JP5531482B2 - Active energy ray-curable resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a curable composition and a cured product thereof. More specifically, the present invention relates to a curable composition having good curability, excellent storage stability, and low hygroscopicity of the cured product, and the cured product thereof.

Since the photocurable composition has a characteristic that it is cured in a short time at room temperature by irradiation with an active energy ray typified by ultraviolet rays, the demand for electronic components is expanding.

One of the materials used for electronic component applications is an adhesive or a sealing material. In addition to requiring adhesive strength, these materials are required to have a low cure shrinkage during curing of the curable composition and a low hygroscopic property of the cured product in order to reduce distortion of the cured product. The Therefore, the most general radical polymerization type photocurable composition is not suitable because of its high curing shrinkage.

  In order to solve this problem, a curing technique using an ene / thiol curing reaction has been proposed. The curable composition of the ene / thiol curing system has characteristics such as small curing shrinkage, no inhibition of curing by air, and high flexibility. However, there were problems such as a unique odor derived from thiol, poor storage stability of the curable composition, and poor moisture resistance of the cured product.

  As a curable composition having excellent storage stability of the curable composition and good moisture resistance of the cured product, for example, one diene compound selected from alkadienes such as polybutadiene glycol, polymers of alkadienes and cyclic dienes A curable composition containing a thiol compound having secondary and tertiary mercapto groups such as butanediol bis (3-mercaptobutyrate) is disclosed (for example, see Patent Document 1). However, the curable composition is not well cured by irradiation with active energy rays and has insufficient wear resistance.

JP 2008-231409 A

  An object of the present invention is to provide a curable composition having good curability, excellent storage stability, and low hygroscopicity of the cured product, and a cured product thereof.

  As a result of intensive studies, the inventors of the present invention have used a condensate of a silane compound having a mercapto group as a thiol compound, so that the cured product has excellent curability, excellent storage stability, and low moisture absorption of the cured product. The present inventors have found that a functional composition can be obtained and completed the present invention.

  That is, the present invention contains at least one diene compound (A) selected from the group consisting of alkadienes, alkadiene polymers and cyclic dienes, and a condensate (B) of a silane compound having a mercapto group. An active energy ray-curable resin composition is provided.

  The present invention also provides a cured product obtained by curing the active energy ray-curable resin composition.

  The active energy ray-curable resin composition of the present invention has good curability and excellent storage stability. A cured product obtained by curing the composition has high hardness and low hygroscopicity.

  The diene compound (A) used in the present invention is at least one selected from alkadienes, alkadiene polymers and cyclic dienes, and imparts water resistance and adhesiveness to the cured product of the active energy ray-curable resin composition of the present invention. It is a component to do.

  Examples of the diene compound (A) include alkadienes such as butadiene, 2,3-dimethylbutadiene, isoprene, pentadiene, hexadiene, octadiene, and 2-chloro-1,3-butadiene; Modified alkadienes such as polybutadiene, polyisoprene, etc .; modified copolymers of alkadienes such as polybutadiene polyol modified with hydroxyl groups, vinyl groups, etc. at their ends; cyclopentadiene, dicyclopentadiene, And cyclic dienes such as cyclohexadiene and ethylidene norbornene. These can be used alone or in combination of two or more.

  Among the diene compounds (A), a diene compound having a number average molecular weight of 200 to 100,000 is preferable because an active energy ray-curable resin composition having a cured product having good strength and low viscosity can be obtained. 000 is more preferable.

  Among diene compounds (A), an active energy ray-curable resin composition having good curability and excellent storage stability can be obtained, so that polybutadiene, polybutadiene polyol, amino group and / or carboxyl group-terminated butadiene-acrylonitrile copolymer A coalescence is preferred, and polybutadiene or polybutadiene polyol is particularly preferred.

  Among the diene compounds (A), a diene compound (urethane-modified polybutadiene resin) obtained by reacting a polyisocyanate compound such as diisocyanate with a hydroxyl-terminated polybutadiene compound increases the curability and the strength of the cured coating film. To preferred.

  In particular, a diene compound obtained by reacting an isocyanate group-containing (meth) acrylate compound obtained by reacting a polyisocyanate compound such as diisocyanate with a hydroxyl group-containing (meth) acrylate compound and a polybutadiene polyol is excellent in curability, It is preferable because it becomes an active energy ray-curable resin composition from which a cured product having high hardness can be obtained.

  Further, it is obtained by reacting a compound having a (meth) acrylate group and an isocyanate group in the molecule (for example, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate) with a hydroxyl group-containing diene compound such as polybutadiene polyol. Diene compounds [polybutadiene urethane (meth) acrylate resins], isocyanate group-containing (meth) acrylate compounds obtained by reacting diisocyanate compounds with hydroxyl group-containing (meth) acrylate compounds, and hydroxyl group-containing diene systems such as polybutadiene polyol The diene compound [polybutadiene-based urethane (meth) acrylate resin] obtained by reacting with a compound is preferred because it becomes an active energy ray-curable resin composition that is excellent in curability and has a high hardness. .

  Examples of the diisocyanate compound include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene isocyanate. Examples thereof include aliphatic or alicyclic diisocyanates such as lenisocyanate. Of these, isophorone diisocyanate is preferred.

  Examples of the hydroxyl group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone or alkylene oxide adduct of each acrylate, glycerin mono ( (Meth) acrylate, glycerin di (meth) acrylate, glycidyl methacrylate-acrylic acid adduct, trimethylolpropane mono (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, ditrimethylolpropane tri (meth) acrylate, trimethylolpropane-alkylene oxide adduct-di (meth) acrylate, etc. That. Of these, hydroxyethyl (meth) acrylate is preferred.

