JPH03199217A - Liquid curable resin composition - Google Patents

Abstract

PURPOSE: To provide a liq. curable resin compsn. which possesses excellent adhesion to a substrate, durability and other properties and is suitable for a coating material for an optical fiber, a top coat for an optical disk and the like by incorporating a specified urethane (meth)acrylate, a plurality of silane coupling agents and the like.

CONSTITUTION: A hydroxyl-contg. (meth)acrylate is reacted with a diol (e.g. ethylene glycol), and a diisocyanate to prepare urethane (meth)acrylate pref. having an no. average mol.wt. of 1,000 to 15,000. This urethane (meth)acrylate is mixed with a polymn. initiator, such as acetophenone, a monomer, such as cyclohexyl acrylate, and a silane coupling agent represented by formula 1 (R¹ represents a 1-20C alkylene; R² represents a 1-5C alkylene; R³ represents a 1-10C alkyl or the like; and x is 1 to 3) and formula II (R⁵ represents H or methyl) to obtain the liq. curable resin compsn.

COPYRIGHT: (C)1991,JPO

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a liquid curable resin composition, and in particular a liquid curable resin composition that has high adhesion to a substrate and is suitable for forming a cured film with excellent durability. The present invention relates to a resin composition.

[Conventional technology]

In the production of optical fibers, glass fibers are coated with a resin immediately after hot melt spinning for the purpose of protection and reinforcement. Such a coating generally consists of a primary coating layer and a secondary coating layer, of which the material forming the secondary coating layer includes:
Conventionally, UV-curable or thermosetting resins such as polyurethane-based, epoxy-based, silicone-based, fluorine-based, polybutadiene-based, etc. have been used. However, these −
The resin material used for the next coating layer generally has poor adhesion to the optical fiber, and has the drawback of reducing the strength of the optical fiber when it absorbs moisture.

In order to improve this drawback, Japanese Unexamined Patent Publication No. 59-9
No. 2947 proposes adding a silane coupling agent having an amino group to the resin material forming the secondary coating layer, and Japanese Patent Application Laid-open No. 63-215707 proposes the following:
The addition of a silane coupling agent having a mercapto group has been proposed.

[Problem to be solved by the invention]

However, with the resin materials added with the silane coupling agent described in these publications, the adhesion between the resulting primary coating layer and the optical fiber is insufficiently improved, and in particular, lateral pressure is applied to the optical fiber coated with these resin materials. However, the second coating layer may easily peel off from the glass fiber, and the durability of the coating is insufficient.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a liquid curable resin composition that has excellent adhesion to various substrates including optical fibers and provides a coating with excellent durability when used as a coating material.

[Means to solve the problem]

The present inventors have found that the above objectives are achieved by a resin composition with a specific composition in which two types of specific silane coupling agents are used in combination, and the adhesion and durability to substrates including optical fibers are significantly improved. It has been found that it is possible to form a coating with

That is, the present invention solves the problems of the prior art, and includes (A) urethane (meth)acrylate, (B) at least one selected from monofunctional monomers and polyfunctional monomers, (C) a polymerization initiator, and (D) a liquid curable resin composition (hereinafter simply referred to as composition) comprising a silane coupling agent represented by the following general formula (1) and a silane coupling agent represented by general formula (II). ).

General formula (I): ! l5-R'-Si(R2)3-x (OR3)x [wherein, R1 is an alkylene group of C1 to Coo, R2 is an alkyl group of C, -C5, and R3 is a C1 to CIO
alkyl group and R'0R2 (R' is C, ~C
1° alkylene group, R2 is the same as above)
It is a group selected from the groups represented by, and X is an integer of 1 to 3. ] General formula (II): R' 0 ]1 C1l□=C-C-0-R'-Si(R2)+-x(O
R") x [wherein, R5 is a hydrogen atom or a methyl group, and R1, RZ, R3, and , what is urethane (meth)acrylate?
It means a compound having a urethane bond and a (meth)acryloyl group. The urethane (meth)acrylate is
The number average molecular weight is usually 1.000-15,000, preferably 1,000-10,000.

