JP2003147217A - Liquid curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid curable resin composition which has good coatability and is easily and quickly cured with UV light, or the like, to form the cured product having good tensile characteristics, good resistance to heat, chemicals and weather, and excellent impact resistance. SOLUTION: This liquid curable resin composition contains a non-curable resin, wherein dispersion phases preferably having an average particle diameter of 0.01 to 20 μm can be formed in the cured product of the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid curable resin composition. More specifically, it has excellent curability and durability, and various base materials, for example, polyesters such as polyethylene terephthalate and polybutylene terephthalate,
Plastics such as polycarbonate, triacetyl cellulose, polymethylmethacrylate, polystyrene, polyolefin, epoxy, melamine, ABS resin, AS resin, norbornene resin, metal, wood, paper, glass,
Good adhesion to slate, plastic, wood,
Coating materials for ceramics, glass, paper, etc., optical molding materials, three-dimensional solid molding materials, printing plate materials, various optical elements, CDs, DVs
A liquid coating that is useful as a protective coating material for preventing scratches and contamination of optical discs such as D, touch panels, and liquid crystal display elements, as well as adhesives and sealing materials for various base materials, and binder materials for printing inks. Resin composition.

[0002]

2. Description of the Related Art A liquid curable resin composition has a good coating property because it is in a liquid state, and it is easily and rapidly cured by ultraviolet rays and the like, and the cured product has good tensile properties, heat resistance and heat resistance.
Since it has chemical resistance and weather resistance, it is widely used as a coating material for surface protection. Such a liquid curable resin composition, which has an oligomer or a monomer as a main component, forms a three-dimensional crosslinked structure through a crosslinking reaction by a photoinitiator, but has properties as a structure, particularly impact resistance. Are low, and in this respect improvements for use in structural members have been needed.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
A photocurable resin composition that is excellent in impact resistance while maintaining the properties of conventional photocurable resins is desired.

[0004]

Means for Solving the Problems The present inventor has found that if a liquid curable resin composition contains a non-curable resin, and a dispersed phase composed of the non-curable resin is formed in a cured product, the cured product is cured. The present invention has been completed by finding that the body has a higher impact strength than ever before.

That is, the present invention relates to a liquid curable resin composition containing a non-curable resin, which is capable of forming a dispersed phase of the non-curable resin in a cured product of the composition. A resin composition is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The dispersed phase contained in the cured product of the liquid curable resin composition of the present invention is dispersed at the stage of the liquid composition before curing from the viewpoint of controlling the particle size of the dispersed phase. It is preferable. The average particle size of the dispersed phase in the resin composition is 0.0
1 to 20 μm, further 0.05 to 15 μm, especially 0.1
It is preferably 10 μm. The content in the resin composition is preferably 0.1 to 50% by weight, and more preferably 0.2 to 40% by weight from the viewpoint of elastic modulus and curability of the cured product.

The component of such a dispersed phase may be a resin that does not cure under the condition that the liquid curable resin composition is cured, that is, a non-curable resin, but is not compatible with the liquid curable resin composition. Are preferred, and various polymers can be used. Examples of the polymer include polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / propylene copolymer, ethylene / α-olefin copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer. Polymer, ethylene / α-olefin / polyene copolymer, acrylic rubber, butadiene /
Examples thereof include (meth) acrylic acid ester copolymers and hydrogenated polybutadiene. Further, polymer particles having a core / shell structure in which these polymers are coated with other polymers can also be used. Examples of the coating polymer that forms such a core / shell structure include a methyl methacrylate polymer and a methyl methacrylate / glycidyl methacrylate copolymer.

The composition of the present invention contains, in addition to the above-mentioned components forming the dispersed phase, a polymerizable oligomer, a polymerizable unsaturated monomer and a photopolymerizable monomer which are used in ordinary photocurable liquid curable resin compositions. A polymerization initiator is added.

Examples of the polymerizable oligomer include urethane (meth) acrylate and poly (meth) acrylate having a (meth) acryl group at the side chain or terminal.

