JPH05287037A - Resin composition, ultraviolet-curable resin composition for transmission screen, and its cured product - Google Patents

Abstract

PURPOSE:To obtain a resin composition which is useful for a transmission screen, can be rapidly cured by ultraviolet radiation, and can give a cured product of a high refractive index by mixing a reaction product of a specified oxazoline compound with a carboxylated, ethylenically unsaturated compound with another ethylenically unsaturated compound and photopolymerization initiator. CONSTITUTION:The title resin composition comprises a reaction product (A) of an oxazoline compound (a) of the formula with a carboxylated, ethylenically unsaturated compound (b), an ethylenically unsaturated compound (B) other than component A, and a photopolymerization initiator (C). Component (b) is used in an amount of desirably 1.0-2.2mol, more desirably 1.95-2.0mol per mol of component (a). Examples of component B include epoxy acrylate of a bisphenol A epoxy resin and phenoxyethyl acrylate. Examples of component (b) include (meth)acrylic acid and (meth)acrylic acid dimer.

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 useful as a transmissive screen for Fresnel lenses, lenticular lenses and the like used in video projectors, projection televisions and the like, 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-63-16730
1, 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

1. Oxazoline compound (a) represented by formula (1)

[0006]

[Chemical 2]

And a reaction product (A) of a carboxyl group-containing ethylenically unsaturated compound (b), an ethylenically unsaturated group-containing compound (B) other than the component (A) and a photopolymerization initiator (C).
1. A resin composition comprising: An ultraviolet-curable type for a transmission screen, comprising the reaction product (A) according to item 1, an ethylenically unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C). Resin composition. 3. The present invention relates to a cured product of the resin composition according to items 1 and 2.

In the present invention, a specific example of the oxazoline compound (a) using the reaction product (A) of the oxazoline compound (a) represented by the formula (1) and the carboxyl group-containing ethylenically unsaturated compound (b) Are, for example, 1,3-bis (2-oxazolin-2-yl) benzene, 1,4-
Examples thereof include bis (2-oxazolin-2-yl) benzene. Specific examples of the carboxyl group-containing ethylenically unsaturated compound (b) include, for example, (meth) acrylic acid, (meth) acrylic acid dimer, and dibasic acid anhydrides (eg, maleic anhydride, succinic anhydride, and anhydride). Glutaric acid, phthalic anhydride, hexahydrophthalic anhydride,
Examples thereof include 3-methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride and the like. ) And a hydroxyl group-containing ethylenically unsaturated group-containing compound (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyethyl ( Ε- of (meth) acrylate
Examples thereof include caprolactone reaction products and pentaerythritol tri (meth) acrylate. The half ester which is a reaction product of 1) can be mentioned.

When reacting the oxazoline compound (a) with the carboxyl group-containing ethylenically unsaturated compound (b),
The compound (b) is preferably used in an amount of 1.9 to 2.2 mol, and particularly preferably 1.95 to 2.05 mol, per mol of the oxazoline compound (a). The reaction temperature is preferably 50 to 170 ° C, particularly 80 to 150 ° C.
Is preferred. The reaction time is preferably 3 to 24 hours, particularly preferably 5 to 15 hours. In order to prevent the polymerization during the reaction, it is preferable to use a known polymerization inhibitor (eg, methoquinone, hydroquinone, methylhydroquinone, phenothiazine, etc.).

