JPH0451146A - Resin composition and hardned product thereof - Google Patents

Abstract

PURPOSE:To obtain a light shielding film having excellent stability indicating a light shielding property and colored in the case of receiving the irradiation of the light, by incorporating a (meta)acrylate compound having a polyethylene glycol chain and/or a polypropylene glycol chain, polytungustophosphoric acid and/or salt of polytungustophosphoric acid and a photopolymerization initiator as an optional component. CONSTITUTION:This composition incorporates the (meta)acrylate compound having a polyethylene glycol chain and/or polypropylene glycol chain in the structure, polytungustophosphoric acid/or salt of polytungustophosphoric acid and the photopolymerization initiator as the optional component. As the examples of the (meta)acrylate compounds, urethane (meth)acrylate or (meta) acrylate ester, etc., are exemplified. Thus curing with ultraviolet rays is fast, and when the cured product is irradiated with light, it is colored and indicates the light shielding property and the resin composition being transparent as it is discolored when light irradiation is stopped, is obtained.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to an ultraviolet curable resin composition that is cured by ultraviolet rays, etc., and the cured product exhibits a photochromism phenomenon when irradiated with light such as ultraviolet rays, sunlight, and laser beams. and a cured product thereof.

(Prior art) A light-shielding film or a light-shielding molded product that exhibits light-shielding properties by having a photochromic substance present in a plastic film or lume and coloring it when exposed to direct rays such as ultraviolet rays, sunlight, and laser beams. For example, it can be used by adhering to the window glass of an automobile windshield.

As photochromic substances used in light-shielding films or light-shielding molded articles, spirovira y-based compounds, acylated leucomethylene blue-based compounds, spironaphthoxazine-based compounds, and the like are conventionally known.

(Problems to be Solved by the Invention) All of the photochromic substances have problems in that they are poor in stability and are expensive.

If a highly stable light-shielding film or light-shielding molded product that is colored and exhibits light-shielding properties when exposed to light irradiation could be provided, it could be used not only as a light-shielding film for materials but also for various other uses, such as It is expected that it will be used in photoresists for IC and LSI manufacturing, optical recording media, printing image production materials, and the like.

(Means for Solving the Problems) In order to solve the above problems, the present inventors conducted extensive research and found that the cured product is fast cured by ultraviolet rays, and when the cured product is irradiated with light, it becomes colored and exhibits light-shielding properties. We succeeded in providing a resin composition that both loses its color and becomes transparent when irradiation with light is stopped.

That is, the present invention comprises: a (meth)acrylate compound (A) having a polyethylene glycol chain and/or a polypropylene glycol chain in its structure; a polyphosphotungstic acid and/or a polyphosphotungstate salt; and a photopolymerization initiator (
The present invention relates to a resin composition containing Q and a cured product thereof.

It can be represented by a polyethylene glycol chain or a polypropylene chain in the structure of the (meth)acrylate compound, and n preferably has a value of 5 to 50.

Specific examples of (meth)acrylate compounds include urethane (meth)acrylate (a) and (meth)acrylic acid ester (b). For example, urethane (meth)acrylate) which is a reaction product of polyethylene glycol, polypropylene glycol or derivatives thereof, or two or more thereof, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate compound (a),
A reaction product of polyethylene glycol, polypropylene glycol or a derivative thereof, or a mixture of two or more thereof, a polyol such as a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, or a polytetramethylene glycol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate compound. Urethane (meth)acrylate (a): polyethylene glycol, polypropylene glycol or derivatives thereof, or (meth)acrylic ester (b) which is a reaction product of two or more of these and (meth)acrylic acid. can.

