JPH0733841A - Resin composition, ultraviolet-curing type resin composition for transmission type screen and its cured product - Google Patents

Abstract

PURPOSE:To obtain the subject composition containing a specific urethane(meth) acrylate, a specific ethylenic unsaturated group-containing compound and a specific photopolymerization initiator, having high refractive index, capable of providing a cured product excellent in mold release property, mold reproducibility and recovering property and suitable for Fresnel lens, etc. CONSTITUTION:The objective composition contains (A) preferably 5-60wt.% of a urethane (meth)acrylate which is a reactional product of (i) a reactional product of tetrabromobisphenol A and an alkylene oxide and (ii) an aliphatic organic polyisocyanate such as hexamethylene diisocyanate and (iii) a hydroxy groupcontaining (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, (B) preferably 60-90wt.% of an ethylenically unsaturated group-containing compound such as phenoxyethyl (meth)acrylate having 41.510 refractive index (at 23 deg.C) and (C) preferably 0.3-5wt.% of a photopolymerization initiator such as benzoin.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, lenses such as a Fresnel lens and a lenticular lens have been manufactured by molding 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 time to manufacture because a monomer is poured into a mold to polymerize, and a large number of molds are required, resulting in an increase in manufacturing cost. 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 for a screen that meets the demand for thinning projection televisions and the like.

[0004]

In order to solve the above-mentioned problems, the inventors of the present invention have conducted earnest research and as a result, found a soft resin composition which cures rapidly with ultraviolet rays and has a high refractive index. The present invention has been completed. That is, the present invention is a reaction product of tetrabromobisphenol A and an alkylene oxide (a), an aliphatic organic polyisocyanate (b) and a hydroxyl group-containing (meth) acrylate (c), a urethane (meth) acrylate (A). ), Refractive index (23
(° C) of 1.510 or more ethylenically unsaturated group-containing compound (B) and a photopolymerization initiator (C), a resin composition, an ultraviolet curable resin composition for a transmissive screen, and the same. Regarding cured products.

In the present invention, tetrabromobisphenol A is used.
A urethane (meth) acrylate (A) which is a reaction product of an alkylene oxide reaction product (a), an aliphatic organic polyisocyanate (b) and a hydroxyl group-containing (meth) acrylate (c) is used. Tetrabromobisphenol A
Specific examples of the reaction product (a) of alkylene oxide and alkylene oxide include, for example, tetrabromobisphenol A ethylene oxide (average 2 mol reaction product) adduct, tetrabromobisphenol A ethylene oxide (average 4 mol reaction) addition product, Examples thereof include tetrabromobisphenol A ethylene oxide (average 6 mol reaction) adduct, tetrabromobisphenol A propylene oxide (average 2 mol reaction) adduct, and the like.

Specific examples of the aliphatic organic polyisocyanate (b) include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate. it can. 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, pentaerythritol tri (meth) acrylate and the like can be mentioned.

The reaction of the reaction product (a) with the aliphatic organic polyisocyanate (b) is carried out by reacting 1 equivalent of the hydroxyl group of the reaction product (a) with an isocyanate group of the aliphatic organic polyisocyanate (b). It is preferred to use 1.1 to 2.0 equivalents. The reaction temperature is preferably 60 to 100 ° C, particularly preferably 75 to 85 ° C. Reaction time is 5
~ 20 hours is preferred. Then, the hydroxyl group-containing (meth) is added to 1 equivalent of the isocyanate group of the reaction product of the reaction product (a) and the aliphatic organic polyisocyanate (b).
Hydroxyl group of acrylate (c), preferably 0.95
A urethane (meth) acrylate (A) can be obtained by reacting 1.2 equivalents. At this time, it is a polymerization inhibitor in order to prevent polymerization. For example, it is preferable to use methylhydroquinone, P-methoxyphenol, hydroquinone or the like. The amount of the polymerization inhibitor used is preferably 0.01 to 0.5% by weight based on the reaction mixture. The reaction temperature is preferably 60 to 100 ° C, particularly preferably 75 to 8
It is 5 ° C. The reaction time is preferably 5 to 20 hours.

