JP2003048928A - Reactive diluent and curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reactive diluent which can overcome the problems of a radically curable reactive diluent and a cationic curable reactive diluent and can be applied to various uses such as a coating, ink, adhesive, tacky agent, surface modifying material, molding material, etc., and a curable resin composition, an active energy ray-curable resin composition and a thermosetting resin composition comprising the reactive diluent. SOLUTION: This reactive diluent comprises a vinyl ether group-containing (meth)acrylic acid ester represented by general formula (1) CH2 =CR<1> -COO-R<2> -O- CH=CH-R<3> (1) (R<1> is a hydrogen atom or a methyl group; R<2> is a 2-20C organic residue; R<3> is a hydrogen atom or a 1-11C organic residue).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a reactive diluent, a curable resin composition containing the same, and uses thereof. Specifically, a reactive diluent that can be used for a curable resin that can be cured by heat or irradiation with an active energy ray, and a curable resin composition containing the reactive diluent, an active energy ray curable composition The present invention relates to a resin composition and a thermosetting resin composition.

[0002]

2. Description of the Related Art In a curing technique utilizing active energy rays such as heat, ultraviolet rays or electron rays, a solventless curable composition using a reactive diluent without using a conventional organic solvent has been attracting attention. In particular, active energy ray curing has advantages such as energy saving, space saving, and short-time curing, and its range of use is expanding.

Of the constituents of the curable resin composition, the polymerizable monomer used for the purpose of lowering the viscosity of the resin composition, improving the adhesiveness, etc. is called a reactive diluent, and a wide variety of polymerizations are carried out. Monomers have been developed.

The reactive diluents developed so far are
It is classified into a radical curing type represented by (meth) acrylic acid esters and vinyl compounds and a cationic curing type represented by vinyl ethers, epoxy compounds and alicyclic ether compounds. However, in general, radical-curable reactive diluents are 1) subject to polymerization inhibition by oxygen, 2) have large volume shrinkage during curing, 3) have strong odor and skin irritation, and 4) have poor adhesion to metals. It has problems such as not being very good. In addition, the cationically curable reactive diluent is 1) subject to polymerization inhibition by water or base,
2) The polymerization reaction proceeds even after irradiation with light (dark reaction), 3) the cation-curable resin and the catalyst are expensive, and 4) the types that are industrially available are limited. However, a reactive diluent capable of overcoming such problems has been desired.

Japanese Patent Publication No. 7-505439 discloses that
(A) oligomers and monomers of polyfunctional acrylates containing (meth) acryloyl groups; (b) vinyl ether monomers; (c) effective amounts of free radical initiators,
A radiation curable coating composition comprising is disclosed. That is, a method in which radical-curable acrylates and cation-curable vinyl ethers are used in combination is disclosed. However, it is difficult to sufficiently ameliorate the problems of the above reactive diluents by simply using them together, and there is room for improvement.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and can overcome the problems of the radical-curable reactive diluent and the cation-curable reactive diluent. Reactive diluents that can be applied to various applications such as paints, inks, adhesives, pressure-sensitive adhesives, surface-modifying materials, and molding materials, as well as curable resin compositions and active energy ray curable resin compositions containing them. And a thermosetting resin composition.

[0007]

Means for Solving the Problems The present inventors have conducted various studies on reactive diluents and found that they contain a vinyl ether group having a cation-curable vinyl ether group and a radical-curable (meth) acryloyl group in one molecule. (Meta)
By using acrylic acid esters as a reactive diluent, the above-mentioned problems of the radical-curable reactive diluent having only radical-curable groups and the cationic-curable reactive diluent having only cation-curable groups can be solved. In addition to being overcome, the compound has a radical-curable group and a cation-curable group in one molecule,
A cured product that is superior in curability and adhesion to the substrate, and that has excellent surface hardness and solvent resistance compared to the case of using a mixture of a radical curable reactive diluent and a cationic curable reactive diluent. I found what I could do. A curable resin composition containing a reactive diluent containing such a compound and a curable resin having at least one polymerizable group curable by heat or irradiation with active energy rays, Since the active energy ray-curable resin composition and the thermosetting resin composition are excellent in curability and have improved adhesiveness, it is thought that they can be suitably applied to various uses, and the present invention Arrived The curable resin in the present invention is composed of a macromonomer or a prepolymer, but the form of the macromonomer or the prepolymer is not particularly limited to solid (powder), liquid or the like. The form of the reactive diluent is preferably a liquid (liquid substance) at 25 ° C.

The present invention will be described in detail below. Reactive diluent of the present invention is represented by the following general formula _{(1); CH 2 = CR} 1 -COO-R 2 -O-CH = CH-R 3 (1) ( wherein, R ¹ represents a hydrogen atom or methyl Represents a group, R ² is
It represents an organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or an organic residue having 1 to 11 carbon atoms. ) The vinyl ether group-containing (meth) acrylic acid ester represented by The vinyl ether group-containing (meth) acrylic acid ester used as the reactive diluent component of the present invention is
Any compound represented by the general formula (1) may be used, in which the substituent represented by R ¹ is a hydrogen atom or a methyl group, and the substituent represented by R ² is an organic residue having 2 to 20 carbon atoms. A substituent represented by R ³ is a hydrogen atom or a carbon number of 1 to
11 organic residues. Such vinyl ether group-containing (meth) acrylic acid esters may be used alone or in combination of two or more.

Examples of the organic residue having 2 to 20 carbon atoms represented by R ² in the above general formula (1) include a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms in the structure. An alkylene group having 2 to 20 carbon atoms having an oxygen atom through an ether bond and / or an ester bond, and an optionally substituted aromatic group having 6 to 11 carbon atoms are preferable. Among these, an alkylene group having 2 to 6 carbon atoms and an alkylene group having 2 to 9 carbon atoms having an oxygen atom in the structure by an ether bond are preferably used.

As the organic residue having 1 to 11 carbon atoms represented by R ³ in the above general formula (1), a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and 6 carbon atoms From 11 to optionally substituted aromatic groups are preferred. Among these, an alkyl group having 1 to 2 carbon atoms and an aromatic group having 6 to 8 carbon atoms are preferably used.

The following compounds are preferable as the vinyl ether group-containing (meth) acrylic acid esters represented by the above general formula (1). 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate,
4-Vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate ,
3-Methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, 1-methyl-2- (meth) acrylate Vinyloxypropyl, 2-vinyloxybutyl (meth) acrylate,
4-vinyloxycyclohexyl (meth) acrylate,
5- (vinyl) pentyl (meth) acrylate, (meth)
6-vinyloxyhexyl acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethylcyclohexylmethyl (meth) acrylate, (meth) P-vinyloxymethylphenylmethyl acrylate, m-vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenylmethyl (meth) acrylate, 2- (meth) acrylic acid
(Vinyloxyethoxy) ethyl, (meth) acrylic acid 2
-(Vinyloxyisopropoxy) ethyl, 2- (vinyloxyethoxy) propyl (meth) acrylate, (meth)
2- (vinyloxyethoxy) isopropyl acrylate,
(Meth) acrylic acid 2- (vinyloxyisopropoxy)
Propyl, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate,
2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate.