According to the production example, this urethane (meth)acrylate typically contains about n moles of diol (II: number from 1 to 30) and about (, n+1) moles of diisocyanate per 12 moles of hydroxyl group-containing (meth)acrylate. It can be produced by reacting the following, and if necessary, a diamine may also be used as a reaction raw material. Each reaction raw material used in the production method will be explained below.

First, examples of hydroxyl group-containing (meth)acrylates include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate;
Polyoxyalkylene mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.
(Meth)acrylate; Partial (meth)acrylate of polyhydric alkanol such as trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate etc. Even if these are used alone,
Two or more types of diols may be used in combination, and examples of the diols used in the above production method include polyethers obtained by ring-opening (co)polymerizing one or more alkylene oxides such as ethylene oxide, propylene oxide, and tetrahydrofuran. Diol; ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,
6-hexanediol, neopentyl glycol, 1.
4-Cyclohexane dimetatool, bisphenol A1
Dihydric alcohol such as bisphenol F; an alkylene oxide adduct of a dihydric alcohol obtained by adding the alkylene oxide to the dihydric alcohol; acid, polyester diol obtained by reacting polybasic acids such as maleic acid, adipic acid, and sebacic acid;
Polycaprolactone diol obtained by reacting caprolactone with an alkylene oxide adduct of a hydrohydric alcohol; and dihydric alcohols such as bisphenol A, halogenated bisphenol A, bisphenol F, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, etc. Examples include polycarbonate diol obtained by reacting polydimethylsiloxane with phosgene; carpitol-modified polyol at the terminal or side chain of polydimethylsiloxane. Among these diols, polypropylene glycol, polytetramethylene glycol, ring-opened copolymers of tetrahydrofuran and propylene oxide, adducts obtained by adding alkylene oxide to bisphenol A or bisphenol F, polycarbonate diol, polycaprolactone diol, etc. preferable.

Further, as the diol, commercially available products may be used, such as PTMGlooO (Mitsubishi Chemical Industries @), PTMG200
0 (same), PTMG3000 (same), PPTG20
00 (Odogaya Chemical Industry @), -PPTG3000
(same), PPTG4000 (same), PTGL20
00 (same), DA300F (NOF ■), D
A400 (same), DB400 (same), DB900
(Same), DN-980 (Japan Polyurethane ■), 0
N-987 (same), 0N-982 (same), 0N-9
83 (same), PC-8000 (PPC, USA), EX
CENOL2020 (Asahi Olin ■), EXCEN
Product names include OL3020 (same) and Plaxel (Daicel).

These diols may be used alone or in combination of two or more.

Further, as the diisocyanate used in the above manufacturing method, for example, 2.4-)luene diisocyanate, 2.6-)
-) Luene diisocyanate, 1,3 xylene diisocyanate, 1,4-xylene diisocyanate, 1,5
-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3
'-Dimethyl 4.4'-diphenylmethane diisocyanate, 4.4'-diphenylmethane diisocyanate,
3.3'-dimethylphenylene diisocyanate, 4.
Examples include 4'-biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Among these diisocyanates, preferred are 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, and the like. These diisocyanates may be used alone or in combination of two or more.

Examples of diamines that can be used as appropriate in the above production method include diamines containing heteroatoms such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, paraphenylenecyamine, and 4,4'-diaminodiphenylmethane; D-230 (manufactured by Texakoke Gocal), Chefamine D-400 (same), Dix
Examples include polyether diamines such as 77'i 7D-2000 (same). The amount of these diamines used is usually 50% by weight or less of the amount of diol used.

As a more specific embodiment of the method for producing urethane (meth)acrylate, for example, (1) a diisocyanate and a diol are reacted to produce a polyurethane having an isocyanate group at the terminal, and a hydroxyl group-containing (meth)acrylate is added to this. (2) First, a hydroxyl group-containing (meth)acrylate and a diisocyanate are reacted in such a proportion that some of the isocyanate groups remain, and then the isocyanate groups of the resulting reaction product are reacted with a diol. and (3) a method in which predetermined amounts of hydroxyl group-containing (meth)acrylate, diisocyanate, and diol are mixed, and these three raw materials are reacted simultaneously.