  The isocyanate group-containing (meth) acrylate compound is, for example, a diisocyanate compound and a hydroxyl group-containing (meth) acrylate compound in a molar ratio [diisocyanate compound]: [hydroxyl group-containing (meth) acrylate compound] 1: 0.8 to 1 .2 can be obtained by reaction. The temperature at the time of making it react is 50-100 degreeC, for example, and reaction time is 3 to 8 hours, for example. At this time, a urethanization catalyst may be used.

  As the reaction ratio of the isocyanate group-containing (meth) acrylate compound and the polybutadiene polyol when the isocyanate group-containing (meth) acrylate compound is reacted with the polybutadiene polyol, the isocyanate group (NCO) in the isocyanate group-containing (meth) acrylate compound is used. The ratio of the hydroxyl group (OH) in the polybutadiene polyol [(OH) / (NCO)] may be 1.0 to 1.2. The temperature at the time of making it react is 50-100 degreeC, for example, and reaction time is 3 to 10 hours, for example. At this time, a urethanization catalyst may be used.

  Further, among the diene compounds (A), the diene compound obtained by reacting a carboxyl group-containing (meth) acrylate compound and a polybutadiene polyol has an excellent curability and a cured product with high hardness is obtained. Since it becomes a resin composition, it is preferable.

  Examples of the carboxyl group-containing (meth) acrylate compound include (meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl. Examples include hexahydrophthalic acid and unsaturated monocarboxylic acids having ester bonds such as modified lactones thereof; maleic acid and the like. These may be used alone or in combination of two or more.

  As a reaction ratio of the carboxyl group-containing (meth) acrylate compound and the polybutadiene polyol when the carboxyl group-containing (meth) acrylate compound and the polybutadiene polyol are reacted, for example, the carboxyl group ( The ratio (COOH) to the hydroxyl group (OH) in the polybutadiene polyol [(OH) / (COOH)] may be set to a ratio of 1.0 to 1.2. The temperature at the time of making it react is 40-150 degreeC under pressure, for example.

  It is also possible to use a (meth) acrylate-modified butadiene-acrylonitrile copolymer obtained by a reaction between a carboxyl group-terminated butadiene-acrylonitrile copolymer and glycidyl (meth) acrylate.

  Furthermore, a copolymer of the carboxyl group-containing (meth) acrylate compound, a carboxyl group-terminated butadiene-acrylonitrile copolymer, and an epoxy compound having one or more epoxy groups in the molecule can also be used.

  The condensate (B) used in the present invention is a condensate of a silane compound having a mercapto group. As the silane compound having a mercapto group, for example, a compound represented by the following structural formula can be preferably used.

(In the formula, R ₁ represents an alkylene group having 1 to 10 carbon atoms. R ₂ and R ₃ each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. A and b are 1 to 3, c) Represents an integer of 0 to 2 and a + b + c = 4.)

  Examples of the compound represented by the structural formula include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxy. Silane etc. are mentioned. These may be used alone or in combination of two or more. As the silane compound having a mercapto group, 3-mercaptopropylmethyldimethoxysilane is preferable because the alkoxyl group does not become three-dimensional by condensation and the condensation step is easy.

  In the condensate (B) used in the present invention, for example, water is added to a silane compound having a mercapto group, and alkoxy groups which are hydrolyzable groups hydrolyze with each other, and at the same time or later, a condensation reaction (hydrolytic condensation) is performed. It can be obtained by doing.

In preparing the condensate (B) used in the present invention, the amount of water used for hydrolysis is 0.5 mol or more with respect to 1 mol of the hydrolyzable group of the silane compound having a mercapto group. Is preferably in the range of 0.8 to 2 moles.

  Here, a catalyst may be used for the hydrolysis condensation. When the catalyst is used, any of various known and commonly used catalysts can be used. You may use together.

  Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate, and acetic acid;

  Inorganic bases such as sodium hydroxide or potassium hydroxide; titanates such as tetraisopropyl titanate or tetrabutyl titanate; tin carboxylates such as dibutyltin dilaurate or tin octylate;

Metal carboxylates such as naphthenate or octylate of metals such as iron, cobalt, manganese or zinc; various aluminum compounds such as aluminum trisacetylacetonate;

1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,4-diazabicyclo [2.2.2] Octane (DABCO), tri-n-butylamine, butylamine, octylamine, dimethylbenzylamine,

Amine compounds such as triethylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole or 1,4-diethylimidazole;

Tetramethylammonium salt, tetrabutylammonium salt, trimethyl (2-hydroxylpropyl) ammonium salt, cyclohexyltrimethylammonium salt, tetrakis (hydroxylmethyl) ammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt or o-trifluoromethyl And quaternary ammonium salts such as phenyltrimethylammonium salt.

  The amount of the catalyst used is preferably in the range of 0.001 to 10% by weight, more preferably in the range of 0.005 to 5% by weight, based on the silane compound subjected to the hydrolysis condensation reaction. A range of 01 to 1% by weight is more preferable.

  The reaction temperature for hydrolysis condensation is usually about 0 ° C to 150 ° C, preferably 20 ° C to 100 ° C. As the pressure of the hydrolysis reaction, it can be carried out under any conditions of normal pressure and increased or reduced pressure.

  Alcohol and water are produced as by-products of the hydrolysis reaction, but can be removed out of the system by means such as distillation. If there is no problem, they may be left in the system as they are. .

  In addition, an organic solvent may or may not be used for the hydrolysis condensation reaction.