2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylate, (meth)
Acrylic acid 2- (vinyloxyisopropoxyethoxy)
Propyl, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate,
2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) isopropyl (meth) acrylate, ( 2- (vinyloxyethoxyethoxyethoxy) ethyl meth) acrylate, (meth)
2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl acrylate, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxyethoxy) (meth) acrylate
Ethyl, 2- (vinyloxyisopropoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, polyethylene glycol monovinyl ether (meth) acrylate, ( (Meth) acrylic acid polypropylene glycol monovinyl ether.

Among these, (meth) acrylic acid 2-
Vinyloxyethyl, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, (meth) acrylic Acid 4-vinyloxycyclohexyl, (meth) acrylic acid 5-vinyloxypentyl, (meth) acrylic acid 6-vinyloxyhexyl, (meth) acrylic acid 4
-Vinyloxymethylcyclohexylmethyl, p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate,
2- (Vinyloxyethoxyethoxy) ethyl (meth) acrylate and 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate are preferred.

Regarding the viscosity of the vinyl ether group-containing (meth) acrylic acid ester in the present invention, the lower limit of the viscosity at 25 ° C. is preferably 0.1 mPa · s or more, and the upper limit is preferably 1500 mPa · s or less. 0.1
When it is less than mPa · s, not only is it difficult to adjust the thickness of the coating film, but generally the volatility becomes high and the working environment may deteriorate, and when it exceeds 1500 mPa · s, the viscosity becomes high. It may be difficult to apply. The lower limit is more preferably 0.2 mPa · s or more, and 0.5 mP
a · s or more is more preferable, and the upper limit is 1000 mPa · s.
s or less is more preferable, and 500 mPa · s or less is particularly preferable.

As for the molecular weight of the vinyl ether group-containing (meth) acrylic acid esters, the lower limit is preferably 140 or more, and the upper limit is preferably 2000 or less. If it exceeds 2000, the viscosity may be high and coating may be difficult.
The upper limit is more preferably 1000 or less, further preferably 800 or less, and particularly preferably 500 or less. That is, as the vinyl ether group-containing (meth) acrylic acid esters in the present invention, those having such a viscosity and a molecular weight are suitable.

In the present invention, the proportion of the vinyl ether group-containing (meth) acrylic acid ester in the reactive diluent depends on the kind of the vinyl ether group-containing (meth) acrylic acid ester and the use of the reactive diluent. The lower limit of the ratio is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, with respect to 100% by mass of the reactive diluent.
4 mass% or more is particularly preferable, and the upper limit of the ratio is 100.
It is preferably not more than 95% by mass, more preferably not more than 95% by mass, further preferably not more than 90% by mass, particularly preferably not more than 85% by mass.

In the present invention, vinyl ether group-containing (meth) acrylic acid esters may be used in combination with other polymerizable monomers. As such a polymerizable monomer, any one having compatibility with vinyl ether group-containing (meth) acrylic acid esters may be used, and one kind of monofunctional or polyfunctional radically polymerizable and / or ionically polymerizable compound or Two or more kinds can be appropriately selected.
As the polymerizable monomer other than the vinyl ether group-containing (meth) acrylic acid esters, the viscosity at 25 ° C. is 1
A liquid substance having a viscosity of 000 mPa · s or less is preferable.

The following compounds are suitable as the polymerizable monomers other than the vinyl ether group-containing (meth) acrylic acid esters. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) Acrylate, cyclohexylmethyl (meth)
Acrylate, methoxyethyl (meth) acrylate,
Ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene Glycol (meth) acrylate, (meth) acrylic acid, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate,
Monofunctional (meth) acrylates such as α-hydroxymethyl acrylate; monofunctional (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; methyl vinyl ether, ethyl vinyl ether, Propyl vinyl ether,
Butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4- Monofunctional vinyl ethers such as hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether and chloroethyl vinyl ether.

N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl-N-methylformamide, N-
Vinyl imidazole, N-vinyl formamide, N-
Monofunctional N-vinyl compounds such as vinylacetamide; styrene, α-methylstyrene, vinyltoluene, allyl acetate, vinyl acetate, vinyl propionate, vinyl benzoate and other monofunctional vinyl compounds; maleic anhydride, maleic acid, Dimethyl maleate, diethyl maleate, monomethyl maleate, monoethyl maleate, fumaric acid,
Dimethyl fumarate, diethyl fumarate, monomethyl fumarate, monoethyl fumarate, itaconic anhydride, itaconic acid, dimethyl itaconic acid, diethyl itaconic acid, monomethyl itaconic acid, monoethyl itaconic acid, methylenemalonic acid, dimethyl methylenemalonate, methylenemalon Mono-functional α, β-unsaturated compounds such as monomethyl acid cinnamate, cinnamic acid, methyl cinnamate, ethyl cinnamate, crotonic acid, methyl crotonate, ethyl crotonate; methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl Glycidyl ether, 2-ethylhexyl glycidyl ether, n-nonyl glycidyl ether, lauryl glycidyl ether, cyclohexyl glycidyl ether, methoxyethyl glycidyl ether,
Monofunctional epoxy compounds such as ethoxyethyl glycidyl ether, methoxyethoxyethyl glycidyl ether, ethoxyethoxyethyl glycidyl ether, methoxy polyethylene glycol glycidyl ether; 3-methyl-3-hydroxymethyl oxetane, 3-ethyl-
3-hydroxymethyl oxetane, 3-methyl-3-phenoxymethyl oxetane, 3-ethyl-3-phenoxymethyl oxetane, 3-methyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2
-Ethylhexyloxymethyl) oxetane and other monofunctional alicyclic ether compounds.

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, Cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, ethylene oxide added trimethylolpropane tri (meth) acrylate, ethylene oxide added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide added pentaerythritol tetra (meth) acrylate, ethylene oxide added Dipentaerythritol hexa (meta)
Polyfunctional (meth) acrylates such as acrylates; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene Oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide added trimethylolpropa Trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide adduct of pentaerythritol tetravinyl ether, polyfunctional vinyl ethers such as ethylene oxide adduct of dipentaerythritol hexavinyl ether.

Polyfunctional vinyl compounds such as divinylbenzene; ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexanediol diglycidyl ether,
Bisphenol A alkylene oxide diglycidyl ether, bisphenol F alkylene oxide diglycidyl ether, trimethylolpropane triglycidyl ether, ditrimethylolpropane tetraglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol pentaglycidyl ether, dipenta Erythritol hexaglycidyl ether, ethylene oxide-added trimethylolpropane triglycidyl ether, ethylene oxide-added ditrimethylolpropane tetraglycidyl ether, ethylene oxide-added pentaerythritol tetraglycidyl ether, ethylene oxide-added dipentaerythritol hexaglycidyl ether, etc. Polyfunctional epoxy compounds; di [1
Methyl (3-oxetanyl)] methyl ether, di [1
-Ethyl (3-oxetanyl)] methyl ether, 1,
4-bis {[(3-methyl-3-oxetanyl) methoxy] methyl} benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis {4-[(3- Polyfunctional alicyclic ether compounds such as methyl-3-oxetanyl) methoxy] methyl} benzyl ether and bis {4-[(3-ethyl-3-oxetanyl) methoxy] methyl} benzyl ether. Among these, methyl (meth) acrylate, butyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, (meth) acrylic acid, butyl vinyl ether, cyclohexyl vinyl ether, maleic anhydride, maleic acid, dimethyl maleate, and diethyl maleate are preferable.

