JP2001163939A - Curable resin composition and method for curing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition for a Fresnel lens excellent in adhesion to a substrate, free from separation during cure which causes turbidity and combining a specified refractive index with sufficient flexibility, and to provide a curing method thereof. SOLUTION: The curable resin composition comprises a polymerizable compound (A) comprising an epoxy compound having 5-95% of epoxy groups therein (meth)acryloylated and/or a polymerizable compound (B) obtained by reacting 5-60% of hydroxyl groups in a phenoxy resin with an α,β-unsaturated monoisocyanate, a photoradical polymerization initiator (C) and/or a photocationic polymerization initiator (D) and, if required, further comprising a polymerizable compound comprising a radically polymerizable compound (E) and/or a cationically polymerizable compound (F). The method for curing the curable resin composition for a lens comprises irradiation of the curable resin composition with ultraviolet rays and/or visible rays.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable resin composition used for an optical material and a method for curing the same. More specifically, video printers, projection televisions,
The present invention relates to a photocurable resin composition suitable for lenses such as a Fresnel lens, a lenticular lens, and a prism lens used for a liquid crystal display and the like, and a curing method thereof.

[0002]

2. Description of the Related Art Fresnel lenses have a large number of grooves on their surface, making it difficult to use glass for molding. For this reason, transparent resins such as polystyrene and polymethyl methacrylate are used. A resin sheet of a copolymer of styrene and methyl methacrylate was formed into a Fresnel lens shape by means such as hot press molding. However, the hot press molding has a problem that it is difficult to reproduce a complicated shape having a large area, and the productivity is very low. Therefore, as a method that replaces the conventional heating press, a method of forming a Fresnel lens on a base material in a short time with high production efficiency by using an ultraviolet curing technique has been generally used.

[0003] As the resin used for ultraviolet curing, a radical polymerization type resin diluted with a radical polymerizable monomer such as urethane acrylate or epoxy acrylate is generally used. Had a problem. Therefore, an example in which an epoxy compound having a small shrinkage ratio is mixed and used as a cationically polymerizable compound with a radically polymerizable compound is disclosed in JP-A-8-259649.
However, there is still a problem that a simple blend of an epoxy compound with a radical polymerizable compound cannot be separated during curing to avoid turbidity. In addition, Fresnel lenses are desired to increase scratch resistance because they cause scratches and the like during manufacture and transport and become defective, but if they are made flexible to increase scratch resistance, the refractive index decreases. When the refractive index is increased, the flexibility becomes insufficient, and the balance between the flexibility and the refractive index is still insufficient.

[0004]

SUMMARY OF THE INVENTION In view of these circumstances, the present invention has excellent adhesion to a substrate when used for a lens, particularly for a Fresnel lens, and separates during curing to cause turbidity. It is an object of the present invention to provide a resin composition having sufficient flexibility with a predetermined refractive index and a method for curing the same.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that, as a polymerizable compound, a certain ratio of epoxy groups in an epoxy compound is (meth) acryloylated and / or a phenoxy resin. The above problem was successfully solved by using a polymerizable compound obtained by reacting a certain percentage of hydroxyl groups with α, β-unsaturated monoisocyanate. That is, the present invention relates to a polymerizable compound (A) in which 5 to 95% of epoxy groups in an epoxy compound are (meth) acryloylated and / or 5 to 60% of hydroxyl groups in a phenoxy resin is an α, β-unsaturated monofunctional compound. It contains a polymerizable compound (B) obtained by reacting with an isocyanate and a photo-radical polymerization initiator (C) and / or a cationic photo-polymerization initiator (D). ) And / or a curable resin composition containing a cationically polymerizable compound (E), and a method of curing the curable resin composition for a lens in which the curable resin composition is cured by irradiating ultraviolet light and / or visible light. It is.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerizable compound (A) in which 5 to 95% of the epoxy groups in the epoxy compound used in the present invention have been (meth) acryloylated is referred to as a known thermosetting epoxy resin. By the method of the unsaturated monobasic acid, for example acrylic acid or methacrylic acid,
It is a resin obtained by reacting 95%, preferably 10 to 90%, and has both radical polymerizable and cationic polymerizable functions. When the ratio of the (meth) acryloylated epoxy group is less than 5%, the curing speed becomes low, and
%, The cure shrinkage increases.