In the urethane bond forming reaction in these methods, urethanization catalysts are used, such as copper naphthenate, cobalt naphthenate, zinc naphthenate, zinc laurate, dibutyltin laurate, triethylamine, and the like. This catalyst is about 0.01 to 1 part by weight per 100 parts by weight of total reactants.
Parts by weight are used.

Further, the reaction is usually carried out at about 30 to 80"C.

In the above method for producing urethane (meth)acrylate, the molecular weight of the target urethane (meth)acrylate can be adjusted by appropriately selecting the diol to be used and by changing the amounts of diol and diisocyanate added. .

Furthermore, in this method for producing urethane (meth)acrylate, a polyol other than trifunctional is used for the diol, a polyol other than trifunctional for the diamine, and a polyisocyanate other than trifunctional for the diisocyanate. They can be used together to the extent that the resulting urethane (meth)acrylate does not gel. The amount of polyol, polyamine or polyisocyanate used in combination is usually
The amount is 5 to 30 parts by weight per 100 parts by weight of diol, diamine or diisocyanate.

Here, examples of polyols other than trifunctional include addition products of glycerin and propylene oxide, glycerin, pentanetriol, butanetriol, tri(
Examples include hydroxypolyoxyprobyl) polysiloxane, polycaprolactone triol, polycaprolactone triol, liquid polybutadiene having more than two hydroxyl groups in one molecule, and hydrogenated products of this compound. Examples of the non-trifunctional boria bulk include diethylenetriamine, triaminopropane, polyoxypropyleneamine, and the like. Examples of polyisocyanates other than trifunctional include polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, and the like.

Monomer B and monofunctional monomers include, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, butoxyethyl acrylate, ethyldiethylene glycol acrylate, ethylhexyl acrylate, cyclohexyl acrylate, phenoxyethyl acrylate, dicyclo Pentadiene acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, methyltriethylene diglycol acrylate, isobornyl acrylate, isobornyl methacrylate, N-vinylpyrrolidone, N
-vinyl caprolactam, diacetone acrylic acid,
Examples include isobutoxymethylacrylamide, N,N-dimethylacrylamide, t-octylacrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acryloylmorpholine, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, and the like.

Examples of polyfunctional monomers include trimethylolpropane triacrylate, pentaerythritol triacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, butanediol diacrylate,
Hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane trioxyethyl acrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimetatool dimethacrylate, dicyclopentadiene diacrylate, dicyclopenkune diacrylate, Dicyclopentadiene dimethacrylate and the like can be mentioned.

Among these monofunctional monomers and polyfunctional monomers, preferred are 2-ethylhexyl acrylate,
These include cyclohexyl acrylate, phenoxyethyl acrylate, isobornyl acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, dicyclopentenyl acrylate, tricyclodecane dimetatool diacrylate, and trimethylolpropane triacrylate.

These monofunctional monomers and polyfunctional monomers may be used alone or in combination of two or more thereof, or may be used alone or in combination of two or more thereof.

Examples of the polymerization initiator include dimethoxyphenylacetophenone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, methylacetophenone, chlorobenzophenone, dimethoxybenzophenone, and cyanophenone. Benzophenone, Michler's ketone, benzoinpropyl ether, acetophenone diethyl ketal, benzoin ethyl ether, hydroxycyclohexylphenyl ketone, benzyl dimethyl ketal, (isopropylphenyl)hydroxymethylpropan-1-one, hydroxymethylphenylpropan-1-one, trimethylbenzoyl Examples include polymerization initiators such as diphenylphosphine oxide and thioxanthone compounds. These polymerization initiators can be used alone or in combination of two or more.

In addition, the polymerization initiator may include a sensitizer (polymerization accelerator) such as an akin-based compound, if necessary, within a range that does not impede the effects of the present invention.
Can be used together.