Since the reactive diluent of the present invention comprises vinyl ether group-containing (meth) acrylic acid esters having both radical-curable groups and cationic-curable groups in one molecule, the heat or activation energy is reduced. It can be suitably used as a reactive diluent for a curable resin having at least one type of polymerizable group that can be cured by irradiation with rays. The curable resin composition containing the reactive diluent of the present invention and the curable resin is one of the preferred embodiments of the present invention. The curable resin may be used alone or in combination of two or more.

The curable resin in the present invention is a macromonomer or prepolymer having a curable polymerizable group, which is curable by heat and / or active energy rays such as ultraviolet rays, electron rays and gamma rays. Say. As such a curable resin, a macromonomer or a prepolymer having a radically polymerizable group and / or an ionically polymerizable group can be used.

The lower limit of the viscosity of the curable resin is preferably higher than 1.5 Pa · s at 25 ° C.,
The upper limit is preferably 100,000 Pa · s or less at 80 ° C.
If it is 1.5 Pa · s or less at 25 ° C, it may be difficult to impart thixotropy necessary for sagging in applications such as paints, and if it exceeds 100,000 Pa · s at 80 ° C, the viscosity is high. It may be difficult to apply. The lower limit is 25 ° C
Is more preferably 10 Pa · s or more, still more preferably 50 Pa · s or more, and the upper limit is more preferably 10,000 Pa · s or less at 80 ° C., further preferably 5000 Pa · s or less.

The lower limit of the molecular weight of the curable resin is preferably 300 or more, and the upper limit thereof is preferably 1,000,000 or less. When it is less than 300, not only the strength properties of the cured coating film become brittle, but also thixotropy necessary for preventing sagging may not be easily imparted in applications such as paints, and when it exceeds 1,000,000, the viscosity becomes high. It may be difficult to apply. The upper limit is more preferably 500000 or less, further preferably 100000 or less, and 5000
0 or less is particularly preferable. That is, as the curable resin in the present invention, those having such viscosity and molecular weight are suitable. The molecular weight of the curable resin means the number average molecular weight.

Examples of the macromonomer or prepolymer having a radically polymerizable group include saturated or unsaturated polybasic acids or anhydrides thereof (eg, maleic acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, Terephthalic acid, tetrahydrophthalic acid, etc.) and a saturated or unsaturated polyhydric alcohol (for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1, 5-pentanediol, polyethylene glycol, polypropylene glycol, 1,4-dimethylolbenzene, trimethylolpropane, pentaerythritol, etc.) and a polyester (meth) acrylate obtained by the reaction of (meth) acrylic acid; saturated or unsaturated Polyhydric alcohol (eg Ethylene glycol, neopentyl glycol, polytetramethylene glycol, polyester polyols, polycaprolactone polyols, etc.)
And an organic polyisocyanate (for example, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc.) and a hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
1,4-butanediol mono (meth) acrylate etc.)
Urethane poly (meth) acrylate obtained by reaction with; polysiloxane poly (meth) acrylate obtained by reaction between polysiloxane and (meth) acrylic acid; polyamide poly obtained by reaction with polyamide and (meth) acrylic acid (Meth) acrylate; Obtained by reacting a vinyl ether group-containing (meth) acrylic acid ester represented by the general formula (1) with a cationically polymerizable compound (for example, vinyl ethers, alkylene oxides, glycidyl ethers, etc.). The (meth) acryloyl group pendant polymer to be used is suitable.

As the macromonomer or prepolymer having an ionically polymerizable group, a polyhydric phenol having at least one aromatic nucleus (for example, a bisphenol compound such as bisphenol A, bisphenol F, bisphenol S or a bisphenol compound) or Novolak-type epoxy resins (for example, phenol / novolak-type epoxy resins, cresol / novolac-type epoxy resins) obtained by the reaction of the alkylene side (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct and epichlorohydrin. , Bromine phenol / novolac type epoxy resin, etc.), trisphenol methane triglycidyl ether and other aromatic epoxy resins; 3,4-epoxycyclohexylmethyl-3,4
-Epoxycyclohexanecarboxylate, bis-
Alicyclic epoxy resins such as (3,4-epoxycyclohexylmethyl) adipate, bis (2,3-epoxycyclopentyl) ether, EHPE-3150 (trade name, manufactured by Daicel Chemical Industries, Ltd.); polyhydric alcohols (for example, ethylene Glycol, propylene glycol, 1,
4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, etc.) Aliphatic obtained by reaction of its alkylene side (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adduct with epichlorohydrin Epoxy resin: by reaction of vinyl ether group-containing (meth) acrylic acid ester or the like represented by the general formula (1) with a radically or anionically polymerizable compound (for example, (meth) acrylic acid ester, vinyl compound or the like) Obtained vinyl ether group pendant polymer; alicyclic ether-containing (meth) acrylic acid esters such as ethyl-3- (meth) acryloxyoxetane and radical or anion polymerizable compounds (for example, (meth) acrylic acid esters, Reaction with vinyl compounds, etc.) Thus obtained alicyclic ethers pendant polymers are preferred.

As the macromonomer or prepolymer having both radically polymerizable group and ionic polymerizable group, epoxy resin (for example, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin) is used. , Trisphenolmethane type epoxy resin, polybutanediene modified epoxy resin, alicyclic epoxy resin, brominated phenol novolac epoxy resin, brominated bisphenol A type epoxy resin, amino group-containing epoxy resin, etc.) and (meth) acrylic acid Epoxy poly (meth) acrylate obtained by the reaction of the above; the above epoxy (meth) acrylate and polybasic acid anhydride (for example, maleic anhydride,
A carboxylic acid-modified epoxy (meth) acrylate obtained by a reaction with succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) is preferable.

Among these, the curable resin of the present invention is preferably one having at least one radical-polymerizable group and / or ion-polymerizable group. A curable resin composition comprising the curable resin and the reactive diluent, wherein the curable resin has at least one radically polymerizable group and / or an ionically polymerizable group. Certain curable resin compositions are also part of this invention. Further, as the curable resin, one having at least one or more radically polymerizable groups and / or cationically polymerizable groups in one molecule is more preferable.

The mixing ratio of the reactive diluent containing the vinyl ether group-containing (meth) acrylic acid ester of the present invention and the curable resin may be the kind of the vinyl ether group-containing (meth) acrylic acid ester or the curable resin. combination,
Although it will be appropriately set according to the application of the curable resin composition, the lower limit of the mixing ratio of the reactive diluent is preferably 5 parts by mass or more with respect to 100 parts by mass of the curable resin. The upper limit is preferably 100 parts by mass or less. If it is less than 5 parts by mass, the viscosity of the curable resin composition may be high and it may be difficult to apply, and if it exceeds 100 parts by mass, the physical properties of the cured product obtained by curing the curable resin composition may be reacted. It is not preferable because the polymer in the acidic diluent may be predominant. The lower limit is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and the upper limit is more preferably 95 parts by mass or less, further preferably 90 parts by mass or less, and 85 parts by mass or less. Is particularly preferable.

