JPH09255765A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin compsn. which cures in a short time and is excellent in weathering resistance, chemical resistance, adhesion to a substrate, and flexibility by compounding an epoxy compd., a cationic polymn. catalyst, and a hydroxylated glycerin compd. SOLUTION: 30-98.9wt.% epoxy compd. having a number-average mol.wt. of 100-10,000 is compounded with 0.1-20wt.% cationic polymn. catalyst, and 1-50wt.% glycerin compd. having at least one hydroxyl group in the molecule and having a mol.wt. of 10,000 or lower.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to excellent weather resistance, chemical resistance, adhesion to a substrate and flexibility, which is cured in a short time by irradiation with active energy rays or heating. And a curable resin composition which gives a cured coating film having high surface hardness.

[0002]

2. Description of the Related Art An active energy ray-curable resin that is cured by active energy rays such as ultraviolet rays and electron beams has a characteristic of rapid curing. Therefore, paints, inks, adhesives, coating agents, three-dimensional moldings, resist inks, etc. It is used in many fields. However, when the radical polymerization type active energy ray curable resin is cured in air, the curing of the surface layer is slow, and there is a drawback that the surface is soiled or scratched in a subsequent step. Further, there are drawbacks such as a difficulty in curing in air in a thin coating state of 2 to 3 μm or less which can be produced by spray coating, gravure printing and the like, and poor adhesion to a substrate due to large curing shrinkage.

In order to overcome these drawbacks, new polymerization systems have recently been proposed. For example, ene-thiol polymerization and cationic polymerization systems. In particular, cationic polymerization is a system in which an epoxy resin or vinyl ether compound is polymerized with an acid generation catalyst (cationic polymerization catalyst), unlike conventional radical polymerization, it is not affected by curing inhibition even in air, and the epoxy resin has low curing shrinkage. Therefore, it has excellent adhesiveness to the substrate, and is disclosed in JP-A-62-235318, JP-A-5-125150, and JP-A-6-228.
Although it is reported in Japanese Patent No. 413, etc., it has drawbacks such that the surface is easily scratched due to the slow curing of the coating film and the flexibility is poor.

[0004]

The problem to be solved by the present invention is that it cures in a short time by irradiation with active energy rays or heating, and has excellent weather resistance, chemical resistance, adhesion to a substrate, and It is intended to provide a curable resin composition which is flexible and gives a cured coating film having high surface hardness.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have made a compound (a) having an epoxy group, a cationic polymerization catalyst (b), and a glycerin-based compound having at least one or more hydroxyl groups. When the resin composition containing the compound (c) is irradiated with active energy rays in air or heated,
It was discovered that a cured product having excellent curability, flexibility and adhesion can be obtained, and the present invention has been completed.

That is, the present invention comprises a compound (a) having an epoxy group, a cationic polymerization catalyst (b) and at least 1
It is a curable resin composition containing a glycerin-based compound (c) having three or more hydroxyl groups, and more specifically, 30 wt% to 98.9 wt% of the compound (a) having an epoxy group.
And 0.1 wt% to 20 wt% of the cationic polymerization catalyst (b) and 1 wt% to 50 wt% of the glycerin-based compound (c) having at least one or more hydroxyl groups. Which is a curable resin composition.

The curable resin composition of the present invention is characterized in that the compound (a) having an epoxy group used is a compound having an alicyclic epoxy group, and the curable resin composition of the present invention. At least 1 used for the curable resin composition
A glycerin compound (c) having three or more hydroxyl groups,
A curable resin composition characterized by being a compound having a molecular weight of 10,000 or less, and a curable resin characterized in that the glycerin compound (c) having at least one or more hydroxyl groups is an alkylene glycol-modified product. The composition and the glycerin-based compound (c) having at least one or more hydroxyl groups are, among others, a curable resin composition characterized by being a diglycerin-based compound.

The curable resin composition of the present invention comprises a compound (a) having an epoxy group and a cationic polymerization catalyst (b).
And the content of the glycerin-based compound (c) having at least one or more hydroxyl groups contained in the total 100% by weight of the hydroxyl group-containing compound (c) is particularly 5 to 40% by weight. Resin composition.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
Compound (a) having an epoxy group used in the present invention
Specifically, (methyl) epichlorohydrin and epibis type epoxy resin, epoxy novolac resin, phenol, biphenol, etc. synthesized from bisphenol A, bisphenol F and its ethylene oxide and propylene oxide modified products, and (methyl) Examples thereof include reaction products with epichlorohydrin, and aromatic epoxy resins such as terephthalic acid, isophthalic acid, and glycidyl ester of pyromellitic acid.