As a thermosetting epoxy resin as a raw material, a thermosetting epoxy resin having at least two or more epoxy groups in one component, such as an ether-type bisphenol-type epoxy resin, produced by a known method, Any of novolak type epoxy resin, polyphenol type epoxy resin, aliphatic type epoxy resin, ester type aromatic epoxy resin, cycloaliphatic epoxy resin, ether / ester type epoxy resin, etc. can be used. You may use together.

The polymerizable compound (B) obtained by reacting 5 to 60% of the hydroxyl groups in the phenoxy resin used in the present invention with an α, β-unsaturated monoisocyanate is
It is a resin obtained by reacting a known phenoxy resin with α, β-unsaturated monoisocyanate with 5 to 60%, preferably 10 to 40% of the hydroxyl groups in the phenoxy resin.
If the ratio of hydroxyl groups reacted with the α, β-unsaturated monoisocyanate is less than 5%, the curability becomes insufficient, and conversely, 6%.
If it exceeds 0%, there is almost no effect on improving the curability, but it is economically disadvantageous. The phenoxy resin used as the raw material is, for example, a new heat-resistant polymer translated by Iwakura et al.
A polyhydroxy polyether resin obtained by a polyaddition reaction between a bisphenol compound and a bisepoxy compound described on pages 17 and 1971 (Kagaku Doujinshi), and an example of a commercially available product is Epototh Y.
P-50, YP-50S (Toto Kasei Co., Ltd.), UCA
R, PKHC, PKHH (Union Carbide Co., Ltd.
Examples of commercially available α, β-unsaturated monoisocyanates include methacryloyl isocyanate (manufactured by Nippon Paint Co., Ltd.) and isocyanate ethyl methacrylate (manufactured by Showa Denko KK). . JP-A-11-228688, JP-A-11-228
No. 228689.

In the curable resin composition of the present invention, in addition to the polymerizable compound (A) and / or the polymerizable compound (B), a radical polymerizable compound (E) and / or
Alternatively, a cationically polymerizable compound (F) can be contained. The radical polymerizable compound (E) used in the present invention is not particularly limited as long as it is radical polymerizable. Specific examples thereof include epoxy (meth) acrylate, urethane (meth) acrylate, and (meth)
An acrylate compound, a styrene-based compound, or the like, at least one of which is used.

The epoxy (meth) acrylate used in the present invention is generally a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. Is a compound having a polymerizable unsaturated bond produced by the method described in "Polyester Resin Handbook" (published by Nikkan Kogyo Shimbun, 1988) or "Coating Dictionary"
(Edited by The Coloring Materials Association, published in 1993). More specifically, epoxy (meth) acrylic compounds obtained by reacting an epoxy resin with an unsaturated monobasic acid, for example, acrylic acid or methacrylic acid. Or a saturated dicarboxylic acid and / or unsaturated dicarboxylic acid and a saturated polyester or unsaturated polyester having a terminal carboxyl group obtained from a polyhydric alcohol reacted with an α, β-unsaturated carboxylic acid ester group having an epoxy group. It is a polyester (meth) acrylate of a saturated polyester or an unsaturated polyester obtained by the above method.

Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether, its high molecular weight homologues, and novolak type polyglycidyl ethers. Examples of the saturated dicarboxylic acid used for the terminal carboxyl polyester include dicarboxylic acids having no active unsaturated group, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples of the unsaturated dicarboxylic acid include dicarboxylic acids having an active unsaturated group, such as fumaric acid, maleic acid, maleic anhydride, and itaconic acid.
As the polyhydric alcohol component, for example, ethylene glycol
Propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,
3-butanediol, 1,5-pentanediole, 1,
6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol
And polyhydric alcohols such as ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, and cyclohexane-1,4-dimethanol.

Glycidyl methacrylate is a typical example of the α, β-unsaturated carboxylic acid ester having an epoxy group used in the production of polyester (meth) acrylate.

The urethane (meth) acrylate used in the present invention is a known oligomer obtained by reacting a polyisocyanate with a polyol such as polyether polyol, polyester polyol, polyacryl polyol and hydroxyalkyl acrylate. Specifically, for example, polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate and ethylene glycol, 1,4 butanediol, neopentyl glycol, polycaprolactone diol, polyethylene diol, polyester diol, bisphenol Polyols such as A polyethoxydiol, bisphenol F polyethoxydiol, polycarbonate diol, polytetramethylene glycol, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) A) Reactants of hydroxyl-containing radically polymerizable unsaturated compounds such as acrylates.

