JP3067057B2 - UV curable resin composition for transmission screen 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 pressing method or a casting method. The former press method has poor productivity because it is manufactured by a cycle of heating, pressing and cooling. 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,
(See 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 which is rapidly cured by ultraviolet rays and whose cured product has a high refractive index. Was completed. That is, the present invention provides: Equation (1)

[0005]

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Wherein R 1 is a hydrogen atom or a methyl group;
1 to X4 are each independently a hydrogen atom, a methyl group or a bromine atom, Y is -O- or -S-, R2 is -CH2
The numbers of-, -S- or -C (CH2)-, a and b are 1 to 10, respectively, and the average value of a + b is 5 to 20. ), A diol compound (b) having a molecular weight of 200 or less, and an organic polyisocyanate (c)
Urethane (meth) acrylate (A), which is a reaction product of phenol and a hydroxyl group-containing (meth) acrylate (d), an ethylenically unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C) It relates to a transmission screen for ultraviolet-curable resin composition which comprises a.

In the present invention, a reaction product of a diol (a) represented by the formula (1), a diol compound (b) having a molecular weight of 200 or less, an organic polyisocyanate (c), and a hydroxyl group-containing (meth) acrylate (d) is used. Urethane (meth) acrylate (A) is used. Specific examples of the diol (a) represented by the formula (1) include, for example, bisphenol A
1 mol of a reactant of 15 mol of ethylene oxide, 1 mol of bisphenol A and 10 mol of ethylene oxide, 1 mol of bisphenol F and 8 mol of propylene oxide
Moles of reactant, 1 mole of tetrabromobisphenol A and 15 moles of ethylene oxide,

[0008]

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[0009]

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And the like. Specific examples of the diol compound (b) having a molecular weight of 200 or less include, for example,
Examples thereof include ethylene glycol, propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,4-butanediol, and 1,6-hexanediol.

Specific examples of the organic polyisocyanate (c) include, for example, 2,4-tolylene diisocyanate,
Examples thereof include 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. Particularly preferred are, for example, tolylene diisocyanate 2,4-2,6- and mixtures), xylylene 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, Examples thereof include ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate and (meth) acrylate of phenylglycidyl ether. The urethane (meth) acrylate (A) is an isocyanate group of the organic polyisocyanate (c) per equivalent of the hydroxyl group of the mixture of the diol (a) represented by the formula (1) and the diol compound (b) having a molecular weight of 200 or less. Preferably 1.1 to 2.0 equivalents are added at the reaction temperature, preferably 7
The reaction is performed at 0 to 100 ° C. to synthesize a urethane oligomer. The use ratio of the component (a) and the component (b) is preferably 1 to 50 parts by weight based on 100 parts by weight of the component (a). Next, it can be obtained by reacting the hydroxyl group-containing (meth) acrylate (d) with a hydroxyl group, preferably 1 to 1.5 equivalents, at a reaction temperature, preferably 70 to 100 ° C., per equivalent of the isocyanate group of the urethane oligomer. The refractive index (25 ° C.) of the obtained urethane (meth) acrylate is usually 1.53 or more, and is preferably 1.55 or more under preferable conditions.

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, tetrahydrofurfuryl (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, glycidyl (meth) ) Acrylate, (meth) acrylate of phenylglycidyl ether, phenoxyethyl (meth) acrylate, isobornyl (meth)
Acrylate, dicyclopentanyl (meth) acrylate, phenoxypolyethoxy (meth) acrylate, tribromophenyl (meth) acrylate, tribromobenzyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dibromophenyl glycidiether (Meth) acrylate, O-phenylphenol polyethoxy (meth) acrylate,
Polyethoxy (meth) acrylate of P-phenylphenol, polyethoxydi (meth) acrylate of tetrabromobisphenol A, polyethoxydi (meth) acrylate of bisphenol A, polyethylene glycol di (meth) acrylate, and ε-caprolactone addition of neopentyl glycol hydroxypivalate Monomer such as di (meth) acrylate, bisphenol A
Epoxy resin, which is a reaction product of (meth) acrylic acid with epoxy resins such as epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin modified with organic polyisocyanate, terminal glycidyl ether of propylene oxide adduct of bisphenol A, etc. A) reactive polymer compounds such as acrylates and polyester poly (meth) acrylates.

As the photopolymerization initiator (c), for example,

[0015]

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[0016]

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[0017]

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[0018]

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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 may contain, in addition to the above components, a releasing agent, an antifoaming agent, a leveling agent, an ultraviolet absorber, a light stabilizer (eg, hindered amine), an antioxidant, a polymerization inhibitor, and an antistatic agent. And the like can be used in combination.
Further, an optional amount of an organic solvent can be used for improving the coating property of the resin composition.

The resin composition of the present invention can be obtained by mixing and dissolving each component. The resin composition of the present invention is useful for transmission screens such as Fresnel lenses and lenticular lenses.

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 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 rigid transparent substrate (for example, a polycarbonate substrate, a polyacryl substrate, a polyester sheet, a rigid vinyl chloride substrate, or a substrate provided with a primer layer on these substrates) is adhered onto the layer, and then the rigid transparent substrate side Then, the resin composition is cured by irradiating ultraviolet rays with a high-pressure mercury lamp or the like, and then separated from the stamper. In this way, a transmission screen such as a Fresnel lens or a lenticular lens having a refractive index (25 ° C.) of usually 1.55 or more, and preferably 1.56 or more under preferable conditions is obtained.