Further, glycols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol and neopentyl glycol, and polyglycidyl ethers of alkylene oxide modified products thereof and trimethylol. Propane, trimethylolethane, glycerin, diglycerin, erythritol, pentaerythritol, sorbitol, 1,4-butanediol, aliphatic polyhydric alcohols such as 1,6-hexanediol, and glycidyl ethers of its alkylene oxide-modified products,

Glycidyl esters of carboxylic acids such as adipic acid, sebacic acid, maleic acid, itaconic acid,
Glycidyl ether of polyester polyol of polyhydric alcohol and polycarboxylic acid, copolymer of glycidyl (meth) acrylate and methylglycidyl (meth) acrylate, glycidyl ester of higher fatty acid, epoxidized linseed oil, epoxidized soybean oil, epoxy Aliphatic epoxy resins such as activated castor oil and epoxidized polybutadiene may be mentioned.

Examples of the more preferable compound (a) having an epoxy group include compounds having an alicyclic epoxy group. Specific examples of the compound containing an alicyclic epoxy group include glycidyl ether synthesized by the reaction of hydrogenated bisphenol A, hydrogenated bisphenol F or an alkylene oxide adduct thereof with (methyl) epichlorohydrin, 3,4 -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-
5,5-spiro-3,4-epoxy) cyclohexane-
Metadioxane,

Caprolactone adduct of bis (3,4-epoxycyclohexylmethyl) adipate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (trade name Celoxide 208)
1,2083, manufactured by Daicel Chemical Industries, Ltd.), (methyl) valerolactone adduct of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexenedioxide, 4-vinylepoxycyclohexane,

Dipentene diepoxide, dicyclopentadiene diepoxide, ethylene bis (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, hexahydrophthalic acid ester type epoxy resin, Epolide GT manufactured by Daicel Chemical Co., Ltd.
300, erythritol caprolactone-modified epoxy resin Epolide GT400, and the like.

Compound (a) having these epoxy groups
Can be used alone or in combination of two or more depending on the application. The amount of the compound (a) having an epoxy group used is equal to that of the compound (a) having an epoxy group.
In the total 100% by weight of the cationic polymerization catalyst (b) and the glycerin compound (c) having at least one or more hydroxyl groups, 30 to 98.9% by weight, more preferably 5
It is 0 to 94.5% by weight.

Further, more preferably, when the compound (a) having an epoxy group is a compound having an alicyclic epoxy group having a number average molecular weight of 100 to 10,000, cationic polymerization reactivity, low viscosity and thick film curing are obtained. It exhibits particularly excellent properties such as properties.

Cationic polymerization catalyst (b) used in the present invention
Any substance can be used as long as it can generate a cation, and examples thereof include a photocationic polymerization catalyst that generates a cation by irradiation with an active energy ray and a thermal cationic polymerization catalyst that generates a cation by heat. Specific examples of the thermal cationic polymerization catalyst (b-1) used in the present invention include amine complexes of boron trifluoride, quaternary ammonium salts, and pyridinium salts represented by the general formula 1. .

(General formula 1)

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As the photocation catalyst (b-2), a silicon compound which produces a silanol group upon irradiation with light,
Examples thereof include diazonium salts represented by the general formula 2, sulfonium acetophenones represented by the general formulas 3 to 5, metal allene complexes represented by the general formula 6, and the like. An aromatic onium salt is particularly effective, and an iodonium salt represented by the general formula 7 and a sulfonium salt represented by the general formula 8 or 9 are more preferable.