  In the case of using an organic solvent, any of publicly known organic solvents can be used. Examples of the organic solvent include water-insoluble organic solvents such as aromatic organic solvents such as toluene and xylene, and ester solvents such as ethyl acetate and butyl acetate;

Alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol; ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone ;

Ethylene glycol solvents such as ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, cellosolve acetate; methyl carbitol, ethyl carbitol, butyl carbitol, etc. Diethylene glycol solvent;

Propylene glycol solvents such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether; dipropylene glycol monomethyl ether, dipropylene Di- or tripropylene glycol-based solvents such as glycol mono-n-butyl ether and tripropylene glycol mono-n-butyl ether;

Examples thereof include water-soluble organic solvents having good solubility in water, such as tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, and sulfolane.

  When obtaining the condensate (B) used by this invention, you may use silane compounds other than the silane compound which has a mercapto group in the range which does not impair the effect of this invention. Examples of such silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyl. Triethoxysilane, 3-anilinopropyltrimethoxysilane, 3-anilinopropyltriethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminopropyltriethoxysilane, 3-diethylaminopropyltrimethoxysilane, 3- Diethylaminopropyltriethoxysilane, 3-dipropylaminopropyltrimethoxysilane, 3-dipropylaminopropyltriethoxysilane, 3-diisopropylaminopropyltrimethoxysilane, 3-diisopropylamino Amino group-containing monoorganotrialkoxysilanes such as propyltriethoxysilane, 3-dibutylaminopropyltrimethoxysilane, 3-dibutylaminopropyltriethoxysilane;

3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, 3-anilino Propylmethyldimethoxysilane, 3-anilinopropylmethyldiethoxysilane, 3-dimethylaminopropylmethyldimethoxysilane, 3-dimethylaminopropylmethyldiethoxysilane, 3-diethylaminopropylmethyldimethoxysilane, 3-diethylaminopropylmethyldiethoxysilane 3-dipropylaminopropylmethyldimethoxysilane, 3-dipropylaminopropylmethyldiethoxysilane, 3-diisopropylaminopropylmethyldimethoxysilane, 3-diisopropyl Amino group-containing diorganodialkoxysilanes such as propylaminopropylmethyldiethoxysilane, 3-dibutylaminopropylmethyldimethoxysilane, 3-dibutylaminopropylmethyldiethoxysilane;

  3-aminopropyldimethylmonomethoxysilane, 3-aminopropyldimethylmonoethoxysilane, γ- (2-aminoethyl) aminopropyldimethylmonomethoxysilane, γ- (2-aminoethyl) aminopropyldimethylmonoethoxysilane, 3- Anilinopropyldimethylmonomethoxysilane, 3-anilinopropyldimethylmonoethoxysilane, 3-dimethylaminopropyldimethylmonomethoxysilane, 3-dimethylaminopropyldimethylmonoethoxysilane, 3-diethylaminopropyldimethylmonomethoxysilane, 3-diethylamino Propyldimethylmonoethoxysilane, 3-dipropylaminopropyldimethylmonomethoxysilane, 3-dipropylaminopropyldimethylmonoethoxysilane, 3-diisopropyla Amino group-containing triorganomonoalkoxysilanes such as minopropyldimethylmonomethoxysilane, 3-diisopropylaminopropyldimethylmonoethoxysilane, 3-dibutylaminopropyldimethylmonomethoxysilane, 3-dibutylaminopropyldimethylmonoethoxysilane;

Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-butoxysilane;

  Methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-butoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, vinyltris (2 -Methoxyethoxy) silane, allyltrimethoxysilane, 2-trimethoxysilylethyl vinyl ether, 2-triethoxysilylethyl vinyl ether, 3-trimethoxysilylpropyl vinyl ether , 3-triethoxysilylpropyl vinyl ether, 3- (meth) acryloyloxy propyl trimethoxy silane, 3- (meth) acryloyl mono organotrialkoxysilane such as trimethoxy silane;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-butyldimethoxysilane, Di-n-butyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-butoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, vinylmethyldimethoxysilane, 2- (methyldimethoxysilyl) ethyl Diorganodialkoxysilanes such as vinyl ether, 3- (methyldimethoxysilyl) propyl vinyl ether, 3- (meth) acryloyloxypropylmethyldimethoxysilane;

Tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3- (meth) acryloyloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methylphenyl Chlorosilanes such as dichlorosilane, vinylmethyldichlorosilane, 3- (meth) acryloyloxypropylmethyldichlorosilane;

Acetoxysilanes such as tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane or diphenyldiacetoxysilane;

And monofunctional silicon compounds such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, trimethylchlorosilane, triethylchlorosilane, and triphenylchlorosilane.

  As the condensate (B) used in the present invention, a condensate having a number average molecular weight of 200 to 2,000 is preferable because an active energy ray-curable resin composition having a low viscosity can be obtained.

  The content of the diene compound (A) and the condensate (B) in the active energy ray-curable resin composition of the present invention is the weight ratio of the diene compound (A) and the condensate (B) [(A) / (B)] = 60/40 to 80/20 is preferable, and 65/35 to 75/25 is more preferable.

  The content ratio of the diene compound (A) and the condensate (B) in the active energy ray-curable resin composition of the present invention is [total number of thiol groups contained in the condensate (B)] / [diene compound]. The total number of carbon-carbon double bonds contained in (A)] is preferably in the range of 0.01 to 2.0, and the ratio of 0.01 to 1.0 is in terms of curability and physical properties. Preferably, 0.1 to 0.8 is more preferable.

  The active energy ray-curable resin composition of the present invention includes a compound having an unsaturated double bond other than the diene compound (A) and a thiol compound other than the condensate (B) within a range not impairing the effects of the present invention. It can be included.

  Examples of the compound having an unsaturated double bond other than the diene compound (A) include allyl alcohol derivatives, vinyl ethers, (meth) acrylates, (meth) acrylamides, olefins, styrenes, and other vinyl monomers. A monomer is mentioned.