The viscosity of the curable resin composition is 2
The lower limit of the viscosity at 5 ° C. is preferably 0.5 mPa · s or more, and the upper limit thereof is preferably 100000 mPa · s or less. If it is less than 0.5 mPa · s, the coating film thickness may become uneven, and if it exceeds 100,000 mPa · s, the viscosity may be high and coating may be difficult. The lower limit is more preferably 1 mPa · s or more, further preferably 2 mPa · s or more, and the upper limit is more preferably 10000 mPa · s or less and particularly preferably 5000 mPa · s or less.

The curable resin composition of the present invention preferably contains at least one of a thermal polymerization initiator and a photopolymerization initiator, if necessary. Also, a thermal polymerization accelerator, a photosensitizer,
It is also preferable to add a photopolymerization accelerator or the like.

As the above-mentioned thermal polymerization initiator, a thermal radical polymerization initiator which generates a polymerization initiation radical by heating and a thermal cationic polymerization initiator which generates a polymerization initiation cation by heating are suitable.

The following compounds are preferable as the above-mentioned thermal radical polymerization initiator. Methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide,
1,1-bis (t-hexylperoxy) -3,3,5
-Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -cyclohexane, 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2
-Methylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) butane, 2, 2-bis (4,4-di-
t-butylperoxycyclohexyl) propane, p-
Menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α′- Bis (t-butylperoxy) diisopropylbenzene,
Dicumyl peroxide, 2,5-dimethyl-2,5-
Bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide,
2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,
5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide,
Stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate , Di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di (3-methyl- 3-methoxybutyl) peroxydicarbonate, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoe 1-cyclohexyl-1
-Methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1, 3,3
-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethyl Hexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxyisobutyrate,
t-butyl peroxymalate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2- Ethylhexyl monocarbonate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5- Bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-
Dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate,
t-butyl trimethylsilyl peroxide, 3,
Organic peroxide type initiators such as 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 2,3-dimethyl-2,3-diphenylbutane.

2-phenylazo-4-methoxy-2,4
-Dimethylvaleronitrile, 1-[(1-cyano-1-
Methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2 ′
-Azobis (2-methylbutyronitrile), 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis ( 2-Methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] ] Dihydrochloride, 2,2'-azobis [N- (4-hydrophenyl) -2-methylpropionamidine]] Dihydrochloride, 2,2'-azobis [2-methyl-N- (phenylmethyl) propionamidine] Dihydrochloride,
2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2 '
-Azobis [N- (2-hydroxyethyl) -2-methylpropionamidine]] dihydrochloride, 2,2 '
-Azobis [2- (5-methyl-2-imidazoline-2
-Yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane]
Dihydrochloride, 2,2'-azobis [2- (4,
5,6,7-Tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2′-
Azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,
2'-azobis [2- (5-hydroxy-3,4,5,5
6-Tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis {2- [1- (2
-Hydroxyethyl) -2-imidazolin-2-yl]
Propane} dihydrochloride, 2,2'-azobis [2
-(2-Imidazolin-2-yl) propane], 2,
2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis {2-methyl-N-
[1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2'-azobis [2-methyl-N-
(2-Hydroxyethyl) propionamide], 2,
2'-azobis (2-methylpropionamide), 2,
2'-azobis (2,4,4-trimethylpentane),
2,2'-azobis (2-methylpropane), dimethyl 2,2-azobis (2-methylpropionate), 4,
4'-azobis (4-cyanopentanoic acid), 2,2'-
Azo-based initiators such as azobis [2- (hydroxymethyl) propionitrile].

Among these, metal soaps such as methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butyl peroxybenzoate and benzoyl peroxide, and /
Alternatively, a compound capable of efficiently generating a radical by a catalytic action of an amine compound, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) is preferable. is there.

The following compounds are preferable as the above thermal cationic polymerization initiator. Lewis acids (for example, boron trifluoride, stannous chloride, ferric chloride, ferrous chloride,
Ferric chloride, zinc chloride, zinc bromide, stannous chloride, stannic chloride, stannous bromide, stannic bromide, dibutyl stannic dichloride, dibutyl stannic dibromide, tetraethyl (Tin, tetrabutyltin, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, etc.)
And an electron-donating compound (for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, dimethylsulfoxide, trimethyl phosphate, triethyl phosphate, etc.)
A complex with a protonic acid (for example, halogenocarboxylic acid, sulfonic acid, sulfuric acid monoester, phosphoric acid monoester, phosphoric acid diester, polyphosphoric acid ester, boric acid monoester, boric acid diester, etc.) Base (eg, ammonia, monoethylamine, diethylamine, triethylamine, pyridine, piperidine,
Compounds neutralized with aniline, morpholine, cyclohexylamine, monoethanolamine, diethanolamine, triethanolamine, butylamine, etc.). Among these, amine complexes of various protonic acids are preferable because good pot life can be secured.

As the above-mentioned photopolymerization initiator, a photoradical polymerization initiator which generates a polymerization initiation radical upon irradiation with a light beam and a photocationic polymerization initiator which generates a polymerization initiation cation upon irradiation with a light beam are suitable.

The following compounds are preferable as the above-mentioned radical photopolymerization initiator. Diethoxyacetophenone, 2
-Hydroxy-2-methyl-1-phenylpropane-1
-One, benzyl dimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane Acetophenones such as -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-
4'-methyl-diphenyl sulfide, 3,3 ',
4,4'-Tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2
Benzophenones such as-(1-oxo-2-propenyloxy) ethyl] benzenemethanaminium bromide and (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4
-Thioxanthones such as propoxythioxanthone and 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride. Among these, acetophenones, benzophenones, and acylphosphine oxides are preferable.
2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one are particularly preferable.

The following compounds are preferable as the above-mentioned photocationic polymerization initiator. Aryl sulfonium salts such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate; aryl iodos such as diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate and (trirucumyl) iodonium tetrakis (pentafluorophenyl) borate Aluminum salts; aryldiazonium salts such as phenyldiazonium tetrafluoroborate. Among these, arylsulfonium salts and diazonium salts are preferable. Particularly, (trilycumyl) iodonium tetrakis (pentafluorophenyl) borate is preferable. The above polymerization initiators may be used alone or in combination of two or more kinds.

The lower limit of the total amount of the polymerization initiator added to the entire curable resin composition is preferably 0.05% by mass or more, and the upper limit thereof is preferably 20% by mass or less. If it is less than 0.05% by mass, sufficient curing may not be obtained, and if it exceeds 20% by mass, no further improvement in the physical properties of the cured product is observed, and rather it may have an adverse effect and the economy. It can also impair your sex. The lower limit is 0.1
Mass% or more is more preferable, 0.2 mass% or more is still more preferable, and the upper limit is 15% by mass or less, and 10 is more preferable.
It is more preferably not more than mass%.