Specific examples of polyethylene glycol, polypropylene glycol, or derivatives thereof used here include polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polypropylene glycol monomethyl ether, and polypropylene glycol monomethyl ether. Ethyl ether poly(oxyethylene/oxypropylene) glycol, poly(oxyethylene/oxyph).

pyrene) glycol monomethyl ether, polypropylene glycol mono 2-ethylhexyl ether,
Polyethylene glycol monophenyl ether, reaction products of amines (e.g. evapoethylene diamine, 2-hydroxyethylamine, aniline, etc.) and ethylene oxide or propylene oxide, polyethylene glycol or polypropylene glycol and polybasic acids (e.g. succinic acid,
Phthalic acid, hexahydrophthalic anhydride, terephthalic acid,
adipine, maleic acid, etc.), polyether ester polyols which are reactants with phosphoric acid, poly(oxyethylene) diols of dialkylsiloxanes, polyhydric alcohols (e.g. neopentyl glycol, 1゜6-hexanediol, methylolpropane, pentaerythritol, cichentaerythritol, etc.), poly(oxyethylene) polyol or poly(oxypropylene) polyol, polyethylene glycol, polypropylene glycol, and lactones (e.g., ε-caprolactone, etc.)
Examples include lactone diol, which is a reaction product of , and glycidyl compounds as described below.

The preferred average molecular weight of these polyethylene glycol, polypropylene glycol or derivatives thereof is 2.
00 to 3000, particularly preferably 400 to 200
It is 0.

In addition to these polyethylene glycol, polypropylene glycol, or derivatives thereof, other polyols as described below may be used in combination.

Specific examples of organic polyisocyanates include hexamethylene diisocyanate, inphorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate trimer, hexamethylene diisocyanate trimer, Examples include a reaction product of trimethylolpropane and hexamethylene diisocyanate.

Specific examples of hydroxyl group-containing (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate,
2-hydroxypropyl (meth)acrylate, 1,4
-butanediol mono(meth)acrylate, monocaprolactone adduct of 2-hydroxyethyl(meth)acrylate, pentaerythritol tri(meth)azilylate, and the like.

An example of the manufacturing method of (a) and (b) will be described below.

Urethane (meth)acrylate (a) is, for example, polyethylene glycol, polypropylene glycol or derivatives thereof [polyester polyol (polyhydric alcohol, such as ethylene glycol, neopentyl glycol, 1,6-hexanediol, Reaction products of trimethylolpropane, tricyclodecane dimethylol, etc. and polybasic acids such as succinic acid, phthalic acid, hexahydrophthalic anhydride, adipic acid, azelaic acid, etc.),
Polycarbonate polyol (for example, a reaction product of 1,6-hexanediol and diphenyl carbonate), polycaprolactone polyol (for example, a reaction product of the polyhydric alcohol and ε-caprolactone, a reaction product of the polyhydric alcohol and the polybasic acid) and ε-caprolactone.

), etc.), the proportion of organic polyisocyanate is such that the amount of incyanate groups is 1.1 to 2.0 chemical equivalents per 1 chemical equivalent of hydroxyl groups of [including these]. and preferably the reaction temperature is 70~
A urethane oligomer is synthesized by reacting at 90° C. for 5 to 30 hours, and then a hydroxyl group-containing (meth)acrylate compound is added so that the amount of hydroxyl groups is 1 to 1.5 chemical equivalents per 1 chemical equivalent of incyanate group of the urethane oligomer. Preferably, at a reaction temperature of 70 to 90°C, 5 to 3
It can be obtained by reacting for 0 hours. In addition, the (meth)acrylic acid ester (b) may be, for example, polyethylene glycol, polypropylene glycol, or a derivative thereof [including other polyols such as the above-mentioned polyester polyol, polycarbonate polyol, polycaprolactone polyol, etc., if used together. (meth)acrylic acid is used at a ratio of 1 to 2 chemical equivalents per 1 chemical equivalent of hydroxyl group of the catalyst (for example, sulfuric acid, p
- toluenesulfonic acid, methanesulfonic acid, etc.) and a polymerization inhibitor (e.g., hydroquinone, methoquinone, phenothiazine, etc.), preferably at a reaction temperature of 80 to 15
It can be obtained by performing a dehydration reaction at 0°C for 5 to 30 hours. In addition, derivatives of polyethylene glycol or polypropylene glycol are terminal glycidyl ether compounds, such as diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, trimethylolpropane polyethoxy triglycidyl ether, glycerin polypropoxy triglycidyl ether, pentaerythritol poly In the case of glycidyl compounds such as ethoxytetraglycidyl ether, per chemical equivalent of glycidyl group of the glycidyl compound,
It can be obtained by reacting (meth)acrylic acid in a ratio of about 0.8 to 1.5 chemical equivalents, particularly preferably about 0.9 to 1.1 chemical equivalents. In this case, it is preferable to use a catalyst (for example, benzyldimethylamine, triethylamine, benzyltriethylammonium furomide, triphenylstibine, etc.) in order to accelerate the reaction, and the amount of the catalyst to be used depends on the raw material mixture. 01 to 10% by weight, particularly preferably 0
．． It is 3 to 5% by weight. Preferably, a polymerization inhibitor is used to prevent polymerization during the reaction. The reaction temperature is preferably 60-150°C, particularly preferably 80-120°C.
The reaction time is usually 5 to 50 hours. (meta)
Preferred examples of acrylate compounds include urethane acrylates obtained using a reaction product of polyethylene glycol, polypropylene gelicol, and polypropylene glycol with ε-caprolactone, urethane acrylates obtained using a mixture of polypropylene glycol and polycaprolactone diol, Examples include polyethylene glycol diacrylate, polypropylene glycol diacrylate, glycerin polyethoxy triacrylate, and acrylic ester of polyether ester polyol.