Usually, a urethane (meth) acrylate (hereinafter referred to as a polymerizable oligomer (A)) is synthesized from a polyol compound, a diisocyanate compound and a hydroxyl group-containing (meth) acrylate, or only a diisocyanate compound and a hydroxyl group-containing (meth) acrylate. . That is, it is produced by reacting the isocyanate group of diisocyanate with the hydroxyl group of the polyol compound or the hydroxyl group of the hydroxyl group-containing (meth) acrylate. When synthesizing a polymerizable oligomer (hereinafter referred to as “polymerizable oligomer (A1)”) containing a polyol compound, a diisocyanate compound and a hydroxyl group-containing (meth) acrylate as components,
The isocyanate group contained in the diisocyanate compound is equivalent to 1 equivalent of the hydroxyl group contained in the polyol compound.
It is preferable that 1.1 to 2 equivalents and the hydroxyl groups of the hydroxyl group-containing (meth) acrylate be 0.1 to 1 equivalents.
When synthesizing a polymerizable oligomer having only a diisocyanate compound and a hydroxyl group-containing (meth) acrylate as a component (hereinafter referred to as "polymerizable oligomer (A2)"), the isocyanate group contained in the diisocyanate compound and the hydroxyl group of the hydroxyl group-containing (meth) acrylate Is preferably an equivalent amount. Further, the polymerizable oligomer (A1) and the polymerizable oligomer (A2) can be simultaneously synthesized by adjusting the amounts of the polyol compound, the diisocyanate compound and the hydroxyl group-containing (meth) acrylate.

A specific method for carrying out this reaction is as follows:
For example, a method in which a polyol compound, a diisocyanate compound and a hydroxyl group-containing (meth) acrylate compound are collectively charged and reacted; a method in which a polyol compound and a diisocyanate compound are reacted and then a hydroxyl group-containing (meth) acrylate compound is reacted; a diisocyanate compound and a hydroxyl group A method of reacting a containing (meth) acrylate compound and then a polyol compound; reacting a diisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, then reacting a polyol compound, and finally, a hydroxyl group-containing (meth) acrylate compound. Examples include a method of reacting.

Examples of the diisocyanate compound used in the synthesis of the polymerizable oligomer (A) include aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate. As an aromatic diisocyanate,
For example, 2,4-tolylene diisocyanate, 2,6-
Tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate,
1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate,
3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6 -Isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, tetramethylxylylene diisocyanate, and the like. Examples of the alicyclic diisocyanate include isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, Two
6-bis (isocyanatomethyl) -bicyclo [2.
2.1] Heptane and the like. Examples of the aliphatic diisocyanate include 1,6-hexane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate.
Of these, 2,4-tolylene diisocyanate and isophorone diisocyanate are particularly preferable. These diisocyanates may be used alone or in combination of two or more.

The hydroxyl group-containing (meth) acrylate compound used in the synthesis of the polymerizable oligomer (A) is a hydroxyl group-containing (meth) acrylate having a hydroxyl group bonded to a primary carbon (referred to as a primary hydroxyl group-containing (meth) acrylate). , And a hydroxyl group-containing (meth) acrylate having a hydroxyl group bonded to a secondary carbon (referred to as a secondary hydroxyl group-containing (meth) acrylate) is preferably used. A hydroxyl group-containing (meth) acrylate having a hydroxyl group bonded to a tertiary carbon (referred to as a tertiary hydroxyl group-containing (meth) acrylate) is inferior in reactivity with an isocyanate group and is not preferred. As the primary hydroxyl group-containing (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, Dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, and the following formula (1)

CH ₂ = C (R ¹ ) -COOCH ₂ CH _2- (OCOCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) _n -OH (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and n represents a number of 1 to 3) and the like (meth) acrylate. Examples of the secondary hydroxyl group-containing (meth) acrylate include 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, and 4-hydroxycyclohexyl (meth). ) Acrylate, etc., and also a compound obtained by addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate and (meth) acrylic acid.

Examples of the polyol compound used for producing the polymerizable oligomer (A) include polyether diols such as aliphatic polyether diols, alicyclic polyether diols and aromatic polyether diols, polyester diols, polycarbonate diols, Examples thereof include polycaprolactone diol. These polyols may be used alone or in combination of two or more. As the polyol, a divalent or higher valent polyol synthesized by the reaction of diols and polyisocyanate can also be used. The polymerization mode of each structural unit in these polyols is not particularly limited and may be random polymerization, block polymerization or graft polymerization.

As the aliphatic polyether diol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol and two or more kinds of ion-polymerizable cyclic compounds are opened. Examples thereof include polyether diol obtained by copolymerization.

Examples of the ionically polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-
1-oxide, isobutene oxide, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran,
Dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether. , And cyclic ethers such as glycidyl benzoate.

