JP3128322B2 - 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 1. Field of the Invention 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 video projector, a projection television or 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 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

[0005] Polyurethane (meth) acrylate and / or
Or an epoxy (meth) acrylate (A), a compound (B) represented by the formula (1),

[0006]

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(In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, m is 0 or 1, and n is an integer of 2 to 6.)

[0008] A resin composition comprising an ethylenically unsaturated group-containing compound (C) other than the components (A) and (B) and a photopolymerization initiator (D), and an ultraviolet curable resin for a transmission screen Composition. About.

In the present invention, the polyurethane (meth) acrylate and / or the epoxy (meth) acrylate (A)
Use Specific examples of the polyurethane (meth) acrylate include, for example, polyols (eg, ethylene glycol, neopentyl glycol, 3-methyl 1,
5-pentanediol, 1,4-butanediol, 1,
4-dimethylolbenzene, polyethylene glycol,
Polycaprolactone diol which is a reaction product of these diols and ε-caprolactone, such as polypropylene glycol, polytetramethylene glycol, and polycarbonate diol, or maleic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. And polyester diol which is a reaction product of the above with a polybasic acid. ) And organic polyisocyanates (for example, 2,4-tolylene diisocyanate, 2,6
-Tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
Trizine diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and the like can be mentioned. ) And a hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-
Examples thereof include hydropropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate, and (meth) acrylate of phenylglycidyl ether. . ) Is reacted. In the production method, for example, an isocyanate group of an organic polyisocyanate, preferably 1.1 to 2.0 equivalents, is reacted at a reaction temperature, preferably 70 to 100 ° C., per equivalent of the hydroxyl group of the polyol to synthesize a urethane oligomer. Next, it can be obtained by reacting the hydroxyl group-containing (meth) acrylate with a hydroxyl group, preferably 1 to 1.5 equivalents, at a reaction temperature, preferably 70 to 100 ° C., per equivalent of isocyanate group of urethane otagomer. Polyurethane (meth) acrylate refractive index (2
(5 ° C.) is preferably 1.53 or more.

Specific examples of the epoxy (meth) acrylate include, for example, epoxy resins (for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol type epoxy resin, novolak type epoxy resin, etc.). And (meth) acrylic acid. The production method is, for example, about 0.7 to 1.5 equivalents, more preferably about 0.9 to 1.1 equivalents, of (meth) acrylic acid are reacted with 1 equivalent of epoxy group of epoxy resin, As a diluent during the reaction, a reactive monomer such as phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acryloyl morpholine, (meth) acrylate of phenylglycidyl ether, 2-
It is preferable to use hydroxyethyl (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, and the like. In order to promote the reaction, it is preferable to use a catalyst (for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, triphenylphosphine, etc.). It is preferably used in the range of 0.1 to 10% by weight. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoxy, hydroquinone, phenothiazine, etc.), and the amount used is in the range of 0.01 to 1% by weight based on the reaction raw material mixture. Is preferred. The reaction temperature is usually from 60 to 150 ° C, and the reaction time is usually from 5 to 60 hours. As a preferable epoxy (meth) acrylate, a bisphenol A type epoxy acrylate having a molecular weight of 1,000 or more is preferable.

Specific examples of the compound (B) represented by the formula (1) include, for example,

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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And the like. Ethylenically unsaturated group-containing compounds other than the components (A) and (B) (C)
Specific examples of N-vinylpyrrolidone and N
-Vinylcaprolactone, acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylate of phenylglycidyl ether, dicyclopentane Nyl (meth) acrylate, isobornyl (meth) acrylate, tribromobenzyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, (meth) acrylate of dibromophenylglycidyl ether, polyethoxy (meth) acrylate of o-phenylphenol ,
Examples include polyethoxydi (meth) acrylate of tetrabromobisphenol A, polyethoxydi (meth) acrylate of bisphenol A, and di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate.

As the photopolymerization initiator (D), for example,

[0019]

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[0020]

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[0021]

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[0022]

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Copolymerizable photopolymerization initiators such as 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 (D) 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 100 parts by weight of component (A), and component (B) is 1 part by weight.
The amount is preferably from 0 to 200 parts by weight, particularly preferably from 20 to 1 part by weight.
50 parts by weight. The proportion of the component (C) used is (A) +
When (B) is 100 parts by weight, it is preferably from 10 to 200 parts by weight, particularly preferably from 20 to 150 parts by weight. The proportion of the component (D) used is (A) + (B) + (C)
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 ultraviolet absorber, a flame retardant, a light stabilizer (eg, hindered amine, etc.), an antioxidant,
Additives such as a polymerization inhibitor and an antistatic agent 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 composition of the present invention is particularly suitable for transmission screens such as Fresnel lenses and lenticular lenses, but is useful for applications other than transmission screens, such as paints, coatings and ink adhesives.

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, for example, the ultraviolet-curable resin composition for a transmission screen of the present invention is applied 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 polyacrylic substrate, a polyester sheet, a rigid vinyl chloride substrate, or a substrate provided with a primer layer on these substrates, etc.) is adhered on the substrate, and then the rigid transparent substrate side is attached in that state. After the resin composition is cured by irradiating ultraviolet rays with a high-pressure mercury lamp or the like, 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 usually 1.55 or more and, under preferable conditions, 1.56 or more is obtained.

