TWI602866B - Active energy ray-curable resin composition - Google Patents

Description

Active energy ray-hardening resin composition

The present invention relates to an active energy ray-curable resin composition and a cured product obtained thereby.

The active energy ray-curable resin composition which is provided with an acrylic resin-cured material is excellent in curability, can achieve high productivity, and has almost no use of a solvent, and has a small load on the environment. Therefore, it is used in a coating agent. Adhesives, inks, void fillers and other fields.

However, the active energy ray-curable composition has a large shrinkage upon hardening and a large residual stress in the resin, so that the tightness with respect to the substrate is deteriorated, or the coating film is too hard and brittle to be easily broken. . In order to solve this problem, a composition in which a plasticizer or an adhesive-imparting resin is blended is discussed.

In general, a plasticizer generally uses a phthalate compound such as dioctyl phthalate (DOP), but there is a problem that it oozes out from the hardened acrylic resin layer. In addition, when the adhesive resin of the petroleum resin and the rosin-based resin is blended, the acrylic resin is suitable because it has high hydrophobicity and low compatibility with the acrylic resin. The combination of grease and adhesion imparting resin is limited.

A means for solving the above problem of compatibility is proposed as a composition for blending an acrylic polymer. Japanese Laid-Open Patent Publication No. 2006-28405 discloses an active radiation curable ink composition containing an acrylic polymer as a plasticizer.

On the other hand, in WO2001/083619, a method for efficiently producing an acrylic polymer plasticizer in the absence of a solvent is disclosed in which a monomer containing a (meth)acryl fluorenyl group is 150~ Method of polymerization at 350 ° C. In addition, the applicant proposed an active energy ray-curable resin composition containing the acrylic polymer plasticizer (JP-A-2013-129799).

The acrylic polymer synthesized by the method described in WO2001/083619 has a double bond at the molecular terminal. Therefore, when the composition of Japanese Laid-Open Patent Publication No. 2013-129799, which is added with the acrylic polymer, is cured by the active energy ray, sufficient curability may not be obtained.

An object of the present invention is to provide an active energy ray-curable resin composition which is excellent in curability and can provide a cured product excellent in flexibility.

The inventors have carefully planned to solve the above problems. As a result, it was found that a polymer obtained by polymerizing a vinyl monomer at a temperature of 150 to 350 ° C to form a polymer which causes the double bond at the end of the molecule to disappear, and which is obtained by including the active energy ray-curable resin composition The cured product is excellent in flexibility and hardenability, and thus completed the present invention.

The invention is as follows.

[1] An active energy ray-curable resin composition comprising: (A) a compound containing an ethylenically unsaturated group, and (B) polymerizing a vinyl monomer at a temperature of from 150 to 350 ° C, followed by addition a polymer derived from hydrogen, and (C) a photopolymerization initiator.

[2] The active energy ray-curable resin composition according to the above [1], wherein the compound (A) is contained in an amount of 10 to 90% by mass based on the total of the compound (A) and the polymer (B), and 90 to 10% by mass of the above polymer (B).

[3] The active energy ray-curable resin composition according to the above [1], wherein the polymer (B) has a weight average molecular weight of 1,000 to 50,000.

[4] The active energy ray-curable resin composition according to the above [1], wherein the polymer (B) comprises a structural unit derived from an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms.

[5] The active energy ray-curable resin composition according to [1] above, wherein the polymer (B) has a double bond concentration of 0.20 meq/g or less.

[6] The active energy ray-curable resin composition according to [1] above, wherein the compound (A) contains a polyfunctional (meth) acrylate.

The active energy ray-curable resin composition of the present invention is excellent in curability, and can provide a cured product excellent in flexibility and a cured product excellent in adhesion to a substrate.

The active energy ray-curable resin composition of the present invention is a liquid composition, and may be any one of a composition containing an organic solvent and a composition containing no organic solvent, as will be described later.

The invention is described in detail below. In the specification of the present application, "(meth)acrylate" means acrylate and/or methacrylate, and "(meth)acryloyl group" means propylene fluorenyl group and/or methacryl fluorenyl group. .

1. A compound containing an ethylenically unsaturated group (A)

The compound (A) of the present invention is a compound having an ethylenically unsaturated group in the molecule. Examples of the ethylenically unsaturated group include a vinyl group, a vinyl ether group, a (meth) acrylonitrile group, and a (meth) acrylamide group. The number of the ethylenically unsaturated groups contained in the above compound (A) is not particularly limited, and may be one, two or three or more. Further, when two or more ethylenically unsaturated groups are contained, these ethylenically unsaturated groups may be the same or different from each other.

Various compounds can be used for the above compound (A). Specific examples thereof include (meth) acrylate (hereinafter referred to as "(meth) acrylate (a1)"); (meth) acrylamide; styrene, α-methyl benzene An aromatic vinyl compound such as ethylene or vinyl styrene; a vinyl ester compound such as vinyl acetate; N-vinylpyrrolidone, N-vinylformamide, and N-vinylcaprolactam. The active energy ray-curable resin composition of the present invention may contain only one type of compound (A) or two or more types.

The compound (A) of the present invention is preferably a (meth) acrylate (a1).

The (meth) acrylate (a1) includes a compound having one (meth) acryl fluorenyl group in the molecule (hereinafter referred to as "monofunctional (meth) acrylate)) and two molecules in the molecule. The above (meth) acrylonitrile group compound (hereinafter referred to as "polyfunctional (meth) acrylate").

