JP2001131243A - Liquid radiation-curable resin composition, coating material for optical fiber and optical fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid radiation-curable resin composition excellent in adhesion to a quartz glass, rapidly stabilizing and useful for a primary coating material for an optical fiber. SOLUTION: This liquid radiation-curable resin composition comprises a (meth)acrylate-based oligomer (A), an ethylenically unsaturated compound (B), a photopolymerization initiator (C) and an organic silicon compound bearing at least two polyorganoxysilyl groups having 2-20 silicon atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid radiation-curable resin composition and an optical fiber which are preferably used as a primary or buffer coating material for an optical fiber and which provide a cured product having good adhesion to a quartz glass fiber. The present invention relates to a coating material for an optical fiber. In the present invention, the radiation curing type refers to infrared rays, visible rays, ultraviolet rays, X rays,
It is used in the sense that it is cured by irradiation of radiation such as radiation, electron beam, α-ray, β-ray, and γ-ray.

[0002]

2. Description of the Related Art There are various types of optical communication fibers such as silica glass, multi-component glass, and plastic, but in reality, their light weight, low loss, Due to its high durability and large transmission capacity, quartz glass is widely used in a wide range of fields. However, since the silica glass-based fiber is extremely thin and changes may occur due to external factors, the silica glass-based optical communication fiber is a soft liquid curable material that is previously cured on a fused-spun silica glass fiber. After coating and curing with a resin and performing a primary coating, in order to protect the primary coating layer, it is further coated with a hardened liquid curable resin of a cured product, cured, and then subjected to a secondary coating.

[0003] This primary coating material (primary coating material)
It has low Young's modulus and low temperature dependency, good adhesion to glass fiber, good durability (heat and water resistance), and low water absorption to prevent microbend loss due to external stress or temperature change. In addition, it is required to have low hydrogen generation and high refractive index. Among these properties, the adhesive strength between the glass fiber and the primary fiber affects the interface state between the glass fiber and the primary coating material, and affects the transmission characteristics. That is, if the adhesion is low, the glass fiber and the primary coating material are partially separated, and an air layer or a water layer is formed at the interface, causing microbending and deteriorating transmission characteristics. Thus, it is important that the adhesion is high with respect to the transmission characteristics of the optical fiber. Conventionally, as described in Japanese Patent Publication No. 1-19694, it has been known that an ultraviolet liquid curing composition comprising a urethane acrylate oligomer, a reactive monomer and a polymerization initiator is effective as a primary coating material. However, the adhesion to the glass fiber is not sufficient. As an improvement in this characteristic, as proposed in Japanese Patent Publication Nos. 6-13665, 6-72032 and JP-A-3-199217, an ultraviolet light comprising a urethane acrylate oligomer, a reactive monomer and a polymerization initiator is proposed. It is known that a composition obtained by adding a so-called silane coupling agent such as an aminoalkylalkoxysilane, a mercaptoalkylalkoxysilane, an epoxy group-containing alkoxysilane to a liquid curable composition is effective. However, the effect of these silane coupling agents is not sufficient, and it is necessary to increase the amount of addition in order to obtain the desired adhesion. However, when the added amount is increased, the storage stability of the composition may be deteriorated and the properties of the cured product may be changed.

The present invention has been made in order to solve the above-mentioned problems, and a liquid radiation-curable resin composition capable of providing a cured product having excellent adhesion to a quartz glass fiber for an optical fiber, and a composition comprising the same. It is an object of the present invention to provide a coating material for an optical fiber made of a material, and an optical fiber coated with the coating material.

[0005]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above-mentioned object, and as a result, have found that a liquid radiation-curable resin composition contains an adhesion promoter as an adhesion promoter. A highly reactive polyorganoxysilyl group having at least two organooxy groups bonded to silicon atoms chemically bonded to glass, and the number of silicon atoms containing at least two polyorganoxysilyl groups in the molecule Is 2
Organic silicon compounds represented by the formula (1):
The present inventors have found that the inclusion of the compounds of (10) to (10) enhances the adhesion of the cured product of the composition to the glass fiber, and have accomplished the present invention.

That is, the present invention provides (A) a (meth) acrylate oligomer, (B) an ethylenically unsaturated compound,
A liquid radiation-curable resin composition comprising (C) a photopolymerization initiator and (D) an organosilicon compound containing two or more polyorganoxysilyl groups having 2 to 20 silicon atoms. A coating material for an optical fiber comprising the composition; and an optical fiber coated with the coating material.