[0028]

Next, the present invention will be described more specifically with reference to examples. The evaluation in the examples was performed by the following method. Parts in the synthesis examples indicate parts by weight. (1) Releasability: Difficulty of 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 was observed. ○ ───Good reproducibility × ───Poor reproducibility (3) Restorability: A nail was pressed against the surface of the cured ultraviolet curable resin layer 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

Polyurethane (meth) acrylate (A)
Synthesis Example 1 Synthesis Example 1 Aromatic polyester diol (MPD / TP manufactured by Kuraray)
A (MW 500), reaction product of 3-methyl-1,5-pentanediol and terephthalic acid, molecular weight 500) 500
And 348 parts of tolylene diisocyanate, and after heating, react at 80 ° C. for 10 hours. Then, 244 parts of 2-hydroxyethyl acrylate and 0.55 part of methquinone were charged and reacted at 80 ° C. for 10 hours to perform urethane acrylate (A- 1) was obtained. The refractive index (25 ° C.) was 1.55.

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

Synthesis Example 3 668 parts of a diol prepared by reacting 10 mol of ethylene oxide with 1 mol of bisphenol A, and 348 parts of tolylene diisocyanate were charged, reacted at 80 ° C. for 10 hours after heating, and then 234 parts of 2-hydroxyethyl acrylate.
And 0.6 part of methoquinone were charged and reacted at 80 ° C. for 10 hours to obtain a urethane acrylate (A-3). The refractive index (25 ° C.) was 1.55.

Examples 1 to 5 An ultraviolet-curable resin composition having the composition shown in Table 1 (the numerical values indicate parts by weight) was applied to a Fresnel lens mold and a thickness of 2.5.
It was injected between a polycarbonate substrate having a thickness of 2 mm and irradiated with ultraviolet rays according to a conventional method to cure the resin, thereby obtaining a lens.

[0033]

[Table 1] Example 1 2 3 4 5 (A) Urethane acrylate (A-1) 30 40 Urethane acrylate (A-2) 20 30 minutes Urethane acrylate (A-3) 30 KAYARAD R-310 * 1 15 ( B) B-1 * 2 30 composition B-2 * 3 10 37 minutes B-3 * 4 23 30 (C) KAYARAD R-128 * 5 10 10 10 composition KAYARAD OPP-2 * 6 30 30 30 minutes tribromophenyl Oxyethyl acrylate 18 22 Phenoxyethyl acrylate 10 188 (D) Irgacure 184 * 73 3 33 33 component LA-82 * 8 Other than 0.5 0.5 0.5 0.5 0.5 Other physical properties of cured product Refractive index (25 ° C) 1.565 1.575 1.555 1.573 1.561 Releasability ○ ○ △ ○ ○ Mold reproducibility ○ ○ ○ ○ ○ Restoration ○ ○ △ ○ ○

Note * 1 KAYARAD R-31
0: manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin (Yuka Kazushi Epoxy Co., Ltd.), Epicoat 100
4 (epoxy equivalent 960) epoxy acrylate 50% diluted acrylate of phenylglycidyl ether,
Refractive index (25 ° C.) 1.57 * 2 B-1: Compound of formula (2) * 3 B-2: Compound of formula (3) * 4 B-3: Compound of formula (4) * 5 KAYARAD R-128: Nippon Kayaku Co., Ltd.
Acrylate of phenylglycidyl ether * 6 KAYARAD OPP-2: Nippon Kayaku Co., Ltd.
Acrylate of ethylene oxide adduct of o-phenylphenol * 7 Irgacure 184: manufactured by Ciba-Geigy
Photopolymerization initiator * 8 LA-82: Light stabilizer, manufactured by Asahi Denka Kogyo KK

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.

[0036]

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

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI (C08F 290/06 220: 38) (56) References JP-A-2-83366 (JP, A) JP-A-3-157412 ( JP, A) JP-A-4-4211 (JP, A) JP-A-4-45115 (JP, A) JP-A-4-288314 (JP, A) JP-A-5-65318 (JP, A) (58) ) Surveyed field (Int.Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C08F 2/46-2/50 G02B 1/04 C08F 20/00-20/70 C08F 220/00-220/70 G03B 21/62

Claims (2)

(57) [Claims] 1. Polyurethane (meth) acrylate and / or
Or an epoxy (meth) acrylate (A), a compound (B) represented by the formula (1), (In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a methyl group, m is 0 or 1, and n is an integer of 2 to 6.)
A resin composition comprising an ethylenically unsaturated group-containing compound (C) other than the components (A) and (B) and a photopolymerization initiator (D). 2. Polyurethane (meth) acrylate and / or
Or an epoxy (meth) acrylate (A), an ethylenically unsaturated group-containing compound (C) other than the compounds (B), (A) and (B) represented by the formula (1) according to claim 1.
And an ultraviolet curable resin composition for a transmission screen, comprising a photopolymerization initiator (D).