In order to lower the decomposition temperature of the thermal radical polymerization initiator, a thermal polymerization accelerator capable of promoting the decomposition of the thermal radical polymerization initiator and effectively generating radicals can be used. As the thermal polymerization accelerator, metal soaps such as cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, potassium, etc., primary, secondary, tertiary amine compounds, quaternary ammonium salts, Thiourea compounds and ketone compounds are preferred, and 1
One kind or two or more kinds can be used. Among these, especially cobalt octylate, cobalt naphthenate, copper octylate, copper naphthenate, manganese octylate, manganese naphthenate, dimethylaniline, trietal amine,
Triethylbenzylammonium chloride, di (2-
Hydroxyethyl) p-toluidine, ethylenethiourea, acetylacetone, methyl acetoacetate are preferred.

The lower limit of the total amount of the thermal polymerization accelerator added to the entire curable resin composition is 0.001% by mass.
Is preferred, and the upper limit is preferably 20% by mass. More preferably, it is 0.01% by mass or more and 10% by mass or less. Most preferably, it is 0.05% by mass or more and 5% by mass or less.

As the photosensitizer, 2-chlorothioxanthone and 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone are preferable. The photosensitizer may be used alone or in combination of two or more kinds.

With respect to the total amount of the photosensitizer added to the entire curable resin composition, the lower limit is preferably 0.05% by mass or more, and the upper limit is preferably 20% by mass or less.
If it is less than 0.05% by mass, sufficient curing may not be obtained, and if it exceeds 20% by mass, no further improvement in the physical properties of the cured product is observed, and rather it may have an adverse effect and the economy. It can also impair your sex. The lower limit is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and the upper limit is more preferably 15% by mass or less, and further preferably 10% by mass or less.

As the photopolymerization accelerator, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl p-dimethylaminobenzoate, p
-Ethyl dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid-2
Preferred are -n-butoxyethyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-dimethylaminobenzophenone and 4,4'-diethylaminobenzophenone. Among these, triethanolamine, methyldiethanolamine, and triisopropanolamine are preferable. These may be used alone or in combination of two or more.

The lower limit of the total amount of the photopolymerization accelerator added to the entire curable resin composition is 0.05% by mass.
The above is preferable, and the upper limit is preferably 20% by mass or less. If it is less than 0.05% by mass, sufficient curing may not be obtained, and if it exceeds 20% by mass, no further improvement in the physical properties of the cured product is observed, and rather it may have an adverse effect and the economy. It can also impair your sex. The lower limit is 0.1
Mass% or more is more preferable, 0.2 mass% or more is still more preferable, and the upper limit is 15% by mass or less, and 10 is more preferable.
It is more preferably not more than mass%.

When the above-mentioned thermal polymerization initiator, photopolymerization initiator, thermal polymerization accelerator, photosensitizer, photopolymerization accelerator, etc. are added in combination, the total amount thereof is based on the entire curable resin composition. The lower limit of 0.05 mass% or more is preferable, 0.1 mass% or more is more preferable, 0.2 mass% or more is further preferable,
The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

The reactive diluent of the present invention and the curable resin composition containing the reactive diluent have toxicity reduction, viscosity adjustment, coloring by aqueous stain, impregnation into polar substrate, and wetting into polar substrate. Water may be further added for the purpose of improving properties, improving curability, or improving economy. The preferable amount of water is 0.01 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the reactive diluent of the present invention or the curable resin composition containing the reactive diluent. Below this range, the above-mentioned excellent effects may not be sufficiently exhibited. Further, if it exceeds this range, excessive curing time and energy for evaporating water during curing may be required. More preferably 0.0
2 parts by mass or more, and 500 parts by mass or less,
More preferably, it is 0.05 parts by mass or more, and 2
It is not more than 00 parts by mass. In addition, as a method of adding water,
Water may be added to the reactive diluent or the curable resin in advance, or water may be added after preparing the curable resin composition containing the reactive diluent. Further, the form of water present in the composition may be a composition compatible with the composition, a so-called water-soluble composition, or a suspension (dispersion) or an emulsion (emulsion) composition.

The curable resin composition of the present invention further comprises, if necessary, an inorganic filler, a non-reactive resin (for example, acrylic polymer, polyester, polyurethane, or the like) as an additive.
Polystyrene, polyvinyl chloride, etc.), organic solvents, color pigments, plasticizers, polymerization inhibitors, basic compounds, UV absorbers, antioxidants, matting agents, dyes, defoamers, leveling agents, antistatic agents, A dispersant, a slip agent, a surface modifier, a thixotropic agent, a thixotropic agent and the like can be added. The presence or absence of these additives does not particularly affect the effects of the present invention. These may be used alone or in combination of two or more.

The amount of the above-mentioned additive added to the entire curable resin composition of the present invention is the type of additive, purpose of use of the additive, use of the curable resin composition, method of using the curable resin composition, etc. Will be set accordingly.

For example, as the above-mentioned inorganic filler, the addition amount lower limit is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, based on the entire curable resin composition. The upper limit of the amount added is preferably 800 mass% or less, more preferably 600 mass% or less, and 50
0 mass% or less is more preferable.

The above non-reactive resin, organic solvent, color pigment,
As the plasticizer and the auxiliary change agent, the addition amount lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and the addition amount upper limit, based on the entire curable resin composition. However, 40 mass% or less is preferable, 30 mass% or less is more preferable, and 25 mass% or less is still more preferable.

As the above-mentioned ultraviolet absorber, antioxidant, matting agent, dye, defoaming agent, leveling agent, antistatic agent, dispersant, slip agent, surface modifier, and auxiliary auxiliary agent, a curable resin can be used. The lower limit of addition is 0.000 with respect to the entire composition.
1 mass% or more is preferable, 0.001 mass% or more is more preferable, 0.01 mass% or more is further preferable, 5 mass% or less of an addition amount upper limit is preferable, 3 mass% or less is more preferable, 1 mass% The following are more preferable.

The curable resin composition of the present invention can be obtained by mixing the curable resin, the reactive diluent, other additives and other compounding ingredients, and heating, dissolving and mixing. The obtained curable resin composition of the present invention is hand-coated such as brush coating according to the purpose of use, roll coating, gravure coating, gravure offset coating, curtain flow coating, reverse coating, screen printing, spray coating and dipping. It can be applied to the substrate by a known method such as a method. The coating amount is preferably 0.2 g / m ² or more,
0.5 g / m ² or more is more preferable, and 100 g / m ²
m ² or less is preferable, and 70 g / m ² or less is more preferable.

Examples of the base material include metals such as iron, aluminum, steel plates, tin-free steel plates, tin plates, and polyethylene terephthalate film laminated steel plates; concrete; polyethylene, polypropylene, polyacryl, polyethylene terephthalate, polycarbonate,
Polyamide, polyimide, nylon, polyvinyl chloride,
Resin moldings and films such as polyvinylidene chloride; coated papers such as polyethylene-coated paper and polyethylene terephthalate-coated paper; papers such as uncoated paper; and wood are suitable.

Curing of the curable resin composition of the present invention can be carried out by heating, irradiation with active energy rays, etc. In consideration of the characteristics of the curable resin composition, electromagnetic waves, ultraviolet rays, visible rays, infrared rays, It is preferable to use active energy rays such as electron rays and gamma rays and heat. In particular, ultraviolet rays and electron beams are preferable because they can improve flexibility and processing adhesion of the cured product. That is, a preferred form of the curable resin composition of the present invention is an active energy ray curable resin composition that is cured by irradiation with active energy rays. Such an active energy ray-curable resin composition containing the above reactive diluent is also 1 of the present invention.
Is one.