The refractive index (23 ° C.) used in the present invention is 1.
Specific examples of the 510 or more ethylenically unsaturated group-containing compound (B) include, for example, phenoxyethyl (meth) acrylate, (meth) acrylic acid ester of phenylglycidyl ether, tribromophenyl (meth) acrylate, tribromobenzyl ( (Meth) acrylate, tribromophenyloxyethyl (meth) acrylate, (meth) acrylic acid ester of dibromophenylglycidyl ether, o-phenylphenoloxyethyl (meth) acrylate, p-phenylphenoloxyethyl (meth) acrylate, bisphenol A (Meth) acrylates such as tetraethoxydi (meth) acrylate of bisphenol F, tetraethoxydi (meth) acrylate of bisphenol F, and polyethoxydi (meth) acrylate of tetrabromobisphenol A Tomonoma include bisphenol A type epoxy resin, bisphenol F type epoxy resin,
It is a reaction product of (meth) acrylic acid with an epoxy resin such as a terminal glycidyl ether of a propylene oxide adduct of bisphenol A, a phenolvolac type epoxy resin, and a fluorene epoxy resin. Urethane (meth) acrylates other than the (meth) acrylic acid ester (A) component may be used.

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,
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 '
Examples thereof include bisdiethylaminobenzophenone and Michler's ketone. These can be used alone or in combination of two or more. Furthermore, together with such a photopolymerization initiator (D), known and commonly used photosensitizers 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 preferably 2 to 70% by weight of the component (A), particularly preferably 5 to 60% by weight, and 40% of the component (B).
˜97 wt%, particularly preferably 60 to 90 wt%, component (C) is preferably 0.1 to 10 wt%, particularly preferably 0.3 to 5 wt%.

In the resin composition of the present invention, in addition to the above components,
An ethylenically unsaturated group-containing compound other than the components (A) and (B) (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, acryloylmorpholine. , N-vinylpyrrolidone,
(Meth) acrylates such as isobornyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol diacrylate, urethane (meth) acrylates and the like can be blended.

In addition to the above-mentioned components, the resin composition of the present invention further comprises a release agent, a defoaming agent, a leveling agent, a light stabilizer (eg, hindered amine), an antioxidant, a polymerization inhibitor, an antistatic agent and the like. be able to. 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 resin composition of the present invention is particularly useful for transmission screens such as Fresnel lenses and lenticular lenses, but in addition, various coating agents,
It is useful for potting agents, adhesives, etc. The cured product of the 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 resin composition of the present invention is applied to, for example, a stamper having the shape of a Fresnel lens or a lenticular lens,
After a layer of the resin composition is provided, a hard transparent substrate is adhered on the layer, and then the resin composition is cured by irradiating ultraviolet rays from the hard transparent substrate side with a high pressure mercury lamp or the like. , Peeling from the stamper. Thus, a transmission screen such as a soft Fresnel lens or a lenticular lens having a normal refractive index (23 ° C.) of 1.56 or more, and under the preferable conditions of 1.57 or more can be obtained.

[0018]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The evaluation in the examples was carried out 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 ○: Good releasability from the mold △: Releasing a little difficult ×: Releasing difficult Or, there is a lump in the mold (2) Mold reproducibility: The surface shape of the cured UV-curable resin layer and the surface shape of the mold were observed. ◯: Good reproducibility ×: Poor reproducibility (3) Restorability: A nail was 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. O: No trace of pressing nail is left △: Trace of pressing nail is slightly left ×: Trace of pressing nail is left (4) Refractive index (23 ° C): Measures the refractive index (23 ℃) of the cured UV-curable resin layer

Synthesis Example of Urethane (Meth) Acrylate (A), Synthesis Example 1 Tetrabromobisphenol A Ethylene Oxide 2
Molar adduct (molecular weight 631.6, OH equivalent 315.8)
631.6 parts, hexamethylene diisocyanate 336
Parts, as a diluent, phenoxyethyl acrylate 31
After charging 0 part and reacting at 80 ° C. for 10 hours after heating, 273 parts of 2-hydroxypropyl acrylate and 0.8 part of methquinone were charged and reacted at 80 ° C. for 10 hours to give urethane acrylate (A-1). Obtained. The refractive index (25 ° C.) was 1.585.

