JPH10251378A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition exhibiting good curing property by irradiation of active energy beam or heating and forming a coating film excellent in adhesiveness and flexibility and useful for coating materials, etc., by including a vinylic polymer having a specific function group and a cation polymerization catalyst. SOLUTION: This resin composition comprises (A) a vinylic polymer having epoxy group and OH group (preferably a vinylic polymer forming epoxy group on an aliphatic hydrocarbon ring and having 500-100,000 number-average molecular weight, 10-200KOHmg/g OH value and 100-10,000g/equivalent epoxy equivalent and (B) a cation polymerization catalyst e.g. a compound of formula I [R1 is H, a (thio)alkyl, etc.; X is tetrafluoroborate, etc.] or a compound of formula II (R2 and R3 are each R1 )}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition useful for paints, printing inks, resist inks, adhesives, stereolithography, etc., and more particularly, to curing by irradiation with active energy rays or heating. The present invention relates to a curable resin composition which cures in a short time to provide a cured coating film having excellent weather resistance, chemical resistance, adhesion to a substrate, adhesion and flexibility, and high surface hardness.

[0002]

2. Description of the Related Art Active energy ray-curable resins are characterized in that they cure quickly, and are therefore used in many fields such as paints, inks, adhesives, coatings, stereolithography, and resist inks.

[0003] Conventionally, active energy ray-curable resins of the radical polymerization type suffer from oxygen inhibition. Therefore, when cured in air, the curing of the surface layer is slow, and the surface becomes dirty or scratched in a later step. There are drawbacks such as ease. The radical polymerization type active energy ray-curable resin is used in spray coating, gravure printing and the like.
In the case of a thin film having a thickness of 3 μm or less, there is a problem that it is hard to cure in air. In addition, a radical polymerization type active energy ray-curable resin has a problem that curing shrinkage is large and adhesion to a substrate is poor.

In order to overcome these problems, in recent years,
New polymerization systems such as ene-thiol polymerization and cationic polymerization system have been proposed. Among these, cationic polymerization is a system in which an epoxy resin or vinyl ether compound is polymerized using an acid generating catalyst (cationic polymerization catalyst). Unlike conventional radical polymerization, it is not affected by oxygen, so its curability is good even in air. It is. Further, the epoxy resin used in the cationic polymerization has a low curing shrinkage and thus has excellent adhesion to the substrate.

[0005]

However, as reported in JP-A-62-235318, JP-A-5-125150, JP-A-6-228413, etc., the curing speed is low and the coating speed is low. There are problems such as the film surface being easily damaged and the coating film being brittle, resulting in poor flexibility.

[0006] The problem to be solved by the present invention is to provide a curable resin composition which is excellent in curing speed and can provide a coating film excellent in adhesion and flexibility.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have found that a vinyl polymer having an epoxy group and a hydroxyl group (a) and a cationic polymerization catalyst (b) And that the curable resin composition containing, by active energy ray irradiation or heating in air, shows good curability, and that the obtained coating film has excellent adhesion and flexibility. As a result, the present invention has been completed.

That is, in order to solve the above-mentioned problems, the present invention provides a curable resin composition comprising a vinyl polymer (a) having an epoxy group and a hydroxyl group, and a cationic polymerization catalyst (b). Offer things.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl polymer having an epoxy group and a hydroxyl group (a) used in the present invention is a vinyl polymer having an epoxy group and a hydroxyl group in a side chain and / or a terminal.

The polymer portion of the vinyl polymer having an epoxy group and a hydroxyl group at a side chain and / or a terminal includes an acrylic polymer having (meth) acrylic acid or (meth) acrylate as a main constituent monomer. An aromatic vinyl polymer whose main constituent monomer is an aromatic vinyl monomer such as styrene; a vinyl ester polymer whose main constituent monomer is a vinyl ester such as vinyl acetate; an alkene such as ethylene or propylene. An olefin-based polymer having a main constituent monomer; a fluoroolefin-based polymer having a fluorine-based vinyl monomer such as tetrafluoroethylene and chlorotrifluoroethylene as a main constituent monomer; In particular, among these vinyl polymers, an acrylic polymer is preferred from the viewpoints of diversity and ease of polymerization.