The (meth) acrylate compound used in the present invention includes methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid
n-propyl, i-propyl (meth) acrylate,
N-butyl (meth) acrylate, sec-butyl (meth) acrylate, ter-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid 2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate,
Adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninyl (meth) acrylate , Piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate,
Furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, (meth) acrylic acid-1 , 1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro- (meth) acrylate-
i-propyl, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, (meth) acrylic acid 3
-(N, N-dimethylamino) propyl, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid-
2-hydroxypropyl, oligomers of polyester polyacrylates, N-vinylcaprolactam, acryloylmorpholine, phenoxyethyl (meth) acrylate, phenoxyethyloxy (meth) acrylate, 2-hydroxy-3-phenyloxydipropyl (meth) Acrylate, o-phenylphenyloxyethyl (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, tribromobenzyl (meth)
Acrylate, tetrabromobisphenol A polyethoxydi (meth) acrylate, bisphenol A diethoxydi (meth) acrylate, bisphenol A dipropoxydi (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi ( (Meth) acrylate, diethylene glycol di (meth) acrylate, ethylene guchicol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6 hexanediol di (meth)
Acrylate, nonanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
(Meth) acrylic esters such as trimethylolpropane tri (meth) acrylate and di (meth) acrylate of ε-caprolactone adduct of hydroxypivalate neopentyl glycol are exemplified.

The styrene compound used in the present invention includes styrene, α-, o-, m-, and styrene.
Examples include p-alkyl, nitro, cyano, amide, ester derivatives, butenes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene.

The cationically polymerizable compound (F) used in the present invention is not particularly limited as long as it is cationically polymerizable, and examples thereof include a compound having one or more epoxy groups in a molecule, a vinyl ether compound and the like. Can be used. Specifically, the epoxy compound may be one produced by a known method, for example, bisphenol A, bisphenol F, bisphenol S
And bisphenol-type epoxy resins obtained by reacting bisphenols such as tetrabisphenol A with epihalohydrin; obtained by reacting phenols such as phenol, cresol, halogenated phenol and alkylphenol with formaldehyde under an acidic catalyst. Novolak epoxy resin obtained by reacting phenol novolaks obtained with epihalohydrin; triphenolmethane epoxy resin obtained by reacting trisphenolmethane, triscresol methane, etc. with epihalohydrin; 3,4-epoxycyclohexylmethyl- 3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, vinylcyclohexene dioxide,
Alicyclic epoxy compounds such as modified polybutadiene epoxy (commercially available, for example, Celloxide 3000 and Celloxide EHPE-315 manufactured by Daicel Chemical Industries, Ltd.)
0, EPB-13, EPB-27 manufactured by Nippon Soda Co., Ltd.
Copolymerized epoxy resins such as copolymers of glycidyl (meth) acrylate and styrene, and copolymers of glycidyl (meth) acrylate and styrene and methyl (meth) acrylate (Nippon Oil & Fats Co., Ltd. as a commercial product) Sex CP-5
0, CP-50S, etc.); trimethylolpropane triglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Bisphenol A dipropoxy diglycidyl ether,
Examples thereof include aliphatic epoxy resins such as 2,2-dibromoneopentyl glycol diglycidyl ether. Examples of the vinyl ether compound include tetraethylene glycol divinyl ether.

The amount of the radical polymerizable compound (E) and / or the cationic polymerizable compound (F) used depends on the ratio of the (meth) acryloylated epoxy group in the polymerizable compound (A) used simultaneously, The radical polymerizable compound (E) varies with the total amount of the polymerizable compound (A) and / or the polymerizable compound (B) depending on the ratio of the hydroxyl group reacted with the α, β-unsaturated monoisocyanate in (B). ) And / or 90% by weight or less, preferably 80% by weight or less, as a total amount of the cationically polymerizable compound (F).
% By weight or less is appropriate. If this amount exceeds 90% by weight, strength is undesirably reduced.

