JPH05320286A - Resin composition, ultraviolet-curable resin composition for transmission screen, and cured material thereof - Google Patents

Abstract

PURPOSE:To provide an ultraviolet-curable resin composition for transmission screen, which gives a cured material having a high refractive index and excellent mold release properties, mold reproducibility, restorability and marring resistance. CONSTITUTION:A resin composition which contains a urethane (meth)acrylate (A) comprising a reaction product of a diol compound having a molecular weight of 500 or higher, bis[2-(2-hydroxyethylthio)ethyl] sulfone, an organic polyisocyanate and a hydroxylated (meth)acrylate, a compound (B) containing an ethylenically unsaturated group, other than component A, and a photopolymerization initiator (C); and a cured material of the composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a video projector,
The present invention relates to an ultraviolet curable resin composition suitable for a transmissive screen such as a Fresnel lens or a lenticular lens used for a projection television and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, this type of lens has been molded by a method such as a pressing method or a casting method. The former pressing method had poor productivity because it was manufactured by a cycle of heating, pressurizing and cooling. Further, the latter casting method has a problem that it takes a long production time because a monomer is poured into a mold to polymerize and the manufacturing cost is increased because a large number of molds are required. In order to solve such a problem, various proposals have been made regarding the use of an ultraviolet curable resin composition. (For example, JP-A-61-177215, JP-A-61-248707, JP-A-61-248708, JP-A-63-163330, JP-A-63-167301,
(See JP-A-63-199302, JP-A-64-6935, etc.)

[0003]

The method for producing a transmissive screen by using these ultraviolet curable resin compositions has been successful to some extent. However, no proposal has been made to meet the demand for thinner projection televisions and the like.

[0004]

In order to solve the above problems, as a result of intensive studies by the present inventors, a resin composition having a fast curing by ultraviolet rays and a cured product having a high refractive index was found. Has been completed. That is, the present invention has a molecular weight of 5
Urethane which is a reaction product of a diol compound (a) of 00 or more, bis [2- (2-hydroxyethylthio) ethyl] sulfone (b), an organic polyisocyanate (c) and a hydroxyl group-containing (meth) acrylate (d). (Meth) acrylate (A), a resin composition containing an ethylenically unsaturated group-containing compound (B) other than the component (A) and a photopolymerization initiator (C), and ultraviolet curing for a transmissive screen A mold resin composition and a cured product thereof.

In the present invention, a diol compound (a) having a molecular weight of 500 or more, bis [2- (2-hydroxyethylthio) ethyl] sulfone (b), an organic polyisocyanate (c), a hydroxyl group-containing (meth) acrylate (d) are used. The urethane (meth) acrylate (A) which is a reaction product with () is used. Specific examples of the diol compound (a) having a molecular weight of 500 or more include polytetramethylene glycol,
Polyethylene glycol, polypropylene glycol,
Polycarbonate diol, polycaprolactone diol, bisphenol A polyethoxydiol, tetrabromobisphenol A polyethoxydiol and polyester diol (for example, ethylene glycol, propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1 , 6-hexanediol, nonanediol, 1,4-dimethylolbenzene and other diols and succinic acid, maleic acid, adipic acid,
Reaction products with dibasic acids such as isophthalic acid and terephthalic acid)
Etc. can be mentioned.

Bis [2- (2-hydroxyethylthio)]
Ethyl] sulfone (b) is easily available on the market.
For example, product name SSS-2 manufactured by Meisei Chemical Industry Co., Ltd. (appearance,
White powder, molecular weight 274.1, melting point 79 ° C., sulfur content 35.0%) and the like.