Specific examples of polyether diols obtained by ring-opening copolymerization of two or more of the above ion-polymerizable cyclic compounds include, for example, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran. , A binary copolymer obtained by the combination of tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1-oxide and ethylene oxide; a terpolymer obtained by the combination of tetrahydrofuran, butene-1-oxide and ethylene oxide, and the like. be able to.

Further, ring-opening copolymerization of the above-mentioned ionically polymerizable cyclic compound and cyclic imine such as ethyleneimine; cyclic lactone acid such as β-propiolactone and glycolic acid lactide; or dimethylcyclopolysiloxane is carried out. It is also possible to use polyether diols.

The above-mentioned aliphatic polyether diol is, for example, PTMG650, PTMG1000, PTMG200.
0 (above, manufactured by Mitsubishi Chemical Corporation), PPG400, PPG
1000, EXCENOL 720, 1020, 2020
(Above, manufactured by Asahi Olin Co., Ltd.), PEG1000, Unisafe DC1100, DC1800 (above, manufactured by NOF Corporation), PPTG2000, PPTG1000, P
TG400, PTGL2000 (above, Hodogaya Chemical Co., Ltd.), Z-3001-4, Z-3001-5, P
BG2000A, PBG2000B, EO / BO400
0, EO / BO2000 (above, Daiichi Kogyo Seiyaku Co., Ltd.)
It can also be obtained as a commercial product such as (made by Japan).

Examples of the alicyclic polyether diol include alkylene oxide addition diol of hydrogenated bisphenol A, alkylene oxide addition diol of hydrogenated bisphenol F, and alkylene oxide addition diol of 1,4-cyclohexanediol.

Further, examples of the aromatic polyether diol include alkylene oxide addition diol of bisphenol A, alkylene oxide addition diol of bisphenol F, alkylene oxide addition diol of hydroquinone, alkylene oxide addition diol of naphthohydroquinone, alkylene oxide of anthrahiroquinone. Examples thereof include oxide-added diols. The aromatic polyether diol is, for example, Uniol DA400, DA70.
It can also be obtained as a commercial product such as 0, DA1000, DA4000 (above, manufactured by NOF CORPORATION).

Examples of polyester diols include polyester diols obtained by reacting a polyhydric alcohol with a polybasic acid. Examples of the polyhydric alcohol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 3
-Methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and the like can be mentioned. Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid and the like.

Among the above polyester diols, commercially available products include, for example, Clapol P-2010 and P-101.
0, L-2010, L-1010, A-2010, A-
1010, F-2020, F-1010, PMIPA-
2000, PKA-A, PNOA-2010, PNOA
-1010 (above, Kuraray make) etc. are mentioned.

Examples of the polycarbonate diol include polycarbonate of polytetrahydrofuran, 1,6
-Hexanediol polycarbonate and the like, and commercially available products are DN-980, 981, 982, 9
83 (above, Nippon Polyurethane Co., Ltd. product), PC-80
00 (made by PPG), PC-THF-CD (made by BASF)
And so on.

Examples of the polycaprolactone diol include polycaprolactone diol obtained by reacting ε-caprolactone with a diol. Examples of the diol used here include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, and 1 Examples include 1,4-cyclohexanedimethanol and 1,4-butanediol. These polycaprolactone diols are commercially available from Praxel 205,
205AL, 212, 212AL, 220, 220AL
(These are manufactured by Daicel Chemical Industries Ltd.) and the like.

As other polyols other than the above,
For example ethylene glycol, propylene glycol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
1,4-cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, dimethylol compound of dicyclopentadiene, tricyclodecanedimethanol, pentacyclodecanedimethanol, β-methyl-δ
Valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil modified polyol, polydimethylsiloxane terminal diol compound,
Examples thereof include polydimethylsiloxane carbitol modified polyol.

It is also possible to use a diamine together with the polyol in the production of the polymerizable oligomer (A). As such a diamine, ethylenediamine,
Examples thereof include diamines such as tetramethylenediamine, hexamethylenediamine, paraphenylenediamine, 4,4'-diaminodiphenylmethane, diamines containing a hetero atom, and polyetherdiamines.

A part of the hydroxyl group-containing (meth) acrylate may be replaced with a compound having a functional group capable of being added to an isocyanate group. For example, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane and the like can be mentioned. By using these compounds, it is possible to improve the adhesion to a substrate such as glass.