(General formula 2)

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(General formula 3)

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(General formula 4)

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(General formula 5)

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(General formula 6)

[Chemical 6]

(General formula 7)

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(General formula 8)

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(General formula 9)

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(Where R₁~ R_{twenty two}Are the same or different
Hydrogen atom, alkyl group, alkoxyl group, thioal
Represents a alkyl group, an aryl group, or a hydroxyalkyl group.
You. X ^-Is tetrafluoroborate (BF_Four ^-), Heki
Safurophosphate (PF₆ ^-), Hexafluoro
Antimonate (SbF₆ ^-), Hexafluoroarsene
Auto (AsF₆ ^-), Or hexachloroantimonate
(SbCl_Three ^-). )

In the general formula, R _{17 to} R ₂₂ are particularly preferably sulfonium salts of phenol and biphenol. Such cationic polymerization catalyst (b) can be used alone or in combination of two or more kinds according to the application. The addition amount of these cationic polymerization catalysts (b) is 0.
1 to 20% by weight, preferably 0.5 to 10% by weight
It is. If it is less than 0.1% by weight, curing will be slow,
On the contrary, if it exceeds 20% by weight, the strength of the coating film decreases and the cost increases, which is not preferable.

The glycerin compound (c) having one or more hydroxyl groups, which is an essential component of the present invention, is specifically glycerin, diglycerin, polyglycerin and derivatives thereof. More specifically, glycerin, polyoxyethylene glyceryl ether (glycerin ethylene oxide modified product), polyoxypropylene glyceryl ether (glycerin propylene oxide modified product), polyoxypropylene glyceryl ether (glycerin propylene oxide modified product), polyoxybutylene Glyceryl ether (glycerin butylene oxide modified product),

Polytetramethylene glyceryl ether (tetrahydrofuran modified glycerin), caprolactone modified glycerin, γ-butyrolactone modified glycerin, δ-valerolactone modified glycerin, methylvalerolactone modified glycerin, diglycerin, Polyoxyethylene diglyceryl ether (diglycerin ethylene oxide modified product), polyoxypropylene diglyceryl ether (diglycerin propylene oxide modified product), polyoxybutylene diglyceryl ether (diglycerin butylene oxide modified product),

Polytetramethylene diglyceryl ether (tetrahydrofuran modification of diglycerin), caprolactone modification of diglycerin, γ-butyrolactone modification of diglycerin, δ-valerolactone modification of diglycerin, methylvalerolactone of diglycerin. Modified products, tetraglycerin, hexaglycerin, decaglycerin, polyoxyethylene tetraglyceryl ether (tetraglycerin ethylene oxide modified product), polyoxypropylene hexaglyceryl ether (hexaglycerin propylene oxide modified product), polyoxybutylene tetraglyceryl ether (tetra Glycerin butylene oxide modified product),

Polytetramethylene hexaglyceryl ether (tetrahydrofuran modified product of hexaglycerin)
Such as polyhydric hydroxyl group compounds, mono- and polyhydric hydroxyl group-containing compounds of the terminal ether groups of the above-mentioned polyhydric hydroxyl-containing compounds, formic acid, acetic acid, propionic acid, butyric acid, fumaric acid, phthalic acid of the above-mentioned polyhydric hydroxyl-containing compounds Mono- and polyhydric hydroxyl-containing compounds obtained by esterification with animal or plant fatty acids such as isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid, trimellitic acid, linoleic acid, and oleic acid. Can be

Any of these hydroxyl group-containing compounds (c) can be used as long as they have at least one hydroxyl group in the molecule, but two of them are used from the viewpoint of the strength and curability of the coating film. The compounds having the above hydroxyl groups are more preferable.
These hydroxyl group-containing compounds (c) may be used alone or in combination of two or more, depending on the application.

The glycerin-based compound (c) having at least one hydroxyl group used in the present invention is more preferably a compound having a molecular weight of 10,000 or less from the viewpoint of coating suitability such as viscosity and rapid curing property. When the molecular weight is more than 10,000, the coating suitability is lowered due to an increase in viscosity and the curability is lowered due to a low hydroxyl value, which is not preferable.

Among the above glycerin compounds, glycerin, diglycerin, polyglycerin and ethylene oxide, propylene oxide, butylene oxide,
When an alkylene glycol-modified glycerin-based compound (c) having at least one or more hydroxyl groups obtained by addition reaction with tetrahydrofuran is used, it is preferable in terms of fast curing, flexibility of cured coating film, and adhesion, Of these, alkylene glycol-modified diglycerin is more preferable.