When the other polyol is used in combination when synthesizing the (meth)acrylate compound (2), the amount of the other polyol used is preferably 50 mol% or less based on the total alcohol component.

The preferred average molecular weight of the (meth)acrylate compound is 300 to 50,000.

In the present invention, polyphosphotungstic acid and/or polyphosphotungstate salt (2) is used.

Specific examples of these include polyphosphotungstic acid, lithium polyphosphotungstate, sodium polyphosphotungstate, potassium polyphosphotungstate, and the like.

A photopolymerization initiator (Q
Although any known photopolymerization initiator can be used, it is desirable to use one that has good storage stability after blending. Examples of such photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether,
Benzoin alkyl ethers such as benzoin butyl ether, benzophenone, p-methoxybenzophenone, 4,4-bis(dimethylaminobenzophenone),
Jetoxyacetophenone, α, α-dimethoxyα-
Acetophenones such as phenylacetophinone, 2,2-jetoxyacetophenone, 4-phenoxy-2,2-dichloroacetophenone, 2-hydroxy-2-methylglobiophenone, 4-improbil-2-hydroxy-2 - Glopiophenone series such as methylglobiophenone, anthraquinone series such as 1-hydroxycyclohexylphenyl ketone, benzylmethyl ketone and 2-ethylanthraquinone, 2-chloroanthraquinone,
Thioxanthone-based photopolymerization initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone, methylphenylglyoxylate, ethylphenylglyoxinthate, 2-hydroxy-2-7'thyl-1-phenylpropa:,' -1-one, 1-hydroxycyclohexylphenyl'ydoor, 1-(4-inpropylphenyl-)-2-hydroxy-2-methylpropan-1-one, 2,4.6-1.1 methyl Examples include benzoyrouzifuenoiho, phosphinio, oxido, and the like. Such photopolymerization initiators can be used -S or a mixture of two or more kinds. Preferred photoinitiators include, for example, 1-hydroxycyclohexylphenyl ketone, 2-
Hydroxy-2-methyl-1-phenylpropane-1-
Ong et al.

(Component a dissolves in the captive component, but a solvent (for example, methanol, ethanol, etc.) can also be used to facilitate dissolution. In the resin composition of the present invention, fB
) The usage ratio of the ingredients is 0.
5 to 30 parts by weight is preferred, particularly preferably 1.0 to 30 parts by weight.
It is 20 parts by weight. (The proportion of the Ω component used is preferably 0 to 30 parts by weight, particularly preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of the components.)

Although the resin composition of the present invention can sufficiently achieve the intended purpose using only the above-mentioned component materials, it is also possible to use ethylenically unsaturated group-containing compounds other than the active component. Examples of the tylenically unsaturated group-containing compound other than the carrier component include, for example, a compound having a (meth)acryloyl group, which can be roughly divided into low-molecular monomers and polymeric unsaturated group-containing resins. Specifically, the low molecular monomer is tricyclodecane (meth)acrylate (manufactured by Hitachi Chemical, FA-513A).