Hereinafter, the present invention will be described in more detail. (A) (Meth) acrylate oligomer The (meth) acrylate oligomer which is the first component of the liquid radiation-curable resin composition of the present invention is a polyether (meth) acrylate having a polyether as a main skeleton structure, Polyester having polyester (meta)
Acrylate, polycarbonate (meth) acrylate having polycarbonate, alkyl (meth) acrylate having high molecular weight alkyl group, polyurethane (meth) acrylate having these skeletons, and oligomer having epoxy group in these skeletons and (meth) Epoxy acrylate obtained by reaction with acrylic acid and the like can be mentioned. All of these (meth) acrylate oligomers can be obtained from a polyol or a (meth) acrylate having a hydroxyl group by an esterification reaction or a urethane reaction. The weight average molecular weight of these (meth) acrylate oligomers is, for example, 10
It can be selected from the range of from 00 to 30,000, preferably from 2000 to 20,000.

(I) Polyol polyol components include polyether polyol, polyester polyol, polycarbonate polyol,
Examples thereof include alkyl diols, and specific examples include the following.

(Polyether polyol) As the polyether polyol, for example, a homopolymer or copolymer of an alkylene oxide (eg, a C _2-5 alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and 3-methyltetrahydrofuran) is used. The above alkylene oxide homopolymer or copolymer using bisphenol A as an initiator, an aliphatic _C12-40 polyol (for example, 1,2-hydroxystearyl alcohol, hydrogenated dimer diol, etc.), or an alkylene oxide of bisphenol A (for example, propylene oxide) , Butylene oxide, tetrahydrofuran) adducts, alkylene oxides of hydrogenated bisphenol A (eg, propylene oxide, butylene oxide, tetrahydrofuran, etc.)
Adducts and the like. These polyether polyols can be used alone or in combination of two or more.

Preferred polyether polyols are C
_Homogenous or copolymer (polyoxypropylene glycol, polytetramethylene ether glycol, copolymer of propylene oxide and tetrahydrofuran) of _2-4 alkylene oxide, particularly C _3-4 alkylene oxide (propylene oxide or tetrahydrofuran) is exemplified. . In particular, it is preferable to use a polyether polyol or a polypropylene glycol having an oxypropylene structure in combination to reduce the viscosity of the resin or to generate a low hydrogen gas in the cured product for high-speed tape formation. The weight average molecular weight of the polyether polyol is, for example, 200 to 1
It can be selected from the range of about 0000.

These commercial products include, for example, (1)
As polyethylene glycol, “PEG600”, “PEG1000”, “PEG20” manufactured by Sanyo Chemical Industries, Ltd.
00, (2) Taketake Pharmaceutical Company Limited “Takelac P-22”, “Takelac P-21”, “Takelac P-23” as polyoxypropylene glycol, (3)
As polytetramethylene ether glycol, "PTG650", "PTG850", "P
TG1000, PTG2000, PTG400
0 ", (4) As a copolymer of propylene oxide and ethylene oxide," ED-28 "manufactured by Mitsui Toatsu Chemicals, Inc.
"Exenol 510" manufactured by Asahi Glass Co., and (5) "PPTG1000", "PPTG20" manufactured by Hodogaya Chemical Co., Ltd. as a copolymer of tetrahydrofuran and propylene oxide.
00, PPTG4000, (6) Unisafe DC-1100, Unisafe DC manufactured by NOF Corporation as a copolymer of tetrahydrofuran and ethylene oxide.
-1800 "and (7)" UNIOL DA "manufactured by NOF Corporation as an adduct of bisphenol A with ethylene oxide.
"-400", "Uniol DA-700", and (8) "Uniol DB-400" manufactured by NOF Corporation as adducts of bisphenol A with propylene oxide.

(Polyester polyol) Examples of the polyester polyol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,5-pentaglycol, 3-methyl-1,5-pentanediol and 1,6-hexanediol. Adducts of a diol compound such as neopentyl glycol with ε-caprolactam or β-methyl-δ-valerolactone; such as succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid and tetrahydrophthalic acid Reaction product with a dibasic acid; the diol compound, the dibasic acid and ε-caprolactam or β
And 3-component reaction products with -methyl-δ-valerolactone.

(Polycarbonate polyol) Examples of the polycarbonate polyol include 1,6-hexanediol, 3-methyl-1,5-pentanediol,
Neopentyl glycol, 1,4-butanediol,
1,5-octanediol, 1,4-bis- (hydroxymethyl) cyclohexane, 2-methylpropanediol, dipropylene glycol, dibutylene glycol,
Examples thereof include polycarbonate polyols made of a diol compound such as bisphenol A, or a reaction product of a diol compound and a short-chain dialkyl carbonate such as an ethylene oxide 2 to 6 mol addition reaction product, dimethyl carbonate, or diethyl carbonate.