In the case of curing by the above ultraviolet rays, a wavelength of 150
It is preferable to use a light source containing light in the range of ~ 450 nm. As such a light source, sunlight, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, gallium lamp, xenon lamp, carbon arc lamp and the like are suitable. With these light sources, it is also possible to use heat by infrared rays, far infrared rays, hot air, high frequency heating, and the like.

The lower limit of the accelerating voltage for the curing by the electron beam is preferably 10 kV or more, more preferably 20 kV.
As described above, an electron beam having an upper limit of 30 kV or higher and an upper limit of preferably 500 kV or lower, more preferably 300 kV or lower, and further preferably 200 kV or lower may be used. Further, the lower limit of the irradiation dose is preferably 2 kGy or more, more preferably 3 kGy or more, further preferably 5 kGy or more, and the upper limit is preferably 500 kGy or less, more preferably 300 kGy or less, and 200 kG
It is more preferably y or less. In addition to the electron beam, heat such as infrared rays, far infrared rays, hot air, and high frequency heating can be used together.

The curable resin composition of the present invention becomes a thermosetting resin composition which is cured at room temperature or by heating by containing a thermal polymerization initiator and, if necessary, a thermal polymerization accelerator. A thermosetting resin composition containing such a thermal polymerization initiator and the above reactive diluent is also one aspect of the present invention. A preferable form is a thermosetting resin composition containing a thermal polymerization initiator, a thermal polymerization accelerator and the above reactive diluent. As the above-mentioned thermal polymerization initiator and thermal polymerization accelerator, those mentioned above are suitable, and one kind or two or more kinds can be used respectively.

When the thermosetting resin composition is cured at room temperature, it is preferably -20 ° C or higher, and 50 ° C or lower. If the curing temperature is lower than -20 ° C, the curing speed may be remarkably reduced and productivity may be sacrificed, or incomplete curing may result in excellent cured physical properties. If the temperature exceeds 50 ° C., curing will proceed rapidly, and problems such as foaming, cracking of the cured product and warpage of the molded product may occur. The lower limit is more preferably 0 ° C or higher, and the upper limit is more preferably 40 ° C or lower. Moreover, when hardening the said thermosetting resin composition by heating, 40 degreeC or more is preferable, and 180 degreeC or less is preferable. If the curing temperature is lower than 40 ° C., the curing speed may be remarkably reduced and productivity may be sacrificed, or incomplete curing may result in excellent cured physical properties. If the temperature exceeds 180 ° C., curing will proceed rapidly, and defects such as foaming and cracking of the cured product and warpage of the molded product may occur. The lower limit of heating is more preferably 50 ° C or higher, further preferably 60 ° C or higher, and the upper limit is more preferably 150 ° C or lower, further preferably 120 ° C or lower.

The curable resin composition of the present invention comprises an adhesive, an adhesive, a biomaterial, a dental material, an optical member, an information recording material,
Optical fiber materials, resist materials, insulators, sealing materials,
Inks, inkjet inks, printing inks, screen printing inks, paints, casting materials, decorative boards, WPCs, coating materials, photosensitive resin plates, dry films, lining materials, civil engineering building materials, putty, repair materials, flooring materials, pavements Material gel coat,
Overcoat, hand layup, spray up
Pultrusion / Filament winding / SMC / BM
Molding materials such as C, sheets, plasma display partition walls,
It can be widely used for applications such as polymer solid electrolytes.

Among these, inks, ink-jet inks, printing inks, screen printing inks, paints, optical fiber materials, adhesives, adhesives, encapsulants, photosensitive resin plates, dry films, molding materials, civil engineering and building materials, among others. It is preferably used in fields such as automobiles and vehicles.

When the curable resin composition of the present invention is used for coating, various kinds of fillers such as talc, mica, alumina, silica, aluminum hydroxide can be added if necessary. In the case of a colored paint, pigments, dyes, dispersants and the like can be added in addition to the above fillers. The paint thus obtained is one of the preferred embodiments of the present invention.
Is one. Such a coating is applied to the above-mentioned various base materials and the like, and if necessary, heating, electromagnetic waves, ultraviolet rays, visible light,
It can be cured by irradiation with active energy rays such as infrared rays, electron rays and gamma rays.

When the curable resin composition of the present invention is used for ink, a binder such as a resin, various fillers, pigments, dyes, dispersants and the like can be added, if necessary. The ink thus obtained is one of the preferred embodiments of the present invention. Such an ink is applied on a metal, paper, resin, or other substrate, and if necessary, heating, active energy rays such as electromagnetic waves, ultraviolet rays, visible rays, infrared rays, electron beams, gamma rays, and the like. It can be cured by irradiation with rays. In particular, it is preferable to cure with light such as ultraviolet rays, visible rays, and near infrared rays.

When the curable resin composition of the present invention is used for an adhesive or a pressure-sensitive adhesive (hereinafter referred to as "adhesive adhesive"), it may be provided with tackiness such as tackifier if necessary. Agents, various fillers, pigments, dyes, dispersants and the like can be added. The pressure-sensitive adhesive thus obtained is one of the preferred embodiments of the present invention. Such an adhesive is applied on metal, paper, resin, or other base material, and if necessary, heating, active energy rays such as electromagnetic waves, ultraviolet rays, visible rays, infrared rays, electron rays, gamma rays, etc. It can be cured by irradiation with active energy rays. In particular, it is preferable to cure with light such as ultraviolet rays, visible rays, and near infrared rays.

When the curable resin composition of the present invention is used for a curable molding material, various fillers may be added, if necessary.
Pigments, dyes, dispersants and the like can be added. The curable molding material thus obtained is one of the preferred embodiments of the present invention. Such a curable molding material can be used as it is or by impregnating reinforcing fibers such as glass fibers, carbon fibers, and aramid fibers, and if necessary, heating, electromagnetic waves, ultraviolet rays, visible rays, infrared rays, It can be cured and shaped by irradiation with active energy rays such as electron beams and gamma rays. In particular, it is preferable to cure and shape with heat, a highly transparent electron beam, a visible ray, a near infrared ray or the like.

[0068]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" is
It means "parts by mass".

[Resin Synthesis Example 1] (Synthesis of Curable Resin (1) Having Radical Polymerizable Group) In a 1 liter four-necked flask equipped with a stirrer, a thermometer, a rectification column and a nitrogen gas introduction tube. , Maleic anhydride 39
2 parts, 167 parts of propylene glycol and 229 parts of neopentyl glycol were added, the temperature was gradually raised to 200 ° C. under a nitrogen stream, and the reaction was carried out at the same temperature for 10 hours, and it was confirmed that 72 parts of condensed water was distilled. After cooling, an unsaturated polyester was obtained. The obtained unsaturated polyester is used as a curable resin (1).