  Examples of the allyl alcohol derivatives include triallyl isocyanurate, triallyl cyanurate, diallyl maleate, diallyl adipate, diallyl phthalate, triallyl trimellitate, tetraallyl pyromellitate, glyceryl diallyl ether, trimethylolpropane diallyl ether. , Pentaerythritol, diallyl ether and the like.

  Furthermore, as allyl alcohol derivatives, for example, urethane (meth) allyl ethers obtained by reacting allyl alcohol with at least one organic diisocyanate compound, alkane diol, polyether diol, polybutadiene diol, polyester diol, polycarbonate diol, amide diol. Urethane (meth) allyl ethers in which allyl alcohol is reacted with an isocyanate group of a urethane prepolymer obtained by adding an organic diisocyanate compound to the hydroxyl group of at least one alcohol such as a spiroglycol compound may also be used. it can.

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy vinyl ether, 2-ethylhexyl vinyl ether, methoxyethyl vinyl ether, cyclohexyl vinyl ether, and chloroethyl vinyl ether.

  Examples of the (meth) acrylates include monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional (meth) acrylate, tetrafunctional or higher (meth) acrylate, and other (meth) acrylates. Is mentioned.

  Examples of the monofunctional (meth) acrylate include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, and isodecyl (meth). Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (Meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl ( (Meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4- Butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate Rate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilyl Rupropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide Monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2- (meth) acryloyloxysuccinic acid, 2- ( (Meth) acryloyloxyhexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene oxide modified phenol (meth) Examples include acrylate, ethylene oxide-modified cresol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, propylene oxide-modified nonylphenol (meth) acrylate, and ethylene oxide-modified-2-ethylhexyl (meth) acrylate.

  Examples of the bifunctional (meth) acrylate include 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 2,4- Dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate , Ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A (Meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butylpropane Examples include diol di (meth) acrylate, 1,9-nonane di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and tricyclodecane di (meth) acrylate.

  Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, and pentaerythritol tri (meth). Acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri (( (Meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meta) Acrylate, propoxylated trimethylolpropane tri (meth) acrylate and ethoxylated glycerol triacrylate, and the like.

  Examples of the tetrafunctional or higher functional (meth) acrylate include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, and ethoxy. Pentaerythritol tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) Examples include acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  Examples of the other (meth) acrylates include bisphenol-type epoxy resins obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, or hydrogenated products thereof with epichlorohydrin; A polyepoxy resin such as an alkanediol-based polyepoxy resin obtained by a condensation reaction of an alkanediol such as (repeating unit n = 2 to 15) or polybutylene glycol (repeating unit n = 2 to 15) and epichlorohydrin; Epoxy poly (meth) acrylates reacted with acrylic acid; at least one organic diisocyanate compound having at least one (meth) acryloyloxy group and one hydroxy group in the molecule Urethane (meth) acrylates obtained by reacting at least one kind of silyl group-containing (meth) acrylate; at least one kind of alkanediol, polyether diol, polybutadiene diol, polyester diol, polycarbonate diol, amide diol, spiroglycol compound, etc. Hydroxyl group-containing (meth) acrylate having one (meth) acryloyloxy group and one hydroxy group in the molecule of the isocyanate group of a urethane prepolymer obtained by adding an organic diisocyanate compound to the hydroxyl group of an alcohol And polybasic acids such as phthalic acid, succinic acid, hexahydrophthalic acid, tetrahydrophthalic acid, terephthalic acid, azelaic acid, adipic acid, ethylene glycol, hex Njioru, polyethylene glycol, polytetramethylene glycol, trimethylolethane, polyhydric alcohol and (meth) polyester obtained by the reaction of acrylic acid or its derivative (meth) acrylates such as trimethylolpropane.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (Meth) acrylamide and (meth) acryloylmorpholine are mentioned.

  Examples of the olefins include ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, and vinylidene chloride.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, and vinyl benzoic acid methyl ester. 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene , 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allylstyrene, isopropenylstyrene, butenylstyrene, octenyl Styrene, 4-t-butoxycarbonyl styrene, and 4-methoxystyrene and 4-t-butoxystyrene.

  Examples of the other vinyl monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, and methyl vinyl. Ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, N-vinyl pyrrolidone, vinyl formamide, vinylidene chloride, vinylidene cyanide, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl Phosphate, dibutyl-2-acryloyloxyethyl phosphate, dioctyl-2-methacryloyloxyethyl phosphate, vinyl acetate, vinyl benzoate and N- It includes nil carbazole.

  Examples of the thiol compound other than the condensate (B) include ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), and octanediol. Bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2- Mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentae Sri Tall tetrakis (2-mercaptopropionate), ethylene glycol bis (3-mercapto isobutyrate),

Propylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), penta Erythritol tetrakis (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), ethylene glycol bis (4-me Mercapto valerate), propylene glycol bis (4-mercapto iso valerate), butanediol bis (4-mercapto valerate), octanediol bis (4-mercapto valerate),

Trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), butanediol bis (3 -Mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), 2,5-hexanedithiol, 2,9 -Decanedithiol, 1,4-bis (1-mercaptoethyl) benzene, phthalic acid di (1-mercaptoethyl ester), phthalic acid di (2-mercaptopropyl ester), phthalic acid di (3-mercaptobutyl ester) Le) and phthalate (3-mercapto isobutyl ester),

1,4-butanediol bisthioglycolate, ethylene glycol bismercaptoglycolate, propylene glycol bismercaptoglycolate, butanediol bismercaptoglycolate, octanediol bismercaptoglycolate, trimethylolpropane trismercaptoglycolate, pentaerythritol tetrakis Mercaptoglycolate, ethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), butanediol bis (3-mercaptopropionate), octanediol bis (3-mercaptopropionate) ),

Trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), ethylene glycol bis (4-mercaptobutyrate), propylene glycol bis (4-mercaptobutyrate), butanediol bis (4-mercaptobutyrate), octanediol bis (4-mercaptobutyrate), trimethylolpropane tris (4-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptobutyrate), ethylene glycol bis (6-mercaptobutyrate) Rate), propylene glycol bis (6-mercaptovalerate),

Butanediol bis (6-mercaptovalerate), octanediol bis (6-mercaptovalerate), trimethylolpropane tris (6-mercaptovalerate), pentaerythritol tetrakis (6-mercaptovalerate), 1,6-hexane Dithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 4,4′-bis (mercaptomethyl) phenyl sulfide, 2,4′-bis (mercaptomethyl) phenyl sulfide, 2,4,4′-tri (Mercaptomethyl) phenyl sulfide, 2,2 ′, 4,4′-tetra (mercaptomethyl) phenyl sulfide,

4,4′-bis (4-mercapto-2-thiabutyl) phenyl sulfide, 2,4′-bis (4-mercapto-2-thiabutyl) phenyl sulfide, 2,4,4′-tri (4-mercapto-2) -Thiabutyl) phenyl sulfide, 2,2 ', 4,4'-tetra (4-mercapto-2-thiabutyl) phenyl sulfide, 4,4'-bis (7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 2 , 4′-bis (7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 2,4,4′-tri (7-mercapto-2,5-dithiaheptyl) phenyl sulfide,

2,2 ′, 4,4′-tetra (7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 4-mercaptomethyl-4 ′-(4-mercapto-2-thiabutyl) phenyl sulfide, 2-mercaptomethyl- 4 '-(4-mercapto-2-thiabutyl) phenyl sulfide, 4-mercaptomethyl-2'-(4-mercapto-2-thiabutyl) phenyl sulfide, 4- (4-mercapto-2-thiabutyl) -4'- (7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 2- (4-mercapto-2-thiabutyl) -4 ′-(7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 4- (4-mercapto- 2-thiabutyl) -2 ′-(7-mercapto-2,5-dithiaheptyl) phenyl sulfide,

4-mercaptomethyl-4 ′-(7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 2-mercaptomethyl-4 ′-(7-mercapto-2,5-dithiaheptyl) phenyl sulfide, 4-mercaptomethyl-2 '-(7-mercapto-2,5-dithiaheptyl) phenyl sulfide, bis (2-mercaptoethyl) sulfide, bis (3-mercaptopropyl) sulfide, bis (4-mercaptobutyl) sulfide, bis (8-mercaptooctyl) Sulfide, 1,2-benzenedithiol, 1,4-benzenedithiol, 4-methyl-1,2-benzenedithiol,

4-butyl-1,2-benzenedithiol, 4-chloro-1,2-benzenedithiol, tetrakis- (7-mercapto-2,5-dithiaheptyl) methane, 2,4,6-trimercapto-1, 3,5-triazine, 2,4-dimercapto-6- (2-mercaptoethylthio) -1,3,5-triazine, 2,6-dimercapto-4- (2-mercaptoethylthio) -1,3 5-triazine, 4,6-dimercapto-2- (2-mercaptoethylthio) -1,3,5-triazine, 2,4,6-tri (2-mercaptoethylthio) -1,3,5-triazine 2,4-di (2-mercaptoethylthio) -6-mercapto-1,3,5-triazine,

2,6-di (2-mercaptoethylthio) -4-mercapto-1,3,5-triazine, 4,6-di (2-mercaptoethylthio) -2-mercapto-1,3,5-triazine, 2,4,6-tri (5-mercapto-3-thiapentathio) -1,3,5-triazine, 2,4-di (5-mercapto-3-thiapentathio) -6-mercapto-1,3,5- Triazine, 2,6-di (5-mercapto-3-thiapentathio) -4-mercapto-1,3,5-triazine, 4,6-di (5-mercapto-3-thiapentathio) -2-mercapto-1, 3,5-triazine, 2,4-di (5-mercapto-3-thiapentathio) -6- (2-mercaptoethylthio) -1,3,5-triazine, 2,6-di (5-mercapto-3) -Thiapentathio) 4- (2-mercaptoethyl thio) -1,3,5-triazine,

4,6-di (5-mercapto-3-thiapentathio) -2- (2-mercaptoethylthio) -1,3,5-triazine, 4- (5-mercapto-3-thiapentathio) -2,6-dimercapto -1,3,5-triazine, 2-mercapto-4- (5-mercapto-3-thiapentathio) -6- (2-mercaptoethylthio) -1,3,5-triazine, 2,4,6-tri (8-mercapto-3,6-thiapentathio) -1,3,5-triazine, 2,4,6-tri (11-mercapto-3,6,9-trithiaundecathio) -1,3,5- Triazine, 2,4,6-tri (14-mercapto-3,6,9,12-tetrathiatetradecathio) -1,3,5-triazine,

2- (5-mercapto-3-thiapentathio) -4,6-di (8-mercapto-3,6-dithiaoctathio) -1,3,5-triazine, 2,4-di (5-mercapto-3-thiapentathio) ) -6- (8-mercapto-3,6-dithiaoctathio) -1,3,5-triazine, 2- (2-mercaptoethylthio) -4- (5-mercapto-3-thiapentathio) -6- (8 -Mercapto-3,6-dithiaoctathio) -1,3,5-triazine, 4,6-di (11-mercapto-3,6,9-trithiaundecathio) -2- (5-mercapto-3-thiapentathio ) -1,3,5-triazine,

