JP3058751B2 - Resin composition, ultraviolet 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 or a lenticular lens used for a projection television or the like.

[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 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} X ₄ are a hydrogen atom, Y is -0- or -S-, R ₂ is-
CH ₂ —, —S—, or —C (CH ₃ ) ₂ —, a and b each are a number of 9 to 10, and the average value of a + b is a number of 5 to 20. A urethane (meth) acrylate (A), which is a reaction product obtained by reacting a diol (a) represented by the following formula with an aromatic organic polyisocyanate (b) and then reacting a hydroxyl group-containing (meth) acrylate (c), (A) The cured product comprising an ethylenically unsaturated group-containing compound (B) and a photopolymerization initiator (C) other than the component (A).
C) of 1.55 or more.

In the present invention, the urethane (meth) acrylate (A) which is a reaction product of the diol (a) represented by the formula (1), the aromatic organic polyisocyanate (b) and the hydroxyl group-containing (meth) acrylate (c) is used. ). Specific examples of the diol (a) represented by the formula (1) include, for example, a reaction product of 1 mol of bisphenol A and 8 mol of ethylene oxide, and 1 mol of bisphenol A and ethylene oxide 1
0 mol of reactant, 1 mol of bisphenol F and 8 mol of propylene oxide, 1 mol of tetrabromobisphenol A and 15 mol of ethylene oxide

[0008]

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And the like. Specific examples of the aromatic organic polyisocyanate (b) include, for example, 2,
Examples thereof include 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, and xylylene diisocyanate. Specific examples of the hydroxyl group-containing (meth) acrylate (c) include, for example, 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate,
(Meth) acrylic acid esters of phenylglycidyl ether can be exemplified.

The urethane (meth) acrylate (A)
Is an isocyanate group of the aromatic organic polyisocyanate (b), preferably 1.1 to 2.0 equivalents, per equivalent of the hydroxyl group of the diol (a) represented by the formula (1) at a reaction temperature, preferably 70 to 100 ° C. The reaction is carried out to synthesize a urethane oligomer. Then, the hydroxyl group of the (meth) acrylate (c) containing hydroxyl group, preferably 1 to 1.5 equivalent, is reacted at a reaction temperature, preferably 70 to 100 ° C., per equivalent of isocyanate group of the urethane oligomer. Can be obtained.

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-vinylcaprolactone, acryloylformoline,
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) acrylate, which is a reaction product of epoxy resins with (meth) acrylic acid, and polyols other than the diol (a) represented by the formula (1) (for example, ethylene glycol, 1,4-butanediol,
Neopentyl glycol, polycaprolactone polyol, polyester polyol, polycarbonate polyol, polytetramethylene glycol, etc.) and organic polyisocyanate (for example, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.) and hydroxyl group-containing ethylenically unsaturated. A reactive polymer compound such as urethane (meth) acrylate, which is a reaction product of a compound (for example, the above-mentioned hydroxyl group-containing (meth) acrylate (c) or the like), can be given.

As the photopolymerization initiator (C), for example,

[0013]

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[0014]

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[0015]

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[0016]

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And a copolymerizable photopolymerization initiator, benzoin,
Benzyl, benzoisomethyl 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-morpholino-propan-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 proportions of the components used in the present invention are 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.

In addition to the above components, the resin composition of the present invention comprises 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 can be obtained by mixing and dissolving each component. The resin composition of the present invention is particularly useful for transmission screens such as Fresnel lenses and lenticular lenses, but in addition to various coating agents, potting agents,
Useful for adhesives and the like. A 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. Then, a hard transparent substrate is adhered to the substrate, and then, in this state, the resin composition is cured by irradiating ultraviolet rays from a side of the hard transparent substrate with a high-pressure mercury lamp or the like, and then peeled off from the stamper. In this way, the normal refractive index (25 ° C)
Is 1.55 or more, and under preferable conditions, a transmission screen such as a Fresnel lens or a lenticular lens having 1.56 or more is obtained.

[0020]

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 A diol prepared by reacting 1 mole of bisphenol A with 10 moles of ethylene oxide (molecular weight: 668, OH value: 168)
668 parts and 348 parts of tolylene diisocyanate were charged and reacted at 80 ° C. for 10 hours after heating, then 234.3 parts of 2-hydroxyethyl acrylate and 0.1 part of methquinone were added.
6 parts were charged and reacted at 80 ° C. for 10 hours to obtain a urethane acrylate (A-1). The refractive index (25 ° C)
1.55.