Examples of the monofunctional (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and (meth)acrylic acid. 2-ethylhexyl ester, isooctyl (meth)acrylate, and alkyl (meth)acrylate such as stearyl (meth)acrylate; cyclohexyl (meth)acrylate, (meth)acrylic acid Cyclodecyl ester, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopenteneoxyethyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, An alicyclic (meth) acrylate such as isodecyl (meth) acrylate or adamantyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate a hydroxyl group-containing (meth) acrylate such as 4-hydroxybutyl (meth) acrylate; 2-methoxyethyl (meth) acrylate or methoxy (meth) acrylate Ethylene glycol ester, 2-ethylhexyl carbitol (meth) acrylate, alkoxyalkyl (meth) acrylate such as ethoxyethoxyethyl (meth)acrylate; benzene (meth)acrylate Ester, phenoxyethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate (meth)acrylic acid ester of benzyl (meth)acrylate, alkylene oxide modified product of phenol derivative, and (meth)acrylic acid aromatic ester of 2-hydroxy-3-phenoxypropyl (meth)acrylate ; (meth)acrylic acid tetrahydrofuran ester; N-(methyl) propylene oxiranyl ethyl tetrahydro phthalimide and N-(methyl) propylene oxyethyl hexahydrophthalimide Et-butylimine (meth)acrylate; glycidyl (meth)acrylate, polycaprolactone modification of (meth)acrylic acid, poly(2-hydroxyethyl)(meth)acrylate Caprolactone modification, 3-(trimethoxydecyl)propyl (meth)acrylate, 3-(triethoxydecyl)propyl (meth)acrylate, 3-(methyldi(meth)acrylate Methoxy propyl propyl ester, 3-(methyldiethoxy oxime) (meth) acrylate Yl) propyl and a (meth) acrylate and ethyl-oxazolidinone.

These monofunctional (meth) acrylates may be used alone or in combination of two or more.

Examples of the polyfunctional (meth) acrylate include 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-bis(meth)acrylate. Hexanediol ester, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate , 3-methyl-1,5-pentanediol di(meth)acrylate, 2-butyl-2-B diacrylate 1, 3-decyl glycol ester, 2-methyl-1,8-octanediol di(meth)acrylate, 2-hydroxy-1,3-bis(methyl)propenyloxypropane, 2-hydroxy-3-(methyl)propenyl propyl methacrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl tri(meth)acrylate Tetraol ester, neopentyl tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetrakis(meth)acrylate a poly(meth)acrylic acid polyol ester such as trimethylolpropane); an alkylene oxide [ethylene oxide, propylene oxide, etc.] adduct of the raw material alcohol of such poly(meth)acrylate Poly(meth) acrylate; poly(meth) acrylate of the caprolactone modification of the raw material alcohol of such poly(meth) acrylate; bis (meth) acrylate modified by isomeric cyanuric acid (meth)acrylic acid ester of methacrylate and ethylene oxide modified tris (meth) acrylate such as tris(c) methacrylate, modified poly(meth) acrylate; (meth) acrylate Allyl ester and the like.

As the polyfunctional (meth) acrylate, an oligomer can also be used, and specific examples thereof include ethyl (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate.

Further, the following polymers can also be used for the polyfunctional (meth) acrylate.

(i) After the vinyl monomer having a glycidyl group is separately polymerized, a side chain having a (meth) acrylate having a carboxyl group and a glycidyl group of the obtained vinyl polymer is reacted to have (meth)acrylic acid. Ester-based vinyl polymer.

(ii) copolymerizing a glycidyl group-containing vinyl monomer with After the other vinyl monomers are polymerized together, a vinyl polymer having a (meth) acrylate group in a side chain obtained by reacting a (meth) acrylate having a carboxyl group with a glycidyl group of the obtained vinyl copolymer is obtained.

The polyfunctional (meth) acrylate may be used singly or in combination of two or more.

The (meth) acrylate (a1) can be used by using either one of a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate or a combination of both. In the present invention, a (meth) acrylate (a1) containing a polyfunctional (meth) acrylate is preferably used, and the amount is preferably from 20 to 100 with respect to the entire (meth) acrylate (a1). The mass% is particularly preferably 50 to 100% by mass.

Examples of the (meth) acrylamides include (meth) acrylamide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-isopropyl ( N-alkyl (meth) acrylamide such as methyl) acrylamide; N,N-dimethyl(meth) acrylamide and N,N-diethyl(meth) acrylamide N,N-dialkyl(meth)acrylamide; and (meth)propenylmorpholine and the like.

The compound (A) is preferably a polyfunctional (meth) acrylate from the viewpoint of excellent impact resistance and chemical resistance of the cured product and an appropriate viscosity of the composition. In the present invention, by using the polymer (B) described later as a plasticizer, even if only a polyfunctional (meth) acrylate is used as the compound (A), the softness of the cured product and the tightness with respect to the substrate can be achieved. Sexuality is good.

When the compound (A) contains a polyfunctional (meth) acrylate, The ratio is preferably 20 to 100% by mass, and more preferably 50 to 100% by mass based on the total amount of the compound (A).

2. Polymer (B)

The polymer (B) of the present invention is a step of polymerizing a vinyl monomer by a temperature of 150 to 350 ° C and a step of adding hydrogen to the obtained polymer (hereinafter referred to as "precursor"). The polymer obtained. The active energy ray-curable composition of the present invention may contain only one type of polymer (B) or two or more types.

The vinyl monomer is not particularly limited as long as it has a vinyl bond, and examples thereof include (meth)acrylate (hereinafter referred to as "(meth)acrylate (b1)"); (methyl) An unsaturated acid such as acrylic acid; an aromatic vinyl compound such as styrene or α-methylstyrene; a vinyl cyanide compound such as acrylonitrile; a vinyl ester compound such as vinyl acetate; and the like. These vinyl monomers may be used alone or in combination of two or more. In the present invention, (meth)acrylate (b1) is preferred because it is excellent in copolymerization property in the polymerization step, mechanical properties of the cured product, weather resistance, water resistance, and the like.