Further, polyester diols which are addition products of these polycarbonate polyols with ethylene oxide, propylene oxide and ε-caprolactam or β-methyl-δ-valerolactone can also be used.

As a commercially available polycarbonate polyol, "Desmophen 2020" manufactured by Sumitomo Bayer Ltd. is available.
E "," DN-980 "," D
N-982 "and" DN-983 ".

(Alkyl diol) Examples of the alkyl diol include 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,4-butanediol, 1,5-octanediol, 1,4-dihydroxycyclohexane, 1,4-bis- (hydroxymethyl) cyclohexane, 2-methylpropanediol, tricyclodecanedimethanol,
Examples thereof include low molecular weight alkyl diols such as 1,4-bis- (hydroxymethyl) benzene and bisphenol A, polybutadiene and polyisoprene having terminal diols, and hydrogenated ones thereof.

As these (meth) acrylate oligomers, polyurethane (meth) acrylate oligomers are particularly preferable, and these are (i) the above-mentioned polyols, (ii) polyisocyanates and (iii) (meth) acrylate compounds having a hydroxyl group. Can be obtained by a urethanation reaction with The weight average molecular weight of the polyurethane (meth) acrylate oligomer is, for example, 100
It can be selected from the range of 0 to 30,000, preferably 2000 to 20,000.

(Ii) Polyisocyanate As the polyisocyanate component, for example, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene Diisocyanate,
Isophorone diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, transcyclohexane-1,
4-diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, Bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate and the like are used.

(Iii) (meth) acryl having a hydroxyl group
Examples of the (meth) acrylate having a rate hydroxyl group include hydroxyalkyl (meth) acrylates (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, hydroxy-C _2-10 alkyl (meth) acrylate such as neopentyl glycol mono (meth) acrylate, etc., 2-hydroxy-3-phenyloxy Propyl (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, cyclohexane 1,
4-dimethanol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate and the like, and further, a glycidyl group or epoxy group-containing compound (for example, alkyl glycidyl ether, allyl glycidyl ether,
Compounds formed by an addition reaction between (glycidyl (meth) acrylate) and (meth) acrylic acid are also included. These hydroxyl group-containing (meth) acrylates can be used alone or in combination of two or more. Preferred hydroxyl group-containing (meth) acrylates are hydroxy _C2-4 alkyl (meth) acrylates, especially 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like.

The polyurethane (meth) acrylate oligomer can be prepared by reacting the above components. The ratio of each component constituting the polyurethane (meth) acrylate oligomer is, for example, 1 mole of isocyanate group of polyisocyanate. On the other hand, the hydroxyl group of the polyol component is 0.1 to 0.8 mol, preferably 0.1 to 0.8 mol.
2 to 0.7 mol, particularly about 0.2 to 0.5 mol,
The hydroxyl group-containing (meth) acrylate is used in an amount of 0.2 to 0.9 mol, preferably 0.3 to 0.8 mol, particularly 0.5 to 0.5 mol.
It is about 8 mol.

The method of reacting the above components is not particularly limited, and the components may be mixed and reacted together. The polyisocyanate and any one of a polyol component and a hydroxyl group-containing (meth) acrylate may be used. And then the other component may be reacted.

Examples of the catalyst for the urethanization reaction include stannasoctoate, dibutyltin diacetate, dibutyltin dilaurate, cobalt naphthenate, and the like.
Organometallic urethanization catalysts such as lead naphthenate and amine catalysts such as triethylamine, triethylenediamine and diazabicycloundecene can be used.

(B) Ethylenically unsaturated compound Examples of the ethylenically unsaturated compound (B) used in the present invention include (meth) acrylic acid as an N-vinyl compound and a compound containing an amino group or a hydroxyl group. Examples thereof include compounds having a structure bonded by an amidation reaction or an esterification reaction. For example, the following monofunctional, bifunctional, and polyfunctional compounds can be used.

(Monofunctional compound) Examples of the N-vinyl compound include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, N-vinylformamide, and the like. Examples of compounds having a structure in which (meth) acrylic acid is bonded by an amidation reaction or an esterification reaction include methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, and nonylphenoxypolyethylene glycol (meth). ) Acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, butoxy polyethylene glycol (Meth) acrylate, alkyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, cumylphenol (meth) acrylate, cumylphenoxypolyethylene Glycol (meth) acrylate, cumylphenoxy polypropylene glycol (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentadiene (meth)
Acrylate, polyε-caprolactone mono (meth) acrylate, dialkylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, mono [2-
(Meth) acryloyloxyethyl] acid phosphate, trichloroethyl (meth) acrylate, 2,
2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, perfluorooctylethyl (meth)
Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyalkyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclodecanyloxyethyl (meth) acrylate,
Isobornyloxyethyl (meth) acrylate, morpholine (meth) acrylate and the like can be mentioned.

