JP3058749B2 - Resin composition, transmission screen ultraviolet curable resin composition and cured product thereof - Google Patents

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 transmission screen such as a Fresnel lens and a lenticular lens used for a projection television and the like, and a cured product thereof.

[0002]

2. Description of the Related Art Heretofore, this kind of lens has been formed by a method such as a press method or a cast method. The former press method has poor productivity because it is manufactured by a heating, pressing and cooling cycle. Further, the latter casting method has a problem that the production time is long because a monomer is poured into a mold and polymerization is carried out, and a large number of molds are required, so that the production cost is increased. In order to solve such a problem, various proposals have been made for using 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, JP-A-63-199302, JP-A-64- 6935 etc.)

[0003]

A method for producing a transmission screen by using these ultraviolet-curable resin compositions has been somewhat successful. However, no proposal has been made in response to the demand for thinner projection televisions and the like.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies and as a result, have found a resin composition whose curing by ultraviolet rays is fast and whose cured product has a high refractive index. Was completed. That is, the present invention has a molecular weight of 5
00 or more diol compound (a) and compound (b) represented by formula (1)

[0005]

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(In the formula, R represents a hydrogen atom or a methyl group, n represents an integer of 2 to 6, and m represents an integer of 1 to 5, respectively.)
Is a reaction product of a compound (b) represented by the formula (I), an organic polyisocyanate (c) and a hydroxyl group-containing (meth) acrylate (d), wherein component (b) is added to 100 parts by weight of component (a). A urethane (meth) acrylate (A) obtained by reacting at a ratio of 70 to 300 parts by weight, an ethylenically unsaturated group-containing compound (B) other than the component (A), and a polymerization initiator (C) The present invention relates to an ultraviolet-curable resin composition for transmission screens, characterized by comprising:

In the present invention, a reaction product of a diol compound (a) having a molecular weight of 500 or more, a compound (b) represented by the formula (1), an organic polyisocyanate (c), and a hydroxyl group-containing (meth) acrylate (d) is used. A certain urethane (meth) acrylate (A) is used. Specific examples of the diol (a) having a molecular weight of 500 or more include, for example, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polycarbonate diol, polycaprolactone diol, and polyester diol (for example, ethylene glycol, propylene glycol, neopentyl). Reaction products of diols such as glycol, 3-methyl-1,5-pentanediol and 1,6-hexanediol with dicarboxylic acids such as succinic acid, maleic acid, adipic acid, isophthalic acid and terephthalic acid). Can be.

As a specific example of (b) represented by the formula (1), for example, HOCH ₂ —S—CH ₂ CH ₂ —S—CH ₂ C
_{H 2 OH, HOCH 2 CH 2} -S-CH 2 CH 2 CH 2 CH 2
_{-S-CH 2 CH 2 OH,} HOCH 2 CH 2 -S-CH 2 C
H ₂ —S—CH ₂ CH ₂ —S—CH ₂ CH ₂ OH and the like can be mentioned. The amount of the compound (b) represented by the formula (1) is preferably 70 to 300 parts by weight based on 100 parts by weight of the diol compound (a).

Specific examples of the organic polyisocyanate (c) include, for example, isophorone diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, trimethylhexamethylene diisocyanate, xylylene diisocyanate, , 4'-diphenylmethane diisocyanate. 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, 2-hydroxy Examples thereof include ε-caprolactone adduct of ethyl (meth) acrylate and (meth) acrylate of phenylglycidyl ether. The urethane (meth) acrylate (A) is preferably an isocyanate group of an organic polyisocyanate (c) per equivalent of a hydroxyl group of a mixture of a diol compound (a) having a molecular weight of 500 or more and a compound (b) represented by the formula (1). Reacts 1.1 to 2.0 equivalents at a reaction temperature of preferably 70 to 100 ° C. to synthesize a urethane oligomer. Then, per equivalent of the isocyanate group of the urethane oligomer, the hydroxyl group of the hydroxyl group-containing (meth) acrylate (d) is preferably used. Can be obtained by reacting 1 to 1.5 equivalents at a reaction temperature, preferably 70 to 100 ° C.