The vinyl polymer having an epoxy group and a hydroxyl group can be prepared, for example, by mixing a vinyl monomer mixture containing a vinyl monomer having an epoxy group and a vinyl monomer having a hydroxyl group with a radical polymerization initiator. It can be easily produced by radical polymerization and copolymerization. In addition, a solvent may be used in this radical polymerization reaction as needed. In addition to the monomer having an epoxy group and the monomer having a hydroxyl group, a vinyl monomer other than these monomers can be used in combination.

Examples of the vinyl monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, diglycidyl malate, diglycidyl fumarate, vinyl cyclohexene oxide, and 3,4-epoxycyclohexyl. Methyl methacrylate, butadiene monoepoxide, 4-vinyloxymethylcyclohexene oxide, glycidyl vinyl ether, acrylic glycidyl ether,
Examples thereof include ε-caprolactone adduct of (meth) acryloyloxymethylcyclohexene oxide and methylvalerolactone adduct of 4- (meth) acryloyloxymethylcyclohexene oxide.

The vinyl monomers having a hydroxyl group include:
For example, 2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and their alkylene glycol adducts, caprolactone adducts, glycerol mono (meth) acrylate, 3-chloro-2
Monoglycidyl compounds such as hydroxypropyl (meth) acrylate, butyl glycidyl ether and (meth)
Reactant of acrylic acid, phenoxyhydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, 2- (meth) Hydroxyl-containing (meth) acrylate compounds such as acryloyloxyethyl-2-hydroxypropylphthalic acid;
Hydroxyl group-containing (meth) acrylamide compounds such as methylol acrylamide, hydroxyethyl vinyl ether,
Examples thereof include vinyl ether compounds such as triethylene glycol monovinyl ether and allyl alcohol.

Examples of vinyl monomers other than the monomer having an epoxy group and the monomer having a hydroxyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane (Meth) acrylic esters such as styrene; aromatic vinyl monomers such as styrene, vinyltoluene, p-methoxystyrene and α-methylstyrene; dimethylmalate, diethylmalate, dibutylmalate, dimethylfumarate, dibutyl Fumarate, Jimme Dialkyl esters of unsaturated dibasic acids such as tilitaconate and ibutylitaconate; vinyl acetate, vinyl propionate, vinyl 2,2-dimethylbutanoate, vinyl cyclohexanecarboxylate;
Vinyl esters such as vinyl benzoate and p-tert-butyl vinyl benzoate; and olefin monomers such as ethylene, propylene, vinyl chloride and triethoxysilane.

The vinyl polymer (a) having an epoxy group and a hydroxyl group used in the present invention has a number average molecular weight of 5
Those in the range of 100 to 100,000 are preferable,
Those in the range of 1,000 to 50,000 are particularly preferred. When a vinyl polymer having an epoxy group and a hydroxyl group having a number average molecular weight of less than 500 is used, sufficient physical properties tend not to be obtained.
It is not preferable to use a vinyl polymer having an epoxy group and a hydroxyl group exceeding 000, because the viscosity tends to be high and workability tends to deteriorate.

The vinyl polymer (a) having an epoxy group and a hydroxyl group used in the present invention has a hydroxyl value of 10 to 10.
Those having a range of 200 KOHmg / g are preferable, and
Those having a range of 100 KOHmg / g are particularly preferred. When the hydroxyl value of the vinyl polymer (a) having an epoxy group and a hydroxyl group used in the present invention is less than 10 KOHmg / g, the curing rate tends to decrease, which is not preferable. The hydroxyl value can be easily measured by a titration method.

The vinyl polymer (a) having an epoxy group and a hydroxyl group used in the present invention has an epoxy equivalent of 1
Those having a range of 00 to 10,000 g / equivalent are preferable,
Those having a range of 200 to 5000 g / equivalent are particularly preferred. The vinyl polymer (a) having an epoxy group and a hydroxyl group used in the present invention has an epoxy equivalent of 100 g /
If it is less than the equivalent, it is not preferable because the coating tends to be very brittle and inflexible, and if the epoxy equivalent exceeds 10,000 g / equivalent, the curing rate tends to decrease. Not preferred.

Further, as the vinyl polymer (a) having an epoxy group and a hydroxyl group, a vinyl polymer in which the epoxy group is an epoxy group formed on an aliphatic hydrocarbon ring (hereinafter referred to as an alicyclic epoxy group). In the case of the curable resin composition of the present invention using a polymer, the curability and the strength of the coating film are improved, which is more preferable.