FA-513M), dicyclopentadieneoxyethyl (meth)acrylate, inbornyl (meth)acrylate, 2.2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2.2-bis(4-(meth) ) acryloyloxyethoxyphenyl) methane, trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxyhybalic acid neobentyl glycol di(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, tricyclode Candimethylol di(meth)acrylate, 5-ethyl-2-(2-hydroxy-1,1-dimethylethyl)-5-hydroxymethyl-1,3-dioxane diacrylate ester (manufactured by Nippon Kayaku ■, KAYAR
AD R-604), pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa and penta(meth)acrylate, poly(meth)acrylate of ε-caprolactone adduct of dipentaerythritol (Japan) Examples include (meth)acrylate monomers such as KAYARAD DPCA-20°30.60.120) and ditrimethylolpropane tetra(meth)acrylate.

Specifically, the polymeric unsaturated group-containing resin is, for example, a bisphenol type epoxy resin (for example, a bisphenol A type epoxy resin such as Epikote 828.1001.1004 manufactured by Shell Petrochemical Co., Ltd.) or a novolac type epoxy resin ( For example, epoxy (meth)acrylate obtained by reacting an epoxy resin such as Shell Petrochemical Co., Ltd., Epicoat 152, 154) with (meth)acrylic acid, polyhydric alcohols such as neopentyl glycol, ethylene glycol, propylene glycol, 1,
6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecanedimethylol, bis-(hydroxymethyl)-cyclohexane, etc. and polybasic acids such as succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, Polyester (meth)acrylate obtained by the reaction of a polyester polyol obtained by the reaction with azelaic acid, tetrahydrophthalic anhydride, etc. and (meth)acrylic acid, or a polyester (meth)acrylate obtained by the reaction of the polyhydric alcohol with the polybasic acid. A polyester polyol obtained by the reaction of the polyhydric alcohol, the polybasic acid, and ε-caprolactone, and a polycarbonate polyol, such as a polycarbonate polyol obtained by the reaction of 1,6-hexanediol and diphenyl carbonate, and an organic polyisocyanate,
Examples include urethane (meth)acrylates obtained by reacting isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene/diisocyanate, diphenylmethane-4,4-diisocyanate, etc. with the hydroxyl group-containing (meth)acrylate compound. can.

The amount of the ethylenically unsaturated group-containing compound other than the prisoner component to be used is preferably O to I 000 parts by weight, particularly preferably 50 to It is 200 parts by weight.

Furthermore, if necessary, antioxidants, photostable agents, ultraviolet absorbers, silane coupling agents, polymerization inhibitors, leveling agents, pigments, dyes, inorganic fillers, etc. may be added within the scope of the invention. be able to. Moreover, any amount of solvents can be used to improve coating properties.

The resin composition of the present invention is obtained by mixing each component.

Curing of the resin composition of the present invention by irradiation with ultraviolet rays or the like can be carried out by a conventional method. For example, ultraviolet rays may be irradiated using a low-pressure or high-pressure mercury lamp, a xenon lamp, or the like. Curing can also be done by electron beam irradiation instead of ultraviolet irradiation. In this way, a cured product that is a light-shielding film or a light-shielding molded product is obtained. The cured product of the resin composition of the present invention is useful as a light-shielding window material, but can also be used as an optical recording medium, an image forming material for printing, and the like.

An example of a method for producing a film-like cured product using the resin composition of the present invention is shown below. That is, the resin composition is applied onto a base material, for example, a film made of polycarbonate, vinyl chloride, polyester, etc., or an inorganic base material such as glass, by a roll coating method, a curtain flow coating method, a spin cord method, a screen printing method, etc. A film-like cured product (light-shielding film) can be obtained by coating the film to a thickness of usually about 1 to 100 μm, curing it by irradiating it with ultraviolet rays, and peeling it off from the base material.