(Bifunctional Compound) Specific examples of the bifunctional compound include di (meth) acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, glycol di (meth) acrylate, neopentylglycerin di (meth) acrylate, bisphenol A
Di (meth) acrylate of ethylene oxide adduct of
Di (meth) acrylate of propylene oxide adduct of bisphenol A, di (meth) acrylate of 2,2′-di (hydroxyethoxyphenyl) propane, di (meth) acrylate of tricyclodecane dimethylol, dicyclopentadiene di ( (Meth) acrylate, pentanedi (meth) acrylate, (meth) acrylic acid adduct of 2,2-bis (glycidyloxyphenyl) propane, and the like.

(Polyfunctional compound) Examples of the polyfunctional compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, tris (acryloxymethyl)
Examples include isocyanurate, tris (acryloxyethyl) isocyanurate, tris (acryloxypropyl) isocyanurate, triallyl trimellitic acid, triallyl isocyanurate and the like.

Since the composition of the present invention is used as a primary coating material (primary material) for an optical fiber having a low Young's modulus, it is preferable to use a monofunctional compound.

The compounding amount of the compound having an ethylenically unsaturated group of the component (B) depends on the type of the compound of the component (A),
Depending on the desired viscosity of the resin composition or the physical properties of the cured product, for example, 5 to 100 parts by weight of component (A)
It can be selected from the range of about 200 parts by weight, preferably about 10 to 150 parts by weight, more preferably about 20 to 100 parts by weight.

(C) Photopolymerization initiator As the photopolymerization initiator, known ones can be used. For example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-2-phenylacetophenone, Phenylacetophenone diethyl ketal,
Alkoxyacetophenone, benzophenone and 3,3
Benzophenone derivatives such as dimethyl-4-methoxybenzophenone, 4,4-dimethoxybenzophenone and 4,4-diaminobenzophenone; benzyl derivatives such as alkyl benzoylbenzoate, bis (4-dialkylaminophenyl) ketone, benzyl and benzylmethylketal Benzoyl and benzoin butyl methyl ketal, benzoin derivatives such as benzoin isopropyl ether, 2-hydroxy-2-methylpropiophenone,
Thioxanthone derivatives such as 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone, fluorene, 2-methyl-1- [4- (methylthio) phenyl]
-2-morpholinopropane-1, 2-benzyl-2-dimethylamino-1- (morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)- And phosphine oxide derivatives such as 2,4,4-trimethylpentylphosphine oxide. Among these, a photopolymerization initiator of a phosphine oxide derivative is particularly preferred from the viewpoint of rapid curing.

These may be used alone or in combination of two or more. The amount of the component (C) is (A)
Usually, 0.01 to 15 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total of the component (meth) acrylate oligomer and the component (B) of the ethylenically unsaturated compound.
0 parts by weight.

(D) Poly having 2 to 20 silicon atoms
Organosiliconation containing two or more organooxysilyl groups
Examples of the compound (D) include compounds represented by the following formulas (1) to (10).

[0032]

Embedded image (Wherein R ¹ and R ² are monovalent hydrocarbon groups, R ³ and R ⁵ are divalent hydrocarbon groups, R ⁴ is a hydrogen atom or monovalent hydrocarbon group, a and d are 2 or 3, b is 2, 3 or 4, c represents 1 or 2, X, Y and Z represent a divalent organic group, and A represents a monovalent organic group having a functional group that undergoes an addition reaction with a primary or secondary amino group. , W is a divalent organic group, m is an integer of 1 or more, and n is 0 or an integer of 1 or more.)

Here, R ¹ and R ² preferably have 1 to 8 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group and a propyl group, an aryl group such as a phenyl group, a vinyl group, an allyl group and a propenyl group. And the like, and an alkyl group, particularly a methyl group and an ethyl group are preferred. Therefore, the component (D) preferably has a polyalkoxysilyl group, particularly a polymethoxysilyl group or a polyethoxysilyl group.

In this case, in the above formulas (1) to (10), a and d are 2 or 3, so that these formulas (1) to (10)
The compound of (10) has an organooxy group represented by the following formula, in particular, a silyl group having two or three alkoxy groups, and in the molecule, these polyorganoxysilyl groups;
Particularly, a compound containing a large number of polyalkoxysilyl groups, and by using such a compound having a large number of polyorganoxysilyl groups, particularly a compound having a polyalkoxysilyl group, the reactivity with the base material is high, and the chemical bonding Quick generation.

