JPH10231340A - Photocurable composition resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful for an optical fiber, capable of preventing deactivation of a photopolymerization initiator for a long period of time, by including a urethane (meth)acarylate oligomer, an ethylenically unsaturated compound, a bisacyl phosphine oxide based pohtopolymerization initiator and a specific amine. SOLUTION: (A) A urethane (meth)acrylate oligomer is compounded with (B) an ethylenic unsaturated compound (e.g. N-vinylpyrrolidone), (C) a bisacylphosphine oxide-based photopolymerization initiator of the formula (R1 is a 1-12C alkyl or cycloalkyl; R2 and R3 are each H, etc.; R4 and R5 are each H or a 1-12C alkyl) [e.g. bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphospine oxide] and (D) a tertiary amine (e.g. triethylamine) substantially containing no tin component to give the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can suppress the deactivation of a photopolymerization initiator, and can be applied to coating materials such as plastic, wood, ceramics, glass, metal, and paper, light forming materials, three-dimensional three-dimensional molding materials, and printing plates. The present invention relates to a photocurable resin composition useful as a material and the like, particularly to a photocurable resin composition suitable as an optical fiber coating material, a method for producing the same, and an optical fiber.

[0002]

2. Description of the Related Art Glass fibers used for optical fibers are not only very brittle and easily damaged, but also cause a large optical transmission loss due to contamination. For this reason, in order to protect and reinforce the glass fiber, immediately after drawing the glass fiber, the surface of the glass fiber is soft, has a low Young's modulus, and has a small temperature dependency. After the first coating with UV curable resin having a high Young's modulus.
Next is coating. Further, in order to identify the optical fiber, the optical fiber may be tertiarily coated with a color material. One fiber coated including the tertiary coating is called a fiber strand. Furthermore, what bundled several fiber strands and made into a tape shape by a tape material is called a tape core wire, and UV resin is also used as the tape material. further,
A plurality of tape cores are stored and used as an optical cable. In addition, the optical fiber to be drawn into ordinary households is called drop wire, drop wire, etc.,
As this drop wire, a wire in which one or a few fiber strands are thickly covered with a UV resin having a high Young's modulus is used.

[0003] The properties commonly required for these UV resins for coating materials are that they have an appropriate viscosity, that they have little change in viscosity after long-term storage, and that they are fast-curing, which cures even at a low UV irradiation dose. And the amount of hydrogen gas generated is small, and the long-term reliability of the coated glass fiber is high.

In particular, in recent years, in order to improve the productivity of optical fibers, if the drawing speed from the molten glass fiber preform is increased, the amount of ultraviolet irradiation in the coating step with the UV resin subsequent to drawing is reduced. The Young's modulus of the cured product decreases. Therefore, as a photoinitiator, a resin composition containing a high-activity, fast-curing acylphosphine oxide-based photopolymerization initiator has been proposed. For example, a composition containing a monoacylphosphine oxide is disclosed in
JP-6125 and JP-A-4-296315 disclose polyurethane having an ethylenically unsaturated bond, a monomer having an ethylenically unsaturated bond, a compound having an acylphosphine oxide and a tertiary amino group (a compound having a morpholine ring. And a photocurable resin composition comprising a photoinitiator composed of a mixture with the compound (A). These documents describe examples using a tin compound as a urethanization catalyst.

With respect to a composition containing a bisacylphosphine oxide, JP-A-6-298818 discloses an ethylenically unsaturated polymerizable compound and a bisacylphosphine oxide [bis (2,4,6-trimethylbenzoyl) -2.
-Methylpropylphosphine oxide, etc.]. JP-A-8-2596
No. 42 discloses a polymer having an ethylenically unsaturated bond such as urethane acrylate, a monomer having an ethylenically unsaturated bond, and a bisacylphosphine oxide [bis (2,6-dimethoxy) having higher curability than a monoacylphosphine oxide. Benzoyl) -2,4,4-trimethylpentylphosphine oxide]. This document describes an example using a tin compound as a urethanization catalyst.
Further, JP-A-8-127630 discloses a photocuring method containing urethane (meth) acrylate, N-vinylpyrrolidone, tertiary amines and a photopolymerization initiator (such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide). A resin composition is disclosed. These documents also describe examples using a tin compound as a urethanization catalyst.

JP-A-5-306146 discloses a polyether polyol-based urethane oligomer using an aliphatic polyisocyanate, a reactive diluent, a silane adhesion promoter, and a general photoinitiator. A coating composition is disclosed. This document describes that tin compounds, metal salts of organic acids, amines and the like can be used as a urethanization catalyst.

[0007] A resin composition containing an acylphosphine oxide as a photopolymerization initiator has high photopolymerizability. However, when the resin composition is stored, the acylphosphine oxide is deactivated, and the photocurability is greatly reduced. In particular, even in a small amount, in the presence of water, the acylphosphine oxide is deactivated within a short period of time, and in a significant case, it cannot function as a coating agent at all. Although it is conceivable to exclude water in the resin composition in order to prevent the deactivation of the polymerization initiator, it is practically impossible to keep the water in the resin composition at “0”.

On the other hand, generation of hydrogen gas causes an increase in optical transmission loss. That is, since hydrogen gas has a large diffusion coefficient with respect to resin and glass, hydrogen diffuses into the quartz fiber even under normal use conditions, and the main component of the quartz fiber is SiO 2.
It is considered that the transmission loss is increased by being supplemented by defect sites such as ₂ and the dopant GeO ₂ . Therefore, the ultraviolet curable resin composition for coating an optical fiber is required to generate a small amount of hydrogen gas. Therefore, a coating for a glass fiber obtained by adding a phenolic antioxidant or a sulfuric antioxidant to a composition containing a compound having an ethylenically unsaturated bond such as urethane acrylate and a (meth) acrylate having a piperidine ring. A material is disclosed (JP-A-2-11611). Even with such a resin composition, the amount of hydrogen gas generated can be reduced. However, the addition of the antioxidant decreases the curing speed and the gel fraction. Therefore, it becomes difficult to reduce the amount of hydrogen gas generated while maintaining the high properties of the photocurable resin composition.