(D) Sheen force/pulling In the general formula (1), the alkylene group of R1 is:
Examples of the alkyl group for R2 include methylene group, ethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group, pentadecamethylene group, octadecamethylene group, etc.
Methyl group, ethyl group, propyl group, pentyl group, etc., R
Examples of the alkyl group in R2 include the same alkyl group as R2, hexyl group, octyl group, decyl group, etc., and examples of the alkylene group in R4 include methylene group, ethylene group, propylene group, tetramethylene group, hexamethylene group, octyl group, etc. Examples include methylene group.

Specific examples of the silane coupling agent represented by general formula (I) include T-mercaptomethyltrimethoxysilane,
Examples include T-mercaptoethyltrimethoxysilane, T-mercaptopropyltrimethoxysilane, T-mercaptobutyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and T-mercaptopropylmethyldimethoxysilane. Among these, preferred are γ-mercaptopropyltrimethoxysilane and the like.

Specific examples of the silane coupling agent represented by general formula (II) include γ-methacrylmethyltrimethoxysilane, T-methacrylethyltrimethoxysilane, γ-methacrylpropyltrimethoxysilane, T-methacrylbutyltrimethoxysilane, Examples include T-acrylpropyltrimethoxysilane, γ-methacrylpropyltrimethoxysilane, and γ-methacrylpropylmethyldimethoxysilane. Among these, preferred are T-methacrylpropyltrimethoxysilane and the like.

The composition of the present invention includes general formula (1) and general formula (II).
) Silane coupling agents other than the silane coupling agents mentioned above can be used alone or in combination of two or more, if necessary. Examples of such other silane coupling agents include A 1003 and KBC10.
03, KBE 1003, KBM 1003, KBM3
03, KBM 403, KBE 402, KBM
603, KBM 602, KBM 903, KB
Examples include those commercially available under trade names such as E 573 and KBM 703 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Preferable blending ratio of each component in the composition of the present invention is as follows:
(A) Component urethane (meth)acrylate is 25 to 8
5% by weight, particularly preferably 40-80% by weight, (
B) at least one selected from monofunctional monomers and polyfunctional monomers for fi and min is 10 to 70% by weight, particularly preferably 15 to 60% by weight, and the polymerization initiator as component (C) is 1 to 70% by weight. 5% by weight, preferably 1.5-4% by weight,
The amount of the silane coupling agent represented by general formula (1) and -r formula (II) as component (D) is 0.1 to 10% by weight, particularly preferably 0.1 to 2% by weight, respectively.

In addition, when a silane coupling agent other than the silane coupling agent of general formula (1) and general formula (I[) is used in combination, the amount used is 0.1 to 10% by weight of the composition.
~2% by weight is preferred.

In addition to the above-mentioned components, various additives such as colorants, anti-aging agents, storage stabilizers, leveling agents, etc. may be added to the composition of the present invention as necessary. can. The amount of each of these additives added is usually about 10% by weight or less in the composition.

The composition of the present invention can be prepared by blending the required components in a predetermined ratio, and the mixing method is not particularly limited.

The viscosity of some products of the present invention is usually 1 at 25°C.
00 (1-20000cP, preferably 2000-1
0000 cP.

This composition is cured by various types of radiation, such as X-rays, electron beams, ultraviolet rays, and visible light, and after curing,
At 23°C, typically 0.01-100kg/mm
It shows a Young's modulus of 2.

〔Example〕

EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.

Synthesis Example 1 In a reaction vessel equipped with a stirrer, 261 g of 2.4-)luene diisocyanate, 1 g of dibutyltin dilaurate, and the polymerization inhibitor 2.6-di-t-butyl-4-methylphenol Ig were charged. 116 g of 2-hydroxyethyl acrylate was added while controlling the temperature of the mixture below 20''C.

After the addition, the reaction was further continued for 1 hour at 10 to 20"C, and then polyether diol, which is a copolymer of tetrahydrofuran and 3-methyltetrahydrofuran (manufactured by Fukadogaya Chemical Co., Ltd.: PTGL-2000, number average molecular weight 2000) was added.
; hereinafter referred to as polyether (1)) was added to the reaction I mixture in the reaction vessel while maintaining the temperature at 40-50"C. Then, the reaction was carried out at 40-50°C for 3 hours. After the reaction was continued, the reaction was terminated and a polymer having a number average molecular weight of about 4800 was obtained.Hereinafter, this polymer will be referred to as polymer (A).

