy group, fluorine-substituted alkyl Group, fluorine-substituted alkoxy group, amino group, hydroxyl group and the like are preferable. In particular, the modified silicone introduced with a long-chain polyether group, an alkyl group, a higher fatty acid ester group, an alkoxy group, a fluorine-substituted alkyl group, and a fluorine-substituted alkoxy group has good compatibility with the resin composition of the present invention and is excellent. Surface properties can be obtained. In particular, glycidyl group, (meth) acrylic group, higher fatty acid ester group, alkylene oxide group (especially copolymer group of ethylene oxide and propylene oxide) have good compatibility with the resin composition of the present invention, and excellent surface properties. Is preferable. The organic group to be introduced may be used alone or in combination.

  The compounding quantity of a silicone compound is 0.05-40 mass parts in the resin composition of this invention, Preferably the range of 0.1-30 mass parts is good. If the amount is small, there is no effect of improving the slipperiness. Although only one type of silicone compound may be used, a combination of two or more types is effective.

The resin composition for photocurable coating of this invention can be manufactured using the following method, for example.
That is, (a) a step of obtaining a mixture of the first polyurethane compound (A) and the second polyurethane compound (B), (b) a step of obtaining the third polyurethane compound (C), and (c) step (b). And a step of mixing the mixture of the first polyurethane compound (A) and the second polyurethane compound (B) obtained in step 3 and the third polyurethane compound (C) obtained in the step (b). It can be manufactured by a method.
In the manufacturing method described above, the step (b) and the step (b) may be any one before the step (c) and are not particularly limited.

  In the above production method, as the step (I), for example, a polymerization inhibitor, a reactive diluent and an organic diisocyanate are mixed and reacted with a radical polymerizable group-free monool compound, and then a urethanization catalyst and A step of obtaining a mixture of the first polyurethane compound (A) and the second polyurethane compound (B) by adding and reacting with the radical polymerizable group-containing monol compound is exemplified.

  In addition, as the step (b), for example, a polymerization inhibitor, a reactive diluent, and a polycarbonate diol are mixed and reacted with an organic diisocyanate, and then a urethanization catalyst and a radical polymerizable group-containing monol compound are added. Then, the step of obtaining the third polyurethane compound (C) by reacting with each other can be mentioned.

  Further, as the step (c), for example, a mixture of the first polyurethane compound (A) and the second polyurethane compound (B) obtained in the step (b), and the step obtained in the step (b) The process of mixing a 3rd polyurethane compound (C), a reactive diluent, and a photoinitiator is mentioned.

Furthermore, the manufacturing method of the resin composition for photocurable coatings of this invention is not limited to the manufacturing method mentioned above, For example, it can also manufacture with the following method.
(D) a step of obtaining the third polyurethane compound (C) in the same manner as in the step (b) described above, and (e) an organic diisocyanate and a radical polymerizable group-free monool compound in the third polyurethane compound (C). Then, the urethanization catalyst and the radical polymerizable group-containing monol compound are added and reacted to produce the first polyurethane compound (A) and the second polyurethane compound (B), Furthermore, it can manufacture by the method which has the process of adding and mixing a reactive diluent and a photoinitiator.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
First, the raw materials used in Examples and Comparative Examples are shown below.
Polyol-1:
Polycarbonate diol polyol-2 having a number average molecular weight of 1,200 obtained from a mixed diol of 3-methyl-1,5-pentanediol / 1,6-hexanediol = 9/1 (molar ratio) and diethyl carbonate:
Number average molecular weight 1,200 poly (oxytetramethylene) diol polyol-3:
Polyester diol TDI having a number average molecular weight of 1,200 obtained from 3-methyl-1,5-pentanediol and adipic acid:
2,4-Tolylene diisocyanate IPDI:
Isophorone diisocyanate HPA:
2-hydroxypropyl acrylate IPA:
Isopropyl alcohol IBA:
Isobornyl acrylate N-VP:
N-Vinylpyrrolidone MQ:
Paramethoxyphenol DOTDL:
Dioctyltin dilaurate TPO:
2.4.6-Trimethylbenzoyldiphenylphosphine oxide