[Resin Synthesis Example 2] (Synthesis of Curing Resin (2) Having Radical Polymerizable Group) 1 equipped with a stirrer, a thermometer, a rectification column and a gas introduction pipe
In a liter four-necked flask, 172 parts of methacrylic acid,
Bisphenol type epoxy resin (epoxy equivalent 185)
370 parts and triethylamine 2.7 parts were added, the temperature was gradually raised to 115 ° C. in an air stream, and the reaction was continued for 10 hours at the same temperature to obtain an epoxy methacrylate. The obtained epoxy methacrylate is used as a curable resin (2).

[Resin Synthesis Example 3] (Synthesis of Curable Resin (3) Having Radical Polymerizable Group) 1 equipped with a stirrer, a thermometer, a rectification column and a gas introduction pipe
To a liter four-necked flask, 348 parts of tolylene diisocyanate and 0.3 part of dibutyltin dilaurate were added and maintained at 40 ° C. under a nitrogen stream, and 260 parts of hydroxypropyl acrylate was added dropwise at the same temperature over 2 hours, and then, 141 parts of dipropylene glycol was added dropwise at the same temperature over 2 hours, and further reacted at the same temperature for 5 hours to obtain urethane acrylate. The obtained urethane acrylate is used as a curable resin (3).

[Resin Synthesis Example 4] (Synthesis of Curable Resin (4) Having Radical Polymerizable Group) 1 equipped with a stirrer, a thermometer, a rectification column and a gas introduction pipe
In a liter four-necked flask, 129 parts of methacrylic acid,
750 parts of saturated polyester polyol resin (saturated oligoester obtained by condensing 4 mol of diethylene glycol and 3 mol of adipic acid; acid value 3, hydroxyl value 150), 24 parts of paratoluenesulfonic acid and 300 parts of toluene, and added at 115 ° C. under air flow. After performing azeotropic dehydration for 10 hours and cooling the internal temperature to room temperature, it was washed twice with 800 parts of a saturated sodium hydrogen carbonate aqueous solution and 800 parts of deionized water, and 90 ° C., 1.33
It was devolatilized and dried under reduced pressure of 3 kPa for 5 hours to obtain polyester methacrylate. The obtained polyester methacrylate is used as a curable resin (4).

[Resin Synthesis Example 5] (Synthesis of curable resin (5) having radically polymerizable group) 1 equipped with a stirrer, a thermometer, a rectification column and a gas introduction pipe
In a liter four-necked flask, 172 parts of methacrylic acid,
Bisphenol type epoxy resin (epoxy equivalent 185)
370 parts and 2.7 parts of triethylamine were added, the temperature was gradually raised to 115 ° C. under an air stream, and the reaction was continued for 10 hours at the same temperature. Next, 98 parts of maleic anhydride was added and 10 parts were added.
Reaction was carried out at 0 ° C. for 4 hours to obtain an epoxy methacrylate having a maleic acid unit in its side chain. The obtained epoxy methacrylate is used as a curable resin (5).

[Resin Synthesis Example 6] (Synthesis of Curing Resin (6) Having Radical Polymerizable Group) 1 equipped with a stirrer, a thermometer, a rectification column and a gas introduction pipe
In a liter four-necked flask, 336 parts of hexamethylene diisocyanate and 0.3 parts of dibutyltin dilaurate.
Then, 260 parts of hydroxypropyl acrylate was added dropwise over 2 hours at the same temperature. Next, at the same temperature (630 parts of unsaturated oligoester obtained by condensing 3 mol of dipropylene glycol and 2 mol of fumaric acid, acid value 2, hydroxyl value 195) was added portionwise over 2 hours, and further reacted at the same temperature for 5 hours. Thus, a urethane acrylate having a fumaric acid unit in its main chain was obtained. The obtained urethane acrylate is used as a curable resin (6).

[Resin Synthesis Example 7] (Synthesis of Curable Resin (7) Having Radical Polymerizable Group and Ion Polymerizable Group) 1 equipped with a stirrer, thermometer, rectification column and gas introduction pipe
In a liter four-necked flask, 172 parts of methacrylic acid,
Cresol novolac type epoxy resin (epoxy equivalent 2
30) 690 parts and 4.3 parts triethylamine are added,
Gradually raise the temperature to 115 ° C under an air stream, and at the same temperature 1
The reaction was carried out for 0 hours to obtain an epoxy resin partially modified with a methacryloyl group. The obtained epoxy resin is referred to as a curable resin (7).

[Examples 1 to 25 and Comparative Examples 1 to 19]
(Thermosetting of various curable resin compositions) Table 1 shows curable resins (1) to (7) and commercially available curable resins.
The curable resin composition was prepared by blending the reactive diluent, the thermal polymerization initiator and the polymerization accelerator in the proportions shown in Tables 1 to 5, and the room temperature thermosetting property and thermosetting physical property of each composition were measured. The results are shown in Tables 1-5. The methods for measuring various physical properties are shown below.

(Viscosity) According to JIS K-6901,
It measured at 25 degreeC using the Brookfield type viscometer.

(Dry to touch) Glass plate (size: 150 m)
m × 100 mm) using a bar coater and wet thickness 4
Each curable resin composition was applied so as to have a thickness of 0 μm and left at room temperature. After 6 hours from the end of coating, the tackiness of the surface of the coating film was confirmed by touching with a finger. When the tackiness disappeared, the mark was ○, when the tackiness was slightly left, Δ, when the tackiness was clearly left, ×. And

(Low odor) Bottom area 625 cm ² , height 3
A semiconductor odor sensor (New Cosmos Electric Co., XP329 type) having an intake pipe and an exhaust pipe was attached to the uppermost part of a 0 cm rectangular parallelepiped acrylic transparent closed container.
Next, 10 g of each curable resin composition was weighed in a cylindrical open container having a bottom area of 80 cm ² and a height of 1 cm, left at the bottom of the closed container and left at room temperature for 90 minutes, and the odor intensity at that time was measured. I went. The odor sensitivity (mV) in the table means that the smaller the number, the less the volatilization of the substance generating the odor. In general, when the odor sensitivity is several tens of mV, there is an odor, but the odor is not noticeable. At a level of 100 mV, the odor can be clearly perceived.

(Strength property of cast plate) Each curable resin composition was cast into a glass casting container (thickness: 3 mm), allowed to cure at room temperature and left for one day and then after-cured at 110 ° C. for 2 hours. Regarding the cast plate thus prepared, JIS K-7113
The tensile strength and the tensile elongation were measured according to the above.

(Heat Resistance) Each curable resin composition was cast in a glass casting container (4 mm thick), cured at room temperature, left for one day and night, and then after-cured at 110 ° C. for 2 hours. The deflection temperature under load (HDT) was measured for the template according to JIS K-7207.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

Tables 1 to 5 will be described. (C) In the thermal polymerization initiator, ADEKA OPTON CP-66 (trade name) is a cationic thermal polymerization initiator manufactured by Asahi Denka Co., Ltd., and curing agent 328E (trade name) is manufactured by Kayaku Akzo. It is a radical thermal polymerization initiator. In (A) resin, E
OCN-102 (trade name) is a cresol novolac type epoxy resin manufactured by Nippon Kayaku Co., Ltd., and is CY-179.
(Product name) is an alicyclic epoxy resin manufactured by Ciba-Geigy, and xylylenebisoxetane (Product name) is
An oxetane resin made by Ube Industries, Ltd.
kXI-100 (trade name) is a polyallyl glycidyl ether resin manufactured by Monsanto.