Note that Japanese Patent Application Laid-Open No. 4-77514 discloses that
Polyurethane acrylate using hydrogenated dimer diol obtained by hydrogenating dimer acid having 36 carbon atoms has high adhesion to substrates with low surface tension (printed surface of offset ink, polypropylene, etc.) and low water absorption of cured film It is described. JP-A-5-262848 describes that a polyurethane (meth) acrylate based on a polyester polyol having a dimer acid residue which may be hydrogenated is excellent in low water absorption and hot water aging resistance. ing. JP-A-4-310545 discloses an average molecular weight of 500 having no polymerizable vinyl group.
Polyurethane (meth) acrylate using the following terminal OH compounds (for example, polyhydric alcohols such as 1,10-decanediol and 4,4'-methylenebiscyclohexanol) is coated with a secondary coating having a high Young's modulus and elongation. It is disclosed to provide materials, tape materials.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photopolymerization initiator which is less deactivated even when a UV resin is stored for a long period of time, and has high photocurability and high-speed coating coating over a long period of time. An object of the present invention is to provide a photocurable resin composition (particularly, a photocurable resin composition for coating an optical fiber) capable of maintaining the property, and a method for producing the same. Another object of the present invention is to provide a photocurable resin composition (especially for optical fiber coating) capable of suppressing hydrolysis of bisacylphosphine oxide as a photopolymerization initiator and maintaining excellent rapid curability even at a low UV irradiation dose. Photocurable resin composition) and a method for producing the same. Still another object of the present invention is to provide a photocurable resin composition (particularly, a photocurable resin composition for coating an optical fiber) which generates a small amount of hydrogen gas and a method for producing the same. Another object of the present invention is to provide an optical fiber that can provide a primary coating material, a secondary coating material, a tape material, a drop wire coating material, a waterproof fiber cable coating material, and a submarine cable cushioning material that can suppress an increase in transmission loss. An object of the present invention is to provide a photocurable resin composition for coating. Yet another object of the invention is to provide
An object of the present invention is to provide a method for stabilizing a bisacylphosphine oxide-based photopolymerization initiator.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, even if a very small amount of a tin-based catalyst is present, the viscosity of the UV resin significantly increases during long-term storage. However, to reduce the high-speed coating property, when a tin-based catalyst and water coexist, even with a small amount of water, the bisacylphosphine oxide is hydrolyzed and deactivated, thereby significantly reducing the photocurability. Then, when bisacylphosphine oxide is combined with tertiary amines, it has been found that high photoactivity and photocurability of bisacylphosphine oxide can be maintained over a long period of time even in the presence of moisture, and the present invention has been completed. did.

That is, the photocurable resin composition of the present invention comprises (A) a urethane (meth) acrylate oligomer,
(B) an ethylenically unsaturated compound, (C) the following formula (i)

[0013]

Embedded image (Wherein, R ₁ is a linear or branched C _1-12 alkyl group,
A cycloalkyl group, a linear or branched C _1-12 alkyl group or an aryl group which may be substituted with a halogen atom, wherein R ₂ and R ₃ are the same or different and are a hydrogen atom, a linear or A branched C _1-12 alkyl group or a linear or branched C _1-12 alkoxy group, wherein R ₄ and R ₅ are the same or different and are a hydrogen atom or a linear or branched C _1-12 alkoxy group;
_1-12 alkyl group) and a tertiary amine substantially free of (D) a tin component. In the component (A), a urethane (meth) using a polyol having 14 to 40 carbon atoms (for example, an aliphatic diol derived from a higher fatty acid such as hydrogenated dimer diol or 12-hydroxystearyl alcohol) as a polyol component. Acrylate oligomers are also included. The photocurable resin composition is useful as a liquid photocurable resin composition, particularly a photocurable resin composition for coating an optical fiber. The method of the present invention comprises (A) a urethane (meth) acrylate oligomer, (B) an ethylenically unsaturated compound, and (C)
A method of mixing a bisacylphosphine oxide-based photopolymerization initiator to produce a photocurable resin composition containing (D) a tertiary amine substantially free of a tin component is included. Further, the present invention provides an optical fiber in which a glass fiber is directly or indirectly coated with a cured film of the photocurable resin composition, and a glass fiber is directly or indirectly coated with the photocurable resin composition. The present invention also provides a method for coating an optical fiber, wherein the resin composition is cured by light irradiation. The present invention
A method for stabilizing a bisacylphosphine oxide-based photopolymerization initiator (C) by substantially coexisting a tertiary amine without substantially containing a tin component is also provided.

In the present specification, “substantially contains no tin component” means, unless inevitably mixed,
It means that no tin component is added or a reaction product using the tin component is not contained. In addition, acrylic monomers and methacrylic monomers are collectively referred to as (meth) acrylic monomers.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid photocurable resin composition of the present invention suitable for coating an optical fiber comprises (A) a polyurethane (meth) acrylate oligomer, (B) an ethylenically unsaturated compound, and (C) a compound represented by the formula It is composed of the bisacylphosphine oxide-based photopolymerization initiator represented by (i) and the (D) tertiary amine compound, and contains substantially no tin component. These components (A), (B), (C) and (D) will be described.

[(A) Polyurethane (meth) acrylate oligomer] The polyurethane (meth) acrylate oligomer can be obtained by urethane-forming a polyisocyanate, a polyol component, and a (meth) acrylate having a hydroxyl group. The weight average molecular weight of the polyurethane (meth) acrylate oligomer is, for example, 200 to 20,000, preferably 300 to 20,000.
It can be selected from the range of about 10,000.

Polyisocyanate The polyisocyanate includes aromatic polyisocyanate,
Aromatic polyisocyanates, alicyclic polyisocyanates, aliphatic polyisocyanates and the like are included. Diisocyanates are widely used as polyisocyanates. As the aromatic polyisocyanate, for example,
Diisocyanate [m-phenylene diisocyanate,
p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate,
2,4- or 2,6-tolylene diisocyanate, 4,
4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, etc.], polyisocyanate [triphenylmethane-4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6- Triisocyanate toluene, 4,
4'-diphenylmethane-2,2 ', 5,5'-tetraisocyanate].

The araliphatic polyisocyanates include:
For example, diisocyanate [1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3-
Or 1,4-bis (1-isocyanate-1-methylethyl) benzene or a mixture thereof], and a polyisocyanate [1,3,5-triisocyanatomethylbenzene or the like].

Examples of the alicyclic polyisocyanate include diisocyanates [1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate. (Isophorodiisocyanate),
4,4'-methylenebis (cyclohexylisocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, etc.], polyisocyanate [ 1,
3,5-triisocyanatecyclohexane, 1,3
5-trimethylisocyanatecyclohexane, 2-
(3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane,
2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo ( 2.2.1) Heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl)- 2-isocyanatomethyl-3
-(3-isocyanatopropyl) -bicyclo (2.
2.1) Heptane, 5- (2-isocyanatoethyl)
-2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) -heptane, 6
-(2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, etc.].

Examples of the aliphatic polyisocyanate include diisocyanates [trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate,
1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-
Or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethyl captroate, etc.], polyisocyanate [lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate Undecane,
1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-triisocyanatehexane,
2,5,7-trimethyl-1,8-diisocyanate-
5-isocyanatomethyloctane].

Furthermore, derivatives from isocyanate compounds can also be used. Examples of the derivative of the isocyanate compound include dimers, trimers, burettes, allophanates, carbodiimides, polymethylene polyphenyl polyisocyanates (crude MDI or polymeric MDI), crude TDI, and adducts of isocyanate compounds with low-molecular-weight polyols. Can be

Among these polyisocyanates, diisocyanates (for example, tolylene diisocyanate, 4,4
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate, isophorone diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, etc. Aliphatic diisocyanates, aliphatic diisocyanates such as hexamethylene diisocyanate, etc.) are often used.

Polyol Component The polyol component includes polyols such as polyether polyol, polyester polyol and polycarbonate polyol. The polyether polyols, such as alkylene oxides (e.g., ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, C _2-5 alkylene oxides such as oxetane compound) homopolymers or copolymers of aliphatic The above alkylene oxide homopolymer or copolymer starting with a _C14-40 polyol (eg, 12-hydroxystearyl alcohol, hydrogenated dimer diol, etc.), and an alkylene oxide of bisphenol A (eg, propylene oxide, butylene oxide, Adducts of tetrahydrofuran, oxetane, etc., and alkylene oxide (eg, propylene oxide, butylene oxide, tetrahydrofuran, oxetane) adducts of hydrogenated bisphenol A, etc. Is mentioned. These polyether polyols can be used alone or in combination of two or more. Preferred polyether polyols, and C _2-4 homo- or copolymer (polyoxypropylene glycol alkylene oxide, particularly C _{3- 4} alkylene oxide (propylene oxide and tetrahydrofuran), polytetramethylene ether glycol, tetrahydrofuran and propylene oxide Copolymers), as described below, aliphatic C _14-40
The above-mentioned _C2-4 alkylene oxide homopolymer or copolymer using a polyol as an initiator is included. The weight average molecular weight of the polyether polyol is, for example, 200 to
It can be selected from the range of about 10,000.