The curable resin composition of the present invention may contain an epoxy compound (c) other than the vinyl polymer (a) having an epoxy group and a hydroxyl group. As such an epoxy compound (c), for example, an epibis epoxy resin, an epoxy novolak resin synthesized from (methyl) epichlorohydrin and bisphenol A, bisphenol F or a modified ethylene oxide or propylene oxide thereof, or the like, Reaction products of phenol or biphenol with (methyl) epichlorohydrin, aromatic epoxy resins such as glycidyl ester of terephthalic acid, isophthalic acid or pyromellitic acid, (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol , (Poly) tetramethylene glycol, neopentyl glycol, and other glycols, polyglycidyl ether compounds of alkylene oxide modified products thereof, trimethylolpropane, trimethylo Ruetan, glycerol, diglycerol, erythritol, pentaerythritol, sorbitol,
1,4-butanediol, 1,6-hexanediol,
Such as aliphatic polyhydric alcohols, glycidyl ether compounds of their alkylene oxide modified products, glycidyl esters of carboxylic acids such as adipic acid, sebacic acid, maleic acid, and itaconic acid; polyester polyols of polyhydric alcohols and polycarboxylic acids Glycidyl ether compounds, glycidyl esters of higher fatty acids, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil,
Aliphatic epoxy resins such as epoxidized polybutadiene,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-
Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, bis (3
4-epoxycyclohexylmethyl) adipate, 3,
Caprolactone adduct of 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (trade name “CELLOXIDE 20 manufactured by Daicel Chemical Industries, Ltd.)
81 "," Celoxide 2083 "), (methyl) valerolactone adduct of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, dipentenediepoxide, dipentene Cyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, hexahydrophthalic acid ester-based epoxy resin (trade name “Eporide GT300” manufactured by Daicel Chemical Co., Ltd.), modified erythritol caprolactone Compounds having an alicyclic epoxy group, such as a series epoxy resin (trade name "Eporide GT400" manufactured by Daicel Chemical Industries, Ltd.), and the like.

When the epoxy compound (c) is used in combination with the curable resin composition of the present invention, it is desirable to add one or more of the above-listed epoxy compounds according to the intended use. .

The weight ratio of the vinyl polymer (a) having an epoxy group and a hydroxyl group to the epoxy compound (c) in the curable resin composition of the present invention is in the range of 2: 8 to 10: 0. preferable. If the amount of the vinyl polymer (a) having an epoxy group and a hydroxyl group is less than 2, the curability and the strength of the coating film tend to be unfavorably reduced.

The cationic polymerization catalyst (b) used in the present invention
Can be used without any particular limitation as long as the material generates cations. Such a cationic polymerization catalyst (b) is roughly classified into a thermal cationic polymerization catalyst (b-1) that generates cations by heating, and a photocationic polymerization catalyst (b-2) that generates cations by irradiation with active energy rays. You.

As the thermal cationic polymerization catalyst (b-1),
For example, amine complexes of boron trifluoride and quaternary
Grade ammonium salts, general formula (1)

[0024]

Embedded image

(Wherein R ₁ is a hydrogen atom, an alkyl group,
X represents an alkoxyl group, a thioalkyl group, an aryl group or a hydroxyalkyl group, and X represents tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF
₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ) or hexachloroantimonate (SbCl ₃ ⁻ ). )) And the like.

The photocationic catalyst (b-2) includes, for example, a silicon compound which generates a silanol group upon irradiation with light, a compound of the general formula (2)

[0027]

Embedded image

(Wherein R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, a thioalkyl group, an aryl group or a hydroxyalkyl group;
Are tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (A
sF ₆ ⁻ ) or hexachloroantimonate (SbC
l ₃ ^-) represents the. A) a diazonium salt represented by the general formula (3)

[0029]

Embedded image

Wherein R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, a thioalkyl group, an aryl group or a hydroxyalkyl group. , General formula (4)

[0031]

Embedded image

(Wherein, R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, a thioalkyl group, an aryl group or a hydroxyalkyl group) , General formula (5)

[0033]

Embedded image

(Wherein R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, an alkoxyl group,
Represents a thioalkyl group, an aryl group or a hydroxyalkyl group. ), A sulfonium acetophenone represented by the general formula (6)

[0035]