Specific examples of the ethylenically unsaturated group-containing compound (B) other than the component (A) include, for example, epoxy resins (for example, bisphenol A type epoxy resin, bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac). Type epoxy resin, hydantoin epoxy resin, etc.) and (meth) acrylic acid, which is a reaction product of epoxy (meth) acrylate The epoxy (meth) acrylate and dibasic acid anhydride (for example, maleic anhydride, phthalic anhydride, tetrahydrophthale) Acid anhydride,
Hexahydrophthalic anhydride, etc.), urethane (meth) acrylate (eg, polyethylene glycol, polytetramethylene glycol, polycaprolactone diol, polycarbonate diol, polyester diol, etc. polyol and tolylene diisocyanate,
Organic polyisocyanates such as xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolidine diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4 -Butanediol mono (meth) acrylate, 2-hydroxyethyl (meth)
Oligomer of hydroxyl group-containing (meth) acrylate such as ε-caprolactone adduct of acrylate), 2
-Hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, glycidyl (meth) acrylate, phenylglycidyl ether ( (Meth) acrylic acid ester, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenoxypolyethoxy (meth) acrylate, tribromophenyl (meth) acrylate, tribromobenzyl (meth) acrylate, tribromophenyloxyethyl (meth ) Acrylate,
(Meth) acrylic acid ester of dibromophenyl glycidyl ether, polyethoxy (meth) acrylate of o-phenylphenol, tetrabromobisphenol A
Polyethoxydi (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, polyethylene glycol di (meth) acrylate, di- (meth) acrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, trimethylolpropane tri (meth) Examples thereof include reactive monomers such as acrylate. Examples of preferable component (B) include epoxy acrylate of bisphenol A type epoxy resin, oligomer such as urethane acrylate which is a reaction product of polyester diol, tolylene diisocyanate and 2-hydroxyethyl acrylate, and (meth) acrylic acid of phenyl glycidyl ether. Materials having a high refractive index such as ester, phenoxyethyl acrylate, tribromophenyloxyethyl acrylate, polyethoxy (meth) acrylate of 0-phenylphenol, and polyethoxydiacrylate of bisphenol A are selected. good.

The photopolymerization initiator (C) is, for example,

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

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
-Dimethylaminoacetonephenone, 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, etc. You can 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. Can be used alone or in combination of two or more.

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 proportion of component (C) used is
When (A) + (B) is 100 parts by weight, 0.1-1
0 parts by weight is preferable, and 0.3 to 5 parts by weight is particularly preferable.

In addition to the above-mentioned components, the resin composition of the present invention includes a release agent, a defoaming agent leveling agent, an ultraviolet absorber, a flame retardant, a light stabilizer (eg, hindered amine), an antioxidant, a polymerization inhibitor, an electrostatic charge. Additives such as inhibitors 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. If necessary,
Inorganic fillers (eg talc, barium sulfate, Al ₂ O ₃ ,
It is also possible to use SiO _{2 and the} like), colorants and the like.

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 suitable for transmission screens such as Fresnel lenses and lenticular lenses, but is also useful for applications other than transmission screens, for example, liquid resist inks, paints, coatings, adhesives and the like.

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 transmissive screen of the present invention is applied on a stamper having the shape of a Fresnel lens or a lenticular lens to form a layer of the ultraviolet curable resin composition, and the layer On top of a rigid transparent substrate (eg, polycarbonate substrate,
Polyacryl substrate, polyester tel sheet, hard vinyl chloride substrate, or those having a primer layer provided on these substrates are adhered, and then in that state, ultraviolet rays are irradiated from the rigid transparent substrate side by a high pressure mercury lamp or the like. After the resin composition is cured, it 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.

[0021]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The evaluation in the examples was performed by the following methods. The parts in the synthesis examples are parts by weight. (1) Releasability: Difficulty in releasing the cured resin from the mold ○ ・ ・ ・ ・ Releasability from the mold is good △ ・ ・ ・ ・ Releasing is somewhat difficult × ・ ・ ・The mold is difficult or the mold is rugged. (2) Mold reproducibility: The surface shape of the cured ultraviolet curable resin layer was observed. ○ ・ ・ ・ ・ Reproducibility is good × ・ ・ ・ ・ ・ ・ Reproducibility is poor (3) Restoration: A nail is 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. did. ○ ・ ・ ・ ・ There is no trace of pressing nails △ ・ ・ ・ ・ The trace of pressing nails is slightly left × ・ ・ ・ ・ The trace of pressing nails remains (4) Refractive index (25 ℃): Measure the refractive index (25 ℃) of the cured UV-curable resin layer

Synthesis Example of Reactant (A) Synthesis Example 1 216 parts (1.0 mol) of 1,3-bis (2-oxazolin-2-yl) benzene 144.1 parts (2.
(0 mol) Methoquinone (0.18 parts) was charged, the temperature was raised to 80 ° C, and the mixture was reacted at 80 ° C for 15 hours to give an acid value (mgKOH / g) of 1.0.
Since it became the following, the reaction was terminated and the reaction product (A-1) was obtained. The product is semi-solid at room temperature and has a refractive index (25 ° C) of 1.
It was 556.

Synthesis Example 2 216 parts of 1,3-bis (2-oxysazolin-2-yl) benzene (1 mol) 506 parts of the compound of the following structural formula (2
Mol)

[0024]

[Chemical 7]

0.36 parts of methquinone was charged, and the temperature was 100 ° C.
After the temperature was raised to 100 ° C., the reaction was carried out at 100 ° C. for 10 hours, the acid value became 1.0 or less, the reaction was terminated, and a reaction product (A-2) was obtained.
The product is semi-solid at room temperature and has a refractive index (25 ° C) of 1.56.
It was 5.

