JPH05262837A - Ultraviolet-curing resin composition for transmission screen and cured product thereof - Google Patents

Abstract

PURPOSE:To provide the title composition which can give a cured product having a high refractive index and excellent mold release, reproducibility of form, restorability and scuffing resistance. CONSTITUTION:The title composition comprises a urethane (meth)acrylate (A) which is a reaction product among an aromatic polyester diol or both of this diol and a diol compound of a molecular weight of 200 or below, an organic polyisocyanate and a hydroxylated (meth)acrylate, an ethylenically unsaturated compound (B) other than component A, and a photopolymerization initiator (C).

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 formed 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 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 is a reaction of an aromatic polyester diol (a) or an aromatic polyester diol (a), a diol compound (b) having a molecular weight of 200 or less, an organic polyisocyanate (c), and a hydroxyl group-containing (meth) acrylate (d). (A), which is a substance, an ethylenically unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C), which is used for ultraviolet curing of a transmissive screen. Mold resin composition and cured products thereof.

In the present invention, the aromatic polyester diol (a) or the aromatic polyester diol (a), a diol compound (b) having a molecular weight of 200 or less, an organic polyisocyanate (c), and a hydroxyl group-containing (meth) acrylate (d) are used. The urethane (meth) acrylate (A) which is a reaction product of is used. Aromatic polyester diol (a)
Specific examples of ethylene glycol, propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-dimethylolbenzene. Diol components such as phthalic acid, isophthalic acid,
Examples thereof include aromatic polyester diols composed of an aromatic dicarboxylic acid component such as terephthalic acid. The molecular weight of the aromatic polyester diol is preferably 500.
That is all.

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

Specific examples of the organic polyisocyanate (c) include 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and the like can be mentioned. Particularly preferred examples include tolylene diisocyanate (2,4-, 2,6- or mixture), xylylene diisocyanate and the like.

Specific examples of the hydroxyl group-containing (meth) acrylate (d) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, and the like. Examples thereof include ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid ester of phenylglycidyl ether. The urethane (meth) acrylate (A) is an organic polyisocyanate (a) per equivalent of the hydroxyl group of the aromatic polyester diol (a) or a mixture of the aromatic polyester diol (a) and a diol compound (b) having a molecular weight of 200 or less. Isocyanate groups of c), preferably 1.
A urethane oligomer is synthesized by reacting 1 to 2.0 equivalents at a reaction temperature, preferably 70 to 100 ° C. The use ratio of the component (a) and the component (b) is preferably 0 to 50 parts by weight based on 100 parts by weight of the component (a). Next, isocyanate group 1 of urethane oligomer
It can be obtained by reacting hydroxyl groups of the hydroxyl group-containing (meth) acrylate (d), preferably 1 to 1.5 equivalents, at a reaction temperature, preferably 70 to 100 ° C. per equivalent. Refractive index of the obtained urethane (meth) acrylate (25 ° C)
Is usually 1.53 or more and 1.
55 or more.

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-vinylpyrrolidone. , N-vinylcaprolactam, acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid ester of phenylglycidyl ether, phenoxyethyl (meth) acrylate , Isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenoxypolyethoxy (meth) acrylate, tribromophenyl (meth) acrylate, tribromobenzyl (meth) acrylate, Bromophenyloxyethyl (meth) acrylate, (meth) acrylic acid ester of dibromophenyl glycidyl ether, polyethoxy (meth) acrylate of o-phenylphenol, polyethoxy (meth) acrylate of p-phenylphenol, polyethoxydi (of tetrabromobisphenol A) (Meth) acrylate, polyethoxydi (meth) acrylate of bisphenol A, polyethylene glycol di (meth) acrylate, reactive monomer such as di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, bisphenol A
-Type epoxy resin, bisphenol F-type epoxy resin, organic polyisocyanate-modified bisphenol A-type epoxy resin, terminal glycidyl ether of propylene oxide adduct of bisphenol A, and epoxy (meta) which is a reaction product of (meth) acrylic acid. ) Acrylate, ethylene glycol, neopentyl glycol, polycaprolactone polyol, polytetramethylene glycol, polycarbonate polyol, polypropylene glycol and other polyols and organic polyisocyanates (for example, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.) And a hydroxyl group-containing ethylenically unsaturated compound (for example, the above-mentioned hydroxyl group-containing (meth) acrylate (d) etc.) Which is a reaction product urethane (meth)
Examples thereof include reactive polymer compounds such as acrylate.

As the photopolymerization initiator (c), for example,

[0011]

[Chemical 1]

[0012]

[Chemical 2]

[0013]

[Chemical 3]

[0014]

[Chemical 4]

Etc., 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 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. Alone or 2
A combination of two or more species can be used.

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 usage ratio of component (C) is (A)
When + (B) is 100 parts by weight, it is preferably 0.1 to 10 parts by weight, and particularly preferably 0.3 to 5 parts by weight.