Embedded image

(Wherein R ₁₄ represents a hydrogen atom, an alkyl group,
Represents an alkoxyl group, a thioalkyl group, an aryl group or a hydroxyalkyl group. And the like. Particularly, an aromatic onium salt is effective, and is represented by the general formula (7)

[0037]

Embedded image

Wherein R ₁₅ and R ₁₆ are each independently
X represents a hydrogen atom, an alkyl group, an alkoxyl group, a thioalkyl group, an aryl group or a hydroxyalkyl group;
Are tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (A
sF ₆ ⁻ ) or hexachloroantimonate (SbC
l ₃ ^-) represents the. ), An iodonium salt represented by the general formula (8)

[0039]

Embedded image

(Wherein R ₁₇ and R ₁₈ are each independently
X represents a hydrogen atom, an alkyl group, an alkoxyl group, a thioalkyl group, an aryl group or a hydroxyalkyl group;
Are tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (A
sF ₆ ⁻ ) or hexachloroantimonate (SbC
l ₃ ^-) represents the. ), A sulfonium salt represented by the general formula (9)

[0041]

Embedded image

(Wherein R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ each independently represent a hydrogen atom, an alkyl group, an alkoxyl group,
X represents a thioalkyl group, an aryl group or a hydroxyalkyl group, and X represents tetrafluoroborate (BF ₄ ⁻ );
Represents hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ) or hexachloroantimonate (SbCl ₃ ⁻ ). )) Are more preferable. Among these, a sulfonium salt in which R _{17 to} R ₂₂ represent a phenyl group or a biphenyl group in the general formulas (8) and (9) is particularly preferable.

The cationic polymerization catalysts (b) exemplified above can be used alone or in combination of two or more depending on the intended use. The addition ratio of the cationic polymerization catalyst (b) in the curable resin composition of the present invention is preferably in the range of 0.1 to 20% by weight, particularly preferably in the range of 0.5 to 10% by weight, based on the polymerization component. . When the ratio of the cationic polymerization catalyst to the polymerization component is less than 0.1% by weight, poor curing tends to occur, and when the ratio is more than 20% by weight, the strength of the coating film decreases and the cost increases. , Which is not preferable.

The curable resin composition of the present invention may contain, depending on the application, a photosensitizer, another reactive compound such as a vinyl ether monomer or a (meth) acrylic monomer, a non-reactive compound such as a petroleum resin, or an inorganic filler. Agents, organic fillers, pigments, solvents, coupling agents, leveling agents, and the like can be used as appropriate.

Examples of the photosensitizer include benzophenone, methyl o-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-chloroacrylic Don, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxy-cyclohexylphenyl ketone, and the like.

Examples of the vinyl ether monomer include glycidyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, tripropylene glycol divinyl ether, and butane Examples thereof include diol divinyl ether, 1,6-hexanediol divinyl ether, polytetraethylene glycol divinyl ether, and trimethylolpropane trivinyl ether.

Examples of the (meth) acrylic monomer include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, and isostearyl (meth) acrylate. A) 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- Xandiol di (meth) acrylate, bisphenol A di (meth) acrylate, epichlorohydrin modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, trimethylol Propane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Examples thereof include tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The non-reactive resin is a liquid or solid oligomer or resin having low or non-reactivity. Examples of such non-reactive resin include alkyl (meth) acrylate copolymers. , Epoxy resin, 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 oligomers, silicon-based oligomers, polysulfide-based oligomers, and the like can be given.

Inorganic fillers and organic fillers are generally used to improve mechanical properties such as strength, cushioning property and slipperiness. Such inorganic fillers include, for example, Silicon, silicon oxide, calcium carbonate,
Calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide,
Examples include zinc sulfate, aluminum hydroxide, aluminum oxide, glass, mica, barium sulfate, alumina white, zeolite, silica balloon, glass balloon and the like. Inorganic fillers include silane coupling agents, titanate coupling agents, aluminum coupling agents,
It may have a functional group of a halogen group, an epoxy group, a hydroxyl group, or a thiol group by a method such as adding and reacting a zirconate-based coupling agent. Examples of the organic filler include benzoguanamine resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, crosslinked polystyrene, polydivinylbenzene, and styrene / divinylbenzene copolymer. Coalescence, acrylic copolymer, cross-linked acrylic resin, polymethyl methacrylate resin, vinylidene chloride resin, fluorine resin, nylon 12, nylon 11, nylon 6/66, phenol resin, epoxy resin, urethane resin, polyimide resin and the like. Organic fillers include halogen groups, epoxy groups,
It may have a functional group such as a hydroxyl group and a thiol group.