As the photo-radical polymerization initiator (C) used in the present invention, a known one having photosensitivity between ultraviolet light and visible light can be used. Examples of those having photosensitivity to ultraviolet light include benzoins, acetophenones, benzophenones, anthraquinones, xanthones, thioxanthones, ketals, and phosphine oxides, and visible light polymerization having photosensitivity in the visible light region. As the initiator, for example, Yamaoka et al., “Surface”, 27 (7),
548 (1989), Sato et al., "3rd Collection of Polymer Material Forum", camphor-quinone, benzyl, trimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, bispentadienyltitanium described in 1BP18 (1994). -In addition to a single visible light polymerization initiator such as di (pentafluorophenyl), an organic peroxide catalyst / dye system, diphenyliodonium salt / dye, biimidazole / keto compound, hexaarylbiimidazole compound / In addition to hydrogen-donating compounds, mercaptobenzothiazole / thiopyrylium salts, metal arenes / cyanine dyes, and known composite initiators such as hexaallylbiimidazole / radical generators described in JP-B-45-37377. Agent systems. Further, bisacylphosphine oxide compounds represented by the following general formula (1) and acylphosphine oxide compounds represented by the following general formula (2) are also effective as polymerization initiators having photosensitivity from ultraviolet to visible light region.

[0019]

Embedded image

(Wherein, R ^{1 to} R ³ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group,
Represents an alkynyl group)

[0021]

Embedded image

(Wherein, R ^{4 to} R ⁶ each independently represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group,
These initiators have photosensitivity in a longer wavelength region than the conventionally used UV initiator (visible light region of 400 nm or more), and are excellent in light transmittance. Since it is cleaved by light irradiation to generate an acyl radical and a phosphinoyl radical, it is said that the polymerization initiation efficiency is higher than that of a conventionally used UV initiator.

Specific examples of the bisacylphosphine oxide compound of the general formula (1) used in the present invention include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide and bis (2,6-dichlorobenzoyl). −
2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-biphenylphosphine oxide, bis (2,6- Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2 6-dichlorobenzoyl)
-4-chlorophenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,2-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -dodecylphosphine oxide, bis (2,6-di Chlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,
4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-phenylphosphine oxide,
Bis (2-methyl-1-naphthoyl) -4-biphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxybiphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-naphthylphosphine Oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-methoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)
And -2,4,4-trimethylpentylphosphine oxide.

Specific examples of the acylphosphine oxide compound of the general formula (2) used in the present invention include 2,2.
4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-diphenylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,3,5,6
-Tetramethylbenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, 2-phenyl-6
-Methylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,8-dimethylnaphthalene-1-carbonyl-diphenylphosphine oxide, 1,3-dimethoxynaphthalene-2-carbonyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl-phenylphosphinic acid methyl ester, and the like.

Specifically, for example, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one (trade name: D
arocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl)
75% of 2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.)
Trade name Irgacure-1 mixed at a ratio of% / 25%
700 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (Ciba Special) Tea Chemicals Co., Ltd.
(Trade name) Irgacure 1800 (Ciba Specialty Chemicals Co., Ltd.) mixed at a ratio of 75% / 25%, and Irgacure 1850 (Ciba Specialty) mixed at a ratio of 50% / 50% Chemicals Co., Ltd.), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, Ciba Specialty Chemicals Co., Ltd.), 2,4,6-trimethylbenzoyl-diphenyl Phosphine oxide (trade name Lucirin)
TPO, manufactured by BASF Corporation), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Da)
rocur1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name Lucirin)
Darocur 4265 (trade name) obtained by mixing TPO and BASF (trade name) at a ratio of 50% / 50%.

As the cationic photopolymerization initiator (D) used in the present invention, known ones can be used. Specifically, various compounds such as diazonium compounds, sulfonium compounds, iodonium compounds and metal complex compounds are known, and “Functional Materials”, October 5, 1985, Item 5, “U.
Application and Market of VEB Curing Technology "CMC 198
There is a detailed description on page 78 issued in 9th year. Specific examples include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenyleudonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylhexafluoroantimonate, and 4,4'-bis (bis (P-2-hydroxyethoxyphenyl) sulfonio)
Phenyl sulfide bishexafluoroantimonate, etc. (trade names are Adeka Optomer SP-170 manufactured by Asahi Denka Kogyo Co., Ltd., CI-2855 manufactured by Nippon Soda Co., Ltd.)
Is mentioned.

The amount of the photopolymerization initiator added is such that each of the photoradical polymerization initiator and the photocationic polymerization initiator is
It is 0.05 to 10 parts by weight, preferably 0.5 to 8 parts by weight based on 00 parts by weight. When only the polymerizable compound (B) or only two kinds of the polymerizable compound (B) and the radical polymerizable compound (E) are contained, only the photoradical polymerization initiator may be contained. If the amount of the photopolymerization initiator is too small, curing cannot be performed sufficiently,
On the other hand, if the amount of the photopolymerization initiator is too large, the composition is economically disadvantageous and the physical properties of the cured product deteriorate.