2- (5-mercapto-3-thiapentathio) -4- (8-mercapto-3,6-dithiaoctathio) -6- (11-mercapto-3,6,9-trithiaundecathio) -1,3,5 Triazine, 2- (2-mercaptoethylthio) -4- (5-mercapto-3-thiapentathio) -6- (11-mercapto-3,6,9-trithiaundecathio) -1,3,5- Triazine, 2,4-di (5-mercapto-3-thiapentathio) -6- (11-mercapto-3,6,9-trithiaundecathio) -1,3,5-triazine, 2,4-di ( 5-mercapto-3-thiapentathio) -6- (14-mercapto-3,6,9,12-tetrathiatetradecathio) -1,3,5-triazine,

2- (5-mercapto-3-thiapentathio) -4- (8-mercapto-3,6-dithiaoctathio) -6- (14-mercapto-3,6,9,12-tetrathiatetradecathio) -1, 3,5-triazine, 2- (5-mercapto-3-thiapentathio) -4- (11-mercapto-3,6,9-trithiaundecathio) -6- (14-mercapto-3,6,9, 12-tetrathiatetradecathio) -1,3,5-triazine and 4,6-di (14-mercapto-3,6,9,12-tetrathiatetradecathio) -2- (5-mercapto-3) -Thiapentathio) -1,3,5-triazine.

  Furthermore, a photopolymerization initiator, an inorganic filler, a polymerization inhibitor and the like can be added to the active energy ray-curable resin composition of the present invention as necessary.

  Examples of the initial photopolymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophene, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2- Ethyl anthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ether, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butanone -1, diethyl thioxanthone,

Isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Oxide, methylbenzoylformate, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-benzyl-2-dimethyl Examples include amino-4-morpholinobutyrophenone and 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) -butan-1-one.

  Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morphol At least one selected from linopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and methylbenzoylformate has curability. It is preferable because it becomes better.

  The amount of the photopolymerization initiator is such that the curability of the active energy ray-curable resin composition of the present invention and the mechanical strength of the cured product obtained by curing the composition are improved, so that the diene compound (A) And 30 to 30 parts by mass, more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the condensate (B) component.

  Examples of the inorganic filler include metal oxides such as silica, alumina, and titanium oxide in terms of shape stability, heat resistance, flame retardancy, insulation, etc. of the cured product; and silane coupling of these metal oxides. Surface-treated metal oxides coated with an agent, etc .; hydroxides such as aluminum hydroxide, magnesium hydroxide and potassium hydroxide, and complex oxides thereof are preferred.

  In order to improve conductivity, the inorganic filler includes metal particles such as gold, silver, copper, nickel and alloys thereof, conductive particles such as carbon, carbon nanotube, carbon nanohorn, and fullerene, and glass, ceramic, and plastic. Particles obtained by coating the surface of the nucleus such as metal oxide with metal or ITO are preferable. The conductive particles preferably have an aspect ratio of 5 or more in terms of conductivity. The aspect ratio is determined by (major axis) / (minor axis).

  As the particle diameter of the inorganic filler, an area average particle diameter of 1 μm or less is optically preferable.

  The compounding quantity of an inorganic filler can be adjusted according to the use for which this composition is used, the required mechanical strength, fluidity, etc.

  Examples of the polymerization inhibitor include nitroso polymerization inhibitors such as nitrosophenylhydroxylamine ammonium salt, quinones such as hydroquinone, hydroquinone monomethyl ether and benzoquinone, N, N-diphenylpicrylhydrazyl (DPPH), and triphenyl. Examples thereof include radical scavengers such as methyl and benzotriazole antioxidants. These can be used alone or in combination of two or more.

  Further, the active energy ray-curable composition of the present invention includes addition of a plasticizer, a rheology modifier, a surface modifier, an ultraviolet absorber, a light stabilizer, an antioxidant, a flame retardant, a release agent, an organic filler, and the like. If necessary, the agent can be appropriately blended using a known means.

  The active energy ray-curable resin composition of the present invention can be used as a coating material for coating various films and molded products. Moreover, the film | membrane obtained by hardening | curing the active energy ray hardening-type resin composition of this invention can also be used as a film product.

  Furthermore, the active energy ray-curable resin composition of the present invention is suitable for lens molding and fine molding for optical members such as Fresnel lenses, lenticular lenses, light guide plates, light diffusion plates, and prism sheets.

  Moreover, the active energy ray-curable resin composition of the present invention can be used for various uses such as adhesives, electronic parts, semiconductor sealants, sealants, paste agents, potting agents, etc. in addition to the above uses.

  Examples of the base material when the active energy ray-curable resin composition of the present invention is used as a coating material for the base material include cellulose resin, polyester resin, methacrylic resin, polycarbonate resin, polystyrene resin, crystalline polyolefin resin, Examples thereof include plastic base materials such as crystalline polyolefin resin, polyether sulfone resin, acrylonitrile-styrene copolymer resin, polyamide resin, polyarylate resin, and polymethacrylimide resin, and glass plates. Moreover, what provided the handle | pattern and the easily bonding layer on the base-material surface can also be used.

  The coating method when using the active energy ray-curable resin composition of the present invention as a coating material includes a bar coater coating method, a Mayer bar coating method, an air knife coating method, a gravure coating method, a reverse gravure coating method, and a micro gravure coating. Examples thereof include known coating methods such as coating, brush coating, spray coating, shower flow coating, dip coating, curtain coating, offset printing, flexographic printing, screen printing, and potting.

  When the active energy ray-curable resin composition of the present invention is used as a coating material, the composition can be diluted with an organic solvent in order to adjust the viscosity of the composition according to the coating method.