In the synthesis of the polymerizable oligomer (A),
Copper naphthenate, cobalt naphthenate, zinc naphthenate,
Dibutyltin dilaurate, triethylamine, 1,4-
Diazabicyclo [2.2.2] octane, 2,6,7-
It is preferable to use 0.01 to 1% by weight of a urethanization catalyst selected from trimethyl-1,4-diazabicyclo [2.2.2] octane and the like, based on the total amount of the reactants. The reaction temperature is usually 5 to 90 ° C, preferably 10 to 80 ° C.

The preferred molecular weight of the above-mentioned polymerizable oligomer (A) is usually 500 to 20,0 in terms of polystyrene equivalent by gel permeation chromatography.
00, preferably 700 to 15,000.
If the molecular weight is less than 500, the elongation at break of the cured product may be low, and if it exceeds 20,000, the viscosity may increase, which is not preferable.

The polymerizable oligomer (A) is contained in the liquid curable resin composition of the present invention in an amount of 30 to 90% by weight, particularly 40% by weight.
It is preferable to mix it in an amount of ˜85% by weight. If it is less than 30% by weight, the temperature dependence of the elastic modulus is large, and if it is 90% by weight or more, the viscosity of the liquid curable resin composition may increase.

Further, the liquid curable resin composition of the present invention may further contain urethane (meth) acrylate obtained by reacting 1 mol of diisocyanate with 2 mol of a hydroxyl group-containing (meth) acrylate compound. Examples of the urethane (meth) acrylate include a reaction product of hydroxyethyl (meth) acrylate and 2,5 (or 2,6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, hydroxyethyl (meth). ) Reaction product of acrylate and 2,4-tolylene diisocyanate, reaction product of hydroxyethyl (meth) acrylate and isophorone diisocyanate, reaction product of hydroxypropyl (meth) acrylate and 2,4-tolylene diisocyanate, hydroxypropyl (meth) Examples thereof include a reaction product of acrylate and isophorone diisocyanate.

As the poly (meth) acrylate having a (meth) acrylic group at the side chain or terminal (hereinafter referred to as the polymerizable oligomer (B)), a structural unit of the following general formula (2) and a general formula (3) Examples thereof include a copolymer having a structural unit, which is characterized by having at least one (meth) acrylic group in the molecule.

-(CH ₂ -CR ² X)-(2)-(CH ₂ -CR ³ Y)-(3)

(In the formula, R ² and R ³ each represent a hydrogen atom or a methyl group, and X represents a group —COOR ⁴ (wherein R ⁴
Represents a hydrocarbon group having 1 to 30 carbon atoms. ), An aryl group, a cyano group, a halogen atom or an alkyl group having 1 to 10 carbon atoms, and Y represents a functional group containing a (meth) acryloyloxy group. )

Examples of the hydrocarbon group having 1 to 30 carbon atoms include linear, branched or cyclic alkyl groups, alkenyl groups, aralkyl groups, aromatic hydrocarbons, polycyclic hydrocarbons and the like. Among these, a linear, branched or cyclic alkyl or alkenyl group having 1 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a halogenophenyl group, a methylphenyl group, a methoxyphenyl group and a trialkylsilylphenyl group, and a phenyl group and a methylphenyl group are particularly preferable. Examples of the halogen atom include chlorine, fluorine and bromine. Examples of the alkyl group having 1 to 10 carbon atoms include linear, branched or cyclic alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, amyl, isobutyl, t-butyl,
Examples include pentyl, isoamyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl, cyclohexyl and the like.

The functional group containing a (meth) acryloyloxy group represented by Y is, for example, -AB-OCOCR ⁵ = CH.
₂ (wherein A represents —COO—, phenyl or an alkylene group having 1 to 6 carbon atoms, B represents an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, and R ⁵ represents a hydrogen atom or Group which represents a methyl group).

The structural units of the above general formulas (2) and (3) may be the same repeating units, or may have different structures in combination.

The polymerizable oligomer (B) has, for example, a vinyl-polymerizable compound and a functional group capable of introducing a (meth) acryloyloxy group, and a vinyl-polymerizable compound is copolymerized to form a polymer. After the compound is obtained, it is synthesized by introducing an acrylic copolymer into the terminal or side chain of the compound, preferably at the terminal. The number average molecular weight of the polymerizable oligomer (B) is 1,000 to 10.
It is 20,000, preferably 2,000 or more and 70,000 or less, and more preferably 3,000 or more and 50,000 or less. If the molecular weight is less than 1,000, the viscosity of the liquid curable resin composition will be low and the shape stability of the cured product will be poor. On the other hand, when the molecular weight exceeds 100,000, the viscosity of the liquid curable resin composition increases, and the shape stability of the cured product may deteriorate.