The amount of the glycerin compound (c) having one or more hydroxyl groups, which is an essential component of the curable resin composition of the present invention, is such that the epoxy group-containing compound (a) and the cationic polymerization catalyst (b) are used. It is 1 to 50% by weight, and more preferably 3 to 40% by weight, based on 100% by weight of the total of the hydroxyl group-containing compound (c). If it is less than 1% by weight, the effect of the present invention is not obtained, and if it is more than 50% by weight, the hardness and strength of the coating film are lowered, which is not preferable.

The curable resin composition of the present invention comprises a photosensitizer, a reactive compound such as a vinyl ether monomer and a (meth) acrylic monomer, a non-reactive compound such as a petroleum resin, and an inorganic filler, depending on the application. Further, an organic filler, a coupling agent, a well-known and commonly used pigment, a solvent, a leveling agent and the like can be appropriately used.

Specific examples of the photosensitizer used in the curable resin composition of the present invention include benzophenone and o-
Methyl benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-
Dimethyl-4-methoxybenzophenone, benzoquinone, anthracene,

2-isopropylthioxanthone, 2,4
-Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 2,2- Dimethoxy-2-phenylacetophenone, 1-hydroxy-cyclohexylphenyl ketone and the like.

Specific examples of vinyl ether monomers include glycidyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexyl vinyl ether,
Examples thereof include hydroxybutyl vinyl ether, dodecyl vinyl ether, tripropylene glycol divinyl ether, butanediol divinyl ether, 1,6-hexanediol divinyl ether, polytetraethylene glycol divinyl ether and trimethylolpropane trivinyl ether.

Specific examples of the (meth) acrylic monomer include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate and iso Stearyl (meta)
Acrylate, methoxyethyl (meth) acrylate,
Ethoxyethyl (meth) acrylate, methyl carbitol (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy (meth) acrylate,
Methoxydipropylene glycol (meth) acrylate,

Triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin-modified 1,6-hexanediol di (meth) acrylate, bisphenol A di (Meta)
Acrylate, epichlorohydrin-modified bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate,

Ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Examples thereof include pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

The non-reactive compound referred to in the present invention is a liquid or solid oligomer or resin having low or no reactivity, such as an alkyl (meth) acrylate copolymer, an epoxy resin and a liquid polybutadiene. , Liquid polybutadiene derivative, liquid chloroprene, liquid polypentadiene, dicyclopentadiene derivative, saturated polyester oligomer, polyether oligomer, liquid polyamide, polyisocyanate oligomer, xylene resin, ketone resin, petroleum resin, rosin resin, fluorine-based oligomer, silicon-based Examples thereof include oligomers and polysulfide-based oligomers.

Inorganic fillers and organic fillers are generally used to improve mechanical properties such as strength, cushioning property and slipperiness. As the inorganic filler, known and commonly used ones,
For example, silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, glass,
Mica, barium sulfate, alumina white, zeolite,
Examples thereof include silica balloons and glass balloons.

As the inorganic filler, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, etc. are added.
A halogen group, an epoxy group,
It may be one having a functional group such as a hydroxyl group or a thiol group.

As the organic filler, known conventional ones, for example, benzoguanamine resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, crosslinked polystyrene, polydivinylbenzene, styrene can be used. -Divinylbenzene copolymer, acrylic copolymer, crosslinked acrylic resin, polymethylmethacrylate resin, vinylidene chloride resin, fluororesin, nylon 12, nylon 11,
Examples include nylon 6/66, phenol resin, epoxy resin, urethane resin, and polyimide resin. Further, the organic filler may have a functional group such as a halogen group, an epoxy group, a hydroxyl group, or a thiol group in the above resin.

The coupling agent that may be used in the present invention is not particularly limited as long as it is a known and commonly used one, and for example, γ-glycidoxypropyltrimethoxysilane,
a silane coupling agent having an epoxy group such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, a silane coupling agent having a mercapto group such as γ-mercaptopropyltrimethoxysilane,

Or a silane coupling agent such as a silane coupling agent having a halogen group such as γ-chloropropyltrimethoxysilane; tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, Isopropyl dimethacryl isostearoyl titanate, isopropyl diacryl isostearoyl titanate, isopropyl triisostearoyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate,

Titanate coupling agents such as bis (dioctylpyrophosphate) ethylene titanate, isopropyltridodecylbenzenesulfonyl titanate and isopropyltricumylphenyl titanate; aluminum coupling agents such as acetoalkoxyaluminum diisopropylate and acetylacetone-zirconium complex. And other zirconium-based coupling agents.