Examples of the coupling agent include γ-glycidoxypropyltrimethoxysilane and β- (3,4
A silane coupling agent having an epoxy group such as -epoxycyclohexyl) ethyltrimethoxysilane;
Silane coupling agents such as silane coupling agents having a mercapto group such as mercaptopropyltrimethoxysilane and silane coupling agents having a halogen group such as γ-chloropropyltrimethoxysilane; tetra (2,2-diallyloxymethyl -1-butyl) bis (ditridecyl) phosphite titanate, isopropyldimethacrylisostearoyl titanate, isopropyldiacrylisostearoyl titanate, isopropyltriisostearoyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate,
Titanate-based coupling agents such as bis (dioctyl pyrophosphate) ethylene titanate, isopropyl tridodecylbenzenesulfonyl titanate, and isopropyl tricumylphenyl titanate; aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate; and zirconium such as acetylacetone-zirconium complex And the like.

The curable resin composition of the present invention is obtained by mixing the above components, and the order and method of mixing are not particularly limited.

By irradiating the curable resin composition of the present invention with an active energy ray, a cured coating film having a high surface hardness can be obtained even at a low temperature.

The curable resin composition of the present invention comprises metals such as aluminum, iron and copper, vinyl chloride, acrylic, polycarbonate, polyethylene terephthalate, ABS resin,
In addition to plastics such as polyethylene, polypropylene, and polystyrene, ceramics such as glass, coating materials for various materials such as wood, paper, printing paper, and fiber, surface treatment agents, binders, plastic materials, molding materials, and laminates It can be applied to use as a hard coat agent. In addition, there is an advantage that the curability is improved even in an application that does not require hardening of the surface, such as an adhesive, a pressure-sensitive adhesive, and a binder, and can be applied in these fields. Furthermore, the curable resin composition of the present invention can also be used under a curing atmosphere replaced with an inert gas.

The active energy ray used for curing the curable resin composition of the present invention may be any active energy ray as long as it can generate a cationic species. Electron beam, alpha ray,
ionizing radiation such as β-ray and γ-ray, visible light, microwave,
High frequency and the like can be mentioned. Examples of the ultraviolet light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, a short arc lamp, and the like. May be selected in consideration of the absorption wavelength of the compound that generates.

[0055]

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. In the following Examples and Comparative Examples, all “parts” represent “parts by weight” unless otherwise specified.

<Synthesis Example 1> (Method for producing vinyl polymer a having alicyclic epoxy group and hydroxyl group) 400 parts of methyl ethyl ketone was placed in a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen introduction pipe. It was charged and heated to 80 ° C. in a nitrogen atmosphere. Then, at the same temperature, 125 parts of methyl methacrylate and 153 of butyl acrylate
Part, 3,4-epoxycyclohexylmethyl methacrylate 200 parts, 2-hydroxyethyl acrylate 1
7 parts, 100 parts of methyl ethyl ketone and "Perbutyl O" (radical polymerization initiator manufactured by NOF Corporation) 1
After a mixture of 2.5 parts was added dropwise over 5 hours, the mixture was further reacted at the same temperature for 5 hours to obtain a solution having a number average of 9,200 and containing a target polymer having a solid content of about 50% containing a target polymer. The hydroxyl value of this polymer was 21 KOH mg / g, and the epoxy equivalent was 392 g / equivalent. Hereinafter, this is referred to as “vinyl polymer A-1”.

<Synthesis Example 2> (Same as above) In Synthesis Example 1, the amount of butyl acrylate was changed to 13
In the same manner as in Synthesis Example 1 except that the amount of 2-hydroxyethyl acrylate was changed to 3 parts and the amount of 2-hydroxyethyl acrylate was changed to 42 parts, a solution having a number average of 10,500 and containing a target polymer and having a solid content concentration of about 50% was obtained. . The hydroxyl value of this polymer was 53 KOHmg /
g, epoxy equivalent was 392 g / equivalent. Hereinafter, this is referred to as “vinyl polymer A-2”.