Synthesis Example 2 Same as Synthesis Example 1 except that polyether diol in Synthesis Example I was replaced with 2000 g of polytetramethylene glycol (Mitsubishi Kasei Corporation ■, PTHG 2000; hereinafter referred to as polyether (2)) with a number average molecular weight of 2000. Similarly, a polymer having a number average molecular weight of about 4,800 was obtained. Hereinafter, this polymer will be referred to as polymer (B).

Synthesis Example 3 In Synthesis Example I, polyether diol was replaced with polypropylene glycol (EXENOL3020 manufactured by Asahi Glass).
A polymer having a number average molecular weight of about 6,800 was obtained in the same manner as in Synthesis Example 1 except that 3,000 g of polyether (3) was used.

Hereinafter, this polymer will be referred to as polymer (C).

Synthesis Example 4 In the synthesis example, polyether diol was mixed with 1000 g of polyether (1) and poly-[--thyl (3)
A polymer having a number average molecular weight of about 5,800 was obtained in the same manner as in Synthesis Example 1 except that 1,500 g of the mixture was used. Hereinafter, this polymer will be referred to as polymer (D).

Synthesis Example 5 In Synthesis Example 1, the diisocyanate was changed to 333g of isophorone diisocyanate, and the polyether diol was changed to 1000g of polyether (2) and polyether (3).
A polymer having a number average molecular weight of about 5,800 was obtained in the same manner as Synthesis Example 1 except that 1,500 g of the mixture was used.

Hereinafter, this polymer will be referred to as polymer (E).

Examples 1-10. Comparative Examples 1 to 3 Compositions of Examples and Comparative Examples were obtained according to the formulations shown in Table 1. These compositions were tested for Young's modulus, curing rate, adhesion, adhesion after heat treatment, and ironing resistance using the methods described below. The results are shown in Table 1.

After applying the Yyl' rate Mi precept to a thickness of 0.2 mm on a glass plate, it was cured by irradiating it with ultraviolet rays using a metal halide lamp so that the total irradiation energy amount was IJ/cm2. Ta. The obtained cured film was cut into short pieces with a width of 6 mm, and the Young's modulus of the cured film at -40°C and 23°C was measured using a tensile test method based on JIS K6911 with a test length of 25 mm.

After applying the hardening rate composition to a thickness of 0.04 mm on a glass plate, it was irradiated with ultraviolet rays using a metal halide lamp under two conditions in which the total irradiation energy amount was 10 mJ/c++2 and 500 mJ/cm2. It was cured and a sample was prepared.

Samples of the two types of cured products obtained were extracted using a Soxhlet extractor using methyl ethyl ketone as a solvent for 12 hours, and then vacuum-dried at 50°C for 8 hours. The gel fraction was measured from the change in weight before and after treatment. Then, when the total irradiation energy amount is 10 mJ/cm2 and 5
00 mJ/cm2 (10 mJ/cm2)
The gel fraction (gel fraction in the case of 1500 mJ/cm2) was used as an index of the curing rate.

Shishunsha (a) The thickness of the composition after curing is 0.2 on a quartz plate.
After applying the coating in an amount of 1.0 mm, ultraviolet rays were irradiated thereon using a metal halide lamp so that the total irradiation energy amount was IJ/cm 2 to obtain a cured film.

(b) The cured film on the quartz plate was left on the quartz plate in the form of a tape with a width of 1 cm, one end of the cured film was pulled in a direction perpendicular to the quartz plate to peel it off, and the force required for peeling was measured. Similar measurements were performed three times, and the average value was evaluated as the adhesion of the cured film to the quartz plate.

A cured film was obtained in the same manner as in (a) Adhesion (a) of "Crystal Processing" and used as a sample.