Specific examples of the organic polyisocyanate (c) include, for example, isophorone diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, trimethyl hexamethylene diisocyanate, xylylene diisocyanate, 4 , 4'-diphenylmethane diisocyanate and the like. Specific examples of the hydroxyl group-containing (meth) acrylate (d) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, and 2-hydroxy. Examples include ε-caprolactone adducts of ethyl (meth) acrylate and (meth) acrylic acid esters of phenylglycidyl ether. The production of the urethane (meth) acrylate (A) is carried out, for example, by using an organic polyphenol per equivalent of a hydroxyl group in a mixture of a diol compound (a) having a molecular weight of 500 or more and bis [2- (2-hydroxyethylthio) ethyl] sulfone (b). The isocyanate group of the isocyanate (c) is preferably 1.1 to 2.0 equivalents and the reaction temperature is preferably 7
The reaction is carried out at 0 to 100 ° C. to synthesize a urethane oligomer, and then the hydroxyl group-containing (meth) acrylate (d) is preferably added at 1 to 1.5 equivalents per 1 equivalent of isocyanate group of the urethane oligomer at a reaction temperature of preferably 70
It can be obtained by reacting at -100 ° C. Molecular weight 50
The use ratio of the diol compound (a) of 0 or more and bis [2- (2-hydroxyethylthio) ethyl] sulfone (b) is bis [2- (2-hydroxy) based on 100 parts by weight of the diol compound (a). It is preferable to use 50 to 400 parts by weight of ethylthio) ethyl] sulfone (b), particularly preferably 100 to 300 parts by weight.

Specific examples of the ethylenically unsaturated group-containing compound (B) other than the component (A) include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and N-vinyl. Pyrrolidone, N
-Vinylcaprolactam, acryloylmorpholine, dicyclopentadieneoxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid ester of phenylglycidyl ether, phenoxyethyl (meth) acrylate, isobornyl (meth)
Of acrylate, dicyclopentanyl (meth) acrylate, phenoxypolyethoxy (meth) acrylate, tribromophenyl (meth) acrylate, tribromobenzyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dibromophenylglycidyl ether (Meth) acrylic acid ester, polyethoxy (meth) acrylate of O-phenylphenol, polyethoxy (meth) acrylate of P-phenylphenol, polyethoxydi (meth) acrylate of tetrabromobisphenol A, polyethoxydi (meth) acrylate of bisphenol A, hydroxy Reactive monomer such as di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol pivalate, bisphenol A type epoxy Fat, bisphenol F type epoxy resin, organic polyisocyanate (for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, etc.) modified bisphenol A type epoxy resin, terminal glycidyl ether of bisphenol A type propylene oxide adduct, etc. Epoxy (meth) acrylate, which is a reaction product of the epoxy resin of (4) and (meth) acrylic acid, polyol (for example, ethylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,
5-pentanediol, polyester polyol, polytetramethylene glycol, polycaprolactone polyol, polyethylene glycol, polycarbonate polyol and the like), organic polyisocyanate (for example, the above-mentioned organic polyisocyanate) and a hydroxyl group-containing ethylenically unsaturated compound (for example, the above-mentioned hydroxyl group) Examples thereof include reactive polymer compounds such as urethane (meth) acrylate which is a reaction product of contained (meth) acrylate (c).

The photopolymerization initiator (c) is, for example,

[0010]

[Chemical 1]

[0011]

[Chemical 2]

[0012]

[Chemical 3]

[0013]

[Chemical 4]

A copolymerizable photopolymerization initiator such as benzoin,
Benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, N, N
-Dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4
-Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone,
4,4'-bisdiethylaminobenzophenone, Michler's ketone and the like can be mentioned. These may be used alone or in combination of two or more. Further, such a photopolymerization initiator (c) is a known photosensitizer such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine and triethylamine. Can be used alone or in combination of two or more.

The proportion of each component used in the present invention is such that when the component (A) is 100 parts by weight, the component (B) is 5 parts.
0 to 1000 parts by weight is preferable, and 100 is particularly preferable.
~ 500 parts by weight. The proportion of component (C) used is
0.1-10 when (A) + (B) is 100 parts by weight
Part by weight is preferable, and 0.3 to 5 parts by weight is particularly preferable.