<Synthesis Example 3> (Same as above) In Synthesis Example 1, the amount of butyl acrylate was changed to 11
Except for using 8 parts and using 82 parts of 2-hydroxyethyl acrylate in the same manner as in Synthesis Example 1, a solution containing a target polymer having a number average of 11,900 and a solid content concentration of about 50% was obtained. . The hydroxyl value of this polymer is 98 KOHmg /
g, epoxy equivalent was 392 g / equivalent. Hereinafter, this is referred to as "vinyl polymer A-3".

<Synthesis Example 4> (Same as above) In Synthesis Example 1, the amount of methyl methacrylate was 175 parts, the amount of butyl acrylate was 183 parts, and the amount of 3,4-epoxycyclohexylmethyl methacrylate was A solution having a solid content concentration of about 50% containing a target polymer having a number average of 11,000 was obtained in the same manner as in Synthesis Example 1 except that the amount of 2-hydroxyethyl acrylate was changed to 100 parts and the amount of 2-hydroxyethyl acrylate was changed to 42 parts. . The hydroxyl value of this polymer was 53 KOH mg / g, and the epoxy equivalent was 784 g / g.
Was equivalent. Hereinafter, this is referred to as "vinyl polymer A-4".
And

<Synthesis Example 5> (Same as above) In Synthesis Example 1, the amount of methyl methacrylate was 225 parts, the amount of butyl acrylate was 183 parts, and the amount of 3,4-epoxycyclohexylmethyl methacrylate was Synthesis Example 1 except that the amount was 50 parts and the amount of 2-hydroxyethyl acrylate was 42 parts.
In the same manner as in the above, a solution having a solid content concentration of about 50% containing the target polymer having a number average of 13,900 was obtained. The hydroxyl value of this polymer was 52 KOH mg / g, and the epoxy equivalent was 1568 g / g.
Was equivalent. Hereinafter, this is referred to as "vinyl polymer A-5".
And

<Synthesis Example 6> (Same as above) In Synthesis Example 1, the amount of methyl methacrylate was 225 parts, the amount of butyl acrylate was 213 parts, and the amount of 3,4-epoxycyclohexylmethyl methacrylate was Synthetic Example 1 except that the amount was 20 parts and the amount of 2-hydroxyethyl acrylate was 42 parts.
In the same manner as described above, a solution containing a target polymer having a number average of 11,200 and a solid content concentration of about 50% was obtained. The hydroxyl value of this polymer was 50 KOHmg / g, and the epoxy equivalent was 3920 g / g.
Was equivalent. Hereinafter, this is referred to as "vinyl polymer A-6".
And

<Synthesis Example 7> (Method for producing vinyl polymer a having an epoxy group and a hydroxyl group) A reaction vessel equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen introduction pipe was charged with 400 parts of methyl ethyl ketone. The temperature was raised to 80 ° C. in an atmosphere. Next, at the same temperature, 125 parts of methyl methacrylate and 129 of butyl acrylate
Parts, 200 parts of glycidyl methacrylate, 46 parts of 2-hydroxypropyl acrylate, 100 parts of methyl ethyl ketone and 12.5 parts of “perbutyl O” were added dropwise over 5 hours, and further reacted at the same temperature for 5 hours. A solution containing a target polymer having a number average of 22,000 and a solid content of about 50% was obtained. The hydroxyl value of this polymer is 5
5 KOH mg / g, epoxy equivalent was 284 g / equivalent. Hereinafter, this is referred to as "vinyl polymer A-7".

<Synthesis Example 8> (Method for Producing Vinyl Polymer a Having Epoxy and Hydroxyl Groups) 400 parts of methyl ethyl ketone was charged into a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen introduction pipe. The temperature was raised to 80 ° C. in an atmosphere. Next, at the same temperature, 125 parts of methyl methacrylate, 96 parts of butyl acrylate,
A mixture consisting of 200 parts of "Rica Resin ESA" (methacrylate of epoxidized fatty acid manufactured by Nippon Rika Co., Ltd.), 79 parts of phenoxyhydroxypropyl acrylate, 100 parts of methyl ethyl ketone and 12.5 parts of "Perbutyl O" is dropped over 5 hours. Thereafter, the mixture was further reacted at the same temperature for 5 hours to obtain a solution containing a target polymer having a number average of 13,000 and having a solid content of about 50%. The hydroxyl value of this polymer was 48 KOH mg / g, and the epoxy equivalent was 340 g / equivalent. Hereinafter, this is referred to as "vinyl polymer A-8".