  Examples of the organic solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, cyclohexyl rule, diacetone alcohol; methyl cellosolve, cellosolve, butyl cellosolve, methyl Ether solvents such as carbitol, carbitol, butyl carbitol, diethyl carbitol, propylene glycol monomethyl ether; SWAZOL 1000 (trade name, manufactured by Maruzen Petrochemical Co., Ltd.), SUPERSOL 100 (trade name, Shin Nippon Petrochemical) Co., Ltd.), Supersol 150 (trade name, manufactured by Nippon Petrochemical Co., Ltd.), aromatic solvents such as benzene, toluene and xylene; cyclic hydrocarbon solvents such as cyclohexane; acetone, Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ketone solvents and ethyl acetate and cyclohexanone, n- butyl acetate, isobutyl acetate, n- amyl acetate, include acetate-based solvents such as propylene glycol acetate. These organic solvents can be used alone or in combination of two or more.

  The content of the organic solvent is preferably 30 to 100% by mass of the final composition when the hardened component in the composition is applied, from the viewpoint of coating workability. In addition, when spraying the composition, the Ford Cup No. is usually used. It is preferable to add an organic solvent using a 4 viscometer so that the viscosity is about 15 to 60 seconds at 20 ° C.

  The cured product of the present invention is obtained by curing the active energy ray-curable resin composition of the present invention.

  Examples of the active energy rays irradiated when obtaining the cured product of the present invention include α rays, β rays, γ rays, ultraviolet rays, and the like, and ultraviolet rays are preferable from the viewpoint of versatility.

  Examples of the ultraviolet ray generation source include commonly used ultraviolet lamps from the viewpoint of practicality and economy. For example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, and a magnetron. There may be mentioned an electrodeless UV lamp using

  When obtaining the main cured product, when using active energy rays, the atmosphere for curing may be either air or an inert gas such as nitrogen or argon, but it is cured in an air atmosphere in terms of practicality and economy. It is preferable to make it.

The number average molecular weight of the diene compound (A) used in the present invention and the condensate (B) of a silane compound having a mercapto group was measured according to the following conditions.
Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Guard column H _XL- H manufactured by Tosoh Corporation
+ Tosoh Corporation TSKgel G5000H _XL
+ Tosoh Corporation TSKgel G4000H _XL
+ Tosoh Corporation TSKgel G3000H _XL
+ Tosoh Corporation TSKgel G2000H _XL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate 1.0 ml / min Standard; polystyrene sample; 0.4% by weight tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, all parts and “%” are “% by mass” unless otherwise specified.

Synthesis Example 1 [Preparation of Diene Compound (A)]
Dry air was blown into a flask having a stirring bar, a temperature sensor, a gas introduction tube and a condenser, and then 67.2 g of isophorone diisocyanate and 0.01 g of methoquinone were added to the flask, and the temperature was raised to 40 ° C. while stirring. Next, after 35.3 g of 2-hydroxyethyl acrylate was added for 3 hours, the urethane acrylate having one acryloyl group and one isocyanate group in the molecule was further maintained at 80 ° C. for 6 hours [Gardner viscosity (25 ° C.): Z ₂ -Z _3, Gardner color: 1 or less, to obtain a NCO% = 12.3%] 102.5 g. Furthermore, after cooling the temperature in the flask to 60 ° C., 0.1 g of octyltin was added, and polybutadiene glycol (manufactured by Nippon Soda Co., Ltd., trade name: NISSO PB G-2000, number average molecular weight 2100, hydroxyl value 52.8). 325.1 g was added over 3 hours, held at 80 ° C. for 8 hours, 106.9 g of butyl acetate was added, and a urethane acrylate solution having two acryloyl groups [Gardner color: 1 or less, nonvolatile content = 80.8% ] Was obtained. Hereinafter, this is abbreviated as a diene compound (A1).

Synthesis Example 2 [Preparation of condensate (B)]
A flask having a stir bar, temperature sensor, and rectifying tube was charged with 90.2 g of 3-mercaptopropylmethyldimethoxysilane as a thiol group-containing alkoxysilane compound, and 70 ° C. while stirring by allowing dry nitrogen to flow from the top of 20 ml / min. The temperature was raised in 2 hours. Subsequently, 18.0 g of ion-exchanged water and 0.03 g of isopropyl acid phosphate were added, and a hydrolysis reaction was further performed at 80 ° C. for 5 hours. Methanol and water obtained by the reaction were collected while trapped with dry ice to obtain a total of 35.4 g of methanol and water. Further, 73.2 g of a transparent colorless resinous liquid was obtained in the flask. This is abbreviated as condensate (B1). The number average molecular weight of the condensate (B1) by gel permeation chromatography (GPC) was 436.

Examples 1-8 and Comparative Examples 1-4
A diene compound (A), a condensate (B), and a photoinitiator are blended in the formulations shown in Tables 1 and 2, and the active energy ray-curable resin compositions 1 to 8 of the present invention and the comparative control activity Energy ray curable resin compositions 1 ′ to 4 ′ were prepared. The storage stability of these compositions, the curability of these compositions, the abrasion resistance, the coating film refractive index, the water absorption rate and the gel fraction of the cured products of the compositions were evaluated. The evaluation method is shown below. Also. The evaluation results are shown in Tables 3 and 4.

<Method for evaluating storage stability of composition>
The viscosity immediately after the preparation of the active energy ray-curable resin compositions 1 to 8 of the present invention and the comparative active energy ray-curable resin compositions 1 ′ to 4 ′ and the viscosity after standing at 20 ° C. for 7 days are 25 It measured using the E-type viscosity meter (the Toki Sangyo Co., Ltd. make, RE-800) in the atmosphere of ° C, and the storage stability was evaluated according to the following criteria.
○: Viscosity change rate is less than 5%.
X: Viscosity change rate is 5% or more.