Examples of the (meth) acrylate (b1) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Base) n-butyl acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, n-amyl (meth)acrylate, (meth)acrylic acid Neopentyl ester, n-hexyl (meth) acrylate, (a Base n-heptyl acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isodecyl (meth) acrylate, (methyl) Tricyclodecyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, etc. An aliphatic alkyl (meth)acrylate (alkyl (meth)acrylate); 2-methoxyethyl (meth)acrylate, dimethylamine ethyl (meth)acrylate, (A) a (meth) acrylate containing a hetero atom such as trifluoroethyl acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy (meth) acrylate Butyl ester, hydroxyalkyl (meth) acrylate, etc., such as ε-caprolactone adduct of 2-hydroxyethyl (meth)acrylate; epoxy group-containing (glycidyl) methacrylate Acrylate; 3-trimethoxydecylpropylpropyl (meth)acrylate, 3-triethoxydecylpropylpropyl (meth)acrylate, 3-tris(isopropoxy)decylpropyl (meth)acrylate Ester, 3-methyldimethoxyalkyl (meth)acrylate Ester, 3-methyldiethoxydecyl propyl (meth)acrylate, 3-methylbis(isopropoxy)decylpropyl (meth)acrylate, 3-dimethylmethyl (meth)acrylate Oxyalkyl propyl propyl ester, 3-dimethyl ethoxylated alkyl propyl (meth) acrylate, 3-dimethylisopropoxy alkyl propyl (meth) acrylate, 8-trimethoxy (meth) acrylate (meth) acrylate containing an alkoxyalkyl group such as a decyl octyl ester; phenyl (meth) acrylate, benzyl (meth) acrylate or the like.

These (meth) acrylates (b1) may be used alone or in combination of two or more.

The (meth) acrylate (b1) preferably contains an alkyl (meth) acrylate having an alkyl group, and the lower limit of the ratio is preferably 40% based on the entire (meth) acrylate (b1). The mass% is particularly preferably 60% by mass. In the alkyl (meth)acrylate having an alkyl group, the polymer (B) containing a structural unit derived from an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms imparts flexibility to the cured product. It is also excellent in water resistance and weather resistance. The ratio of the (meth)acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms contained in the vinyl monomer is preferably 40% by mass based on the total of the vinyl monomer used for the production of the precursor polymer. The above is particularly preferably 60% by mass or more. When the amount is less than 40% by mass, the glass transition temperature of the polymer (B) after the addition of hydrogen is increased, and the softness of the cured product may be insufficient.

The precursor polymer can be obtained by a polymerization method such as solution polymerization, bulk polymerization, or dispersion polymerization, but it must be polymerized at a high temperature of 150 to 350 °C. By setting the polymerization temperature to 150 ° C or higher, the amount of the polymerization initiator can be reduced, and the molecular weight of the precursor polymer can be easily controlled even without using a chain transfer agent. Further, when the cured product of the polymer (B) containing hydrogen added is formed, it is excellent in weather resistance. Further, by setting the polymerization temperature to 350 ° C or lower, the conversion ratio of the monomer to the polymer can be improved. Furthermore, the problem of coloring caused by the decomposition product can be avoided. A preferred polymerization temperature is in the range of 170 to 300 ° C, and particularly preferably in the range of 180 to 250 ° C. The reaction procedure may be any of a batch type, a semi-batch type, and a continuous polymerization, and from the viewpoint of uniformity of composition, continuous polymerization is preferred.

High-temperature continuous polymerization method can follow the Japanese special opening 57- A method generally known in the art disclosed in Japanese Patent Laid-Open No. Sho 59-207007, and the like.

For example, after the pressurizable reactor is set to a predetermined temperature under pressure, a vinyl monomer or a monomer mixture containing a vinyl monomer and a polymerization solvent used in combination as necessary may be used. The raw material is supplied to the reactor at a constant supply rate to carry out polymerization, and the reaction liquid in an amount corresponding to the amount of the raw material supplied is taken out. The raw materials may also contain a polymerization initiator as necessary.

The pressure in the reactor depends on the reaction temperature and the boiling point of the raw material used, and does not affect the polymerization reaction, as long as the reaction temperature (150 to 350 ° C) can be maintained.

The residence time of the raw materials in the reactor is preferably from 1 to 60 minutes. When the residence time is less than 1 minute, there is a concern that the monomer does not sufficiently react, and when the residence time exceeds 60 minutes, the productivity sometimes deteriorates. The preferred residence time is 2 to 40 minutes.

The reaction solution containing the precursor polymer taken out from the reactor can be used directly in the subsequent addition hydrogenation step. Further, by supplying the reaction liquid to distillation or the like, the volatile components of the unreacted vinyl monomer, the low molecular weight oligomer, the polymerization solvent, and the like are distilled off, and the polymer is supplied to the polymer after the separation. Add hydrogen to the step. The volatile component distilled from the reaction liquid may be returned to the tank or reactor containing the raw material and reused in the polymerization reaction.

Thus, a method of recovering an unreacted monomer and a polymerization solvent is a preferable method from the viewpoint of economy. When recycling, it must be in the reactor The mixing ratio of the newly supplied vinyl monomer or the like is determined in such a manner that a vinyl monomer having a preferred structure and a preferred amount of the polymerization solvent are used.

When a polymerization solvent is used for the production of the precursor polymer, a cyclic ether such as tetrahydrofuran or dioxane; an aromatic hydrocarbon compound such as benzene, toluene or xylene; and an ester such as ethyl acetate or butyl acetate may be used. A ketone such as acetone, methyl ethyl ketone or cyclohexanone; or an organic solvent such as an alcohol such as methanol, ethanol or isopropanol. These polymerization solvents can be used alone or in combination of two or more. When an organic solvent in which the (meth) acrylate copolymer is not sufficiently dissolved is used, rust is easily deposited on the inner wall of the reactor, and it is likely to cause a problem in production in the washing step or the like.

The amount of the polymerization solvent to be used is preferably 80 parts by mass or less based on 100 parts by mass of the total amount of the vinyl monomer. By having a constitution of 80 parts by mass or less, a high conversion ratio can be obtained in a short time. Especially preferably 1 to 50 parts by mass. Further, when a polymerization solvent is used, a dehydrating agent such as trimethyl orthoacetate or trimethyl orthoformate may be added.

The polymerization initiator used for obtaining the precursor polymer is not particularly limited as long as it is an initiator capable of generating a radical at a predetermined reaction temperature. Specific examples thereof include organic peroxides such as di(tertiary butyl peroxide) and di(tri-hexyl) peroxide; azobisisobutyronitrile, azobiscyclohexacarbonitrile, and azobis(2-A) Butyl nitrile), azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-amidinopropane)dihydrochloride, 4,4'-azobis (4 An azo compound such as valeric acid. The amount of the polymerization initiator to be used is preferably 0.001 to 3 parts by mass based on 100 parts by mass of the total amount of the vinyl monomer.