[0035]

Embedded image

In the formulas (1) to (3), examples of the divalent hydrocarbon group for R ³ include an alkylene group having 1 to 8 carbon atoms, particularly 2 to 6 carbon atoms.
₂ CH ₂ —) and a propylene group (—CH ₂ CH ₂ CH ₂ —) are preferred. As the monovalent hydrocarbon group for R ^4, the same groups as those for R ¹ and R ² can be mentioned, but an alkyl group, particularly a methyl group, is preferred. Therefore, R ⁴ is preferably a hydrogen atom or a methyl group. . Examples of the divalent hydrocarbon group for R ⁵ include the same as those for R ³ , but an alkylene group, particularly a propylene group (—CH ₂ CH ₂ CH ₂ —) is preferred.

Further, the divalent organic group of X and Y is a divalent organic group having 1 to 12 carbon atoms, particularly 2 to 10 carbon atoms.
Preferred structures of are as follows.

[0038]

Embedded image (In the above formula, R ⁶ represents a hydrogen atom or a methyl group.)

Preferred structures of Y include the following.

[0040]

Embedded image (R ⁶ is the same as above.)

On the other hand, in the formulas (4) to (10), d is 2 or 3, and as a compound of the formulas (4) to (10), -Si (OR ¹ ) _d (R ² ) _3-d At least 1 for every 2000 units of molecular weight.
And preferably two or more organosilicon compounds.

In the formulas (4) to (10), R^Four
And R^FiveIs the same as above, especially R ^FourIs a hydrogen atom or
A tyl group is preferred, and R^FiveIs a propylene group (-CH_TwoCH_Two
CH_Two-) Is preferred. X is the same as above and is preferred
Examples of the structure include the following.

[0043]

Embedded image (R ⁶ is the same as above.)

Further, Y is the same as above, but the formula (4)
In (10) to (10), preferable structures of Y include the following.

[0045]

Embedded image

In the formula, R ⁶ is the same as above, and R ⁷ and R ⁸
Is a divalent hydrocarbon group. In this case, R ⁷ is preferably an alkylene group having 1 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and particularly preferably —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) CH ₂ — or the like. Examples of R ⁸ include a linear, branched or cyclic alkylene group having 1 to 20, particularly 2 to 12 carbon atoms, and an arylene group having 6 to 20 carbon atoms, particularly 6 to 12 carbon atoms. Can be exemplified as a preferable structure.

[0047]

Embedded image

Examples of the functional group capable of undergoing an addition reaction with the primary or secondary amino group of A include an epixy group and a (meth) acryl group. Preferred examples of A include the following. .

[0049]

Embedded image

In this case, the following combinations of Y and A are preferred.

[0051]

Embedded image (In the above formula, R ⁶ , R ⁷ and R ⁸ are the same as above.)

The divalent organic group represented by W has 1 to 2 carbon atoms.
0, especially 2-12 -O-, -CO-, -COO-,-
NH -, - NCH ₃ - is interposed may be unsubstituted or hydroxy-substituted alkylene group and can be exemplified as a preferred structure as described below.

[0053]

Embedded image (In the formula, R ⁶ , R ⁷ , and R ⁸ are the same as above.)

The following are examples of the divalent organic group represented by Z.

[0055]

Embedded image

Here, the molecular weight of Z is 300 or more, preferably 300 to 300, in terms of compatibility and assimilation with the cured product of the composition.
4000, more preferably 400-2000,
p, q, r, and s are selected accordingly.
q, r, and s are preferably in the range of 5 to 100.

In the formula (ii), R ¹⁰ and R ¹¹ are each a straight-chain, branched or cyclic divalent hydrocarbon group having 2 to 15 carbon atoms, particularly 4 to 10 carbon atoms, particularly an alkylene group. Is mentioned.

Further, in the formula (iii), as the divalent hydrocarbon group having 15 or more carbon atoms of R ^12, a linear, branched or cyclic divalent hydrocarbon group, particularly an alkylene group,
-Polybutadiene, 1,4-polybutadiene or those having a hydrogenated skeleton thereof. The carbon number of R ¹² is more preferably 15 to 300, further preferably 2
It is 0-100.

Preferred values of m are 1 to 5, more preferably 1 to 3. The preferred value of n is 0
-5, more preferably 0-3.

The amount of the component (D) is 100 parts by weight in total of the (meth) acrylate oligomer of the component (A), the ethylenically unsaturated compound of the component (B), and the photopolymerization initiator of the component (C). Is usually 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

In the resin composition of the present invention, in addition to the above-mentioned components, for example, stabilizers such as antioxidants and ultraviolet absorbers, organic solvents, plasticizers, surfactants, coloring pigments, organic or inorganic particles, etc. Additives can be added as needed as long as the object of the present invention is not impaired.