Next, specific examples of the ethylenically unsaturated group-containing compound (B) other than the component (A) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, N- Vinylpyrrolidone,
N-vinylcaprolactam, acryloylmorpholine,
Dicyclopentadieneoxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylate 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, dibromophenyl glycidyl ether (Meth) acrylic acid ester, O-phenylphenol polyethoxy (meth) acrylate, P-phenylphenol polyethoxy (meth) acrylate, tetrabromobisphenol A polyethoxydi (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, 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), modified bisphenol A type epoxy resin, terminal glycidyl ether of bisphenol A type propylene oxide adduct, etc. Epoxy (meth) acrylates and polyols (e.g., ethylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5)
-Pentanediol, polyester polyol, polytetramethylene glycol, polycaprolactone polyol, polyethylene glycol, polycarbonate polyol, etc.), an organic polyisocyanate (for example, the organic polyisocyanate, etc.) and a hydroxyl group-containing ethylenically unsaturated compound (for example, A reactive polymer compound such as urethane (meth) acrylate, which is a reaction product containing (meth) acrylate (c) or the like.

As the photopolymerization initiator (C), for example,

[0012]

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[0013]

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[0014]

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[0015]

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And a copolymerizable photopolymerization initiator, 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 can be used alone or in combination of two or more. Further, such a photopolymerization initiator (C) may be a known and commonly used photosensitizer such as ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, triethanolamine and triethylamine. Alone or 2
More than one species can be used in combination.

The proportion of each component used in the present invention is as follows: when component (A) is 100 parts by weight, component (B) is 5 parts by weight.
It is preferably from 0 to 1000 parts by weight, particularly preferably 100 parts by weight.
５００500 parts by weight. The proportion of the component (C) used is (A)
When + (B) is 100 parts by weight, it is preferably 0.1 to 10 parts by weight, particularly preferably 0.3 to 5 parts by weight.

The resin composition of the present invention comprises, in addition to the above components, a releasing agent, an antifoaming 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 of the present invention is particularly useful for transmission screens such as Fresnel lenses and lenticular lenses, but is also useful for various coating agents, potting agents, adhesives and the like. The resin composition of the present invention and the ultraviolet-curable resin composition for a transmission screen (hereinafter collectively referred to as a composition) can be obtained by mixing and dissolving each component.
The cured product of the composition of the present invention can be obtained by curing by ultraviolet irradiation according to a conventional method. Specifically, the ultraviolet curable resin composition for a transmission screen of the present invention is applied, for example, on a stamper having the shape of a Fresnel lens or a lenticular lens, and a layer of the ultraviolet curable resin composition is provided. A hard transparent substrate is adhered on top of it, and then in that state from the side of the hard transparent substrate by a high-pressure mercury lamp or the like,
After the resin composition is cured by irradiating ultraviolet rays, the resin composition is separated from the stamper. In this manner, a transmission screen such as a Fresnel lens or a lenticular lens having a refractive index (25 ° C.) of preferably 1.55 or more, and particularly 1.56 or more under particularly preferable conditions is obtained.

[0019]

Next, the present invention will be described more specifically with reference to examples. The evaluation in the examples was performed by the following method. In addition,
Parts in the synthesis examples indicate parts by weight. (1) Releasability: Difficulty in releasing the cured resin from the mold ○ ─── Good releasability from the mold △ ─── Slightly difficult to release × ─── Difficult to release Or there is mold residue. (2) Mold reproducibility: The surface shape of the cured ultraviolet curable resin layer and the surface shape of the mold were observed. ○ ───Good reproducibility × ───Poor reproducibility (3) Restorability: The nail was pressed against the surface of the cured UV-curable resin layer which had been released from the mold, and a mark was formed. ○ ─── There is no trace of pressing the nail. △ ─── There is a slight trace of pressing the nail. × ─── There is a trace of pressing the nail. (4) Refractive index (25 ° C): Measure the refractive index (25 ° C) of the cured UV-curable resin layer

Synthesis Example of Urethane (meth) acrylate (A) Synthesis Example 1 Adipate of 3-methyl-1,5-pentanediol (Kuraray Co., Ltd., Kurapol P-510, molecular weight 50)
0) 70 parts, ethylene bis- (2-hydroxyethyl sulfide) 130 parts, tolylene diisocyanate 29
After charging 7 parts, the mixture was heated and reacted at 80 ° C. for 10 hours. Then, 200 parts of 2-hydroxyethyl acrylate and 0.3 part of methoquinone were charged and reacted at 80 ° C. for 10 hours to obtain a urethane acrylate (A-1). Was. Refractive index (25 ° C)
Was 1,565.