Examples of the polyester polyol include diol components (for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentane C _2-40 aliphatic low molecular weight diols such as diol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, 1,10-decanediol, 12-hydroxystearyl alcohol, hydrogenated dimer diol, Alkylene oxide adduct of bisphenol A, etc.)
With lactones (eg, ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone); the above diol component and dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid) Reaction products with aliphatic dicarboxylic acids such as dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydrophthalic acid and tetrahydrophthalic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; An addition reaction product of a diol component, the above-mentioned dicarboxylic acid component, and a lactone, for example, may be used.

Examples of the polycarbonate polyol include the above-mentioned polyether polyols, polyester polyols and diol components (2-methylpropanediol,
Dipropylene glycol, 1,4-butanediol,
1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,5-octanediol, 1,4-bis (hydroxymethyl) cyclohexane, etc.) and short-chain dialkyl carbonate (for example, dimethyl Polycarbonate diols obtained by reaction with a C _1-4 alkyl carbonate such as carbonate and diethyl carbonate. Furthermore, a polyether which is a reaction product obtained by adding an alkylene oxide (such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran) or a lactone (such as ε-caprolactone, β-methyl-δ-valerolactone) to the polycarbonate polyol. Diols and polyester diols can also be used.
Commercially available polycarbonate diols include, for example,
"Desmophen 2020E" (manufactured by Sumitomo Bayer Urethane Co., Ltd.), "DN-980", "DN-982" and "DN-983" (manufactured by Nippon Polyurethane Co., Ltd.) and the like.

If necessary, a low molecular weight polyol can be used. Examples of the low molecular weight polyol include ethylene glycol, propylene glycol,
1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, higher fatty acid polyols and higher hydrocarbon polyols [derived from higher fatty acids Saturated or unsaturated aliphatic _C14-40 polyols such as castor oil, coconut oil, monomyristine (1-
Myristin, 2-monomyristin), monopalmitin (1-monopalmitin, 2-monopalmitin), monostearin (1-monostearin, 2-monostearin), monoolein (1-monoolein, 2-monoolein), 9,10-dioxystearic acid, 12-hydroxyricinoleyl alcohol, 12-hydroxystearyl alcohol, 1,16-hexadecanediol (reduction of juniperic acid or tapsiaic acid), 1,21
-Hemicosandiol (reduction of Japanese acid), chimyl alcohol, batyl alcohol, seralkyl alcohol, dimer acid diol, polybutadiene diol or a hydrogenated product thereof]. In addition to these polyols, silicone polyols, fluorine polyols, polyolefin polyols and the like can be used as required.

In order to suppress the amount of hydrogen generated and to reduce the transmission loss of the optical fiber, a urethane (meth) acrylate oligomer is used as a polyol component in a polyol having 14 to ₄₀ carbon atoms (ie, aliphatic C _14-40 polyol, In particular, it is advantageous to include an aliphatic C _14-40 diol). As the urethane (meth) acrylate oligomer, it is particularly advantageous to use an aliphatic C _16-38 diol or a diol having an aliphatic C _16-38 diol unit.

The aliphatic C _14-40 polyol can be used in combination with a polyether polyol, a polyester polyol, a polycarbonate polyol, a relatively low-molecular polyol, and the like. The polyurethane (meth) acrylate oligomer containing the aliphatic C _14-40 polyol unit can be roughly classified into the following three embodiments. (A1) The polyol component is an aliphatic C _14-40 polyol (a
Polyurethane (meth) acrylate oligomer composed of (1) (A2) polyol component is an aliphatic C _14-40 polyol (a
Polyurethane (meth) acrylate oligomer composed of a mixture of 1) and another polyol (a2) (A3) The polyol component is an aliphatic C _14-40 polyol (a
1) the polyurethane (meth) acrylate oligomer (A1) composed of
A mixture with a polyurethane (meth) acrylate oligomer composed of a polyol (a2) other than the _14-40 polyol (a1).

Aliphatic C_14-40The polyol is (a1) fat
Tribe C_14-40The polyol alone may be used, and the aliphatic C
_14-40Polyols having polyol units, especially fats
Tribe C _14-40Alkylene oxide adduct of polyol,
It may be used as a carbonate adduct. further,
(A2) The above aliphatic C_14-40Polyol (a1) and the above examples
Can also be used as a mixture with other polyols. fat
Tribe C_14-40Polyols such as polybutadienediol
Or its hydrogenated product can also be used,
Aliphatic diols derived from fatty acids, such as hydrogenated
Immerdiol, monostearin, 12-hydroxys
Tearyl alcohol and the like can be used. Hydrogenated dimer
All is a terminal diol obtained by hydrogenating dimerized fatty acids
(Especially, hydrogenated high-purity dimer acid having 36 carbon atoms
Diol), and the structure of the main component is represented by the following formula
(Ii) and (iii).

[0030]

Embedded image The composition ratio of the hydrogenated dimer diol is not particularly limited. For example, the diol represented by the formula (ii) and the diol represented by the formula (ii)
A typical ratio of the thiol represented by i) is, for example, (i
i) / (iii) = about 3/1 (weight ratio). Commercially available hydrogenated dimer diols include, for example,
"Dimerdiol KX-501" (Arakawa Chemical Industries, Ltd.), "Pespol HP-1000" (Toa Gosei Co., Ltd.) and the like. As a commercially available product of 12-hydroxystearyl alcohol, "Roxanol" (Henkel Hakusui Co., Ltd.) can be mentioned. The polyol (particularly, diol) derived from higher fatty acid does not need to be an isolated pure compound, and a polyol containing a polyol as a main component (for example, 60 to 100% by weight, preferably 75 to 100% by weight) It may be used as a composition.

The (a1) alkylene oxide adduct of the aliphatic C _14-40 polyol (particularly diol) includes a C _2-5 alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran or 3-methyltetrahydrofuran. Examples of the adduct and the carbonate adduct include adducts with ethylene carbonate. Particularly, an adduct of an aliphatic C _14-40 polyol (particularly, a diol) and an alkylene oxide is preferred. Preferred alkylene oxides include, for example, propylene oxide, butylene oxide, and tetrahydrofuran. In order to form a coating material having a low water absorption, a small amount of hydrogen gas generation, and a high Young's modulus, the alkylene oxide preferably contains at least propylene oxide. preferable. In the alkylene oxide adduct, the content of the aliphatic C _14-40 polyol residue is, for example, 5 to 90% by weight, preferably 10 to 8% by weight.
0% by weight, more preferably about 15 to 70% by weight. (A1) The average molecular weight of the polyol containing an aliphatic _C14-40 polyol unit is, for example, about 230 to 10,000,
Preferably it is about 286-5000. Aliphatic C
The proportion of the _14-40 polyol is, for example, 1 to 50% by weight, preferably 2% by weight of the entire polyurethane (meth) acrylate.
To 40% by weight, more preferably about 3 to 30% by weight. For example, in hydrogenated dimer diol, 3 to 30 of the entire polyurethane (meth) acrylate
%, Preferably about 5 to 25% by weight.
In the case of hydroxystearyl alcohol, it is about 1 to 14% by weight, preferably about 2 to 10% by weight of the entire polyurethane (meth) acrylate.