The pigment, solvent and leveling agent used in the curable resin composition of the present invention are not particularly limited as long as they are known and commonly used, as long as the curability and resin properties are not impaired. Can be used. In order to obtain the curable resin composition of the present invention, the above components may be mixed, and the order and method of mixing are not particularly limited.

The active energy rays used in the present invention are ionizing radiations such as ultraviolet rays, electron rays, α rays, β rays and γ rays,
Visible light, microwave, high frequency, etc. are used, but any energy species may be used as long as it can generate a cation species. Examples of those that generate ultraviolet rays include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, chemical lamps, black light lamps, mercury-xenon lamps, short arc lamps, etc., and generate cationic active species. It may be selected in consideration of the absorption wavelength of the compound.

The curable resin composition of the present invention can obtain a cured coating film having a high surface hardness at a low temperature by using an active energy ray.
Coating materials for metals such as copper, vinyl chloride, acrylic, polycarbonate, polyethylene terephthalate, plastics such as ABS resin, polyethylene, polypropylene, polystyrene, ceramics such as glass, wood, paper, printing paper, fibers, etc. And surface treatment agents, binders, plastic materials, molding materials, laminated plates, and other applications requiring surface hardness.

Further, even when it is used in applications where it is not required to harden the surface of adhesives, pressure-sensitive adhesives, binders, etc., it has the advantage of improved curability. Even when the curing atmosphere is replaced with an inert gas, the curable resin composition of the present invention can be used without any problem.

[0056]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. All% in the examples are% by weight unless otherwise specified. In addition, in the examples and comparative examples, the curability and surface height were measured by the following methods.

(1) UV curability: A resin composition was applied onto an acrylic plate by an applicator so that the film thickness after curing was 20 μm, and then 160 W / c in air.
Ultraviolet irradiation was carried out using a m high pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.) under conditions of a lamp height of 15 cm and a conveyor speed of 10 m / min, and the surface hardness was evaluated immediately after irradiation and after 1 day after irradiation.

(2) Thermosetting: A resin composition was applied onto a glass plate using an applicator so that the film thickness after curing was 20 μm, and then it was dried at 150 ° C. using a hot air dryer.
The surface hardness was evaluated by heating for 1 hour and 1 day after cooling by heating for 20 minutes.

(3) Surface hardness: A coating film was prepared by the same method as in the above-mentioned measurement of ultraviolet curing property, and based on JIS K-5400, a surface property measuring instrument TYPE: 14D (manufactured by Shinto Kagaku).
Was used to measure the pencil hardness.

Example 1 87% by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and polyoxypropylene glyceryl ether (RT manufactured by Dainippon Ink and Chemicals, Inc.)
266) in an amount of 10% by weight, triarylsulfonium hexafluoroantimonate (U manufactured by Union Carbide Co.)
VI-6970) was mixed by stirring at 3% by weight to obtain a transparent and uniform curable resin composition. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 1 shows the results.

Example 2 77% by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and polyoxypropylene glyceryl ether (RT manufactured by Dainippon Ink and Chemicals, Inc.)
266) in an amount of 20% by weight and triarylsulfonium hexafluoroantimonate (U produced by Union Carbide Co.).
VI-6970) was mixed by stirring at 3% by weight to obtain a transparent and uniform curable resin composition. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 1 shows the results.

(Example 3) 57% by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and polyoxypropylene glyceryl ether (RT manufactured by Dainippon Ink and Chemicals, Inc.)
266) 40% by weight, triarylsulfonium hexafluoroantimonate (U manufactured by Union Carbide Co., Ltd.
VI-6970) was mixed by stirring at 3% by weight to obtain a transparent and uniform curable resin composition. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 1 shows the results.

Example 4 The polyoxypropylene glyceryl ether of Example 2 (manufactured by Dainippon Ink and Chemicals, Inc.)
RT266) as poly (oxyethylene, oxypropylene) glyceryl ether (SANYO KASEI GEP28
(00) A curable resin composition was obtained in the same manner except that the amount was changed to 20% by weight. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation.
Table 1 shows the results.