Synthesis Example 3 1,4-bis (2-oxazolin-2-yl) benzene 216 parts (1.0 mol) 384 parts (2.0 mol) of the compound of the following structural formula

[0027]

[Chemical 8]

After charging 0.3 parts of methquinone and heating to 110 ° C., the reaction was carried out at 110 ° C. for 7 hours. Since the acid value became 1.0 or less, the reaction was terminated and the reaction product (A-3) Obtained. The product was semisolid at room temperature and had a refractive index (25 ° C.) of 1.545. Synthesis example of urethane acrylate

Synthesis Example 4 Polyester diol (manufactured by Kuraray Co., Ltd., MPD / TP
A (MW1000), reaction product of 3-methyl-1.5-pentanediol and terephthalic acid, molecular weight 1000) 50
0 parts, 26.3 parts of ethylene glycol and 321.6 parts of tolylene diisocyanate were charged, and the temperature was raised to 10 at 80 ° C.
After reacting for 2 hours, 225 parts of 2-hydroxyethyl acrylate and 0.54 part of methone were charged, and the mixture was heated at 80 ° C. for 10 hours.
The reaction was carried out for a time to obtain urethane acrylate (B-1). The refractive index (25 ° C.) was 1.59.

Synthesis Example 5 1 mol of bisphenol A was charged with 668 parts of a diol obtained by reacting 10 mol of ethylene oxide and 348 parts of tolylene diisocyanate. After heating, the mixture was reacted at 80 ° C. for 10 hours and then 2-hydroxyethyl acrylate 234.
And 0.6 part of methoquinone were charged and reacted at 80 ° C. for 10 hours to obtain urethane acrylate (B-2). The refractive index (25 ° C.) was 1.550.

Examples 1 to 5 An ultraviolet-curable resin composition having a composition (numerical values represent parts by weight) as shown in Table 1 was used with a Fresnel lens mold and a thickness of 2.5.
It was injected into a polycarbonate substrate having a thickness of 10 mm and was irradiated with ultraviolet rays by a conventional method to be cured to obtain a lens.

[0032]

Table 1 Example 1 2 3 4 5 (A) Reactant (A-1) 30 40 Composition Reactant (A-2) 30 30 minutes Reactant (A-3) 30 (B) Urethane acrylate Composition (B -1) 10 minutes Urethane acrylate (B-2) 10 KAYARAD R-310 * 1 15 KAYARAD R-128 * 2 10 20 10 KAYARAD OPP-2 * 3 30 30 17 30 Tribromophenyl oxyethyl acrylate 18 22 Phenyloxy Ethyl acrylate 10 10 18 18 10 KAYARAD HX-220 * 4 10 10 10 10 (C) Irgacure 184 * 5 3 3 3 3 3 component LA-82 * 6 0.5 0.5 0.5 0.5 0.5 Other physical properties of cured product Refraction Rate (25 ℃) 1.565 1.578 1.562 1.563 1.558 Mold release ○ ○ △ ○ ○ Mold reproducibility ○ ○ ○ ○ ○ Restoration ○ ○ △ ○ ○

Note * 1 KAYARAD R-3
10: Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin (Yukaka Shell Epoxy Co., Ltd., Epicoat 100)
4) Epoxy acrylate of phenyl glycidyl ether 50% diluted with epoxy acrylate * 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 HX-220: diacrylate of epsilon-caprolactone adduct of neopentyl glycol hydroxypivalate manufactured by Nippon Kayaku Co., Ltd. * 5 Irgacure 184: Ciba・ Made by Geigy
Photopolymerization initiator * 6 LA-82: Asahi Denka Kogyo Co., Ltd.
As shown in 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. ..

[0034]

EFFECTS OF THE INVENTION 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. An oxazoline compound (a) represented by the formula (1): And a reaction product (A) of a carboxyl group-containing ethylenically unsaturated compound (b), an ethylenically unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C). Resin composition. 2. A transmission type comprising the reaction product (A) according to claim 1, an ethylenically unsaturated group-containing compound (B) other than the component (A) and a photopolymerization initiator (C). Ultraviolet curable resin composition for screen. 3. A cured product of the resin composition according to claim 1.