(Meth) acryle having hydroxyl group
The (meth) acrylate having a over preparative hydroxyl groups, such as hydroxyalkyl (meth) acrylates [e.g., 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
-Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate Such as hydroxy-C _2-10 alkyl (meth) acrylate), 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, Trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like; and glycidyl or epoxy group-containing compounds (eg, alkyl glycidyl ether). 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 (meth) acrylates having a hydroxyl group are hydroxy C _2-4 alkyl (meth) acrylates, especially 2- (meth) acrylates.
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like.

The polyurethane (meth) acrylate oligomer can be prepared by reacting the above-mentioned components. The proportion of each component constituting the polyurethane (meth) acrylate oligomer may be, for example, an isocyanate group (NCO group) of a polyisocyanate. ) 0.1 mole of hydroxyl group (OH group) of the polyol component per mole.
To 0.8 mol, preferably 0.2 to 0.7 mol, particularly about 0.2 to 0.5 mol, containing a hydroxyl group (meth)
Acrylate 0.2-0.9 mol, preferably 0.3-
It is about 0.8 mol, especially about 0.5 to 0.8 mol. The method of reacting the components is not particularly limited, and the components may be mixed and reacted at once, with a polyisocyanate,
After reacting either one of the polyol component and the hydroxyl group-containing (meth) acrylate,
The other component may be further reacted. To prevent the deactivation of the bisacylphosphine oxide-based photopolymerization initiator,
It is advantageous to use a nonmetallic organic catalyst, especially an amine catalyst (particularly a tertiary amine catalyst), instead of a tin catalyst, in the urethanization reaction of the above components.

[(B) Ethylenically unsaturated compound] As the ethylenically unsaturated compound, a polymerizable compound which functions as a reactive diluent and is liquid or solid at room temperature (about 15 to 30 ° C) can be used. Ethylenically unsaturated compounds include:
Includes monofunctional, difunctional and polyfunctional compounds.

Examples of the monofunctional compound (monofunctional polymerizable diluent) include, for example, a heterocyclic ethylenically unsaturated compound [eg, N-vinylpyrrolidone, N-vinylpyridine, N-vinylpyridine).
N-vinyl heterocyclic compounds such as vinylcaprolactam,
Heterocyclic (meth) acrylates such as morpholine (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc.], N-vinylacetamide, N-vinylformamide, dialkylaminoethyl (meth) acrylate [for example, dimethylaminoethyl ( Meth) acrylate, diethylaminoethyl (meth) acrylate, etc.), N, N'-dimethylacrylamide, alkoxy (poly) alkylene glycol (meth) acrylate [for example, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, Butoxy polyethylene glycol (meth) acrylate, etc.), alkylphenoxyethyl (meth)
Acrylate [eg, nonylphenoxyethyl (meth) acrylate], phenoxy (poly) alkylene glycol (meth) acrylate [eg, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate], cumylphenol (poly) Alkylene (meth) acrylate, alkyl (meth) acrylate [eg, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.], cycloalkyl (meth) acrylate [eg, cyclohexyl (meth) acrylate, etc.], aralkyl (meth) A) acrylates such as benzyl (meth) acrylate, and (meth) acrylates having a crosslinked alicyclic hydrocarbon group such as isobornyl (meth) acrylate, Pentadiene (meth) acrylate, dicyclopentenyl (meth) acrylate,
Tricyclodecanyl (meth) acrylate, dicyclopentenyloxyalkyl (meth) acrylate, tricyclodecanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, etc.], hydroxyl group-containing (meth) acrylate [ For example, 2-
Hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-
Hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc.], polyε-caprolactone mono (meth) acrylate, glycidyl ( Meth) acrylate, mono [2- (meth) acryloyloxyethyl] acid phosphate, etc.], halogen-containing (meth) acrylate [for example, trifluoroethyl (meth) acrylate, 2,
2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, and the like].

Examples of the bifunctional compound (bifunctional polymerizable diluent) include di (meth) acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, (Polyoxy) alkylene glycol di (meth) acrylate [for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene 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, neopentyl Rikoruji (meth) acrylate,
Pentanediol di (meth) acrylate, etc.], glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, neopentyl glycol hydroxypivalate (meth) acrylate, alkylene oxide of bisphenol A (E.g., ethylene oxide, propylene oxide, butylene oxide) adduct di (meth) acrylate [e.g., di (meth) acrylate of 2,2-bis (2-hydroxyethoxyphenyl) propane, etc.], crosslinked alicyclic hydrocarbon group Di (meta) having
Acrylate [for example, tricyclodecane dimethanol di (meth) acrylate, dicyclopentadiene di (meth) acrylate, etc.], and a (meth) acrylic acid adduct of a bifunctional epoxy resin [for example, 2,2-bis (glycidyloxyphenyl) ) (Meth) acrylic acid adduct of propane, etc.].

As the polyfunctional compound (polyfunctional polymerizable diluent), for example, trimethylolpropane tri (meth)
Acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (acryloyloxy)
Examples include isocyanurate, tris (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, tri (meth) acrylate of tris (hydroxypropyl) isocyanurate, triallyl trimellitic acid, triallyl isocyanurate and the like.

These ethylenically unsaturated compounds can be used alone or in combination of two or more. The ethylenically unsaturated compound can be selected according to the coating form of the substrate or the optical fiber. For example, when used for the primary coating and the secondary coating of an optical fiber, a tape material, a drop wire, and the like, the ethylenically unsaturated compound is used as an ethylenically unsaturated compound. , N-vinyl-nitrogen-containing heterocyclic compounds [eg, N-vinylpyrrolidone, N-vinylcaprolactam, etc.], acrylates having a crosslinked alicyclic hydrocarbon group [eg, isobornyl acrylate, dicyclopentadiene acrylate, isovol Monofunctional compounds such as nyloxyethyl acrylate, tricyclodecane dimethanol acrylate, etc.] are often used, and when a hard film is formed, a bifunctional compound may be further added together with the monofunctional compound, if necessary. [For example,
(Polyoxy) alkylene glycol di (meth) acrylate, di (meth) acrylate of alkylene oxide adduct of bisphenol A, etc.) and polyfunctional compound [trimethylolpropane tri (meth) acrylate, etc.]
Often used together.

The amount of the ethylenically unsaturated compound used depends on the type of the polyurethane (meth) acrylate oligomer and the ethylenically unsaturated compound, the desired viscosity of the resin composition, and the like. Parts by weight, 10 to 200 parts by weight, preferably 20 to 150 parts by weight, more preferably 30 to 1 part by weight.
It can be selected from a range of about 00 parts by weight.

[(C) Photopolymerization Initiator of Formula (i)] In the present invention, a bisacylphosphine oxide compound represented by the following formula (i) is used as a photopolymerization initiator.