The polymer (B) can be obtained by subjecting the precursor polymer obtained by the above method to hydrogen addition. Addition of hydrogen can be carried out by the method previously described.

For example, after adding a homogeneous catalyst or a non-uniform catalyst to the reaction liquid containing the precursor polymer obtained by the above method, the system is formed into a hydrogen atmosphere, and the pressure is set to a normal pressure of ~10 MPa, and the temperature is heated. Addition of hydrogen to about 20 to 180 ° C and reaction for about 2 to 20 hours. Examples of the homogeneous catalyst include ruthenium complexes such as chlorotris(triphenylphosphine) ruthenium; ruthenium tris(triphenylphosphine) ruthenium, chlorohydrocarbonyltris(triphenylphosphine) ruthenium or the like; A complex; a platinum complex such as dichlorobis(triphenylphosphine)platinum; a ruthenium complex such as carbonyl bis(triphenylphosphine) ruthenium or the like. Further, examples of the non-uniform catalyst include a solid catalyst in which a transition metal such as nickel, ruthenium, rhodium, palladium or platinum is supported on carbon, ruthenium dioxide, alumina, fiber or organic colloid. When a non-uniform catalyst is used, it is preferable to remove the catalyst or the like by filtration or the like after the addition hydrogenation step, and the expensive catalyst can be reused. Further, the polymer (B) having a terminal double bond concentration which is sufficiently lowered can be obtained with high quality. The amount of the catalyst used is preferably about 10 to 1,000 ppm based on the precursor polymer when it is a homogeneous catalyst. In the case of a non-uniform catalyst, it is preferably about 1,000 to 10,000 ppm based on the precursor polymer.

Preferably, the concentration of the double bond in the precursor polymer is reduced to 0.30 meq/g or less, more preferably 0.20 meq/g or less by the addition hydrogenation step. When the polymer (B) of 0.20 meq/g or less is used, the hardenability of the composition can be further improved. The double bond concentration is particularly preferably 0.10 meq/g or less, more preferably 0.05 meq/g or less. The concentration of the double bond in the polymer (B) can be measured by ¹ H-NMR in the NMR spectrum from the signal of the double bond observed at 5 to 6.5 ppm, and observed at 3 to 4.5 ppm. The ratio of the integral value of the signal of the methylene group and the methyl group adjacent to the ester is calculated.

The weight average molecular weight (hereinafter also referred to as "Mw") of the polymer (B) of the present invention is preferably from 1,000 to 50,000, particularly preferably from 1,500 to 20,000. When the Mw is 1,000 or more, the cured product can be stably present in the system without oozing for a long period of time, and when the Mw is 50,000 or less, an appropriate viscosity can be obtained when the composition is formed, and excellent properties can be secured. Workability. The weight average molecular weight (Mw) is a polystyrene-converted value measured by gel permeation chromatography (GPC).

Further, the glass transition temperature of the polymer (B) of the present invention is preferably -80 ° C to 20 ° C, particularly preferably -80 ° C to -10 ° C. By setting the glass transition temperature to 20 ° C or lower, flexibility can be imparted. The glass transition temperature is determined by the intermediate point of the endothermic peak measured by a differential scanning calorimeter (DSC).

In the active energy ray-curable resin composition of the present invention, the mass ratio of the compound (A) to the polymer (B) is not particularly limited. The content of the polymer (B) is preferably from 10 to 90% by mass, particularly preferably from 20 to 70% by mass, based on the total of the compound (A) and the polymer (B). When it is 10% by mass or more, flexibility can be imparted to 90% by mass or less, and the strength of the cured product can be exhibited.

3. Photopolymerization initiator (C)

The active energy ray-curable resin composition of the present invention contains a photopolymerization initiator (C) for the purpose of curing by an active energy ray such as ultraviolet light or visible light.

Examples of the photopolymerization initiator (C) include an aromatic ketone compound, a diphenyl ketone compound, a mercaptophosphine oxide, a thioxanthone compound, an acridone compound, an oxime ester, and 2,4. 5-triaryl imidazole dimer, acridine derivative, and the like. The photopolymerization initiators may be used singly or in combination of two or more.

Examples of the aromatic ketone compound include benzyldimethylketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl benzophenone, and 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligomeric [2- Hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]acetone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl) )-benzyl]-phenyl}-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinepropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1 -(4-morpholin-4-yl-phenyl)-butan-1-one, 3,6-bis(2-methyl-2-morpholinepropanyl)-9-n-octylcarbazole, Methyl phenylglyoxylate, ethyl hydrazine, phenanthrenequinone, and the like.

Examples of the diphenyl ketone compound include diphenyl ketone, 2-methyl diphenyl ketone, 3-methyl diphenyl ketone, 4-methyl diphenyl ketone, and 2, 4, 6-trimethyl. Diphenyl ketone, 4-phenyl diphenyl ketone, 4-(methylphenyl thio) phenyl phenyl methane, methyl-2-diphenyl ketone, 1-[4-(4-benzene Nonylphenylsulfonyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)di Phenyl ketone, 4,4'-bis(diethylamino) Diphenyl ketone, N,N'-tetramethyl-4,4'-diaminodiphenyl ketone, N,N'-tetraethyl-4,4'-diaminodiphenyl ketone and 4 -Methoxy-4'-dimethylaminodiphenyl ketone or the like.

The mercaptophosphine oxide can be exemplified by bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide and 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. , ethyl-(2,4,6-trimethylbenzylidene)phenylphosphonate and bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl A pentylphosphine oxide or the like.

Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, and 1-chloro-4-propylthioxanthone. 3-[3,4-Dimethyl-9-oxo-9H-thioxanthone-2-yloxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothiazide Tons of ketone and so on.

Examples of the acridone compound include acridone and 10-butyl-2-chloroacridone.

Examples of the oxime esters include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzylidene decyl decyl)] and ethyl ketone 1-[9-ethyl-6 -(2-Methylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidoxime) and the like.

The 2,4,5-triaryl imidazole dimer may, for example, be 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5- Di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-phenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl Imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer and 2-(2,4-methoxyphenyl)-4,5-diphenylimidazole dimer, and the like.