(b) The above sample was stored under 60'CX95%R11 conditions for 7 days.

(C) This was carried out for one day at 23°C x 50%.
After adjusting the condition, the cured film on the quartz plate was left in the form of a tape with a width of 1 cm, and one end of the cured film was peeled off by pulling it in a direction perpendicular to the quartz plate, and the force required for peeling was measured. A similar test was conducted three times, and the average value was evaluated as the adhesion after heat treatment.

A quartz rod was heated to 2000°C using an optical fiber drawing device, and the outer diameter was 125 μm at a drawing speed of 60 m/min.
The composition was applied to the quartz fiber immediately after production, and the composition was applied using an ultraviolet lamp with an output of 3 kW.
It was cured by irradiating it with ultraviolet light. A secondary coating composition prepared as described below was further applied onto the quartz fiber thus pre-coated, and cured by irradiation with ultraviolet rays in the same manner as above. The optical fiber thus obtained had an outer diameter of 200 μm after the secondary coating and an outer diameter of 250 μm after the secondary coating.

The optical fiber thus produced was cut into a length of 30 cm, and with a load of 200 g applied thereto, the fiber was hung on a round rod of 5.2 mm diameter and reciprocated over a distance of 5 cm. After each IO cycle, observation was performed using an optical microscope (magnification: 100 times) to check for peeling between the coating layer and the fiber. The results were expressed as the number of strokes until peeling occurred.

(Composition for secondary coating) In a reaction vessel equipped with a stirrer, 145 g of 2,4-)luene diisocyanate and 0.5 g of diptyltin dilaurate were added.
and 0.2 g of polymerization inhibitor 2,6-di-t-butyl 4-methylphenol were charged, and then 127 g of 2-hydroxyethyl acrylate was added while controlling the temperature of the mixture to 20'C or less. After adding 10 more
After continuing the reaction for 1 hour at ~20 °C, the number average molecular ff
A mixture of 70 g of an ethylene oxide adduct of bisphenol A (DA400, manufactured by NOF ■) and 225 g of polyether (2) was added while maintaining the temperature of the reaction mixture in the reaction vessel at 40-50°C. Then, after continuing the reaction at 40-50°C for 3 hours,
The reaction was completed to obtain a polymer.

Next, to 567 g of the polymer thus obtained, 89 g of vinylpyrrolidone, 177 g of isobornyl acrylate, and 1-162 g of tricyclodecane dimethanol diacryle were added.
, trimethylolpropane triacrylate 70 g 1 and 1-hydroxycyclohexylphenyl ketone 29
g to prepare a secondary coating composition.

[Effects of the Invention] The liquid curable resin composition of the present invention has excellent adhesion to a base material, so when used as a material for the primary coating layer of an optical fiber, excellent adhesion to the optical fiber can be obtained, resulting in improved durability of the optical fiber. performance is significantly improved. Moreover,
Since the resulting coating has all the basic properties required of an optical fiber coating material, this liquid curable resin composition is extremely excellent as a coating material for optical fibers. In addition, due to its excellent adhesion to the base material, it can be used as a 2P resin or top coat for optical discs, for example.
It is also suitable as a coating material for substrates made of various materials such as paper, wood, plastic and metal.

Claims (1)

[Scope of Claims] (A) urethane (meth)acrylate, (B) at least one selected from monofunctional monomers and polyfunctional monomers, (C) a polymerization initiator, and (D) the following general formula (I) A liquid curable resin composition comprising a silane coupling agent represented by the formula (II) and a silane coupling agent represented by the general formula (II). General formula (I): HS-R^1-Si(R^2)_3_-_x(OR^3
)_x [wherein R^1 is an alkylene group of C_1 to C_2_0, R^2 is an alkyl group of C_1 to C_5, R^3 is an alkyl group of C_1 to C_1_0 and the formula: -R^4OR^ 2 (R^4 is an alkylene group of C_1 to C_1_0, R^2 is the same as above), and x is an integer of 1 to 3. ] General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^5 is a hydrogen atom or a methyl group,
R^1, R^2, R^3 and x are as defined for general formula (I)]