[0041]

Embedded image (Wherein, R ₁ is a linear or branched C _1-12 alkyl group,
A cycloalkyl group, a linear or branched C _1-12 alkyl group or an aryl group which may be substituted with a halogen atom, wherein R ₂ and R ₃ are the same or different and are a hydrogen atom, a linear or A branched C _1-12 alkyl group or a linear or branched C _1-12 alkoxy group, R ₄ and R ₅ Are the same or different and represent a hydrogen atom or a linear or branched C
_{A 1-12} alkyl group) The linear or branched C _1-12 alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, pentyl, isopentyl, 4,
4-trimethylpentyl, hexyl, isohexyl,
2,4,4-trimethylhexyl, octyl, decyl,
A dodecyl group can be exemplified. Preferred R ₁ is a branched C _6-12 alkyl group, especially a branched C _6-10 alkyl group. Examples of the cycloalkyl group include C _3-10 cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups, particularly C _5-10 cycloalkyl groups.

The aryl group includes a phenyl and naphthyl group, and the aryl group may be substituted with a linear or branched C _1-12 alkyl group or a halogen atom. C _1-12
The alkyl group includes the same alkyl group as described above, and includes a linear or branched C _1-4 alkyl group (methyl, ethyl,
Propyl, isopropyl, butyl, t-butyl, etc.)
It is preferred that Halogen atoms include fluorine, chlorine, bromine and iodine atoms.

The linear or branched C _1-12 alkoxy group includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t
-Butoxy, pentyloxy, hexyloxy, octyloxy, groups and the like. Preferred alkoxy groups are straight-chain or branched C _1-4 alkoxy groups.

Preferred combinations of the substituents are as follows.

R ₁ : a C _1-12 alkyl group (particularly a branched C
_6-12 alkyl group) or aryl group (particularly phenyl group) R ₂ and R ₃ : C _1-4 alkyl group (particularly C _1-2 alkyl group) or C _1-4 alkoxy group (particularly C _1-2 alkoxy group) ) R ₄ and R ₅ : Hydrogen atom or C _1-4 alkyl group (particularly methyl group) Specific examples of the bisacylphosphine oxide-based photopolymerization initiator include, for example, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide (BAPO) bis (such as 2,6-di-C _1-2 alkoxy benzoyl) - branched C _6-12 alkyl phosphine oxide, bis (2,4,6-trimethylbenzoyl)
Bis (2,4,6-triC _1-2 such as methylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ethylphosphine oxide and bis (2,4,6-trimethylbenzoyl) n-butylphosphine oxide Alkyl (benzoyl) C _1-6 alkylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (for example, “Irgacure 819” manufactured by Ciba Specialty Chemicals), and the like. such as C _1-2 alkyl benzoyl) aryl phosphine oxide. These bisacylphosphine oxide-based photopolymerization initiators can be used alone or in combination of two or more.

These bisacylphosphine oxide-based photopolymerization initiators include other photopolymerization initiators (for example, acetophenone-based or propiophenone-based photopolymerization initiators, benzoin-based, benzophenone-based photopolymerization initiators, and thioxanthone-based photopolymerization initiators). Initiators).

Examples of the acetophenone or propiophenone-based photopolymerization initiator include, for example, alkyl phenyl ketone or a derivative thereof [eg, acetophenone such as 2,2-dimethoxy-2-phenylacetophenone, acetophenone diethyl ketal, diethoxyacetophenone or the like] Derivative, 2-hydroxy-2-methyl-1-phenylpropan-1-one (for example, manufactured by Ciba Specialty Chemicals)
"Darocur 1173"), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (for example, manufactured by Ciba Specialty Chemicals,
“Irgacure 369”), 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (for example, Ciba Specialty Chemicals,
"Irgacure 907"), oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone (for example, "Esacure-KIP", manufactured by Lambertie Spie Co.) Piophenone or a derivative thereof], benzyl or a derivative thereof [eg, benzyl, benzyldimethyl ketal (eg,
"Irgacure 651," manufactured by Ciba Specialty Chemicals, "Lucirin BDK" manufactured by BASF, etc.]].

Examples of the benzoin-based photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Benzoin isobutyl ether and the like. As the benzophenone-based photopolymerization initiator, benzophenone or a derivative thereof, for example, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 3,
3'-dimethyl-4-methoxybenzophenone, 4,
4'-methoxybenzophenone, 4-benzoyl-4 '
-Methyldiphenyl sulfide, 2,4,6-trimethylbenzophenone, (4-benzoylbenzyl) trimethylammonium chloride and the like. Examples of the thioxanthone-based photopolymerization initiator include 2- or 4
-Isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and the like. Further, as other photopolymerization initiators, for example, 1-hydroxycyclohexyl phenyl ketone (for example, “Irgacure 184” manufactured by Ciba Specialty Chemicals), methylphenylglyoxyester (manufactured by AKZO NOBEL Coating KK, “Vicure 5”)
5 ") or 3,6-bis (2-morpholinoisobutyl)-
9-butylcarbazole (manufactured by Asahi Denka Co., Ltd., “A-Cure
3 "), titanocene compounds and the like.

A photopolymerization initiator system in which a bisacylphosphine oxide-based photopolymerization initiator is combined with another photopolymerization initiator is, for example, a product name “Irgacure 1700” [bis (2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide / 2-hydroxy-2-methylphenylpropan-1-one = 25/75
(% By weight)], trade name “Irgacure 1800” [bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenyl ketone = 25/75 (% by weight) (Both manufactured by Ciba Specialty Chemicals Co., Ltd.). The amount of the photopolymerization initiator used is 100% of the total amount of the urethane (meth) acrylate oligomer (A) and the ethylenically unsaturated compound (B).
0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per part by weight.
It is often selected from the range of about 5 to 5 parts by weight (for example, 1 to 5 parts by weight).

[(D) Tertiary amine] The feature of the present invention is that
By combining the bisacylphosphine oxide-based photopolymerization initiator (C) and the tertiary amine (D) in a system substantially free of a tin component, even if water is present, the system can be used for a long period of time. The point is that the deactivation of the component (C) is remarkably suppressed, and the high photoactivity of the component (C) is maintained. Further, the composition of the present invention generally does not substantially contain a lead component. The tertiary amine in the composition of the present invention is:
(A) It may be caused by a urethanization catalyst for synthesizing the component, or may be caused by a tertiary amine added to the composition.

As the tertiary amine compound, a compound having at least one tertiary nitrogen atom in one molecule can be used. Examples of the tertiary amine having one nitrogen atom in the molecule include aliphatic amines [tri-C _1-6 alkylamine such as triethylamine and tributylamine;
(Dimethylamino) propionitrile], alicyclic amines [N, N-dimethylcyclohexylamine, N, N
- di C _1-6 alkyl -C _3-10 cycloalkyl amines such as diethyl cyclohexylamine, N, N- dicyclohexyl methylamine, etc.], heterocyclic amines [N- methylmorpholine, N- ethylmorpholine, N- (2 -Hydroxyethyl) morpholine, N-methylpyrrolidone, etc.], and aromatic amines (N, N-dimethyl-p-toluidine, etc.).