When the cured product of the resin composition of the present invention is irradiated with light such as ultraviolet rays, sunlight, and laser light, it becomes colored gray, and when the light irradiation is stopped, the color disappears and becomes transparent. Excellent durability and fogging properties.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. In addition,
Parts in the examples are parts by weight.

Example 1 100 parts of polyethylene glycol diacrylate (manufactured by Kyoeisha Yushi Co., Ltd., 14EGA), 10 parts of sodium polyphosphotungstate, and 100 parts of ethyl alcohol were heated and dissolved at 70°C, and then the ethyl alcohol was distilled and removed. 10 parts of tetrahydrofurfuryl acrylate and 6 parts of Irgakia-184 (manufactured by Ciba Geigy, photopolymerization initiator) were mixed and dissolved to obtain an ultraviolet curable resin composition of the present invention. The above ultraviolet curable resin composition was coated onto a polycarbonate film to a thickness of 50 μm using a roll coater, and the composition was cured by irradiation with a high-pressure mercury lamp (manufactured by Nippon Battery ■, 2 seats).

After exposing the obtained cured product to sunlight for 30 minutes, it was found to have photochromic properties (○ colored gray; x not colored at all).

) The cloudiness (○ is cloudy; X: not cloudy at all and is transparent) was visually evaluated. The results are shown in Table 1. When this cured product was left indoors for 1 hour, the gray coloring disappeared and it became a transparent cured product.

Example 2 1 mole of polypropylene glycol (molecular weight 2000) was reacted with 2 moles of inphorone diincyanate at 80°C for 15 hours, and then 2-hydroxyethyl acrylate)
50 parts of urethane acrylate obtained by reacting 2.1 mol at 80°C for 10 hours, 5 parts of polyphosphotungstic acid, and 100 parts of ethyl alcohol were charged, heated and dissolved at 70°C, and then ethyl alcohol was distilled and removed. Next, 25 parts of carpitol acrylate, a mixture of pentaerythritol tri- and tetraacrylate (Nippon Kayaku ■
25 parts of KAYARADPET-30) and 1845 parts of Irgacure were mixed and dissolved to obtain an ultraviolet curable resin composition of the present invention. This was cured in the same manner as in Example 1, and the resulting cured product was tested in the same manner as in Example 1 and evaluated for photochromic properties and haze properties.The results are shown in Table 1. When the cured product after photochromic property and haze evaluation was left indoors for 1 hour, the gray coloring disappeared and it became a transparent cured product.

Example 3 Reactant of chrycerin and ethylene oxide (molecule f[1
000) triacrylate, 10 parts of sodium polyphosphotungstate, and 100 parts of ethyl alcohol were heated and dissolved at 70°C, the ethyl alcohol was then distilled off, and a mixture of dibe/taerythritol penta and hexaacrylate (Nippon Ka Made by Pharmaceutical Company, KAYA
30 parts of RAD DPHA), 20 parts of tetrahydrofurfuryl acrylate, and 1848 parts of Irgacure were mixed and dissolved to obtain an ultraviolet curable resin composition of the present invention. This was cured in the same manner as in Example 1, and the resulting cured product was tested in the same manner as in the Example to evaluate photochromic properties and haze properties. The results are shown in Table 1.

Furthermore, when the cured product after evaluating photochromic properties and fogging properties was left indoors for 1 hour, the gray coloring disappeared and it became a transparent cured product.

Comparative Example 1 A UV-curable resin composition was obtained by mixing and dissolving in the same manner as in Example 1, except that tungstic acid was omitted. This was cured in the same manner as in Example 1, and the resulting cured product was tested in the same manner as in Example 1 to evaluate photochromic properties and haze.

Table 1 (Effects of the Invention) The cured product obtained by curing the resin composition of the present invention exhibits good photochromic properties and fogging properties, and is useful as a light shielding material for window glass and the like.

Claims (1)

[Claims] 1. A (meth)acrylate compound (A) having a polyethylene glycol chain and/or a polypropylene glycol chain in its structure, polyphosphotungstic acid and/or polyphosphotungstic acid salt (B), and photopolymerization as an optional component. A resin composition comprising an initiator (C). 2. A cured product of the composition according to claim 1.