In addition to the above-mentioned components, the resin composition of the present invention contains a releasing agent, a defoaming agent, a leveling agent, an organic solvent, a light stabilizer (eg, hindered amine), an antioxidant, a polymerization inhibitor,
An antistatic agent or the like can be used in combination. The resin composition and the ultraviolet curable resin composition for a transmissive screen of the present invention can be obtained by mixing and dissolving the respective components.
The resin composition of the present invention is particularly useful for transmission screens such as Fresnel lenses and lenticular lenses,
In addition, it is useful as various coating agents, potting agents, adhesives and the like. The cured product of the resin composition of the present invention can be obtained by irradiating the resin composition of the present invention with ultraviolet rays according to a conventional method. Specifically, the ultraviolet curable resin composition for a transmissive screen of the present invention is applied to, for example, a stamper having the shape of a Fresnel lens or a lenticular lens to form a layer of the ultraviolet curable resin composition, and the layer A hard transparent substrate is adhered onto the above, and in that state, ultraviolet rays are irradiated from the side of the hard transparent substrate with a high pressure mercury lamp to cure the resin composition, and then the resin composition is peeled off. In this way, the normal refractive index (25 ° C) is 1.
It is possible to obtain a transmission screen such as a Fresnel lens or a lenticular lens having 55 or more, and 1.56 or more under the preferable conditions.

[0017]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The evaluation in the examples was performed by the following methods. In addition,
Parts in the synthesis examples are parts by weight. (1) Releasability: Difficulty in releasing the cured resin from the mold ○ ・ ・ ・ ・ Releasability from the mold is good △ ・ ・ ・ ・ Releasing is somewhat difficult × ・ ・ ・The mold is difficult or the mold is dull. (2) Mold reproducibility: The surface shape of the cured UV-curable resin layer and the surface shape of the mold were observed. ○ ・ ・ ・ ・ Reproducibility is good × ・ ・ ・ ・ ・ ・ Reproducibility is poor (3) Restoration: A nail is pressed against the surface of the cured UV-curable resin layer released from the mold to leave a mark for 30 minutes and then observed. did. ○ ・ ・ ・ ・ There is no trace of pressing nails △ ・ ・ ・ ・ The trace of pressing nails is slightly left × ・ ・ ・ ・ The trace of pressing nails remains (4) Refractive index (25 ℃): Measure the refractive index (25 ℃) of the cured UV-curable resin layer

Synthesis Example of Urethane (Meth) Acrylate (A) Synthesis Example 1 3-Methyl-1,5-pentanediol adipate (Kuraray Co., Ltd., Clapol P510, molecular weight 50)
0) 70 parts, bis [2- (2-hydroxyethylthio)]
Ethyl] sulfone (130 parts) and tolylene diisocyanate (213.8 parts) were charged and reacted at 80 ° C. for 10 hours after heating, and then 2-hydroxyethyl acrylate 149.
6 parts and 0.3 parts of methoquinone were charged and reacted at 80 ° C. for 10 hours to obtain urethane acrylate (A-1). The refractive index (25 ° C.) was 1.571.

Synthesis Example 2 100 parts of polyester diol (molecular weight 1000) of 3-methyl 1,5-pentanediol and terephthalic acid, 100 parts of bis [2- (2-hydroxyethylthio) ethyl] sulfone, 162 parts of tolylene diisocyanate Was charged and reacted at 80 ° C. for 10 hours, then 113.2 parts of 2-hydroxyethyl acrylate and 0.24 of methquinone.
Parts were charged and reacted at 80 ° C. for 10 hours to obtain urethane acrylate (A-2). Refractive index (25 ° C) is 1.
It was 575.