Synthesis Example 2 Diol (molecular weight: 552, OH value: 203) 5 obtained by reacting 8 moles of ethylene oxide with 1 mole of bisphenol F
After adding 52 parts and 328 parts of xylylene diisocyanate, the mixture was heated and reacted at 80 ° C. for 10 hours. Then, 234.3 parts of 2-hydroxyethyl acrylate and 0.2 part of methoquinone were added.
Five parts were charged and reacted at 80 ° C. for 10 hours to obtain a urethane acrylate (A-2). The refractive index (25 ° C)
1.56.

Synthesis Example 3 A diol prepared by reacting 15 mol of ethylene oxide with 1 mol of tetrabromo and bisphenol A (molecular weight: 120
7.6, OH value 92.9), 1207.6 parts, and 348 parts of tolylene diisocyanate.
After reacting for 23 hours, 234.3 parts of 2-hydroxyethyl acrylate and 0.8 part of methquinone were charged and reacted at 80 ° C. for 10 hours to obtain urethane acrylate (A-3). The refractive index (25 ° C.) was 1.57.

Synthesis Example 4 690 parts of the diol represented by the above formula (2) and 348 parts of tolylene diisocyanate were charged, and after heating, 10 parts at 80 ° C.
After reacting for 23 hours, 234.3 parts of 2-hydroxyethyl acrylate and 0.6 part of methquinone were charged, and 80 ° C.
And react for 10 hours with urethane acrylate (A-4)
I got The refractive index (25 ° C.) was 1.58.

Examples 1 to 5 An ultraviolet-curable resin composition having the composition shown in Table 1 (the numerical values are in parts by weight) was prepared by mixing a Fresnel lens mold with 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-301 * 1 15 KAYARAD R-128 * 2 10 10 10 KAYARAD OPP-2 * 3 30 30 30 Tribromophenyloxy ethyl 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 Composition physical properties Viscosity (25 ° C, CPS) 3500 8000 2800 3100 5000 Refractive index (25 ° C) 1.541 1.557 1.530 1.543 1.549 Cured physical properties Refractive index (25 ° C) 1.562 1.576 1.550 1.564 1.570 Releasability ○ ○ △ ○ ○ Mold reproducibility ○ ○ ○ ○ ○ Restorability ○ ○ △ ○ ○

Note * 1 KAYARAD R-31
0: Bisphenol A type epoxy resin manufactured by Nippon Kayaku Co., Ltd. (Epicoat 100 manufactured by Yuka Shell Epoxy Co., Ltd.)
4) Epoxy acrylate of phenyl glycidyl ether, 50% dilution * 2 KAYARAD R-128: Nippon 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.

[0028]

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.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI // C09D 5/00 C09D 5/00 C 175/16 175/16 (56) References JP-A-54-133527 (JP, A JP-A-55-16064 (JP, A) JP-A-62-30640 (JP, A) JP-A-61-64716 (JP, A) JP-A-3-200949 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) G03B 21/62 C08F 2/46-2/50 C08F 290/00-290/14 C08F 299/00-299/08 C08L 1/00-101/14 G02B 1 / 04 G02B 3/08 C09D 1/00-201/10

Claims (1)

(57) [Claims] (1) (Wherein, R ₁ is a hydrogen atom or a methyl group, X _{1 to} X ₄ are a hydrogen atom, Y is —O— or —S—, R ₂ is —CH ₂ —,
—S— or —C (CH ₃ ) ₂ —, a and b each represent 1 to 1
The number of 0 and the average value of a + b are numbers of 5 to 20. Urethane (meth) acrylate (A), which is a reaction product obtained by reacting a diol (a) represented by the formula (1) with an aromatic organic polyisocyanate (b) and then reacting a hydroxyl group-containing (meth) acrylate (c); The cured product containing an ethylenically unsaturated group-containing compound (B) other than the component (A) and a photopolymerization initiator (C) has a refractive index (25 ° C.) of 1.
An ultraviolet-curable resin composition for a transmission screen having a molecular weight of 55 or more.