Examples of the acridine derivative include 9-phenyl acridine and 1,7-bis(9,9'-acridinyl)heptane.

In the active energy ray-curable resin composition of the present invention, the content ratio of the photopolymerization initiator (C) is 100 by mass from the total of the compound (A) and the polymer (B) from the viewpoint of curability. The portion is preferably 0.01 to 10 parts by mass, particularly preferably 0.1 to 8 parts by mass. By setting the content ratio of the photopolymerization initiator (C) to 0.01 parts by mass or more, the composition can be cured by an appropriate amount of ultraviolet rays or visible light to improve productivity. In addition, when it is 10 parts by mass or less, the weather resistance and transparency of the cured product can be excellent.

4. Other ingredients

The active energy ray-curable resin composition of the present invention is required to contain the above components (A), (B), and (C), but may contain an organic solvent, a catalyst for moisture curing, a polymerization inhibitor, and Other components such as an antioxidant, a UV absorber, a light stabilizer, a leveling agent, an antifoaming agent, a surface conditioner, a tightness imparting agent, a rheology control agent, a wax, an inorganic filler, an organic filler, and the like.

4-1. Organic solvents

When the composition of the present invention contains an organic solvent, coatability can be improved. As the organic solvent, for example, the above-mentioned polymerization solvent used in the production of the precursor polymer can be used.

When the active energy ray-curable resin composition of the present invention contains an organic solvent In the case of the agent, the content ratio of the organic solvent can be appropriately set depending on the purpose, use, and the like, and the content ratio in the composition is preferably from 10 to 90% by mass, particularly preferably from 30 to 80% by mass.

4-2. Catalyst for moisture hardening

The composition of the present invention can also be used as a moisture-curing composition. In this case, it is preferred to use a catalyst for moisture curing.

As the catalyst for moisture curing, a user of a conventional moisture-curing composition can be used. Further, any compound can be used as long as it can condense an alkoxyalkyl group-containing copolymer or an alkoxyalkyl group-containing (meth) acrylate by moisture.

Specific examples of the catalyst for moisture curing include tin-based catalysts such as dibutyltin laurate, dibutyltin diacetate, and dibutyldiacetylpyruvate; tetrabutyl titanate and titanic acid; Titanate such as tetrapropyl ester; organoaluminum compound such as aluminum triacetate pyruvate, aluminum triethylacetate acetate and ethyl isopropoxide acetate; tetrazine zirconium pyruvate, tetraethyl a chelating compound such as titanium pyruvate; lead octoate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleic acid amine, cyclohexylamine, Benzylamine, diethylaminopropylamine, xylenediamine, triethylenediamine, anthracene, diphenylanthracene, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N- An amine compound such as methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicyclo(5,4,0)undecene-7 (DBU); such amine compounds a salt with a carboxylic acid or the like; a carboxylic acid; a metal carboxylate; an organic sulfonic acid; an acid phosphate; an organometallic compound containing a Group 3B or Group 4A metal; A sterol-based condensation catalyst such as an acidic catalyst or an alkaline catalyst.

When the active energy ray-curable resin composition of the present invention contains a catalyst for moisture curing, the content ratio of the catalyst for moisture curing can be used for a purpose, a purpose, or the like, or a copolymer having an alkoxyalkyl group and The type (A) or the polymer (B) of the alkoxyalkyl group (meth) acrylate or the like is appropriately set, and the content ratio in the composition is preferably 0.1 to 10% by mass. It is preferably 0.5 to 5% by mass.

4-3. Polymerization inhibitor

The polymerization inhibiting agent is preferably a phenolic antioxidant such as hydroquinone, hydroquinone monomethyl ether or 2,6-di(tributyl)-4-methylphenol. Further, a sulfur-based secondary oxidizing agent, a phosphorus-based secondary oxidizing agent, or the like may be added.

4-4. UV absorber

Examples of the ultraviolet absorber include 2-(2'-hydroxy-5-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di(tertiarybutyl)phenyl group. a benzotriazole compound such as benzotriazole or 2-(2'-hydroxy-3'-tertiarybutyl-5'-methylphenyl)benzotriazole; 2,4-bis(2, a triazine compound such as 4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-symmetric-triazine; 2,4-dihydroxydiphenyl ketone, 2-hydroxyl 4-methoxydiphenyl ketone, 2-hydroxy-4-methoxy-4'-methyldiphenyl ketone, 2,2'-dihydroxy-4-methoxydiphenyl ketone, 2 , 4,4'-trihydroxydiphenyl ketone, 2,2',4,4'-tetrahydroxydiphenyl ketone, 2,3,4,4'-tetrahydroxydiphenyl ketone, 2,3' a diphenyl ketone compound such as 4,4'-tetrahydroxydiphenyl ketone or 2,2'-dihydroxy-4,4'-dimethoxydiphenyl ketone Things.

4-5. Light stabilizer

The light stabilizer may, for example, be N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-N,N'-dimethylhydrazine hexamethylenediamine, bis ( 1,2,6,6-)pentamethyl-4-piperidinyl)-2-(3,5-di(tributyl)-4-hydroxybenzyl-2-n-butylmalonate Low molecular weight hindered amine compound such as bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; N,N'-bis(2,2,6,6- Tetramethyl-4-piperidinyl)-N,N'-dimethylhydrazine hexamethylenediamine, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)fluorene A hindered amine light stabilizer such as a high molecular weight hindered amine compound such as an acid ester.

5. Active energy ray-curable resin composition

As described above, the active energy ray-curable resin composition of the present invention contains the compound (A), the polymer (B) obtained by a specific production method, and a photopolymerization initiator (C), and may be necessary Contains other ingredients. The viscosity of the composition is not particularly limited, and the viscosity at 25 ° C measured by an E-type viscometer is preferably 200 to 20,000 mPa ‧ s. By setting the viscosity in this range, coating workability can be excellent, and smooth coating can be easily performed.

6. Method for producing active energy ray-curable resin composition

The composition of the present invention can be produced by mixing the raw material components at normal temperature or under heating using a conventionally known apparatus or the like. When heating on one side When the composition is produced, the temperature can be set by considering the volatility of each raw material component.