The resin composition of the present invention can be prepared by mixing, stirring, and mixing the above-mentioned necessary components, and its viscosity is compatible with ordinary production conditions of optical fiber cores in terms of workability. From, usually 500 to 10000 cp (25 ° C),
Particularly under high-speed production conditions, 500 to 4000 cp (25
C) is desirable. In addition, this composition can be cured by irradiating ultraviolet rays to form a cured product in the same manner as in the case of an ordinary ultraviolet-curable composition, and the cured film obtained in this manner has an external force and 2MPa desirable to protect the core from microbends due to temperature changes
It is desirable to have the following Young's modulus.

The radiation for curing the liquid radiation-curable resin composition of the present invention is not only ultraviolet rays but also infrared rays,
There are visible light and ionizing radiation such as X-rays, electron beams, α-rays, β-rays, and γ-rays.

In particular, the liquid radiation-curable resin composition of the present invention is useful as a primary coating material (primary material) for an optical fiber coating material, is directly coated on an optical glass fiber, and has a high Young's modulus on its upper layer. The secondary covering material (secondary material) is covered. As the secondary coating material, a urethane acrylate composition which is a radiation-curable resin composition is suitably used.

Further, the composition of the present invention can be used as a buffering material for waterproof fiber optic cables, submarine cable optical fiber units, and the like.
It can be applied to fillers and can be applied to release coatings, water-repellent coatings, protective coatings, various inks, paints, etc.

[0066]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. All parts in each example are parts by weight.

Polyurethane (meth) acrylate oligo
Synthesis of Mer (A) [Synthesis Example 1] 600 g of polypropylene glycol having a number average molecular weight of 3,000 and 52.2 g of 2,4-tolylene diisocyanate were charged into a reaction vessel, stirred for 1 hour under aeration with nitrogen, and then dibutyltin laurate. 1.0 g was added and reacted at 40-50 ° C. for 2 hours. Thereafter, the reaction temperature was lowered to 40 ° C. or lower, 23.2 g of 2-hydroxyethyl acrylate was added, and the mixture was reacted at 50 to 60 ° C. for 5 hours to obtain a polyurethane acrylate oligomer (A) having a molecular weight of about 6,800.

Preparation of Liquid Radiation Curable Resin Intermediate 60 parts of the polyurethane acrylate oligomer (A) obtained in Synthesis Example 1 above, 40 parts of Aronix M-113 (acrylic compound manufactured by Toa Gosei Kogyo KK), 2,4,6-trimethyl A liquid radiation-curable resin intermediate was prepared by mixing 1.5 parts of benzoyldiphenylphosphine oxide.

Organic compounds containing polyalkoxysilyl groups
Synthesis of iodine compound (D) [Synthesis Example 2] 81 g of allyltrimethoxysilane, 100 g of toluene, and 0.05 g of a 2-ethylhexyl alcohol solution of chloroplatinic acid (2% dissolved as platinum metal) were charged into a reaction vessel, and the internal temperature was adjusted. Was heated to 70 ° C., and 67 g of trimethoxysilane was added dropwise so that the internal temperature became 80 ° C. or lower. After completion of the dropwise addition, the reaction was carried out at 70 to 80 ° C for 4 hours. Thereafter, toluene and unreacted substances were stripped and distilled off under reduced pressure to obtain a compound AD-1 having the following structure. (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

[Synthesis Example 3] 44.7 g of 3-aminopropyltrimethoxysilane and 58.5 g of 3-glycidyl-propyltrimethoxysilane were charged into a reaction vessel and reacted at 100 ° C. for 4 hours under dry nitrogen. 120 under reduced pressure
Stripped at ℃ to obtain a compound AD-2 having the following structure.

[0071]

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[Synthesis Example 4] 17.9 g of 3-aminopropyltrimethoxysilane and 46.8 g of 3-glycidyl-propyltrimethoxysilane were charged into a reaction vessel and reacted at 100 ° C. for 4 hours under dry nitrogen. 120 under reduced pressure
Stripped at ℃ to obtain a compound AD-3 having the following structure.