Example 5 77% by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and 20% by weight of polyoxypropylene diglyceryl ether (SY-DP4 manufactured by Sakamoto Yakuhin). , Triarylsulfonium hexafluoroantimonate (UVI-69 manufactured by Union Carbide Co., Ltd.
70% of 3% by weight was stirred and mixed to obtain a transparent and uniform curable resin composition. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation.
Table 1 shows the results.

Example 6 70% by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and 20% by weight of polyoxypropylene diglyceryl ether (SY-DP4 manufactured by Sakamoto Yakuhin). , Triarylsulfonium hexafluoroantimonate (UVI-69 manufactured by Union Carbide Co., Ltd.
70% of 10) was mixed by stirring to obtain a transparent uniform curable resin composition. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 1 shows the results.

Example 7 The polyoxypropylene glyceryl ether of Example 2 (manufactured by Dainippon Ink and Chemicals, Inc.)
A curable resin composition was obtained in the same manner except that RT266) was changed to 20% by weight of polyoxypropylene diglyceryl ether (SY-DP14 manufactured by Sakamoto Yakuhin). Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 1 shows the results.

Example 8 50% by weight of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 27% by weight of dipentene diepoxide (Celoxide 3000 manufactured by Daicel Chemical Industries) and polyoxypropylene. 20% by weight of diglyceryl ether (SY-DP4 manufactured by Sakamoto Yakuhin) and 3% by weight of triarylsulfonium hexafluoroantimonate (UVI-6970 manufactured by Union Carbide Co., Ltd.) were stirred and mixed to give a transparent and uniform curable resin composition. Got Next, this curable resin composition is irradiated with ultraviolet rays, and immediately after irradiation and irradiation 1
The surface hardness after the day was measured. Table 1 shows the results.

Example 9 50% by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate (manufactured by Union Carbide Co.)
27% by weight of UVR-6128) and polyoxypropylene diglyceryl ether (SY-DP manufactured by Sakamoto Yakuhin)
4) 20% by weight, triarylsulfonium hexafluoroantimonate (UVI manufactured by Union Carbide)
-6970) was stirred and mixed at 3% by weight to obtain a transparent and uniform curable resin composition. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 2 shows the results.

(Example 10) In a four-necked flask equipped with a stirrer, a thermometer, and a condenser, 9.2 g (0.1 mol) of glycerin and 21.6 g (0.3 of 1,2-butylene oxide) were added.
Mol) in the presence of a potassium hydroxide catalyst at 80 ° C. for 5 hours to give polyoxybutylene glyceryl ether (C
-1) was obtained. Next, 77% by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 20% by weight of the above polyoxybutylene glyceryl ether (C-1), and triarylsulfonium hexafluoroantimonate. (Union Carbide UVI-6970) was stirred and mixed at 3% by weight to obtain a transparent and uniform curable resin composition. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 2 shows the results.

Example 11 In a four-necked flask equipped with a stirrer, a thermometer, and a condenser, 9.2 g (0.1 mol) of glycerin and 34.2 g (0.3 mol) of ε-caprolactone were added to titanium tetrachloride. 16 in the presence of isopropoxide catalyst
The reaction was carried out at 0 ° C for 5 hours to obtain a glycerin caprolactone-modified product (C-1). Next, 77% by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 20% by weight of the glycerin caprolactone modified product, triarylsulfonium hexafluoroantimonate (UVI manufactured by Union Carbide Co., Ltd.). -6970) by stirring and mixing 3% by weight,
A transparent and uniform curable resin composition was obtained. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 2 shows the results.

(Comparative Example 1) 77% by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, and ε-caprolactone-modified trimethylolpropane (manufactured by Union Carbide Co.)
20% by weight of TONE-0301) and 3% by weight of triarylsulfonium hexafluoroantimonate (UVI-6970 manufactured by Union Carbide Co.) were mixed by stirring to obtain a transparent and uniform curable resin composition. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 2 shows the results.

(Comparative Example 2) 20% by weight of ε-caprolactone-modified trimethylolpropane (TONE-0301 manufactured by Union Carbide) of Comparative Example 1 was used as polypropylene oxide-modified trimethylolpropane (New Pol TP-400 manufactured by Sanyo Kasei Co., Ltd.). A curable resin composition was obtained in the same manner except that the above was changed. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 2 shows the results.