Next, the polymeric polymerizable polyurethane compounds of Synthesis Examples 1 to 5 shown in Table 1 described later were produced by the method shown below with the formulation shown in Table 1.
Synthesis example 1 (PR-1)
[Production of polymer polymerizable polyurethane compound (third polyurethane compound)]
A 1-liter flask equipped with a stirrer, thermometer, nitrogen seal tube, and condenser was replaced with nitrogen, and 0.05 g of MQ, 200 g of IBA, and 603.1 g of polyol-1 were charged and stirred at 50 ° C. for 1 hour. And mixed uniformly. Next, 130.1 g of TDI was charged and reacted at 80 ° C. for 3 hours with stirring. Thereafter, 0.05 g of DOTDL was charged, and 66.8 g of HPA was gradually added dropwise and reacted while stirring. After completion of the dropwise addition of HPA, the mixture was further reacted for 6 hours and reacted until the peak of the isocyanate group of FT-IR disappeared to obtain a polymer polymerizable polyurethane compound liquid PR-1. As shown in FIG. 1, the PR-1 FT-IR chart has allophanate group peaks (3340 cm ⁻¹ : N—H stretching) and isocyanurate group peaks (1690 cm ⁻¹ : CO vibration). ) Was not confirmed.

Synthesis Example 2 (LC-1)
[Production of low molecular weight polymerizable urethane compounds (first and second polyurethane compounds)]
The same apparatus as in Synthesis Example 1 was purged with nitrogen, and 0.05 g of MQ, 200 g of IBA, and 350.2 g of TDI were charged and stirred to mix uniformly. Subsequently, the internal temperature was set to 80 ° C., and 72.5 g of IPA was gradually dropped to react. After completion of the dropwise addition of IPA, the reaction was further continued for 2 hours. Next, 0.05 g of DOTDL was charged, and 377.3 g of HPA was gradually added dropwise to react. After completion of the dropwise addition of HPA, the reaction was further continued for 6 hours, and it was confirmed that the peak of the isocyanate group of FT-IR had disappeared. Thus, a low molecular weight polymerizable urethane compound liquid LC-1 was obtained. In addition, as shown in FIG. 2, neither an allophanate group nor an isocyanurate group was confirmed in the FT-IR chart of LC-1.

Synthesis Example 3 (LC-2)
[Production of low molecular weight polymerizable urethane compounds (first and second polyurethane compounds)]
The same apparatus as in Synthesis Example 1 was purged with nitrogen, and 0.05 g of MQ, 200 g of IBA, and 398.7 g of IPDI were charged and stirred to mix uniformly. Subsequently, the internal temperature was set to 80 ° C., and 64.6 g of IPA was gradually dropped to react. After completion of the dropwise addition of IPA, the reaction was further continued for 2 hours. Next, 0.05 g of DOTDL was charged, and 336.7 g of HPA was gradually added dropwise to react. After completion of the dropwise addition of HPA, the reaction was further continued for 6 hours, and it was confirmed that the peak of the isocyanate group of FT-IR had disappeared. Thus, a low molecular weight polymerizable urethane compound liquid LC-2 was obtained. In the FT-IR chart, neither an allophanate group nor an isocyanurate group was confirmed.

Synthesis Example 4 (LC-3)
[Production of low molecular weight polymerizable urethane compound (second polyurethane compound)]
The same apparatus as in Synthesis Example 1 was purged with nitrogen, and 0.05 g of MQ, 200 g of IBA, and 311.2 g of TDI were charged and stirred to mix uniformly. Subsequently, the internal temperature was set to 80 ° C., 0.05 g of DOTDL was charged next, and 488.8 g of HPA was gradually added dropwise to react. After completion of the dropwise addition of HPA, the reaction was further continued for 6 hours, and it was confirmed that the peak of the isocyanate group of FT-IR had disappeared. Thus, a low molecular weight polymerizable urethane compound liquid LC-3 was obtained. In the FT-IR chart, neither an allophanate group nor an isocyanurate group was confirmed.

Synthesis Example 5 (LC-4)
The same apparatus as in Synthesis Example 1 was purged with nitrogen, and 0.05 g of MQ, 200 g of IBA, and 464.0 g of TDI were charged and stirred to mix uniformly. Subsequently, the internal temperature was set to 80 ° C., and 0.05 g of DOTDL was then added, and then 336.0 g of IPA was gradually dropped to react. After completion of the dropwise addition of IPA, the reaction was further continued for 2 hours, and it was confirmed that the peak of the isocyanate group of FT-IR had disappeared. Thus, a low molecular polymerizable urethane compound liquid LC-4 was obtained. In the FT-IR chart, neither an allophanate group nor an isocyanurate group was confirmed.