The above vinyl-polymerizable compound includes
For example, (meth) acrylate compounds, styrene compounds, acrylonitrile, vinyl halide compounds and the like can be mentioned.

Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. Acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate Relate, octadecyl (meth) acrylate, stearyl (meth) acrylate,
Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, Bornyl (meth) acrylate etc. are mentioned. Among these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, isobornyl acrylate and dicyclopentenyl (meth) acrylate are preferred.

Styrene compounds include styrene and α
-Methylstyrene, p-bromostyrene, p-chlorostyrene, p-methoxystyrene, p-methylstyrene,
Examples thereof include p-trialkylsilylstyrene, and styrene and α-methylstyrene are particularly preferable.

Examples of the vinyl halide compound include vinyl chloride, 1,1-dichloroethylene, 1,2-dichloroethylene, vinyl bromide, fluoroethylene, 1,1-difluoroethylene, 1,2-difluoroethylene, trifluoroethylene and tetra. Fluoroethylene may be mentioned, with vinyl chloride, 1,1-dichloroethylene and the above fluorinated ethylene compounds being particularly preferred.

Examples of the compound having a functional group capable of introducing a (meth) acryloyloxy group include a (meth) acrylate compound having a hydroxyl group, a (meth) acrylate compound having an epoxy group, and an allyl compound having an epoxy group. Examples include styrene derivatives having a hydroxyl group on the benzene ring. Specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, allyl glycidyl ether, and p-hydroxystyrene. .

The polymerization method of these vinyl compounds is not particularly limited, and any method such as a cationic polymerization method, an anionic polymerization method and a polymerization method using a Ziegler-Natta catalyst may be used. Also, an emulsion polymerization method can be applied. A solvent may or may not be used in the polymerization.

The polymer thus obtained is reacted with acrylic acid, maleic acid, fumaric acid, (meth) acrylic acid chloride in order to introduce a (meth) acrylic group. In this case, the solvent may be selected appropriately. Also, a suitable catalyst can be used in this reaction, and examples thereof include amine-based or ammonium chloride-based substances.

The amount of the (meth) acrylic group in the above polymer is preferably in the range of 1 to 50 mol%, particularly preferably 2 to 30 mol%, based on the polymer. As such a reactive polymer, B-3000, B-3001, B-3002, B-30 manufactured by Shin-Nakamura Chemical Co., Ltd.
03, B-3004, B-3005, B-3006, A
P-2150 etc. are mentioned.

The polymerizable unsaturated monomer (C) used in the liquid curable resin composition of the present invention may be a monofunctional compound and / or a polyfunctional compound. Examples of the monofunctional compound include vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl ( Alicyclic structure-containing (meth) acrylates such as (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4
-Butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinyl imidazole, vinyl pyridine, etc. are mentioned. Furthermore, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, Octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth)
Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl ( (Meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth)
Acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth)
Acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide,
Mention may be made of N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether.

As commercial products of the above-mentioned monofunctional compounds of polymerizable unsaturated monomers, Aronix M-111, M
-113, M-114, M-117 (all manufactured by Toagosei Co., Ltd.); KAYARAD, TC110S, R62
9, R644 (above, manufactured by Nippon Kayaku Co., Ltd.); IBXA,
Viscoat 3700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like can be mentioned.

Examples of polyfunctional compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris ( 2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate Di (meth) acrylate of bisphenol A ethylene oxide or propylene oxide adduct, diol di (meth) acrylate of hydrogenated bisphenol A ethylene oxide or propylene oxide adduct, bisphenol A diglycidyl ether ( Epoxy (meth) acrylate to which (meth) acrylate is added, triethylene glycol divinyl ether and the like can be mentioned. Also,
Examples of commercially available products include Uupimer UV SA1002,
SA2007 (above, manufactured by Mitsubishi Chemical Co., Ltd.); Viscoat 700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); KAYARAD
R-604, DPCA-20, -30, -60, -1
20, HX-620, D-310, D-330 (above,
Nippon Kayaku Co., Ltd.); Aronix M-210, M-2
15, M-315, M-325 (above, Toagosei Co., Ltd.)
Manufactured) and the like.