The tertiary amine having two nitrogen atoms in the molecule includes, for example, aliphatic amines [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, bis (2-dimethylaminoethyl) ether, ethylene glycol bis (3-dimethylaminopropyl) Ether, etc.], alicyclic amine [N'-cyclohexyl-
N, N-dimethylformamidine, etc.], heterocyclic amines [N, N'-dimethylpiperazine, trimethylpiperazine, 1,2-piperidinoethane, bis (aminopropyl) piperazine, N-methyl-N '-(2-hydroxy Ethyl) piperazine, N- (N ′, N′-dimethylaminoethyl) morpholine, bis (morpholinoethyl) ether, bis (2,6-dimethylmorpholinoethyl) ether, 1,2-dimethylimidazole, N-methylimidazole, Diazabicyclo [2.2.2] -octane (DABCO), 1,4-diazabicyclo [3.3.0] oct-4-ene-,
5-diazabicyclo [4.3.0] non-5-ene (D
BN), 1,8-diazabicyclo- [5.4.0] -undec-7-ene (DBU) and phenol salts thereof,
Octylates and the like].

The tertiary amine having three nitrogen atoms in the molecule includes, for example, aliphatic amines [N, N, N ',
N ', N "-pentamethyldiethylenetriamine, N,
N, N ', N ", N" -pentamethyldipropylenetriamine, tetramethylguanidine and the like], alicyclic amines [N-cyclohexyl-N', N ', N ", N" -tetramethylguanidine and the like], A heterocyclic amine [N-methyl-N '-(2-dimethylamino) ethylpiperazine,
1,5,7-Triazabicyclo [4.4.0] dec-5
-En etc.]. Examples of the tertiary amine having four nitrogen atoms in the molecule include aliphatic amines [1,1,4,7,10,10-hexamethyltriethylenetetramine and the like] and heterocyclic amines [1,3 , 5-tris (N, N-dimethylpropyl) hexahydro-1,3,5-triazine and the like].

These tertiary amines can be used alone or in combination of two or more. Of these tertiary amines, 1
Compounds having at least two tertiary nitrogen atoms in the molecule are preferred.

The amount of the tertiary amine to be used can be selected within a range that does not impair the stability of the photopolymerization initiator (C). For example, the amount of the tertiary amine is 0.001 to 0.001 to the polyurethane (meth) acrylate oligomer (A). 1.0% by weight, preferably 0.005 to 0.5% by weight, more preferably 0.01%
To 0.2% by weight (particularly 0.01 to 0.1% by weight). When the use amount of the tertiary amine is less than 0.001% by weight, the activity of the component (C) tends to decrease in the presence of moisture,
If the content exceeds 1.0% by weight, the Young's modulus of the cured film tends to decrease. The ratio of the bisacylphosphine oxide-based photopolymerization initiator (C) to the tertiary amine (D) is in a range where the stability of the component (C) can be maintained, for example, the former / the latter = 100
/0.1 to 100/10 (weight ratio), preferably 100
/0.5 to 100/5 (weight ratio), more preferably 1
It is about 00/1 to 100/3 (weight ratio).

[Photopolymerization Accelerator (Sensitizer)] In order to accelerate the photopolymerization reaction by a photoinitiator, if necessary, various photopolymerization accelerators such as dialkyl Aminobenzoic acid or a derivative thereof (eg, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, etc.), phosphine-based photopolymerization accelerator (arylphosphine such as triphenylphosphine, alkylphosphine such as trialkylphosphine, etc.) (A phosphine-based compound) or the like. These polymerization accelerators can be used alone or in combination of two or more. The addition amount of the polymerization accelerator is, for example, 100 parts by weight of the total amount of (A) the polyurethane (meth) acrylate oligomer and (B) the ethylenically unsaturated compound. Can be selected from the range of about 0.01 to 10 parts by weight.

[Stabilizer, Antioxidant] A small amount of a stabilizer may be added to the composition of the present invention. As the stabilizer, for example, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a sulfur-based antioxidant, and the like can be used. As the hindered phenol-based stabilizer, a compound having a hydroxyphenyl group substituted with a t-butyl group,
For example, 2,6-di-t-butylhydroxytoluene,
2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), triethylene glycol-bis [(3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3 , 5-Di-t-butyl-
4-hydroxyphenyl) propionate], 2,4-
Bis [(n-octylthio) -6- (4-hydroxy-
3,5-di-t-butylanilino)]-1,3,5-triazine, 2,2-thio-diethylenebis [3- (3
5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,
2'-thiobis (4-methyl-6-t-butyl) phenol, 4,4'-thiobis (3-methyl-6-t-butyl) phenol, N, N'-hexamethylenebis (3,
5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, and the like.

The hindered amine antioxidants include:
For example, bis- (2,2,6,6-tetramethylpiperidinyl-4-sebacate), dimethyl-1-succinate
(2-hydroxyethyl) -4-hydroxy-2,2,
6,6-tetramethylpiperidyl polycondensate and the like. Examples of the sulfur-based antioxidants include dilauryl-3,3'-dithiopropionate, dimyristyl-
3,3'-dithiopropionate, distearyl-3,
3'-dithiopropionate, pentaerythritol-
Tetrakis- (β-lauryl-thiopropionate),
Ditridecyl-3,3'-dithiopropionate, 2-
And mercaptobenzimidazole.

The addition amount of these antioxidants is usually 2.0% by weight or less (0 to 2% by weight) based on the whole resin composition.
From the balance between the amount of hydrogen gas generated and the curing speed,
It is preferably about 0.1 to 1.0% by weight.

The resin composition of the present invention may further contain, if necessary, other than the above components, for example, stabilizers such as antioxidants and ultraviolet absorbers other than those described above, plasticizers, organic solvents, silane coupling agents, Various additives such as a surfactant, a coloring pigment, and organic or inorganic fine particles may be added. The photocurable resin composition of the present invention containing a tertiary amine substantially without a tin component comprises (A) a urethane (meth) acrylate oligomer, (B) an ethylenically unsaturated compound, and (C) a bisacylphosphine. It can be prepared by mixing an oxide-based photopolymerization initiator, and (D) the tertiary amine may be due to an additional addition to the above components, and the tertiary amine used in the preparation of the component (A) It may be due to an amine catalyst. For example, (A) a urethane (meth) acrylate oligomer prepared in the absence of a catalyst or in the presence of a catalyst other than a tin-based catalyst, a lead-based catalyst, and a tertiary amine catalyst;
The photocurable resin composition may be obtained by mixing (B) an ethylenically unsaturated compound, (C) a bisacylphosphine oxide-based photopolymerization initiator, and (D) a tertiary amine. , (D) a urethane (meth) acrylate oligomer prepared in the presence of a tertiary amine, (B) an ethylenically unsaturated compound, and (C) a photopolymerization initiator. A composition is obtained. After the component (A) is prepared by the urethane-forming reaction in the presence of the (D) tertiary amine, the composition contains
If necessary, the component (D) may be further added.

In the method of the present invention, the (C) bisacylphosphine oxide-based photopolymerization initiator can be stabilized by coexisting with the (D) tertiary amine without containing a tin component. In particular, even in the presence of moisture, the above (C)
The photopolymerization initiator can be prevented from being deactivated, and can be stabilized for a long period of time. Therefore, the photocurable resin composition of the present invention does not deactivate due to hydrolysis of the photoinitiator bisacylphosphine oxide even when stored for a long period of time, has high coatability at high speed, and has a low ultraviolet irradiation dose. However, it shows high curability. Therefore, the method using the resin composition of the present invention is useful as a coating material for substrates such as plastic, wood, ceramics, paper, and glass, a light forming material, a three-dimensional three-dimensional molding material, a printing plate material, and the like. Further, the photocurable resin composition generates a small amount of hydrogen. Therefore, it is particularly useful for coating optical fibers.