<Synthesis Example 9> (Production method of vinyl polymer a having alicyclic epoxy group and hydroxyl group) In a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen introducing pipe, 200 parts of methyl ethyl ketone was placed. It was charged and heated to 80 ° C. in a nitrogen atmosphere. Then, at the same temperature, 125 parts of methyl methacrylate and 133 parts of butyl acrylate
Part, 3,4-epoxycyclohexylmethyl methacrylate 200 parts, 2-hydroxyethyl acrylate 4
A mixture of 2 parts, 100 parts of methyl ethyl ketone and 12.5 parts of “perbutyl O” was added dropwise over 3 hours, and the mixture was further reacted at the same temperature for 5 hours to obtain a number average of 49,00.
Thus, a solution containing a target polymer having a solid content of about 65% was obtained. The hydroxyl value of this polymer was 56 KOH mg / g, and the epoxy equivalent was 392 g / equivalent. Hereinafter, this is referred to as "vinyl polymer A-9".

<Synthesis Example 10> (Method for producing vinyl polymer a having alicyclic epoxy group and hydroxyl group) In a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen introducing pipe, 500 parts of methyl ethyl ketone was placed. It was charged and heated to 80 ° C. in a nitrogen atmosphere. Then, at the same temperature, 125 parts of methyl methacrylate and 133 parts of butyl acrylate
Part, 3,4-epoxycyclohexylmethyl methacrylate 200 parts, 2-hydroxyethyl acrylate 4
A mixture consisting of 2 parts, 100 parts of methyl ethyl ketone and 7.5 parts of “perbutyl O” was added dropwise over 5 hours, and the mixture was further reacted at the same temperature for 5 hours to obtain a number average of 6,800.
A solution having a solid content of about 45% containing the target polymer was obtained.
The hydroxyl value of this polymer was 49 KOH mg / g, and the epoxy equivalent was 392 g / equivalent. Hereinafter, this is referred to as "vinyl polymer A-10".

<Synthesis Example 11> (Method for producing vinyl polymer a having alicyclic epoxy group and hydroxyl group) 400 parts of methyl ethyl ketone was placed in a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen introduction pipe. It was charged and heated to 80 ° C. in a nitrogen atmosphere. Then, at the same temperature, 125 parts of styrene, 129 parts of butyl acrylate, 200 parts of 3,4-epoxycyclohexylmethyl acrylate,
A mixture consisting of 46 parts of hydroxypropyl acrylate, 100 parts of methyl ethyl ketone and 12.5 parts of “perbutyl O” was added dropwise over 5 hours, and then 10 parts at the same temperature.
The reaction was carried out for a period of time to obtain a solution having a solid content concentration of about 50% containing 9,000 number-average target polymers. The hydroxyl value of this polymer was 46 KOH mg / g, and the epoxy equivalent was 392 g / equivalent. Hereinafter, this is referred to as "vinyl polymer A-11".
And

<Synthesis Example 12> (Vinyl polymer having an alicyclic epoxy group) 400 parts of methyl ethyl ketone was charged into a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen introduction pipe, and placed under a nitrogen atmosphere. The temperature was raised to 80 ° C. Then, at the same temperature, 125 parts of methyl methacrylate and 175 butyl acrylate
, 200 parts of 3,4-epoxycyclohexylmethyl methacrylate, 100 parts of methyl ethyl ketone and 12.5 parts of "perbutyl O" were added dropwise over 5 hours, and the mixture was further reacted at the same temperature for 5 hours to obtain a number average. 1
A solution having a solid content of about 50% containing 2,000 target polymers was obtained. The epoxy equivalent of this polymer was 392 g / equivalent. Hereinafter, this is referred to as "vinyl polymer A-12".

<Examples 1 to 17> As vinyl polymers (a) having an epoxy group and a hydroxyl group, Synthesis Examples 1 to 11
Using the various vinyl polymer solutions obtained in the above, the compositions shown in Tables 1 and 2 below were blended to obtain resin compositions. In addition,
Examples of the epoxy compound (c) include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (hereinafter, C-1) and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Caprolactone adduct ("Celoxide 2081" manufactured by Daicel Chemical Industries, Ltd .; hereinafter, C
-2), bisphenol A diglycidyl ether ("Epiclon 840" manufactured by Dainippon Ink and Chemicals, Inc.)
S ", hereinafter, C-3), and as the cationic polymerization catalyst (b), triarylsulfonium hexafluoroantimonate (" UVI-697 "manufactured by Union Carbide Co., Ltd.)
0 ", hereinafter B-1). Tables 1 and 2
The amount of the vinyl polymer (a) having an epoxy group and a hydroxyl group in the above is shown by solid content.