The polymerizable unsaturated monomer (C) is contained in the liquid curable resin composition of the present invention in an amount of 0 to 50% by weight, particularly 1 to 50% by weight.
It is preferable to add 40% by weight.

Examples of the photopolymerization initiator (D) used in the liquid curable resin composition of the present invention include 1-hydroxycyclohexyl phenyl ketone and 2,2-dimethoxy-2.
-Phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone,
Triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoinpropyl ether,
Benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-
2-Methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1. -One, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-
Examples include (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Further, examples of commercially available products include IRGACURE 184,
369, 651, 500, 907, CGI1700, C
GI1750, CGI1850, CG24-61, DA
ROCURE 1116, 1173, 4625 (above, manufactured by Ciba Specialty Chemicals); LUCIRINT
PO (manufactured by BASF); Yubecryl P36 (manufactured by UCB) and the like. Also, a photosensitizer can be added,
Examples include triethylamine, diethylamine,
N-methyldiethanolamine, ethanolamine, 4
-Dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate; Yubecryl P10
2, 103, 104, 105 (above, made by UCB) and the like.

The photopolymerization initiator (D) is preferably incorporated in the liquid curable composition of the present invention in an amount of 0.1 to 10% by weight, particularly 0.3 to 7% by weight.

In addition to the above components, various additives such as antioxidants, colorants, ultraviolet absorbers, light stabilizers, silane coupling agents, thermal polymerization inhibitors, leveling agents, surfactants, storage stabilizers, A plasticizer, a lubricant other than a hydrocarbon compound, a solvent, a filler, an antiaging agent, a wettability improver, a coating surface improver and the like can be added as necessary. Here, as the antioxidant, for example, IRGANOX 101
0, 1035, 1076, 1222 (above, manufactured by Ciba Specialty Chemicals), ANTIGENE P, 3
C, FR, GA-80 (made by Sumitomo Chemical Co., Ltd.), etc. are mentioned. Examples of the ultraviolet absorber include TINUVI
NP, 234, 320, 326, 327, 328, 3
29, 213 (above, Ciba Specialty Chemicals), Seesorb 102, 103, 501, 20
2, 712, 704 (above, manufactured by Cypro Kasei) and the like. Examples of the light stabilizer include TINUVIN 29
2, 144, 622LD (above, Ciba Specialty Chemicals), Sanol LS770 (Sankyo Co., Ltd.)
Manufactured by Sumitomo Chemical Co., Ltd.) and the like. Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and as commercially available products, SH6062, 6
030 (above, Toray Dow Corning Silicone Co., Ltd.)
Manufactured by Shin-Etsu Chemical Co., Ltd., and the like. As a paint surface improving agent,
For example, a graft polymer of dimethylsiloxane polycarbinol and the like can be mentioned. As a commercially available product, SH28P is used.
A, SH190 (above, Toray Dow Corning Silicone Co., Ltd. product) etc. are mentioned.

If desired, the composition of the present invention may contain other oligomers, polymers, other additives, etc. within a range that does not impair the characteristics of the liquid curable resin composition of the present invention.

Other oligomers and polymers include, for example, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate,
Examples thereof include a siloxane polymer having a (meth) acryloyloxy group and glycidyl (meth) acrylate.

In order to prepare a structure using the liquid curable resin composition of the present invention, it can be cured by an existing optical molding machine, or after being injected into a thick mold, it can be irradiated with ultraviolet rays to be cured.

[0060]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Preparation of liquid curable resin composition 1 In a reaction vessel equipped with a stirrer, 14.5 g of 2,4-tolylene diisocyanate, 0.012 g of 2,6-di-t-butyl-p-cresol, dibutyl Tin dilaurate 0.0
40 g and 0.004 g of phenothiazine were charged, and these were stirred and ice-cooled until the liquid temperature became 10 ° C or lower. 12.5 g of hydroxyethyl acrylate was added dropwise while controlling the liquid temperature to 20 ° C. or lower, and the mixture was further stirred for 1 hour for reaction. Next, number average molecular weight 10
00 ring-opening polymer of ethylene oxide and butylene oxide (trade name: H-3988 (Daiichi Kogyo Seiyaku Co., Ltd.)
19.4 g), and an alkylene oxide addition diol of bisphenol A having a number average molecular weight of 400 (trade name:
Uniall DA400 (manufactured by NOF CORPORATION) 4.1g
Was added and stirring was continued for 3 hours at a liquid temperature of 70 to 75 ° C., and the reaction was terminated when the residual isocyanate was 0.1% by weight or less. Liquid temperature is cooled to 50 to 60 ° C., and trimethylolpropane triacrylate 30.0 g, N-
Vinylpyrrolidone 4.7 g, SA1002 (manufactured by Mitsubishi Chemical Corporation) 11.8 g, LUCIRIN TPO (BA
1.5 g (manufactured by SF Co.) was added and stirred to obtain a composition (S1).