[0024]

Next, the present invention will be described more specifically with reference to examples. The evaluation in the examples was performed by the following method. The parts in the synthesis examples are parts by weight. (1) Releasability: Difficulty in releasing the cured resin from the mold ○ ────Good release from the mold △ ────Slightly difficult to release × ────Release The mold is difficult or has mold residue. (2) Mold reproducibility: The surface shape of the cured ultraviolet curable resin layer was observed. ○ ────Good reproducibility × ────Poor reproducibility (3) Restorability: Press the nail against the surface of the cured UV-curable resin layer released from the mold, make a mark, and observe after standing for 30 minutes did. ○ ──── There is no trace of pressing the nail. △ ──── There is a 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 ultraviolet curable resin layer

Synthesis Example of Urethane (meth) acrylate (A) Synthesis Example 1 A diol prepared by reacting 10 mol of ethylene oxide with 1 mol of bisphenol A (molecular weight: 668, OH value: 168)
500 parts, 26.3 parts of ethylene glycol, and 408 parts of tolylene diisocyanate were charged, and the temperature was raised to about 1 at 80 ° C.
After reacting for 0 hour, 258.7 parts of 2-hydroxyethyl acrylate and 0.6 part of methquinone were charged and reacted at 80 ° C. for about 10 hours to perform urethane acrylate (A-1).
I got The refractive index (25 ° C.) was 1.56.

Synthesis Example 2 A diol prepared by reacting 1 mol of bisphenol F with 8 mol of ethylene oxide (molecular weight: 480, OH value: 233.
8) 500 parts, 26.3 parts of ethylene glycol and 551.2 parts of xylylene diisocyanate were charged, and after heating,
The mixture was reacted at 80 ° C. for about 10 hours, and then 357 parts of 2-hydroxyethyl acrylate and 0.7 part of methoquinone were charged and reacted at 80 ° C. for about 10 hours to obtain urethane acrylate (A-2). The refractive index (25 ° C.) was 1.57.

Synthesis Example 3 A diol prepared by reacting 1 mol of tetrabromobisphenyl A with 15 mol of ethylene oxide (molecular weight: 1207.
7, OH value 92.9) 500 parts, neopentyl glycol 55.6 parts, tolylene diisocyanate 330 parts were charged, and after heating, reacted at 80 ° C. for about 10 hours, and then 231 parts of 2-hydroxyethyl acrylate and 0 of methoquinone were added. .
56 parts were charged and reacted at 80 ° C. for about 10 hours to obtain urethane acrylate (A-3). The refractive index (25 ° C.) was 1.58.

Synthesis Example 4 500 parts of the diol represented by the formula (2), 26.3 parts of 1,4-butanediol, and tolylene diisocyanate 3
99.7 parts were charged, reacted at 80 ° C. for about 10 hours after the temperature was raised, and then 2-hydroxyethyl acrylate 278 was added.
And 0.6 part of methoquinone were charged and reacted at 80 ° C. for about 10 hours to obtain a urethane acrylate (A-4). The refractive index (25 ° C.) was 1.59.

Examples 1 to 5 A UV-curable resin composition having a composition as shown in Table 1 (numerical values indicate parts by weight) was combined 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 Urethane acrylate (A-3) 30 Urethane acrylate (A-4) 30 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 * 73 33 33 33 Physical properties of cured product Refractive index (25 ° C) 1.564 1.581 1.552 1.566 1.572 Releasability ○ ○ △ ○ ○ Mold reproducibility ○ ○ ○ ○ ○ Restorability ○ ○ △ ○ ○

Note * 1 KAYARAD R-310:
Nippon Kayaku Co., Ltd. Bisphenol A type epoxy resin (Yuika Ciel Epoxy Co., Ltd. Epicoat 1004) epoxy acrylate and phenyl glycidyl ether acrylate, 50% dilution * 2 KAYARAD R-128: Nippon Kayaku Co., Ltd. Acrylate of phenylglycidyl ether * 3 KAYARAD OPP-2: Acrylate of ethylene oxide adduct of o-phenylphenol manufactured by Nippon Kayaku Co., Ltd. * 4 KAYARAD R-551: Bisphenol A tetraethoxy manufactured by Nippon Kayaku Co., Ltd. Diacrylate * 5 KAYARAD HX-220: Nippon Kayaku Co., Ltd.
Of neopentyl glycol hydroxypivalate
-Diacrylate of caprolactone adduct * 6 LA-82: Light stabilizer manufactured by Asahi Denka Kogyo Co., Ltd. * 7 Irgacure 184: Photopolymerization initiator manufactured by Ciba Geigy

As is evident from Table 1, the cured product of the resin composition of the present invention has excellent releasability, mold reproducibility and restorability.
It had a high refractive index of 55 or more.

[0033]

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

Continuation of front page (56) References JP-A-5-255464 (JP, A) JP-A-5-247156 (JP, A) JP-A-5-88265 (JP, A) JP-A-61-98716 (JP) , A) JP-A-5-246931 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/16 C08F 299/00-299/08 C08F 2/00 -2/60 G03B 21/62 C08G 18/00-18/87

Claims (1)

(57) [Claims] 1. A diol represented by formula (1) (a) and ## STR1 ## (Wherein R1 is a hydrogen atom or a methyl group, X1 to X4 are each independently a hydrogen atom, a methyl group or a bromine atom, Y is -O- or -S-, R2 is -CH2-, -S-, or −
The number of C (CH3) 2-, a and b is 1-10,
The average of a + b is a number from 5 to 20. ) Molecular weight 200
Urethane (meth) acrylate (A) which is a reaction product of the following diol compound (b), organic polyisocyanate (c), and hydroxyl group-containing (meth) acrylate (d);
An ultraviolet curable resin composition for a transmission screen, comprising a compound (B) containing an ethylenically unsaturated group other than the component (A) and a photopolymerization initiator (C).