The photocurable resin composition for coating an optical fiber comprises:
Useful for coating glass fibers directly or indirectly with a cured film. According to the resin composition of the present invention, a photocurable coating material for directly coating a glass fiber with a primary coating layer (primary layer), at least a primary coating layer ( It is suitable as an ultraviolet curing type coating material for indirectly coating the optical fiber via the primary layer), and the coating material for indirectly coating the optical fiber includes a secondary coating layer (secondary layer) of the optical fiber, 3
Material (coating material) for the fiber strand, such as the secondary coating layer (coloring material layer), tape-forming material for tape-forming a tape composed of multiple fiber cores, coating material for drop wire, waterproofing Examples include fiber cable covering materials and optical submarine cable cushioning materials. The optical fiber coated with the cured film of such a resin composition is obtained by directly coating a glass fiber with the resin composition or indirectly coating the optical fiber, and irradiating the fiber with light (particularly ultraviolet light). It can be obtained by curing the resin composition.

[0063]

The photocurable resin composition of the present invention can prevent inactivation of bisacylphosphine oxide-based photopolymerization initiator due to hydrolysis for a long period of time by combining with a tertiary amine, and achieve low UV light. High photocurability can be maintained even at the irradiation dose, and high-speed coating property is also high. Further, the characteristics of the resin composition can be maintained at a high level for a long time, and the amount of generated hydrogen is small. Therefore, it is possible to form a coating material in which the characteristics of the cured film are stable, and it is possible to enhance the long-term reliability of the optical fiber. Therefore, the photocurable resin composition of the present invention is extremely useful as an optical fiber coating material.

[0064]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. (1) Preparation of polyether [Synthesis Example 1] Hydrogenated dimer diol (Toagosei Co., Ltd.)
Made, trade name "Pespol HP-1000", OH value 20
049 mg / KOH) 5.49 kg, potassium hydroxide 25 g
Was added and 4.51 kg of propylene oxide was subjected to addition polymerization at 110 to 120 ° C. in a nitrogen stream. After the reaction,
Water and synthetic magnesium silicate (Kyowa Chemical Co., Ltd.)
"Kyoward 600") was added, potassium hydroxide was adsorbed, and the mixture was removed by filtration. Next, the water content is reduced to 0.1.
Dewater until the weight is less than 0.05% by weight, and the number average molecular weight is 100
0 (hereinafter referred to as “DDP-1000”. Hydrogenated dimer diol residue content: 56.0% by weight)
was gotten.

[Synthesis Example 2] Roxanol (content of 12-hydroxystearyl alcohol: about 80% by weight, manufactured by Henkel Hakusui Co., Ltd., OH value: 357 mg / KOH) 3.1 k
g, 25 g of potassium hydroxide, and 11
6.90 kg of propylene oxide was subjected to addition polymerization at 0 to 120 ° C. After completion of the reaction, water and synthetic magnesium silicate (Kyowa Chemical Co., Ltd., "Kyoward 600") were added, potassium hydroxide was adsorbed, and then removed by filtration. Next, dehydration is performed until the water content becomes 0.05% by weight or less.
Called "LXP-1000". 12-hydroxystearyl alcohol residue content: 21.8% by weight).

(2) Synthesis of tertiary amine-containing polyurethane (meth) acrylate oligomer [Synthesis Example 3] 2,4-tolylene diisocyanate 69
6.8 g, "DDP-1000" 1 obtained in Synthesis Example 1
000 g of the mixed solution was reacted at a temperature of 70 to 80 ° C. for 3 hours under a nitrogen atmosphere. The reaction mixture is then added to 40
After cooling to ℃, replace the inside of the reaction vessel with dry air,
2,6-di-t-butylhydroxytoluene (BHT)
0.72 g, 2-hydroxyethyl acrylate 69
6.0 g was charged, the temperature was gradually raised, and the reaction was carried out at a temperature of 60 to 70 ° C. for 2 hours. Then, 1.20 g of 1,5,7-triazabicyclo [4.4.0] decene-5 (TABD)
And further reacted for 4 hours, and an isocyanate group (NCO) was detected in an infrared absorption spectrum (IR spectrum).
It was confirmed that there was no absorption caused by the above, and a polyurethane acrylate oligomer (hereinafter, simply referred to as “oligomer A”) was obtained.

[Synthesis Example 4] In the same manner as in Synthesis Example 3,
209.2 g of 4-tolylene diisocyanate, polytetramethylene ether glycol (number average molecular weight 300
0) 171.9 g of "DDP-10" obtained in Synthesis Example 1
00 "79.6 g, tripropylene glycol 28.7
g, ethylene bis (hydroxyethyl sulfide) 5.
8 g were reacted, and the resulting reaction mixture was mixed with BHT 0.1 g.
21 g, 2-hydroxyethyl acrylate 204.8
g, and 0.7 g of TABD, and a polyurethane acrylate oligomer (hereinafter, simply referred to as “oligomer B”) was obtained in the same manner as in Synthesis Example 3.

[Synthesis Example 5] 696.8 g of 2,4-tolylene diisocyanate was obtained using LXP-1 obtained in Synthesis Example 2.
000 "and 1000 g of a mixed solution in a nitrogen atmosphere at 70 to 8
The reaction was performed at a temperature of 0 ° C. for 3 hours. Next, after cooling the reaction mixture to 40 ° C., the inside of the reaction vessel was replaced with dry air, and 0.72 g of BHT and 696.0 g of 2-hydroxyethyl acrylate were charged.
The reaction was performed at 0 to 70 ° C for 2 hours. Then, 1,1,4
0.48 g of 7,10,10-hexamethyltriethylenetetramine (HMTA) was charged and reacted for further 4 hours, and it was confirmed by IR spectrum that there was no absorption due to NCO groups. "Oligomer C").

[Synthesis Example 6]
662.0 g of 4-tolylene diisocyanate, polytetramethylene ether glycol (number average molecular weight 300
0) 474.0 g, polyoxypropylene glycol (number average molecular weight 1000) 220.0 g, tripropylene glycol 96.4 g, “Roxanol” 37.7
g, and the resulting reaction product was added with BHT 0.6
4 g, 2-hydroxyethyl acrylate 649.6
g, N, N, N ', N'-tetramethylethylenediamine (TMEDA) 2.14 g, and a polyurethane acrylate oligomer (hereinafter, simply referred to as "oligomer D") was obtained in the same manner as in Synthesis Example 3.

[Synthesis Example 7]
696.8 g of 4-tolylene diisocyanate, polytetramethylene ether glycol (number average molecular weight 650)
552.5 g and 450.0 g of polyoxypropylene glycol (number average molecular weight 3000) were reacted, and the obtained reaction product was mixed with 0.72 g of BHT, 696.0 g of 2-hydroxyethyl acrylate, N, N, N ', N ″,
N "-pentamethyldiethylenetriamine (PMDET
A) 1.20 g was added, and a polyurethane acrylate oligomer (hereinafter, simply referred to as “oligomer E”) was obtained in the same manner as in Synthesis Example 3.

(3) Synthesis of tin catalyst-containing polyurethane (meth) acrylate oligomer [Synthesis Example 8] Urethane-forming catalyst TMEDA.
Instead of 14 g, dibutyltin dilaurate (DBTD
L) A polyurethane acrylate oligomer (hereinafter, simply referred to as "oligomer F") was obtained in the same manner as in Synthesis Example 6 except that 0.43 g was used.