7. Method for forming hardened material

When the cured product is formed using the active energy ray-curable resin composition of the present invention, the method can be appropriately selected depending on the constitution of the composition and the like. For example, when the composition does not contain an organic solvent, a cured film (cured material) can be formed by directly irradiating the active energy ray after forming a coating film or the like. However, when the composition contains an organic solvent, after forming a coating film or the like, it is preferably dried or the like, and the active energy ray is irradiated in a state where the content of the organic solvent is lowered. When the cured product is formed in close contact with the adherend, the constituent material of the adherend is not particularly limited, and may be either an organic material or an inorganic material, or both.

Specific examples of the active energy ray include ultraviolet rays, electron beams, visible light, and the like, but ultraviolet rays are particularly preferred. Examples of the ultraviolet irradiation device include a high pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED. The irradiation energy can be appropriately set depending on the configuration of the composition, the type of the active energy ray, and the like. The amount of light when irradiated with ultraviolet rays is preferably 500 to 5,000 mJ/cm ² .

Since the active energy ray-curable resin composition of the present invention is excellent in curability, the amount of irradiation of the active energy ray can be reduced as compared with the conventional composition, and the cured product can be formed at low cost.

[Examples]

The invention is specifically illustrated by the following examples. In the following, "parts" means parts by mass.

1. Production of polymer (B)

The vinyl polymer (B) used for the production and evaluation of the active energy ray-curable resin composition was produced by the following Production Examples 1 to 10 (refer to Table 1).

Production Example 1 (Production of Vinyl Polymer B1)

The jacket temperature of a pressurized stirred tank reactor having a fuel jacket of 1,000 mL was maintained at 248 °C. Then, the pressure of the reactor was kept constant, and at a certain supply rate (48 g/min, residence time: 12 minutes), n-butyl acrylate (100 parts) as a monomer was used as a polymerization solvent from the raw material tank. A monomer mixture composed of isopropyl alcohol (4.2 parts) and methyl ethyl ketone (12.2 parts) and bis(tributyl) peroxide (1.0 parts) as a polymerization initiator is continuously supplied to the reactor, and The outlet continuously takes out a reaction liquid corresponding to the supply amount of the monomer mixture. Shortly after the start of the reaction, once the reaction temperature was lowered, the temperature rise due to the heat of polymerization was observed, but the internal temperature of the reactor was maintained at 239 to 241 ° C by controlling the temperature of the oil jacket. At the point of 36 minutes after the internal temperature of the reactor was stabilized, the starting point of the reaction liquid was collected, and the reaction was continued for 25 minutes from the starting point. In this production, 1.2 kg of a monomer mixture was supplied, and 1.2 kg of the reaction liquid was recovered. Then, the reaction liquid is introduced into a thin film evaporator, and the volatile component of the unreacted monomer or the like is separated and removed to obtain a polymer B1. As a result of GPC measurement of the polymer B1, the polystyrene-equivalent number average molecular weight (hereinafter also referred to as "Mn") was 1,600, and the weight average molecular weight (Mw) was 3,000, which was measured by an E-type viscometer. The viscosity at 25 ° C is 1,000 mPa ‧ s. Further, the glass transition temperature measured by DSC was -77 ° C, and the double bond concentration measured by ¹ H-NMR was 0.36 meq/g.

Production Example 2 (Production of Vinyl Polymer B2)

The jacket temperature of a pressurized stirred tank reactor having a fuel jacket of 1,000 mL was maintained at 245 °C. Then, the pressure of the reactor was kept constant, and at a certain supply rate (48 g / min, residence time: 12 minutes), starting from the raw material tank, 2-ethylhexyl acrylate (75 parts) and a monomer were used as monomers. A monomer mixture composed of methyl acrylate (25 parts), methyl ethyl ketone (4.6 parts) as a polymerization solvent, and di(tributyl) peroxide (0.77 parts) as a polymerization initiator is continuously supplied to The reactor was continuously taken out from the outlet to the reaction liquid corresponding to the supply amount of the monomer mixture. Shortly after the start of the reaction, once the reaction temperature was lowered, the temperature rise due to the heat of polymerization was observed, but the internal temperature of the reactor was maintained at 240 to 242 ° C by controlling the temperature of the oil jacket. At the point of 36 minutes after the internal temperature of the reactor was stabilized, the starting point of the reaction liquid was collected, and the reaction was continued for 25 minutes from the starting point. In this production, as a result, 1.2 kg of the monomer mixture was supplied, and 1.2 kg of the reaction liquid was recovered. Then, the reaction liquid is introduced into a thin film evaporator, and the volatile component of the unreacted monomer or the like is separated and removed to obtain a polymer B2. As a result of GPC measurement of the polymer B2, the polystyrene-converted Mn was 1,500, the Mw was 2,400, and the viscosity at 25 ° C measured by an E-type viscometer was 3,600 mPa·s. Further, the glass transition temperature measured by DSC was -64 ° C, and the double bond concentration measured by ¹ H-NMR was 0.63 meq/g.

Production Example 3 (Production of Vinyl Polymer B3)

The jacket temperature of a pressurized stirred tank reactor having a fuel jacket of 1,000 mL was maintained at 181 °C. Then, the pressure of the reactor was kept constant, and at a certain supply rate (48 g / min, residence time: 12 minutes), starting from the raw material tank, the n-butyl acrylate (45 parts), 2-2-acrylic acid as a monomer Hexyl hexyl ester (45 parts) and methyl methacrylate (10 parts), isopropanol (9 parts) and butanone (9 parts) as a polymerization solvent, and peroxide 2 (third stage) as a polymerization initiator A monomer mixture composed of butyl) (0.25 parts) was continuously supplied to the reactor, and a reaction liquid corresponding to the supply amount of the monomer mixture was continuously taken out from the outlet. Shortly after the start of the reaction, once the reaction temperature was lowered, the temperature rise due to the heat of polymerization was observed, but the internal temperature of the reactor was maintained at 183 to 185 ° C by controlling the temperature of the oil jacket. At the point of 36 minutes after the internal temperature of the reactor was stabilized, the starting point of the reaction liquid was collected, and the reaction was continued for 25 minutes from the starting point. In this production, as a result, 1.2 kg of the monomer mixture was supplied, and 1.2 kg of the reaction liquid was recovered. Then, the reaction liquid is introduced into a thin film evaporator, and the volatile component of the unreacted monomer or the like is separated and removed to obtain a polymer B3. As a result of GPC measurement of the polymer B3, the polystyrene-converted Mn was 2,500 and the Mw was 7,500, and the viscosity at 25 ° C measured by an E-type viscometer was 20,000 mPa·s. Further, the glass transition temperature measured by DSC was -57 ° C, and the double bond concentration measured by ¹ H-NMR was 0.34 meq/g.