Synthesis Example 2 100 parts of a polyester diol of neopentyl glycol and adipic acid (molecular weight 1000), 100 parts of tetramethylene bis- (2-hydroxyethyl sulfide),
200 parts of tolylene diisocyanate was charged, and after heating, 8
The mixture was reacted at 0 ° C. for 10 hours, and then 135 parts of 2-hydroxyethyl acrylate and 0.27 part of methquinone were charged.
The reaction was carried out at 0 ° C for 10 hours, and urethane acrylate (A-
2) was obtained. The refractive index (25 ° C.) was 1.555.

Synthesis Example 3 Polytetramethylene glycol (molecular weight: 850) 60
Parts, ethylene bis- (2-hydroxyethyl sulfide) 140 parts and tolylene diisocyanate 292 parts, and after heating, react at 80 ° C. for 10 hours, then 196.6 parts of 2-hydroxyethyl acrylate, 0.3 part of methoquinone And reacted at 80 ° C. for 10 hours to obtain a urethane acrylate (A-3). Refractive index (25 ° C)
Was 1.570.

Examples 1 to 5 A UV-curable resin composition having a composition shown in Table 1 (numerical values indicate parts by weight) was mixed with a Fresnel lens mold at a thickness of 2.5 m.
m, and the mixture was cured by irradiating 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 Physical properties of composition Viscosity (25 ° C, CPS) 3800 9000 3000 3300 5000 Refractive index (25 ° C ) 1.545 1.565 1.535 1.552 1.559 Physical properties of cured product Refractive index (25 ° C) 1.565 1.584 1.556 1.571 1.580 Releasability ○ ○ △ ○ ○ Mold reproducibility ○ ○ ○ ○ ○ Restorability ○ ○ △ ○ ○

Note * 1 KAYARAD R-31
0: Epoxy acrylate of bisphenol A type epoxy resin manufactured by Nippon Kayaku Co., Ltd. (Epicoat 1004 manufactured by Yuka Shell Epoxy Co., Ltd.), acrylate of phenylglycidyl ether, 50% dilution * 2 KAYARAD R-128: Japan Kayaku Co., Ltd.
Acrylate of phenyl glycidyl ether * 3 KAYARAD OPP-2: Nippon Kayaku Co., Ltd.
Acrylate of ethylene oxide adduct of O-phenylphenol * 4 KAYARAD R-551: Nippon Kayaku Co., Ltd.
Bisphenol A tetraethoxydiacrylate * 5 KAYARAD HX-220: Nippon Kayaku Co., Ltd. diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate * 6 LA-82: Hikari manufactured by Asahi Denka Kogyo Co., Ltd. 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 was excellent in mold releasability, mold reproducibility and restorability, and had a high refractive index of 1.55 or more.

[0026]

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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI G02B 1/04 G02B 1/04 3/08 3/08 // C09D 5/00 C09D 5/00 C 175/16 175/16 ( 56) References JP-A-61-108619 (JP, A) JP-A-63-90525 (JP, A) JP-A-54-48888 (JP, A) JP-A-61-106617 (JP, A) Hei 1-242612 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03B 21/62 C08F 2/46-2/50 C08F 290/00-290/14 C08F 299/00- 299/08 C08G 18/00-18/87 C08L 1/00-101/14 G02B 1/04 G02B 3/08 C09D 1/00-201/10

Claims (1)

(57) [Claims] 1. A diol compound (a) having a molecular weight of 500 or more and a compound of the formula (1) (Wherein R represents a hydrogen atom or a methyl group, n represents an integer of 2 to 6, and m represents an integer of 1 to 5), and an organic polyisocyanate (c). A reaction product with a hydroxyl group-containing (meth) acrylate (d), wherein 70 to 300 parts of component (b) is added to 100 parts by weight of component (a).
It contains urethane (meth) acrylate (A) obtained by reacting at a ratio of parts by weight, an ethylenically unsaturated group-containing compound (B) other than the component (A), and a polymerization initiator (C). Characteristic UV-curable resin composition for transmission screen