<Comparative Examples 1 to 5> As in Example, Table 3
And a resin composition was prepared. As the epoxy compound (c '), epoxidized polybutadiene ("Eporide PB4700" manufactured by Daicel Chemical Industries, Ltd .; hereinafter, C-4) was used.

The curability and surface hardness in the following Examples and Comparative Examples were measured by the following methods.

<< Evaluation >> Examples 1 to 17 and Comparative Examples 1 to 5
The resin composition obtained in the above was evaluated for ultraviolet curability and flexibility by surface hardness measurement, and the results were shown in Tables 1 to 3.
It was shown to. The evaluation method is as follows.

(1) Ultraviolet ray curability Each resin composition was cured on a glass plate to a thickness of 20 μm.
After applying using an applicator so that
After drying at 5 ° C. for 5 minutes, using a high-pressure mercury lamp (manufactured by Eye Graphics) of 160 W / cm ^{2 in} the air,
Each resin composition was cured by irradiating ultraviolet rays under the 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 one day after irradiation.

The surface hardness was evaluated based on JIS K-5400 by measuring the pencil hardness using a surface property measuring machine TYPE: 14D (manufactured by Shinto Kagaku).

(2) Flexibility A film sample according to JIS-K-7127 (light irradiation 1
Days after), the tensile elongation at break was evaluated. Using a strograph (manufactured by Toyo Seiki Co., Ltd.) as a tensile tester, the load cell was 25 N, and the tensile speed was 50 mm / min.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3] However,-indicates <4B.

Example 18 70 parts by weight of a vinyl polymer (A-2) having an epoxy group and a hydroxyl group, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (C-1) 30% by weight and 3 parts by weight of "CI-2481" (a cationic polymerization catalyst manufactured by Nippon Soda Co., Ltd .; hereinafter, B-2) were stirred and mixed to obtain a transparent and uniform resin composition.

Comparative Example 6 70 parts by weight of a vinyl polymer (A-12) having an epoxy group and an epoxy compound (C-
1) 30 parts by weight and 3 parts by weight of the cationic polymerization catalyst (B-2) were stirred and mixed to obtain a transparent and uniform resin composition.

<< Evaluation >> The resin compositions obtained in Example 18 and Comparative Example 6 were evaluated for thermosetting properties and flexibility by measuring surface hardness, and the results are shown in Table 4. The evaluation method is as follows.

(1) Thermosetting The film thickness after curing each resin composition on a glass plate is 20 μm.
After applying using an applicator so as to obtain, each resin composition is cured by heating at 150 ° C. for 5 minutes using a hot air drier, and the surface hardness after 1 hour and 1 day after cooling is evaluated. did.

The surface hardness was evaluated in the same manner as in the evaluation of Examples 1 to 17 and Comparative Examples 1 to 5.

(2) Flexibility A film sample (one day after cooling) was subjected to a tensile test according to JIS-K-7127 to evaluate the elongation at break. Using a strograph (manufactured by Toyo Seiki Co., Ltd.) as a tensile tester, the load cell was 25 N, and the tensile speed was 50 mm / min.

[0084]

[Table 4]

[0085]

The curable resin composition of the present invention cures in a short time by irradiating with active energy rays or by heating, and the cured film obtained has excellent flexibility, In addition, there is an advantage that the surface hardness is high.

Claims (4)

[Claims] 1. A (1) vinyl polymer having an epoxy group and a hydroxyl group and (2) a cationic polymerization catalyst (b)
A curable resin composition comprising: 2. The curable resin composition according to claim 1, wherein the epoxy group of the vinyl polymer (a) having an epoxy group and a hydroxyl group is an epoxy group formed on an aliphatic hydrocarbon ring. 3. The curable resin composition according to claim 1, further comprising an epoxy compound (c) other than the vinyl polymer (a) having an epoxy group and a hydroxyl group. 4. The vinyl polymer (a) having an epoxy group and a hydroxyl group has a hydroxyl value of 10 to 200 KOH mg / g.
And an epoxy equivalent of 100 to 10,000.
4. The curable resin composition according to claim 1, wherein the amount is in the range of 00 g / equivalent.