Synthesis Example 2 Tetrabromobisphenol A ethylene oxide 2
Molar adduct (molecular weight 631.6, OH equivalent 315.8)
631.6 parts, trimethylhexamethylene diisocyanate 420 parts, and phenoxyethyl acrylate 323.9 parts as a diluent were charged and reacted at 80 ° C. for 18 hours after heating, and then 2-hydroxyethyl acrylate 2
44 parts and methoquinone (0.8 parts) were charged and reacted at 80 ° C. for 10 hours to obtain urethane acrylate (A-2).
The refractive index (25 ° C.) was 1.584.

Examples 1 to 3 and Comparative Examples 1 and 2 An ultraviolet curable resin composition having a composition (numerical values indicate parts by weight) as shown in Table 1 was used in a Fresnel lens mold and a thickness of 2.5.
It was injected into an acrylic resin plate (having a primer layer) having a thickness of mm and was irradiated with ultraviolet rays to be cured by a conventional method to obtain a Fresnel lens.

[0022]

Table 1 Examples Comparative Examples 1 2 3 1 2 (A) component Urethane acrylate (A-1) 62.5 37.5 〃 (A-2) 50 (B) component KAYARAD OPP-1 * 1 10 20 25 10 10 Tribromo Phenyloxyethyl acrylate 10 Phenoxyethyl acrylate 7.5 7.5 10 Ethylene oxide 10 mol of bisphenol A 7.5 Diacrylate of adduct KAYARAD R-310 * 2 10 60 Urethane acrylate (1) * 3 15 Urethane acrylate (2) * 4 62.5 (C ) Component Irgacure 184 * 5 2 2 2 2 2 Others: 1,6-hexanediol diacrylate 20 10 15 20 20 Releasability ○ ○ ○ △ × Mold reproducibility ○ ○ ○ ○ ○ Restorability ○ ○ ○ × ○ Refractive index (23 ℃) 1.574 1.577 1.586 1.582 1.560

Note * 1 KAYARAD OPP-1: Nippon Kayaku Co., Ltd., acrylate of ethylene oxide adduct of o-phenylphenol, 1.575 * 2 in refractive index (23 ° C) KAYARAD R-310: Japanized Yaku Co., Ltd.
Made by phenyl glycidyl ether of bisphenol A type epoxy acrylate diluted with 50%, refractive index (23 ° C) 1.567 * 3 Urethane acrylate (1): 3-methyl-1,
A product obtained by reacting 2 mol of 2-hydroxypropyl acrylate with a reaction product of 2 mol of polyester diol (molecular weight 1000) of 5-pentanediol and terephthalic acid and 3 mol of hexamethylene diisocyanate. Refractive index (23
1.530 * 4 Urethane acrylate (2): 2 mol of 2-hydroxyethyl acrylate is reacted with a reaction product of 1 mol of an ethylene oxide 2 mol adduct of tetrabromobisphenol A and 2 mol of tolylene diisocyanate to obtain a phenoxyethyl acrylate. Diluted at 20% by weight. Refractive index (23 ° C.) 1.610 * 5 Irgacure 184: Ciba-Geigy photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone

As is clear from Table 1, the resin composition of the present invention is excellent in mold releasability, mold reproducibility and restorability, and has a refractive index (2
(3 ° C.) had a high refractive index of 1.57 or more.

[0025]

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.

Claims (3)

[Claims] 1. A urethane (meth) acrylate (A) which is a reaction product of a reaction product (a) of tetrabromobisphenol A and an alkylene oxide, an aliphatic organic polyisocyanate (b) and a hydroxyl group-containing (meth) acrylate (c). ) A resin composition comprising an ethylenically unsaturated group-containing compound (B) having a refractive index (23 ° C) of 1.510 or more, and a photopolymerization initiator (C). 2. A urethane (meth) acrylate (A) which is a reaction product of a reaction product (a) of tetrabromobisphenol A and alkylene oxide, an aliphatic organic polyisocyanate (b) and a hydroxyl group-containing (meth) acrylate (c). ), A refractive index (23 ° C.) of 1.510 or more, an ethylenically unsaturated group-containing compound (B), and a photopolymerization initiator (C). 3. A cured product of the resin composition according to claim 1 or 2.