Production Example 4 (Production of Vinyl Polymer B4)

The jacket temperature of a pressurized stirred tank reactor having a fuel jacket of 1,000 mL was maintained at 244 °C. Then, the pressure of the reactor was kept constant, and at a certain supply rate (48 g / min, residence time: 12 minutes), starting from the raw material tank, 2-ethylhexyl acrylate (77 parts) was used as a monomer. Methyl acrylate (20 parts) and 3-methyl propyleneoxytrimethoxy decane (3 parts), as a polymerization solvent butanone (13.1 parts) and methyl orthoacetate (3.8 parts), and as a polymerization initiator A monomer mixture composed of di(tertiary butyl peroxide) (1.0 part) was continuously supplied to the reactor, and a reaction liquid corresponding to the supply amount of the monomer mixture was continuously taken out from the outlet. Shortly after the start of the reaction, once the reaction temperature was lowered, the temperature rise due to the heat of polymerization was observed, but the internal temperature of the reactor was maintained at 231 to 233 ° C by controlling the temperature of the oil jacket. At the point of 36 minutes after the internal temperature of the reactor was stabilized, the starting point of the reaction liquid was collected, and the reaction was continued for 25 minutes from the starting point. In this production, as a result, 1.2 kg of the monomer mixture was supplied, and 1.2 kg of the reaction liquid was recovered. Then, the reaction liquid is introduced into a thin film evaporator, and the volatile component of the unreacted monomer or the like is separated and removed to obtain a polymer B4. As a result of GPC measurement of the polymer B4, the polystyrene-converted Mn was 1,400 and the Mw was 2,400, and the viscosity at 25 ° C measured by an E-type viscometer was 2,200 mPa·s. Further, the glass transition temperature measured by DSC was -65 ° C, and the double bond concentration measured by ¹ H-NMR was 0.56 meq/g.

Production Example 5 (Addition of hydrogen to vinyl polymer B1)

Polymer B1 (700 g) obtained in Production Example 1 and 5% palladium carbon (3.5 g) after drying were placed in a pressurized stirred tank reactor having a capacity of 1,000 mL with an oil jacket, and The atmosphere inside the reactor is formed into a vacuum. The internal temperature was then warmed to 130 ° C and pressurized with hydrogen to about 1.5 MPa. The mixture was stirred for 8 hours in this state to carry out an addition hydrogen reaction. After releasing the pressure, the diatomaceous earth "Radiolite #100" manufactured by Showa Chemical Industry Co., Ltd. was used as a filtration aid to carry out filtration to obtain a polymer B5. As a result of GPC measurement of the polymer B5, the polystyrene-converted Mn was 1,600 and the Mw was 3,000, and the viscosity at 25 ° C measured by an E-type viscometer was 1,000 mPa·s. Further, the glass transition temperature measured by DSC was -77 ° C, and the double bond concentration measured by ¹ H-NMR was below the detection limit (0.01 meq/g).

Production Example 6 (Addition of hydrogen to vinyl polymer B2)

The polymer B2 obtained in Production Example 2 was used instead of the polymer B1, the internal temperature was set to 60 ° C, the pressure of hydrogen gas was set to about 0.3 MPa, and the mixture was stirred for 4 hours to carry out an addition hydrogen reaction, and the like. The same operation as in Production Example 5 was carried out to obtain a polymer B6. As a result of GPC measurement of the polymer B6, the polystyrene-converted Mn was 1,500, the Mw was 2,400, and the viscosity at 25 ° C measured by an E-type viscometer was 3,600 mPa·s. Further, the glass transition temperature measured by DSC was -64 ° C, and the double bond concentration measured by ¹ H-NMR was 0.22 meq/g.

Production Example 7 (Addition of hydrogen to vinyl polymer B2)

The polymer B2 obtained in Production Example 2 was used instead of the polymer B1, the internal temperature was set to 100 ° C, the pressure of hydrogen gas was set to about 0.3 MPa, and the mixture was stirred for 4 hours to carry out an addition hydrogen reaction, and the like. The same operation as in Production Example 5 was carried out to obtain a polymer B7. As a result of GPC measurement of the polymer B7, the polystyrene-converted Mn was 1,500, the Mw was 2,400, and the viscosity at 25 ° C measured by an E-type viscometer was 3,600 mPa·s. Further, the glass transition temperature measured by DSC was -64 ° C, and the double bond concentration measured by ¹ H-NMR was 0.13 meq/g.

Production Example 8 (Addition of hydrogen to vinyl polymer B2)

The polymer B2 obtained in Production Example 2 was substituted for the polymer B1, the internal temperature was set to 130 ° C, the pressure of hydrogen gas was set to about 1.5 MPa, and the mixture was stirred for 8 hours to carry out an addition hydrogen reaction. The same operation as in Production Example 5 was carried out to obtain a polymer B8. As a result of GPC measurement of the polymer B8, the polystyrene-converted Mn was 1,500, the Mw was 2,400, and the viscosity at 25 ° C measured by an E-type viscometer was 3,600 mPa·s. Further, the glass transition temperature measured by DSC was -64 ° C, and the double bond concentration measured by ¹ H-NMR was below the detection limit.

Production Example 9 (Addition of hydrogen to vinyl polymer B3)

The polymer B3 obtained in Production Example 3 was substituted for the polymer B1, the internal temperature was set to 130 ° C, the pressure of hydrogen gas was set to about 1.5 MPa, and the mixture was stirred for 8 hours to carry out an addition hydrogen reaction, and the like. The same operation as in Production Example 5 was carried out to obtain a polymer B9. As a result of GPC measurement of the polymer B9, the polystyrene-converted Mn was 2,500 and the Mw was 7,500, and the viscosity at 25 ° C measured by an E-type viscometer was 20,000 mPa·s. Further, the glass transition temperature measured by DSC was -57 ° C, and the double bond concentration measured by ¹ H-NMR was below the detection limit.