<Method for preparing test piece used for evaluation of curability of composition and abrasion resistance and refractive index of coating film of cured product of composition>
Active energy ray curable resin compositions 1 to 8 of the present invention and comparative active energy ray curable resin compositions 1 'to 4' are dissolved in butyl acetate, and active energy ray curable with a nonvolatile content (NV) of 40%. A solution of the mold composition was obtained. After applying this solution to a PET film (Toyobo Co., Ltd., A-4300 (125 μm)) using a bar coater, it was left in an oven at 70 ° C. for 3 minutes to evaporate the solvent in the composition. Was used to irradiate ultraviolet rays having an integrated light amount of 400 mJ / cm ² to obtain a coated film having a cured coating film having a thickness of 5 μm.

<Evaluation method of curability>
The curability was evaluated according to the following criteria.
○: There is no tackiness when the finger is pressed against the cured coating film.
(Triangle | delta): When a finger is pressed on a cured coating film, there exists a feeling of a little tack.
X: When a finger is pressed against the cured coating film, there is a feeling of tack.

<Method for evaluating wear resistance>
A disc-shaped indenter having a diameter of 2.4 centimeters was wrapped with 0.5 g of steel wool # 0000 (manufactured by Nippon Steel Wool Co., Ltd.), and the cured coating film was worn 10 times with a load of 500 g. The HAZE value of the cured coating film before abrasion and the HAZE value of the cured product after the abrasion test measured in advance were measured using an automatic haze computer (manufactured by Suga Test Instruments Co., Ltd., HZ-2). The difference (ΔHAZE) was determined to evaluate the wear resistance. In addition, it was judged that abrasion resistance was so favorable that (DELTA) HAZE value was small.

<Evaluation method of coating film refractive index>
The refractive index of the coating film was measured using a refractive index measuring device (Model 2010, manufactured by METORICON). A wavelength of 594 nm was used as the light source.

<Method for creating test piece used for evaluation of gel fraction and water absorption of cured product>
Active energy ray curable resin compositions 1 to 8 of the present invention and comparative active energy ray curable resin compositions 1 'to 4' are dissolved in butyl acetate, and active energy ray curable with a nonvolatile content (NV) of 40%. A solution of the mold composition was obtained. After applying this solution to a mirror-finished aluminum plate (A1050P manufactured by Engineering Test Service Co., Ltd.) with an applicator, the solution is left in an oven at 70 ° C. for 5 minutes to volatilize the solvent in the composition, and the integrated light intensity using an 80 W high-pressure mercury lamp. The coated film was cured by irradiating with 400 mJ / cm ² of ultraviolet rays. Then, the coating film was peeled from the mirror surface aluminum plate to obtain a cured coating film having a thickness of 50 μm.

<Evaluation method of gel fraction of cured product>
The cured coating film was immersed in acetone at 20 ° C. for 24 hours. The weight retention before and after immersion was expressed as a gel fraction (%).

<Evaluation method of water absorption of cured product>
The cured coating film was immersed in ion exchange water at 20 ° C. for 24 hours. The weight change rate before and after the immersion was expressed as a water absorption rate (%).

Footnotes in Tables 1 and 2 Diene compound (A2): polybutadiene diacrylate (number average molecular weight 2000)
Diene compound (A3): polybutadiene glycol (number average molecular weight 1350)
Diene compound (A4): polybutadiene glycol (number average molecular weight 2100)
Diene compound (A5): polybutadiene glycol (number average molecular weight 1300)
Diene compound (A6): polybutadiene glycol (number average molecular weight 1250)
Diene compound (a7): hydrogenated polybutadiene glycol (number average molecular weight 1500)
Thiol compound (b2): butanediol bis (3-mercaptobutyrate) (calculated molecular weight 294)
Thiol compound (b3): 1,4-butanediol bisthioglycolate (calculated molecular weight 238)
Photoinitiator: Benzophenone

Footnotes in Table 2 x in storage stability: gelled during stirring.
In terms of curability—: It was not possible to test because it gelled when the composition was made.
In terms of abrasion resistance-: The test could not be performed because a cured coating film could not be obtained.
In the refractive index of the coating film: The test could not be performed because a cured coating film was not obtained.
In gel fraction--: A cured coating film could not be obtained and could not be tested.

Claims (8)

Active energy ray curing comprising at least one diene compound (A) selected from the group consisting of alkadienes, alkadiene polymers and cyclic dienes, and a condensate (B) of a silane compound having a mercapto group Mold resin composition. The active energy ray-curable resin composition according to claim 1, wherein the condensate (B) of the silane compound having a mercapto group is a condensate obtained by condensing a compound represented by the following structural formula.

(In the formula, R1 represents an alkylene group having 1 to 10 carbon atoms. R2 and R3 each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. A and b are 1 to 3, and c is 0 to 0. Represents an integer of 2 and a + b + c = 4.) The active energy ray-curable resin composition according to claim 1, wherein the condensate (B) of the silane compound having a mercapto group is a condensate having a number average molecular weight of 200 to 2,000. The active energy ray-curable resin composition according to claim 1, wherein the diene compound (A) is polybutadiene or polybutadiene polyol. 2. The diene compound (A) is a diene compound obtained by reacting an isocyanate group-containing (meth) acrylate compound obtained by reacting an isocyanate compound and a hydroxyl group-containing (meth) acrylate compound with a polybutadiene polyol. The active energy ray-curable resin composition described. The active energy ray-curable resin composition according to claim 1, wherein the diene compound (A) is a diene compound obtained by reacting a carboxyl group-containing (meth) acrylate compound with a polybutadiene polyol. The diene compound (A) is of number average molecular weight 200 to 100,000 claim 1 active energy ray curable resin composition. The diene compound (A) and the condensate (B) are contained at a ratio of [(A) / (B)] = 60/40 to 80/20 by weight ratio. The active energy ray-curable resin composition described.