[Synthesis Example 9] The urethanization catalyst P of Synthesis Example 7
Instead of 1.20 g of MDETA, tetra-n-butyl-
1,3-diacetoxydistannoxane (TK-1)
A polyurethane acrylate oligomer (hereinafter, simply referred to as “oligomer G”) was obtained in the same manner as in Synthesis Example 7 except that 24 g was used.

(4) Stability of bisacylphosphine oxide in the presence of water 100 g of isobornyl acrylate (IBXA), bisacylphosphine oxide photoinitiator [Irgacure 1700: bis (2,6-dimethoxybenzoyl)-
2,4,4-trimethylpentylphosphine oxide /
2-hydroxy-2-methylphenylpropan-1-one = 25/75 (% by weight) mixture, Ciba Specialty Chemicals Co., Ltd.] 3 g, the following urethanization catalyst 0.0
Water is added to 4 g of the mixture to provide a water content of 0.15% by weight.
Were prepared. Urethane-forming catalyst 1,8-diazabicyclo- [5.4.0] -undecene-7 (DBU) N, N, N ', N ", N" -pentamethyldiethylenetriamine (PMDETA) N, N, N', N '-Tetramethylethylenediamine (TMEDA) Dibutyltin dilaurate (DBTDL) Tetra-n-butyl-1,3-diacetoxydistannoxane (TK-1) The above sample was heated at 60 ° C. for 48 hours, and then acylated by NMR. The decomposition rate of phosphine oxide was measured. Table 1 shows the results.

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[Table 1] (5) Preparation of UV-curable resin composition Examples 1 to 5 and Comparative Examples 1 to 2 “Oligomer A” to “Oligomer G” obtained in Synthesis Examples 3 to 9 and acrylic monomer [isobornyl acrylate (IBXA) ), N-vinylpyrrolidone (NVP), tricyclodecane dimethanol diacrylate (R-68)
4)], photoinitiator [Irgacure 1700: bis-
(2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide / 2-hydroxy-
2-methylphenylpropan-1-one = 25/75
(Weight%) mixture, manufactured by Ciba Specialty Chemicals Co., Ltd.], to prepare an ultraviolet-curable resin composition having the composition shown in Table 2. The amount of generated hydrogen and the change in physical properties of the cured film of the obtained resin composition were examined as follows. Table 2 shows the results. In Table 2, the amount of the tertiary amine is as follows:
The amount is based on the polyurethane acrylate oligomer.

(6) Evaluation method (a) Preparation of cured film (cured film) At 40 ° C. for a certain period (0, 15, 30, and 45 days)
Each of the left ultraviolet curable resin compositions was applied on a glass plate to a thickness of about 200 μm, and irradiated with ultraviolet rays (wavelength: 350 nm, metal halide lamp) in a nitrogen atmosphere at 25 mJ / cm ² and 500 mJ / cm.
Irradiation was performed in step ² to obtain a cured film (cured film). (B) Measurement of hydrogen gas generation amount A film obtained by curing the ultraviolet curable resin composition immediately after the production with an irradiation amount of ultraviolet light (wavelength: 350 nm) of 500 mJ / cm ² was subjected to 24 hours in an atmosphere of 23 ° C. and 50% RH. After leaving for more than an hour, the cured film was put into a headspace bottle, left at 100 ° C. for 48 hours, and the amount of hydrogen gas generated was measured by gas chromatography. (C) Measurement of Young's Modulus and Retention Rate The cured film obtained in (a) above was peeled off from the glass plate and allowed to stand in an atmosphere of 23 ° C. and 50% RH for 24 hours or more. Under the condition of 1 mm / min, the Young's modulus (2.5% tensile modulus) was measured. 45
The retention was calculated by the following equation based on the Young's modulus of the cured film prepared with the resin composition left standing for one day and the cured film prepared with the initial (left standing) resin composition. Retention rate = (Young's modulus after 45 days) / (Young's modulus on day 0) × 100%

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[Table 2]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Setsu Uemura 2-17-85 Jusanhoncho, Yodogawa-ku, Osaka Takeda Pharmaceutical Co., Ltd. Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (72) Inventor Shohei Kosakai Matsuda-cho, Gunma Prefecture, Usui-gun Matsuda-cho 1-10, Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (72) Inventor Masatoshi Asano 1-chome, Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture 10 Silicone Electronic Materials Technology Laboratory, Shin-Etsu Chemical Co., Ltd.

Claims (11)

[Claims] 1. A urethane (meth) acrylate oligomer, (B) an ethylenically unsaturated compound, and (C) a compound represented by the following formula (i): (Wherein, R ₁ is a linear or branched C _1-12 alkyl group,
A cycloalkyl group, a linear or branched C _1-12 alkyl group or an aryl group which may be substituted with a halogen atom, wherein R ₂ and R ₃ are the same or different and are a hydrogen atom, a linear or A branched C _1-12 alkyl group or a linear or branched C _1-12 alkoxy group, R ₄ and R ₅ Are the same or different and represent a hydrogen atom or a linear or branched C
_A photocurable resin composition containing a bisacylphosphine oxide-based photopolymerization initiator represented by the formula ( _1-12 alkyl group), and (D) a tertiary amine substantially free of a tin component. 2. A compound according to claim 1, wherein R ₁ is a branched C _6-12 alkyl group,
_5-10 cycloalkyl group, an aryl group which may be substituted by a linear or branched C _1-4 alkyl group, wherein R ₂ and R ₃ are the same or different and are a hydrogen atom, a linear or A branched C _1-4 alkyl group or a linear or branched C _1-4
An alkoxy group, R ₄ and R ₅ are the same or different and each represents a hydrogen atom or a linear or branched C _1-4 photocurable resin composition of claim 1 wherein the alkyl group. 3. The ratio of the bisacylphosphine oxide-based photopolymerization initiator to the tertiary amine is 100 / l = 100.
The photocurable resin composition according to claim 1, wherein the ratio is in the range of /0.1 to 100/10 (weight ratio). 4. The photocurable resin composition according to claim 1, wherein the urethane (meth) acrylate oligomer (A) contains a polyol having 14 to 40 carbon atoms as a polyol component. 5. The photocurable resin composition according to claim 1, wherein the polyol having 14 to 40 carbon atoms is an aliphatic diol derived from a higher fatty acid. 6. The polyol having 14 to 40 carbon atoms is at least one selected from hydrogenated dimer diol and 12-hydroxystearyl alcohol.
The photocurable resin composition according to the above. 7. The photocurable resin composition according to claim 1, wherein the proportion of the polyol having 14 to 40 carbon atoms is 1 to 50% by weight of the entire polyurethane (meth) acrylate oligomer. 8. The photocurable resin composition according to claim 1, which is used for coating an optical fiber. 9. A mixture of (A) a urethane (meth) acrylate oligomer, (B) an ethylenically unsaturated compound, and (C) a bisacylphosphine oxide-based photopolymerization initiator according to claim 1, and (D) tin Third containing substantially no components
A method for producing a photocurable resin composition containing a secondary amine. 10. An optical fiber in which a glass fiber is directly or indirectly coated with a cured film of the photocurable resin composition according to claim 1. 11. A method for coating an optical fiber, wherein a glass fiber is directly or indirectly coated with the photocurable resin composition according to claim 1, and the resin composition is cured by light irradiation.