Preparation of liquid curable resin composition 2 B-30 manufactured by Shin-Nakamura Chemical Co., Ltd. containing 20 wt% of isobornyl acrylate in a reaction vessel equipped with a stirrer.
00 50 g with isobornyl acrylate 50 g and 1-
3 g of hydroxycyclohexyl phenyl ketone was added and stirred at 50 ° C. for 1 hour to obtain a composition (S2).

Test Example A liquid curable resin composition having the composition shown in Table 1 was prepared and the following tests were conducted.

[0064] using an applicator bar for measuring 200 micron thick and elastic modulus curing rate of the liquid curable resin composition was coated on a glass plate, which of ^{0.1J / cm 2, 1J / cm} 2 under air A test film was obtained by irradiating with ultraviolet rays of energy and curing. From the film thus obtained, the stretched part has a long side of 25 mm and a width of 6
Cut out to have a temperature of 23 mm and a relative humidity of 50%.
The elastic modulus was calculated from the tensile strength at a tensile rate of 1 mm / min and a tensile strain of 2.5%. The curing rate was measured by the following formula from the elastic modulus of 0.1 J / cm ^{2 and} the elastic modulus of 1 J / cm ² . Curing rate = elastic modulus (0.1 J / cm ² ) / elastic modulus (1 J / c
m ² )

Measurement of Impact Strength Using a solid creator JSC-2000, the laser power on the irradiation surface was 100 mW and the curing depth was 0.1 m.
A test piece conforming to JIS K7110 was prepared under the condition of 3 mm. Using the test piece thus obtained, the temperature was 23 ° C. and the relative humidity was 50%, and the JIS standard K7110 was used.
The Izod impact strength was measured according to.

Judging curing speed of 0.5 or more and Izod impact strength of 8 k
Those showing gcm / cm or more were accepted.

Measurement of average particle size of dispersed phase A test film as a cured product was obtained in the same manner as in the evaluation of elastic modulus. For the average particle size of the dispersed phase, the cured product is immersed in chloroform to dissolve only the dispersed phase, and the cured product is treated with a high-definition digital microscope (KEYENCE).
VH-6300 and VH-Z450 manufactured by Co., Ltd. are observed and measured at a magnification of 450 times, or an electron microscope (2000FX type manufactured by JEOL Ltd.) is used at a magnification of 30,000 times. It was observed and measured.

[0068]

[Table 1]

As can be seen from Table 1, Comparative Examples 1 and 2 have low impact strength because they do not form a dispersed phase.
In Comparative Examples 3 and 4, the curability is poor because the blending amount of the dispersed phase component is too large.

[0070]

According to the present invention, the coating property is good,
To provide a liquid curable resin composition which is easily and rapidly cured by ultraviolet rays or the like, has a good tensile property, heat resistance, chemical resistance, weather resistance, and forms a cured product excellent in impact resistance. You can

Continued front page    F-term (reference) 4J002 AC02W AC06W AC07W AC11W                       BB05W BB11W BC04W BG00W                       BG07X BG10W BL01W CK04X                       CK05X FD146                 4J011 AA05 PA54 PA64 PA69 PA83                       PB22 PB40 PC02 PC08                 4J027 AG04 AG13 AG14 AG23 AG24                       AG27 BA04 BA07 BA08 BA10                       BA11 BA12 CA03 CA04 CA08                       CA31 CB04 CB08 CB10 CD01                       CD08

Claims (3)

[Claims] 1. A liquid curable resin composition containing a non-curable resin, which is capable of forming a dispersed phase of the non-curable resin in a cured product of the composition. 2. The liquid curable resin composition according to claim 1, which contains a polymerizable oligomer, a polymerizable unsaturated monomer and a photopolymerization initiator. 3. The average particle size of the dispersed phase in the cured product is 0.0
The liquid curable resin composition according to claim 1, which has a content of 1 to 20 μm and a content of 1 to 50% by weight.