In the present invention, ultraviolet rays are 280 to 38.
0 nm and visible light refer to light rays in a wavelength range of 380 to 780 nm. As a light source of the active energy ray used in the present invention, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and the like can be used.

In the resin composition of the present invention, a release agent,
An antifoaming agent, a leveling agent, an antioxidant, an antistatic agent and the like can be added. In order to improve the surface slippage of the cured product, it is effective to add silicon.

[0030]

The contents of the present invention will be described in detail with reference to the following examples and comparative examples, in which "parts" and "%" are based on weight. The evaluation tests were performed by the following methods. (1) Mold releasability test The mold releasability when the cured resin was released from the mold was examined based on the following criteria. ：: Easy release ×: Easy release but heavy (2) Adhesion to acrylic plate A cross-cut test according to JIS K 5400 was performed. ：: 100/100 ×: 50/100 <(3) Restorability The time required for restoring the mark after strongly pressing a metal round bar having a diameter of 5 mm against the cured product was measured. ：: Immediately recovers trace ×: Recovers within 2 minutes (4) Transparency (light transmittance) Transparency is visually determined, and manufactured by Nippon Denshoku Industries Co., Ltd., optical unit for turbidity measurement (NDH) Using a mold ($ 80), C light source,
The light transmittance was measured by measuring with the den wavelength.

Synthesis Example 1 (Synthesis of Partial Epoxy Acrylate HE-1)
Epoxy resin Epicoat 828 (manufactured by Yuka Shell Co., Ltd., epoxy equivalent 189): 1 equivalent (189 g), Epicoat 834 (epoxy equivalent 250): 1 equivalent in a reactor equipped with a reflux condenser, a gas inlet tube, and a thermometer. (250g),
Chromium naphthenate: 1.57 parts was charged, and while stirring at 110 ° C. while blowing air, hydroquinone:
Acrylic acid dissolved 0.026 g: 1 equivalent (72 g)
The reaction was terminated at 110 to 130 ° C. for 3 to 4 hours when the acid value became 0, and 50% of the epoxy groups were
Is an acryloylated partial epoxy acrylate HE-
1 was obtained.

Synthesis Example 2 (Synthesis of Resin P-1 Obtained by Reacting Hydroxyl Groups in Phenoxy Resin with Specific Ratio of α, β-Unsaturated Monoisocyanate) A stirrer, a reflux condenser, a thermometer, and a dropping funnel were attached. In a 500 ml four-necked flask, a phenoxy resin epototo YP-50S (manufactured by Toto Kasei, Mn = 15)
000, Mw / Mn = 4.1): 56.8 g to 195.
3 g of phenoxyethyl acrylate (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd., trade name PO-A).
1 g of hydroquinone was added, and while maintaining the temperature at 70 ° C., a solution in which 12.4 g of isocyanatoethyl methacrylate (trade name: Karenz MOI, manufactured by Showa Denko KK) and 0.124 g of dibutyltin dilaurate were previously charged. And reacted at 70 ° C. for 90 minutes to complete
Resin P-1 in which 40% of the hydroxyl groups had reacted with isocyanate ethyl methacrylate was obtained.

Synthesis Example 3 (Synthesis of Partial Epoxy Acrylate HE-2)
Epoxy resin Epicoat 828 (manufactured by Yuka Shell Co., Ltd., epoxy equivalent: 189): 1 equivalent (189 g), 0.62 parts of chromium naphthenate was charged into a reactor equipped with a reflux condenser, a gas inlet tube, and a thermometer. , While blowing air 1
Hydroquinone: 0.06 g while stirring at 10 ° C
Acrylic acid in which was dissolved: 0.25 equivalents (18 g) were charged and reacted at 110 to 130 ° C. for 3 to 4 hours, and when the acid value became 0, the reaction was terminated, and 25% of the epoxy groups were acryloylated. A partial epoxy acrylate HE-2 was obtained.