[0073]

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[Synthesis Example 5] 65.3 g of 3-mercaptopropyltrimethoxysilane, 54 g of 3-allyltrimethoxysilane and 1.5 g of 1-hydroxy-cyclohexyl-phenyl ketone were charged into a reaction vessel equipped with a high-pressure mercury lamp. Irradiation with ultraviolet light was performed under aeration of nitrogen to carry out stirring reaction for 1 hour to obtain compound AD-4 having the following structure. (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ —S—CH ₂ CH ₂ C
H ₂ Si (OCH ₃ ) ₃

[Synthesis Example 6] 40.8 g of 3-aminopropyl-methyl-dimethoxysilane and 54.5 g of 3-glycidylpropyl-methyl-dimethoxysilane were charged into a reaction vessel and reacted at 100 ° C. for 4 hours under dry nitrogen. After
Stripping was performed at 120 ° C. under reduced pressure to obtain a compound AD-5 having the following structure.

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[Synthesis Example 7] 36.8 g of 3-aminopropyl-dimethyl-methoxysilane and 50.5 g of 3-glycidylpropyl-dimethyl-methoxysilane were charged into a reaction vessel and reacted at 100 ° C. for 4 hours under dry nitrogen. After
Stripping was performed at 120 ° C. under reduced pressure to obtain a compound AD-6 having the following structure (Comparative Example).

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[Synthesis Example 8] 100 g of polypropylene glycol having a number-average molecular weight of 400 and allyl-terminated at both ends, 100 g of toluene, and 0.03 g of a 2-ethylhexyl alcohol solution of chloroplatinic acid (2% dissolved as platinum metal) were placed in a reaction vessel. After charging, the internal temperature was raised to 70 ° C., and 73.2 g of trimethoxysilane was added dropwise so that the internal temperature became 80 ° C. or less. After completion of the dropwise addition, the reaction was carried out at 70 to 80 ° C for 4 hours. Then, it stripped at 120 degreeC under reduced pressure, and obtained the compound AD-7 which has a following structure.

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Synthesis Example 9 100 g of aminated polypropylene glycol having amino groups at both terminals having a number average molecular weight of 2,000 (Jeffamine D-2000, Huntsman Corporation) and 46.8 g of 3-glycidyl-propyltrimethoxysilane were reacted. After charging in a container and reacting at 100 ° C. for 4 hours under dry nitrogen,
Stripped at ℃ to obtain a compound AD-8 having the following structure.

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Synthesis Example 10 Aminated polypropylene glycol having a branched structure having a number average molecular weight of 3000 and having amino groups at three terminals (Jeffamine T-300)
0, Huntsman Corporation) 100 g, 3-acryloxy-propyltrimethoxysilane 25.7 g,
2,6-di-tert-butylhydroxytoluene
05 g was charged into a reaction vessel, reacted at 70 ° C. for 5 hours under dry air, and then stripped at 120 ° C. under reduced pressure to obtain a compound AD-9 having the following structure.

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Synthesis Example 11 A reaction vessel was charged with 102 g of glycidyl ether of bisphenol A and 35.8 g of 3-amino-propyltrimethoxysilane, and reacted at 80 ° C. for 5 hours under dry nitrogen. Stripped at ℃ to obtain compound AD-10 having the following average structure.

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[Synthesis Example 12] 100 g of polypropylene glycol having a number average molecular weight of 1000 and 34.8 g of 2,4-tolylene diisocyanate were charged into a reaction vessel, and the mixture was stirred for 1 hour under a stream of nitrogen, and then 1.0 g of dibutyltin laurate. Was added and reacted at 40-50 ° C. for 2 hours.
Thereafter, the reaction temperature was lowered to 40 ° C. or lower, 11.6 g of allyl alcohol was added, and the mixture was reacted at 50 to 60 ° C. for 5 hours.
A polyurethane oligomer having an allyl group at a terminal was obtained. 117 g of this polyurethane oligomer, 34.5 g of 3-mercapto-propyltrimethoxysilane, and 1.5 g of 1-hydroxy-cyclohexyl-phenyl ketone were charged into a reaction vessel equipped with a high-pressure mercury lamp, and irradiated with ultraviolet light under nitrogen aeration. After stirring for an hour, compound AD-11 having the following structure was obtained.

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Examples 1 to 13 and Comparative Examples 1 to 5
As shown in 2, the liquid radiation-curable resin intermediate synthesized and prepared above was mixed with the organosilicon compound of AD-1 to AD-11 to prepare the resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5. Prepared. The adhesion of the obtained composition was measured as described below. The results are shown in Tables 1 and 2.