Synthesis Example 3 Polytetramethylene glycol (molecular weight 850) 60
Part, bis [2- (2-hydroxyethylthio) ethyl]
Sulfone 140 parts, xylylene diisocyanate 21
Charge 8.6 parts and react at 80 ° C. for 10 hours, then charge 141.6 parts of 2-hydroxyethyl acrylate and 0.28 part of methquinone and react at 80 ° C. for 10 hours to give urethane acrylate (A-3). Obtained. Refractive index (2
5 ° C) was 1.577.

Examples 1 to 5 An ultraviolet-curable resin composition having the composition shown in Table 1 (numerical values indicate parts by weight) was applied to a Fresnel lens mold and a thickness of 2.5 m.
m methacrylic resin plate (primed)
Then, the mixture was injected between the two and cured by irradiation with ultraviolet rays by a conventional method to obtain a Fresnel lens.

Table 1 Example 1 2 3 4 5 Urethane acrylate (A-1) 30 40 Urethane acrylate (A-2) 20 15 Urethane acrylate (A-3) 30 15 KAYARAD R-310 * 1 15 KAYARAD R- 128 * 2 10 10 10 KAYARAD OPP-2 * 3 30 30 30 Tribromophenyloxyethyl acrylate 18 22 Phenyloxyethyl acrylate 10 18 8 Bisphenol A poly (n = 10) ethoxydiacrylate 23 37 10 KAYARAD R-551 * 4 20 10 20 KAYARAD HX-220 * 5 10 LA-82 * 6 0.5 0.5 0.5 0.5 0.5 Irgacure 184 * 7 3 3 3 3 3 3 Physical properties of composition Viscosity (25 ° C, CPS) 3300 8100 4500 3100 6200 Refractive index (25 1.547 1.567 1.539 1.554 1.563 Physical properties of cured product Refractive index (25 ° C) 1.568 1.587 1.559 1.574 1.583 Release property ○ ○ △ ○ ○ Mold reproducibility ○ ○ ○ ○ ○ Restorability ○ ○ △ ○ ○

Note * 1 KAYARAD R-31
0: Nippon Kayaku Co., Ltd., bisphenol type epoxy resin (Yukaka Shell Epoxy Co., Ltd., Epicoat 1004)
50% of phenyl glycidyl ether acrylate diluted with epoxy acrylate * 2 KAYARAD R-128: Nippon Kayaku Co., Ltd.
Acrylate of phenyl glycidyl ether * 3 KAYARAD OPP-2: Nippon Kayaku Co., Ltd.
Made by O-phenylphenol ethylene oxide adduct acrylate * 4 KAYARAD R-551: Nippon Kayaku Co., Ltd.
Bisphenol A tetraethoxydiacrylate * 5 KAYARAD HX-220 manufactured by Nippon Kayaku Co., Ltd.
Made of neopentyl glycol hydroxypivalate ε
-Diacrylate of caprolactone adduct * 6 LA-82: Asahi Denka Co., Ltd., light stabilizer * 7 Irgacure 184: Ciba Geigy, photopolymerization initiator

As is clear from Table 1, the cured product of the resin composition of the present invention is excellent in mold releasability, mold reproducibility and restorability, and has a high refractive index of 1.55 or more at a refractive index (25 ° C.). Met.

【The invention's effect】

The cured product of the resin composition of the present invention has a high refractive index, excellent releasability, mold reproducibility and restorability, and is particularly suitable for a transmission screen.

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Claims (3)

[Claims] 1. A diol compound (a) having a molecular weight of 500 or more, bis [2- (2-hydroxyethylthio) ethyl] sulfone (b), an organic polyisocyanate (c), and a hydroxyl group-containing (meth) acrylate (d). A resin composition comprising a urethane (meth) acrylate (A), which is a reaction product with the above, an ethylenically unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C). .. 2. A urethane (meth) acrylate (A) according to claim 1, an ethylenically unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C). An ultraviolet curable resin composition for a transmissive screen. 3. A cured product of the resin composition according to claim 1 or 2.