[Preparation and Evaluation of Photocurable Coating Resin Composition-1]
Next, it manufactured by mixing the resin composition for photocurable coatings (CR-1 to 4) of Examples 1-2 and Comparative Examples 1-2 shown in Table 2 to be described later with the formulation shown in Table 2. Evaluation was made by the method described later. The results are shown in Table 2.
In addition, as shown in FIG. 3, neither an allophanate group nor an isocyanurate group was confirmed in the FT-IR chart of CR-1.

Number average molecular weight measurement, composition ratio analysis The number average molecular weight of the polymer polymerizable polyurethane compound and the urethane component composition ratio of the photocurable coating resin composition were analyzed using GPC (gel permeation chromatography). The measurement conditions are shown below.
GPC measurement conditions Apparatus: Tosoh HLC-8220
Column: Two TSKgel G3000H _XL
Series piping with two TSKgel G2000H _XL Fluid medium: THF (tetrahydrofuran)
Flow rate: 1 ml / min
Measurement temperature: 40 ° C
Detector: RI detector Injection volume: 100 μl
* Calculated as relative molecular weight with polystyrene

Physical property evaluation method Normal stress:
Using a rheometer, shear stress is measured while changing the shear rate, and this is plotted on a graph to create a shear rate / shear stress curve. The stress was evaluated just before the yield point.
○: No increase in stress was confirmed immediately before the yield point.
Δ: Some increase in stress is confirmed immediately before the yield point.
X: A significant increase in stress is confirmed immediately before the yield point.
Tensile strength, elongation, Young's modulus:
Each resin composition for photocurable coating is apply | coated to a glass plate so that it may become 200 micrometers in wet. Thereafter, the coating is formed by curing at a dose of 1,000 mJ / cm ² using a metal halide lamp in a nitrogen atmosphere. Thereafter, the film was peeled off from the glass plate, and the tensile strength, elongation and Young's modulus at a measurement temperature of 23 ° C. were measured according to JIS K7127 (1989).
High temperature Young's modulus retention:
The Young's modulus at a measurement temperature of 60 ° C. was measured according to JIS K7127 (1989), and the ratio to the Young's modulus at a measurement temperature of 23 ° C. (60 ° C. Young's modulus / 23 ° C. Young's modulus) was calculated and evaluated.
○: Young's modulus retention is 40% or more Δ: Young's modulus retention is 10% or more and less than 40% ×: Young's modulus retention is less than 10%

From Table 2, the photocurable coating resin compositions of the examples are good even if the raw material organic diisocyanate of the polymerizable low molecular weight urethane compound or the composition ratio of the polymerizable high molecular weight polyurethane compound and the polymerizable low molecular weight urethane compound is changed. The physical properties were shown.
On the other hand, since Comparative Example 1 has both terminal polymerizable low molecular weight urethane compound (second polyurethane compound (B)), but one terminal polymerizable low molecular weight urethane compound (first polyurethane compound (A)) does not exist, Insufficient normal stress improvement and high cross-linking density of the coating, it was hard but lacked flexibility.
Moreover, since the comparative example 2 does not have both terminal polymerizable low molecular weight urethane compound (second polyurethane compound (B)) or one terminal polymerizable low molecular weight urethane compound (first polyurethane compound (A)), normal stress Evaluation was the lowest, and physical properties other than elongation were insufficient.

[Preparation and Evaluation of Photocurable Coating Resin Composition-2]
Next, the photocurable coating resin compositions of Examples 3 to 6 shown in Table 3 to be described later were produced by the method shown below with the formulation shown in Table 3, and evaluated in the same manner as in Evaluation-1 described above. . The results are shown in Table 3.
Examples 3-6
The same apparatus as in Synthesis Example 1 was purged with nitrogen, charged with 0.05 g of MQ, 350 g of IBA, and 263.9 g of polyol-1 and stirred at 50 ° C. for 1 hour, and mixed uniformly. Next, 56.9 g of TDI was charged and reacted at 80 ° C. for 3 hours with stirring. Thereafter, 29.2 g of HPA and 0.05 g of DOTDL were charged, and the mixture was reacted with stirring at 80 ° C. until the peak of the isocyanate group of FT-IR disappeared (first-stage reaction).
Next, 87.6 g of TDI was charged and stirred to mix uniformly. Subsequently, the internal temperature was set to 80 ° C., and 18.0 g of IPA was gradually added dropwise to react. After completion of the dropwise addition of IPA, the reaction was further continued for 2 hours. Next, 0.05 g of DOTDL was charged, and 94.4 g of HPA was gradually added dropwise to react. After completion of the dropwise addition of HPA, the reaction was further continued for 6 hours (second stage reaction).
Then, after confirming that the peak of the isocyanate group of FT-IR disappeared, 150 g of N-VP and 10 g of TPO were charged and mixed and stirred (final preparation). Resin composition for photocurable coating CR-5 ~ 7 were prepared and evaluated. The results are shown in Table 3. In the CR-5 to FT-IR charts, allophanate groups and isocyanurate groups were not confirmed.