Example 1 Partial epoxy acrylate HE- synthesized in Synthesis Example 1
1:40 parts, phenoxy polyethylene glycol diacrylate (manufactured by Kyoeisha Yushi Kagaku Kogyo KK, trade name P-2)
00A): 40 parts, polypropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester APG-700): 100 parts of a mixture consisting of 20 parts,
1-hydroxy-cyclohexyl-phenyl-ketone:
25% bis (2,6-dimethoxybenzoyl) -2,
4,4-trimethylpentylphosphine oxide: 7
Bisacylphosphine oxide-based polymerization initiator having a sensitivity of from 5% to 5% in the ultraviolet to visible region (trade name: Irgacure 1800: manufactured by Ciba Specialty Chemicals Co., Ltd.): 1.5 parts, phosphorus-based sulfonium salt cation Catalyst (product name CI-2855, Nippon Soda Co., Ltd.)
): 1.5 parts was added to obtain a photocurable resin composition. Next, the above photocurable resin composition was placed on a mold to a thickness of 200 μm.
μm, and an acrylic plate is placed on the acrylic plate, and light is irradiated with a 3KW gallium metal halide lamp (Ushio Inc., trade name: Unirec URM-300) that emits visible light from ultraviolet light from above the acrylic plate ( 2000
An evaluation test was carried out on the cured product at mJ / cm ² ), and the results are shown in Table 1.

Example 2 Partial epoxy acrylate HE- synthesized in Synthesis Example 1
1:40 parts, Resin P-1 synthesized in Synthesis Example 2: 40 parts,
Polypropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester APG-700):
Irgacure 180 is added to 100 parts of the mixture consisting of 20 parts.
0: 1.5 parts and CI-2855: 1.5 parts were added to obtain a photocurable resin composition. Next, in the same operation as in Example 1, the light source was changed to a 1 kW high-pressure mercury lamp, and the above photocurable resin composition was cured by light irradiation (2000 mJ / cm ² ). The test was performed and the results are shown in Table 1.

Example 3 Resin P-1 synthesized in Synthesis Example 2: 70 parts, polypropylene glycol diacrylate (Shin-Nakamura Chemical Co., Ltd.)
NK Ester APG-700), 30 parts by weight, and Irgacure 1800: 1.5
And a photocurable resin composition was obtained. Next, the above photocurable resin composition was photocured in the same manner as in Example 1, and the same test was performed. The results are shown in Table 1.

Example 4 Resin P-1 synthesized in Synthesis Example 2: 35 parts, epoxy acrylate (Lipoxy VR-60: 3 manufactured by Showa Polymer Co., Ltd.)
To 100 parts of a mixture consisting of 5 parts and NK ester APG-700: 30 parts, Irgacure 1800: 1.5 parts was added to obtain a photocurable resin composition. Next, the above photocurable resin composition was photocured in the same manner as in Example 1, and the same test was performed. The results are shown in Table 1.

Example 5 Partial epoxy acrylate HE- synthesized in Synthesis Example 3
2: 100 parts, Irgacure 1800: 1.0 parts, C
I-2855: 3.0 parts was added to obtain a photocurable resin composition. Next, the above photocurable resin composition was heated at 40 ° C., photocured in the same manner as in Example 1, and the same test was performed. The results are shown in Table 1.

Comparative Example 1 Epicoat 828: 17 g, Epicoat 834: 23
g, P-200A: 40 parts, NK ester APG-70
0:20 parts of a mixture consisting of 20 parts are mixed with Irgacure 1
800: 1.5 parts and CI-2855: 1.5 parts were added to obtain a photocurable resin composition. Next, the above photocurable resin composition was photocured in the same manner as in Example 1, and the same test was performed. The results are shown in Table 1.

[0040]

[Table 1]

[0041]

According to the present invention, when used for a lens, particularly for a Fresnel lens, it has excellent adhesion to a substrate and does not separate during curing to cause turbidity. Provided is a resin composition having sufficient flexibility at a low rate and a method for curing the same.

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Claims (4)

[Claims] 1. The method according to claim 1, wherein said epoxy compound has 5 to 9 epoxy groups.
5% (meth) acryloyl polymerizable compound (A)
And / or photo-radical polymerization initiator (C) and / or photo-cationic polymerization obtained by reacting 5 to 60% of the hydroxyl groups in phenoxy resin with α, β-unsaturated monoisocyanate A curable resin composition containing an initiator (D). 2. A curable resin composition comprising the curable resin composition according to claim 1 and a radically polymerizable compound (E) and / or a cationically polymerizable compound (F). 3. The curable resin composition according to claim 1, wherein the polymerizable compound (B) is obtained from a phenoxy resin having a bisphenol skeleton. 4. A method for curing a curable resin composition for a lens, comprising irradiating the curable resin composition according to claim 1, 2 or 3 with ultraviolet rays and / or visible rays.