Evaluation Method of Adhesion (1) Preparation of Sample The above-mentioned liquid radiation-curable resin composition was placed on a quartz glass plate by two steps.
Coating to a film thickness of 00 μm, 500 mJ / cm ² (wavelength 3
(50 nm) ultraviolet rays to obtain a cured film on the quartz glass plate. (2) Adhesion force measurement After conditioning the cured film at 25 ° C. and 50% relative humidity for 24 hours, a fluorine-based adhesive tape having a width of 13 mm and a thickness of 0.08 mm was adhered to the surface of the cured film, and the width of the tape was adjusted. Then, a cut was made in the cured film to the quartz glass plate, and the adhesive tape and the cured film were unitarily pulled at 90 ° to the quartz glass plate at a pulling speed of 100 mm / min, and the peeling force was measured. The adhesion force per 1 cm width of the cured film was calculated from the peeling force. Further, as a change with time of the adhesion, the cured film was measured after being left at 25 ° C. and 50% relative humidity for 7 days and 30 days.

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[Table 1]

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[Table 2]

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The liquid radiation-curable resin composition of the present invention has excellent adhesion to quartz glass, and its stabilization is fast.
It is useful as a primary coating material for optical fibers.

Continued on front page F term (reference) 4J011 PA47 PA88 PA90 PB16 PB40 PC02 PC08 QA03 QA13 QA32 QA38 QA39 QB14 QB16 QB20 QB24 SA04 SA06 SA14 SA22 SA26 SA32 SA34 SA42 SA52 SA63 SA64 SA78 SA84 UA01 VA01 WA03 AG01AG01 AG01 AG27 AG28 AJ01 BA07 BA09 BA10 BA13 BA15 CA29 CB10 CC05 CD03 4J038 FA281 JC32 JC35 KA04 PA17 PC03

Claims (10)

[Claims] (A) a (meth) acrylate oligomer, (B) an ethylenically unsaturated compound, (C) a photopolymerization initiator, and (D) a polyorganoxysilyl group having 2 to 20 silicon atoms. A liquid radiation-curable resin composition comprising an organosilicon compound containing at least two organosilicon compounds. 2. The liquid radiation-curable resin composition according to claim 1, wherein the (meth) acrylate oligomer of the component (A) is a polyurethane (meth) acrylate oligomer. 3. The composition according to claim 1, wherein the component (D) is any of the following general formulas (1) to (1).
The liquid radiation-curable resin composition according to claim 1, wherein the composition is at least one selected from the organosilicon compounds represented by formula (0). Embedded image (Wherein R ¹ and R ² are monovalent hydrocarbon groups, R ³ and R ⁵ are divalent hydrocarbon groups, R ⁴ is a hydrogen atom or monovalent hydrocarbon group, a and d are 2 or 3, b is 2, 3 or 4, c represents 1 or 2, X, Y and Z represent a divalent organic group, and A represents a monovalent organic group having a functional group that undergoes an addition reaction with a primary or secondary amino group. , W is a divalent organic group, m is an integer of 1 or more, and n is 0 or an integer of 1 or more.) 4. In the formulas (1) to (3), R^ThreeIs -C
H_TwoCH_Two-Or -CH_TwoCH_TwoCH_Two-And R^FourIs hydrogen
An atom or a methyl group;^FiveIs -CH_TwoCH _TwoCH_TwoIn
Yes, X is(However, R⁶Is a hydrogen atom or a methyl group. )
And Y isThe liquid radiation-curable resin composition according to claim 3, which is 5. In the formulas (4) to (10), -Si
_{^{(OR 1) d (R 2}} ) 3-d polyorganosiloxanes silyl group which is an organic silicon compound having at least one per molecular weight of 2,000 units Claim 3 liquid radiation curable resin composition according represented by. 6. In the formulas (4) to (10), R ⁴ is a hydrogen atom or a methyl group, R ⁵ is —CH ₂ CH ₂ CH ₂ —, and X is And Y and A are And W is ^6. The liquid radiation-curable resin composition according to claim 3, wherein R ⁶ is a hydrogen atom or a methyl group, and R ⁷ and R ⁸ are divalent hydrocarbon groups. 7. In the formulas (4) to (10), Z is (Wherein, R ⁹ is a hydrogen atom or a methyl group, and p, q, and r are 0
Although the above integers, p, q, and r do not become 0 at the same time. A) a polyether represented by the formula: Wherein R ¹⁰ and R ¹¹ are divalent hydrocarbon groups, and s is an integer of 1 or more. —OR—R ¹² —O— (wherein, R ¹² has 15 or more carbon atoms) Or a group represented by the formula: 7. The liquid radiation-curable resin composition according to claim 3, 5 or 6, wherein R ¹³ is a hydrogen atom or a methyl group. 8. The method according to claim 3, wherein the molecular weight of Z is 300 or more.
A liquid radiation-curable resin composition according to any one of claims 1 to 7. 9. An optical fiber coating comprising the liquid radiation-curable resin composition according to claim 1. Description: 10. An optical fiber coated with the coating material for an optical fiber according to claim 9.