Example 6
A resin composition CR-8 for photocurable coating was prepared and evaluated using the raw materials shown in Table 3 using the same apparatus and the same procedure as in Synthesis Example 1. The results are shown in Table 3. Allophanate groups and isocyanurate groups were not confirmed in the FT-IR chart of CR-8.

  From Table 3, the photocurable coating resin compositions of the examples showed good physical properties even when the raw material polymer polyol of the polymerizable polymer polyurethane compound was changed or the organic diisocyanate in the second stage reaction was changed. .

[Peak qualitative]
In order to qualify the GPC peak in the resin composition for photocurable coating, GPC measurement was performed on PR-1, LC-1, 3, and 4. The results are shown in Table 4 below.

  In Table 4, the peak of LC-3 is a complete urethanation product of TDI by HPA (both ends low molecular weight polymerizable urethane compound, TDI HPA double molar adduct) in consideration of the charged raw materials and the reaction procedure. Similarly, the peak of LC-4 is a complete urethanized product of TDI by IPA (TDI IPA 2-fold molar adduct). Therefore, the retention times of PR-1 and LC-1 (peak top time 34.2 minutes peak) are qualitatively determined as complete urethanized products of TDI by HPA in consideration of the charged raw materials and reaction procedure.

  The peak of LC-1 retention time of 34.8 minutes is a problem, but the peaks on both sides of 34.8 minutes, that is, the peaks at 34.2 minutes and 35.6 minutes, are completely urethanated by TDI HPA, respectively. It is qualified as a complete urethanized product by TDI's IPA. Moreover, it can be said that the peak of 34.8 minutes is a compound having a molecular weight between a complete urethanation product of TDI by HPA (theoretical molecular weight: 434) and a complete urethanization product of TDI by IPA (theoretical molecular weight: 294). Furthermore, FT-IR shows that LC-1 does not contain allophanate groups or isocyanurate groups. In consideration of the above facts, the charged raw materials and the reaction procedure, the peak of 34.8 minutes is qualitatively defined as a complete urethanized product (one-end polymerizable low molecular weight urethane compound, theoretical molecular weight 364) of HPI and IPA of TDI. Become.

[Manufacture and evaluation of optical fiber cores]
UC-1, which will be described later as a resin for the primary coating layer, is applied to a glass fiber having an outer diameter of 125 ± 1 μm at a linear speed of 800 m / min so as to be 30 μm by wet, and 10 mJ / cm using a metal halide lamp in a nitrogen atmosphere. Curing with a dose of ² forms a primary coating. Next, CR-1 is applied as a resin for the secondary coating layer at a linear velocity of 800 m / min so as to be 30 μm in wet. Then, it hardened | cured with the irradiation amount of 10 mJ / cm < ² > using the metal halide lamp in nitrogen atmosphere, the secondary film was formed, and the optical fiber core wire was obtained.

Production of Resin for Primary Film (UC-1) A device similar to that in Synthesis Example 1 was replaced with nitrogen, and 0.05 g of MQ, 400 g of 2-ethylhexyl acrylate, and 477.1 g of polyol-2 were charged at 50 ° C. Stir for 1 hour and mix uniformly. Next, 99.5 g of TDI was charged and reacted at 80 ° C. for 3 hours with stirring. Thereafter, 0.05 g of DOTDL was charged, and 53.4 g of HPA was gradually added dropwise and reacted while stirring. After completion of the dropwise addition of HPA, the reaction was further continued for 6 hours until the isocyanate group peak of FT-IR disappeared. Thereafter, 10 g of TPO was charged and mixed uniformly to obtain a primary coating resin UC-1.