[Examples 26 to 50 and Comparative Examples 20 to 4]
2] (UV curing of various curable resin compositions) Table 6 shows curable resins (1) to (7) and commercially available curable resins.
A reactive diluent and a photopolymerization initiator were blended in the proportions shown by 10 to 10 to prepare a curable resin composition, and the photocurability and photocured physical properties of each composition were measured. The results are shown in Tables 6 to 10.
Shown in. The methods for measuring various physical properties are shown below.

(Photocurable) The composition was applied on a degreased oak veneered decorative plywood (size 150 mm × 100 mm) using a bar coater to a wet thickness of 40 μm, and then a high pressure of 80 W / cm. Exposure was carried out using a belt conveyor UV irradiation device equipped with one mercury lamp.
Distance from light source is 10 cm, conveyor speed is 15 m
/ Min, the effective exposure length was set to 60 cm (with respect to the traveling direction of the conveyor), and the number of passes until tackiness disappeared from the coating film surface was measured by touching with a finger. By the way, when this UV irradiation device is used to perform exposure under the above conditions, the amount of UV irradiation energy per pass is 140 mJ / cm ² (3
(65 nm conversion). In each of the measured values in the table, it means that the composition having a smaller number of passes has a better photocurability.

(Pencil Hardness) A cured coating film obtained by exposing the belt conveyor ultraviolet ray irradiation device and other conditions and materials at a pass number of 10 has a pencil hardness according to JIS K-5400. It was measured.

(Adhesion) The number of passes is set to 2 by using the above belt conveyor ultraviolet irradiation device and other conditions and materials.
A cellophane adhesive tape having a width of 18 mm was attached to the cured coating film obtained by performing exposure as 0 times with a length of 20 mm, and a tape peeling test was performed. In the table, ◯ indicates that the coating film did not change, Δ indicates that the coating was partially peeled, and × indicates that the coating was peeled.

[0092]

[Table 6]

[0093]

[Table 7]

[0094]

[Table 8]

[0095]

[Table 9]

[0096]

[Table 10]

Tables 6 to 10 will be described. (C) In the photopolymerization initiator, Irgacure 184 (trade name) is a radical photopolymerization initiator manufactured by Ciba-Geigy,
ADEKA OPTOMER SP-100 (trade name) is a cationic photopolymerization initiator manufactured by Asahi Denka Co., Ltd. The description of the resin (A) in Table 10 is the same as that in Table 5.

[Examples 51 to 55 and Comparative Examples 43 to 4
8] (Electron beam curing of various curable resin compositions) Curable resins (1), (5), (7) and commercially available curable resins were mixed with reactive diluents at a ratio shown in Table 11 and cured. Resin compositions were prepared, and the electron beam curability and the physical properties of the electron beam cured products of each composition were measured. The results are shown in Table 11. The methods for measuring various physical properties are shown below.

(Electron beam curability) The composition was coated on a glass plate using a bar coater so that the wet thickness was 100 μm, and then electron beam irradiation was performed using an electro curtain type electron beam irradiation device. Check the coating surface by touching the finger,
The amount of electron beam irradiation until the tackiness disappeared was measured. In each of the measured values in the table, a composition having a smaller electron beam irradiation amount has a higher electron beam curability.

(Appearance of coating film) Using the above-mentioned electron beam irradiation apparatus and other conditions and materials, the irradiation energy amount was 50 kG.
The gloss and color of the cured coating film obtained by irradiation as y were visually evaluated. A sample with excellent gloss was marked with O, a sample with slightly deteriorated gloss was marked with Δ, and a sample with no gloss (matte appearance) was marked with X. The uncolored ones are ○,
The one that was slightly colored was marked with Δ, and the one that was clearly colored was marked with x.

(Solvent resistance) Using the above electron beam irradiation apparatus and other conditions and materials, the irradiation energy amount was 50 kG.
The cured coating film obtained by irradiation as y was rubbed 10 times with gauze impregnated with MEK (methyl ethyl ketone), and finally up to 50 times, to visually evaluate the change in gloss of the coating surface (1 gauze was used). 1 by going back and forth
Counted as times. ). When the gloss did not change, it was evaluated as ◯, when the gloss was slightly decreased, it was evaluated as Δ, and when the gloss was completely lost, it was evaluated as x.

(Pencil hardness) Using the above electron beam irradiation apparatus and other conditions and materials, the irradiation energy amount was 50 kG.
The pencil hardness of the cured coating film obtained by irradiating y was measured according to JIS K-5400.

(Weather resistance) The irradiation energy amount was 50 kGy using the above electron beam irradiation apparatus and other conditions and materials.
About the cured coating film obtained by irradiating as
2 in carbon arc type sunshine weatherometer
After accelerated exposure for 000 hours, the color difference between the cured coating film after exposure and the initial (before exposure) cured coating film was visually evaluated. Those having no difference from the initial cured coating film were marked with ◯, slightly colored ones with Δ, and clearly colored ones with x.

[0104]

[Table 11]

[0105]

EFFECTS OF THE INVENTION The present invention has the above-mentioned constitution, and by using vinyl ether group-containing (meth) acrylic acid ester as a reactive diluent, a radical-curable reactive diluent and a cation-curable reactive diluent can be obtained. Can overcome the problems of agents, inks, inkjet inks,
It can be applied to various applications such as printing inks, screen printing inks, paints, optical fiber materials, adhesives, pressure-sensitive adhesives, sealing materials, photosensitive resin plates, dry films, and molding materials. The curable resin composition such as the active energy ray-curable resin composition and the thermosetting resin composition containing the reactive diluent of the present invention is an ink, an inkjet ink, a printing ink, a screen printing ink, a paint. , Optical fiber materials, adhesives, pressure-sensitive adhesives, encapsulants, photosensitive resin plates, dry films, molding materials, and various other applications.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Ryohiko Fukada             5-8 Nishiomitabicho, Suita City, Osaka Prefecture             Within Nippon Shokubai F-term (reference) 4J027 AB10 AB15 AB16 AB17 AB18                       AB23 AB24 AB25 AD02 AG03                       AG04 AG12 AG23 AG24 AG27                       BA17 BA18 BA21 BA22 CB04                       CB09 CB10 CC02 CC03 CD08                       CD09                 4J036 AB01 AC02 AF06 AF08 AF10                       AJ09 AJ10 AK09 CA21 EA02                       EA04 HA01 JA01 JA06

Claims (4)

[Claims] 1. The following general formula (1); CH ₂ ═CR ¹ —COO—R ² —O—CH═CH—R ³ (1) (In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² is
It represents an organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or an organic residue having 1 to 11 carbon atoms. And a vinyl ether group-containing (meth) acrylic acid ester represented by the formula (1). 2. A curable resin composition comprising a curable resin and the reactive diluent according to claim 1, wherein the curable resin comprises at least one or more radically polymerizable groups and / or
Alternatively, a curable resin composition having an ionic polymerizable group. 3. An active energy ray curable resin composition comprising the reactive diluent according to claim 1. 4. A thermosetting resin composition comprising a thermal polymerization initiator and the reactive diluent according to claim 1.