Comparative Example 3 20% by weight of ε-caprolactone-modified trimethylolpropane (TONE-0301 manufactured by Union Carbide Co., Ltd.) of Comparative Example 1 was used as polycaprolactone diol (Placcel 205 manufactured by Daicel Chemical Co., Ltd.).
A curable resin composition was obtained in the same manner except that the above was changed.
Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 2 shows the results.

Comparative Example 4 ε-caprolactone-modified trimethylolpropane (TONE-0301 manufactured by Union Carbide Co.) of Comparative Example 1 was used as polypropylene glycol (New Pol PP-400 manufactured by Sanyo Chemical Industry Co., Ltd.) 20.
A curable resin composition was obtained in the same manner except that the content was changed to wt%. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation. Table 2 shows the results.

Comparative Example 5 3,4-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate 37% by weight and polyoxypropylene diglyceryl ether (SY-DP4 manufactured by Sakamoto Yakuhin) 60% by weight. , Triarylsulfonium hexafluoroantimonate (UVI-69 manufactured by Union Carbide Co., Ltd.
70% of 3% by weight was stirred and mixed to obtain a transparent and uniform curable resin composition. Next, this curable resin composition was irradiated with ultraviolet rays, and the surface hardness was measured immediately after the irradiation and one day after the irradiation.
Table 2 shows the results. In addition, x in Table 2 indicates that <4B.

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[Table 1]

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[Table 2]

(Example 12) 77% by weight of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and polyoxypropylene glyceryl ether (R manufactured by Dainippon Ink and Chemicals, Inc.)
20% by weight of T266) and 3% by weight of an antimony onium salt (CI-2481 manufactured by Nippon Soda Co., Ltd.) were mixed with stirring to obtain a transparent and uniform curable resin composition. Next, this curable resin composition was heated, and the surface hardness after cooling for 1 hour and after cooling for 1 day was measured. Table 3 shows the results.

Comparative Example 6 Polyoxypropylene glyceryl ether of Example 12 (RT266 manufactured by Dainippon Ink and Chemicals, Inc.) was mixed with ε-caprolactone-modified trimethylolpropane (TONE-03 manufactured by Union Carbide Co., Ltd.).
01) A curable resin composition was obtained in the same manner except that the amount was changed to 20% by weight. Next, this curable resin composition was heated and the surface hardness after cooling for 1 hour and after cooling for 1 day was measured. Table 3 shows the results.

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[Table 3]

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INDUSTRIAL APPLICABILITY The present invention cures in a short time by irradiation with active energy rays or heating, has excellent weather resistance, chemical resistance, adhesion to a substrate, and flexibility, and has a surface hardness. It is possible to provide a curable resin composition that gives a cured coating film having high viscosity.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03F 7/029 G03F 7/029

Claims (7)

[Claims] 1. A curable resin composition containing a compound (a) having an epoxy group, a cationic polymerization catalyst (b), and a glycerin compound (c) having at least one or more hydroxyl groups. 2. The compound (a) having an epoxy group is 30
% To 98.9% by weight, 0.1% to 20% by weight of the cationic polymerization catalyst (b), and 1% to 5% by weight of the glycerin compound (c) having at least one or more hydroxyl groups.
0% by weight is contained, The curable resin composition of Claim 1 characterized by the above-mentioned. 3. The curable resin composition according to claim 1, wherein the compound (a) having an epoxy group is a compound having an alicyclic epoxy group. 4. The curable resin according to claim 1, wherein the glycerin compound (c) having at least one hydroxyl group is a compound having a molecular weight of 10,000 or less. Composition. 5. The glycerin compound (c) having at least one or more hydroxyl groups is an alkylene glycol-modified product, and any one of claims 1 to 3 is provided.
The curable resin composition described in 1. 6. The curable resin composition according to claim 5, wherein the glycerin compound (c) having at least one hydroxyl group is a diglycerin compound. 7. A glycerin-based compound having at least one hydroxyl group contained in 100% by weight of the compound (a) having an epoxy group, the cationic polymerization catalyst (b) and the hydroxyl group-containing compound (c) ( The content rate of c) is 5 to
The curable resin composition according to claim 1, wherein the curable resin composition is 40% by weight.