Table 5 shows the results of evaluating basic characteristics of the optical fiber core obtained by coating the glass fiber with the primary coating resin UC-1 and the secondary coating resin CR-1. Various loss characteristics of the optical fiber were all good results.
<Initial loss measurement>
Three 1000 m bundles of optical fiber cores were prepared, and transmission loss at wavelengths of 1.31 μm and 1.55 μm was measured using an OTDR (Optical Time Domain Refractometer) method in accordance with IEC 60793-1-40.
<Temperature characteristics test>
Three 1000m bundles of optical fiber cores were prepared and 10 cycles were performed at a temperature cycle of -60 ° C to 70 ° C (temperature change rate of 1 ° C / min) in accordance with IEC 60793-1-52. Was measured.
<Moist heat test>
Three 1000 m bundles of optical fiber cores were prepared, and the loss change of the optical fiber after 30 days was measured at 85 ° C.-85% RH in accordance with IEC 60793-1-50.
<Hot water test>
Three 1000 m bundles of optical fiber cores were prepared and immersed in warm water at 60 ° C. for 30 days, and the loss change of the optical fiber was measured.
<Jelly immersion test>
Three 1000 m bundles of optical fiber core wires were prepared, and the loss change of the optical fiber after 30 days immersion in 85 ° C. jelly was measured according to Bellcore standard GR-20. Jerry used Bufferite150.
<Curl radius>
About the produced optical fiber core wire, based on IEC60739-1-34, the curl radius was measured.

It is a FT-IR chart of PR-1. It is a FT-IR chart of LC-1. It is FT-IR chart of CR-1.

Claims (5)

Low molecular polymerizable first polyurethane compound (A) having a radical polymerizable group at one end, obtained by reacting an organic diisocyanate, a radical polymerizable group-containing monool compound, and a radical polymerizable group-free monool compound ,
A low-molecular-polymerizable second polyurethane compound (B) having radically polymerizable groups at both ends, obtained by reacting an organic diisocyanate and a radically polymerizable group-containing monool compound, and an organic diisocyanate and containing a radically polymerizable group It contains a high molecular polymerizable third polyurethane compound (C) having a radical polymerizable group at both ends, obtained by reacting a monool compound and a polycarbonate diol having a side chain alkyl group, Photocurable coating resin composition.   The composition ratio of the first polyurethane compound (A), the second polyurethane compound (B), and the third polyurethane compound (C) is the peak area ratio of gel permeation chromatography, {(A) + (B)}: (C) = 20: 80 to 60:40, The photocurable coating resin composition according to claim 1. It is a manufacturing method of the resin composition for photocurable coatings of Claim 1 or 2, Comprising:
(A) reacting an organic diisocyanate with a radical polymerizable group-free monool compound and a radical polymerizable group-containing monool compound;
Obtaining a mixture of a low-molecular polymerizable first polyurethane compound (A) having a radical polymerizable group at one end and a low-molecular polymerizable second polyurethane compound (B) having a radical polymerizable group at both ends; ,
(B) After mixing and reacting an organic diisocyanate, a radical polymerizable group-containing monool compound and a polycarbonate diol having a side chain alkyl group, a urethanization catalyst and a radical polymerizable group-containing monool compound are added. A step of obtaining a polymer-polymerizable third polyurethane compound (C) having radically polymerizable groups at both ends by reacting ;
(C) mixing a mixture of the first polyurethane compound (A) and the second polyurethane compound (B) and the third polyurethane compound (C);
And having at least a method for producing a photocurable coating resin composition. It is a manufacturing method of the resin composition for photocurable coatings of Claim 1 or 2, Comprising:
(D) An organic diisocyanate, a radical polymerizable group-containing monool compound and a polycarbonate diol having a side chain alkyl group are mixed and reacted, and then a urethanization catalyst and a radical polymerizable group-containing monool compound are added. A step of obtaining a polymer-polymerizable third polyurethane compound (C) having radically polymerizable groups at both ends by reacting ;
(E) In the presence of the third polyurethane compound (C), an organic diisocyanate, a radical polymerizable group-free monool compound and a radical polymerizable group-containing monool compound are reacted to form a radical polymerizable group at one end. A step of obtaining a low molecular weight polymerizable first polyurethane compound (A) having a low molecular weight polymerizable second polyurethane compound (B) having radical polymerizable groups at both ends;
And having at least a method for producing a photocurable coating resin composition.   An optical fiber core, a colored core, a unit, or an overcoat core, wherein the glass fiber is coated with a cured product of the photocurable coating resin composition according to claim 1.

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