Production Example 10 (Addition of hydrogen to vinyl polymer B4)

The polymer B4 obtained in Production Example 4 was substituted for the polymer B1, the internal temperature was set to 130 ° C, the pressure of hydrogen gas was set to about 1.5 MPa, and the mixture was stirred for 8 hours to carry out an addition hydrogen reaction, and the other was The same operation as in Production Example 5 was carried out to obtain a polymer B10. As a result of GPC measurement of the polymer B10, the polystyrene-converted Mn was 1,400 and the Mw was 2,400, and the viscosity at 25 ° C measured by an E-type viscometer was 2,200 mPa·s. Further, the glass transition temperature measured by DSC was -65 ° C, and the double bond concentration measured by ¹ H-NMR was below the detection limit.

2. Manufacture and evaluation of active energy ray-hardening resin composition

Examples 1 to 11 and Comparative Examples 1 to 10

The polymer (B) obtained in Production Examples 1 to 10, and the compound (A) and the photoinitiator (C) shown below were blended and uniformly mixed at the ratio of the second table and the third table. An active energy ray-curable resin composition was obtained.

‧Compound (A)

(a1) M-211B: Ethylene oxide modified diacrylate of bisphenol A (manufactured by Toagosei Co., Ltd., trade name "Aronix M-211B")

(a2) M-402: dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., trade name "Aronix M-402")

(a3) FA-513AS: Dicyclopentyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name "Fancryl FA-513AS")

‧Photopolymerization initiator (C)

(c1) Irg184: 1-hydroxy-cyclohexyl benzophenone (manufactured by BASF Corporation, trade name "Irgacure 184")

The resulting compositions were then evaluated by the evaluation methods described below. The results are shown together in Tables 2 and 3.

(1) Hardenability

The composition was applied to a glass plate so that the film thickness became 50 μm using a wet film coater. Then, the ultraviolet ray irradiation apparatus "ECS-401GX" manufactured by Eye Graphics Co., Ltd. was used to irradiate the ultraviolet ray to the coating film under the following conditions. The sclerosis was evaluated by irradiating the ultraviolet rays once, that is, touching the surface with a finger and observing the surface of the coating film, and the number of times the liquid was no longer attached to the fingers (pass times).

<Ultraviolet irradiation conditions>

Light source: 80W/cm concentrating high pressure mercury lamp

Lamp height (distance between light source and coating film): 10cm

Conveyor speed: Adjust the amount of exposure per pass to 100mJ/cm ²

(2) Breaking strength of hardened material

The composition was applied to a surface untreated polyethylene terephthalate film manufactured by Toray Co., Ltd., 300 mm wide × 300 mm long × 50 μm thick, using a wet film coater, "Lumiror 50". -T60" (hereinafter referred to as "Lumirror").

Then, the ultraviolet ray irradiation device was used to irradiate the ultraviolet ray to the coating film so that the integrated light amount became 3000 mJ/cm ² . The cured product was then peeled off from Lumirror and cut into a sample of 15 mm x 150 mm x 50 μm. The sample was subjected to a tensile test at a tensile speed of 50 mm/min using a tensile tester "Autograph AGS-J" manufactured by Shimadzu Corporation, and the breaking strength was determined.

(3) Softness of hardened material

The composition was applied to a cohesive PET film "Cosmoshine A4300" (100 μm thick) manufactured by Toyobo Co., Ltd. using a bar coater so that the film thickness was 10 μm.

Then, the ultraviolet ray irradiation device was used to irradiate the ultraviolet ray to the coating film so that the integrated light amount became 3000 mJ/cm ² . Then, it was cut into a size of 100 mm × 50 mm, and a bending resistance test was carried out in accordance with JIS K5600-5-1. The softness was evaluated by the diameter of the cylinder at the time of cracking or peeling at the time of bending.

The compositions of Examples 1 to 11 showed less hardening and showed good hardenability. In the examples other than the second embodiment, in the case of using the composition of the polymer (B) having a double bond concentration of 0.20 meq/g or less, the composition can be cured even under low irradiation conditions of four or less passes.

Further, it was confirmed that the cured product had sufficient strength and was excellent in flexibility.

On the other hand, in Comparative Examples 1 to 9 in which the composition of the polymer having a high double bond concentration was not subjected to the hydrogen addition treatment, the number of passes required for curing was large, and the hardenability was poor. Further, Comparative Example 10 is an example in which the composition of the polymer (B) was not used, and it was confirmed that the obtained cured product was insufficient in flexibility.

[Industrial Applicability]

The active energy ray-curable resin composition of the present invention has excellent curability by an active energy ray and can obtain a cured product excellent in flexibility. Therefore, various coating agents, adhesives, inks, and void fillers are used. Useful for use.

Claims (6)

An active energy ray-curable resin composition comprising: (A) a compound containing an ethylenically unsaturated group, and (B) polymerizing a vinyl monomer at a temperature of from 150 to 350 ° C, followed by addition of hydrogen The polymer, and (C) a photopolymerization initiator, wherein the polymer (B) has a double bond concentration of 0.30 meq/g or less and contains a structural unit derived from (meth) acrylate. The active energy ray-curable resin composition of claim 1, wherein the compound (A) and the mass of 90 to 10 are contained in an amount of 10 to 90% by mass based on the total of the compound (A) and the polymer (B). % of the aforementioned polymer (B). The active energy ray-curable resin composition of claim 1, wherein the polymer (B) has a weight average molecular weight of 1,000 to 50,000. The active energy ray-curable resin composition according to claim 1, wherein the (meth) acrylate has an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms. The active energy ray-curable resin composition of claim 1, wherein the polymer (B) has a double bond concentration of 0.20 meq/g or less. The active energy ray-curable resin composition of claim 1, wherein the aforementioned compound (A) comprises a polyfunctional (meth) acrylate.