In addition to the above-mentioned components, the resin composition of the present invention includes a release agent, a defoaming agent, a leveling agent, an ultraviolet absorber, a light stabilizer (eg, hindered amine), an antioxidant, a polymerization inhibitor, an antistatic agent. Additives such as can be used in combination.
Further, in order to improve the coating property of the resin composition, any amount of organic solvent can be used.

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 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, A hard transparent substrate (for example, a polycarbonate substrate, a polyacrylic substrate, a polyester sheet, a hard vinyl chloride substrate, or a substrate provided with a primer layer on these substrates) is adhered onto the layer, and then the hard transparent substrate side in that state. After the resin composition is cured by irradiating it with ultraviolet rays from a high pressure mercury lamp or the like, the resin composition is peeled from the stamper. In this way, a transmission screen such as a Fresnel lens or a lenticular lens having a normal refractive index (25 ° C.) of 1.55 or more, and under the preferable conditions of 1.56 or more can be obtained.

[0020]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The evaluation in the examples was performed by the following method. In addition, the part in a synthesis example shows a weight part. (1) Releasability: Difficulty in releasing the cured resin from the mold ○ ──── Good releasability from the mold △ ──── Releasing is somewhat difficult × ──── Release The mold is difficult or the mold is rugged. (2) Mold reproducibility: The surface shape of the cured ultraviolet curable resin layer was observed. ○ ──── Good reproducibility × ──── Poor reproducibility (3) Restoration: Make a mark by pressing a nail on the surface of the cured UV-curable resin layer released from the mold, and leave it for 30 minutes for observation. did. ○ ──── No trace of pressing nails △ ──── Traces of pressing nails slightly remain × ──── Traces of pressing nails remain (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 Aromatic polyester diol (manufactured by Kuraray Co., Ltd., MTD / TP)
A (MW500), a reaction product of 3-methyl-1,5-pentanediol and terephthalic acid, a molecular weight of 500) 500 parts, and tolylene diisocyanate 348 parts were charged and reacted at 80 ° C. for 10 hours after heating, and then 2- 244 parts of hydroxyethyl acrylate and 0.55 part of methoquinone were charged and reacted at 80 ° C. for 10 hours to obtain urethane acrylate (A-1). The refractive index (25 ° C.) was 1.55.

Synthesis Example 2 Aromatic polyester diol (manufactured by Kuraray Co., Ltd., MTD / TP)
A (MW1000), a reaction product of 3-methyl-1,5-pentanediol and terephthalic acid, molecular weight 1000) 500 parts, ethylene glycol 26.3 parts, tolylene diisocyanate 321.6 parts were charged, and after heating, 80 ° C. For 10 hours and then 2-hydroxyethyl acrylate 225
And 0.54 parts of metoquinone were charged and reacted at 80 ° C. for 10 hours to obtain urethane acrylate (A-2). The refractive index (25 ° C.) was 1.59.

Synthesis Example 3 Aromatic polyester diol (MPD / IP manufactured by Kuraray Co., Ltd.)
A (MW1000), a reaction product of 3-methyl-1,5-pentanediol and isophthalic acid, molecular weight 1000) 500 parts, ethylene glycol 26.3 parts, and xylylene diisocyanate 347 parts were charged, and the temperature was raised to 10 ° C at 10 ° C. Reacts for a time, then 2-hydroxyethyl acrylate 225
And 0.55 part of metoquinone were charged and reacted at 80 ° C. for 10 hours to obtain urethane acrylate (A-3). The refractive index (25 ° C.) was 1.59.

Examples 1 to 5 An ultraviolet curable resin composition having the composition shown in Table 1 (numerical values indicate parts by weight) was used and a Fresnel lens mold and a thickness of 2.5 m.
m of the acrylic resin plate, and was irradiated with ultraviolet rays by a conventional method to be cured to obtain a Fresnel lens.

Table 1 Example 1 2 3 4 5 Urethane acrylate (A-1) 30 40 Urethane acrylate (A-2) 20 30 Urethane acrylate (A-3) 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 * 7 3 3 3 3 3 3 Physical properties of cured product Refractive index (25 ° C) 1.562 1.576 1,558 1,568 1,572 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 acrylate, 50% diluted * 2 KAYARAD R-128: Nippon Kayaku Co., Ltd.
Phenyl glycidyl ether acrylate * 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: 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.

[0027]

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

Claims (2)

[Claims] 1. An aromatic polyester diol (a) or the aromatic polyester diol (a), a diol compound (b) having a molecular weight of 200 or less, an organic polyisocyanate (c) and a hydroxyl group-containing (meth) acrylate (d). Urethane (meth) acrylate (A) which is a reaction product, and an ethylenically unsaturated group-containing compound (B) other than the component (A)
And a photopolymerization initiator (C), which is an ultraviolet-curable resin composition for a transmissive screen. 2. A cured product of the resin composition according to claim 1.