JP5617458B2 - 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 and a low hygroscopic property 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. These materials are required to have an adhesive force and are required to have a low hygroscopic property of the cured product.

  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 cured well by irradiation with active energy rays.

JP 2008-231409 A

  It is an object of the present invention to provide a curable composition having good curability and low hygroscopicity of the cured product, and a cured product thereof.

  As a result of intensive studies, the present inventors have improved curability by using an unsaturated polyester resin obtained by using an unsaturated fatty acid or an unsaturated fatty acid ester instead of the diene compound described in Patent Document 1. The present inventors have found that a cured product having excellent moisture resistance can be obtained even if various thiol compounds are used without being limited to thiol compounds having secondary and tertiary mercapto groups, and the present invention has been completed. .

  That is, the present invention contains an unsaturated polyester resin (A) obtained by using an unsaturated fatty acid or an unsaturated fatty acid ester and a compound (B) having a mercapto group, which is an active energy ray-curable resin. A 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 a cured product obtained by curing the composition has low hygroscopicity.

  The polyester resin (A) used in the present invention is obtained using an unsaturated fatty acid or an unsaturated fatty acid ester. Examples of unsaturated fatty acids include monounsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid; linoleic acid, eicosadienoic acid Diunsaturated fatty acids such as docosadienoic acid; triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid; stearidonic acid, arachidonic acid, eicosa Tetraunsaturated fatty acids such as tetraenoic acid and adrenic acid; pentaunsaturated fatty acids such as boseopentaenoic acid, eicosapentaenoic acid, ozbond acid, sardine acid and tetracosapentaenoic acid; hexaunsaturated fatty acids such as docosahexaenoic acid and nisic acid, etc. Is mentioned.

  Examples of unsaturated fatty acid esters include animal and vegetable oils, and specific examples include esters (fatty oils) of unsaturated fatty acids and glycerin. Examples of fatty oils include salad oil, white squeezed oil, corn oil, soybean oil, sesame oil, rapeseed oil (canola oil), rice bran oil, coconut oil, straw oil, safflower oil (safflower oil), palm kernel oil, coconut oil, cottonseed oil , Sunflower oil, camellia oil, olive oil, peanut oil, almond oil, avocado oil, hazelnut oil, walnut oil, grape seed oil, mustard oil, lettuce oil, fish oil, whale oil, salmon oil, liver oil, etc. It is done.

  Of the polyester resins (A), polyester resins obtained using unsaturated fatty acid esters are preferred. Of the unsaturated fatty acid esters, natural fats and oils are preferable, and among them, one or more fats and oils selected from the group consisting of linseed oil, soybean oil, tung oil, and tall oil are preferable.

  In order to obtain the unsaturated polyester resin (A) used in the present invention using an unsaturated fatty acid, for example, a condensation reaction between the unsaturated fatty acid and, if necessary, an acid containing a saturated fatty acid and an alcohol may be performed. Examples of saturated fatty acids that may be used as necessary include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydro Phthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene Examples include dicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof.

  Examples of the alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1, 3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1 , 2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexaneglycol -L, 1,4-cyclohexanedimethanol, para-xylene glycol, bicyclohexyl Le 4,4' Geo - le, 2,6-decalin glycolate - le, 2,7-decalin glycolate - le, and the like.

  In order to obtain the unsaturated polyester resin (A) used in the present invention using an unsaturated fatty acid ester, for example, a condensation reaction between a reaction product obtained by a transesterification reaction between an unsaturated fatty acid ester and an alcohol and an acid is performed. good.

  The number average molecular weight of the unsaturated polyester resin (A) is preferably 1,000 to 30,000, and more preferably 1,500 to 5,000, since both coating workability and curability can be achieved.

  Further, the iodine value of the unsaturated polyester resin (A) is preferably 20 to 150, more preferably 40 to 100, since both storage stability and curability can be achieved.

  Examples of the compound (B) having a mercapto group used in the present invention include ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 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) Pentaerythritol 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;

Ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 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-mercaptopropioate) Nate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate) Ethylene glycol bis (3-mercaptoisobutyrate), propylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), trimethylol Propane tris (3-mercaptoisobutyrate), pentaerythritol 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- Lucaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), propylene glycol bis (4-mercaptoisovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate) ), 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-mercaptovalere) ), 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis (1-mercaptoethyl) benzene, diphthalic acid di (1-mercaptoethyl ester), diphthalic acid di (2-mercaptopropyl) Ester), di (3-mercaptobutyl ester) phthalate, and di (3-mercaptoisobutyl ester) phthalate.

  Moreover, as a compound (B), the condensate of the alkoxysilane which has a mercapto group, or the alkoxysilane which has a mercapto group can be illustrated preferably. Examples of the alkoxysilane having a mercapto group include mercaptotrimethoxysilane, mercaptodimethoxymethylsilane, mercaptotriethoxysilane, mercaptodiethoxymethylsilane, and the like.

  Among the compounds (B), a mixture of a condensate obtained by dealcoholizing an alkoxysilane having a mercapto group and then condensing by a dehydration reaction and an alkoxysilane having a mercapto group, and an alkoxy having a mercapto group A mixture having a silane content of 5 to 80 parts by mass with respect to the condensate is preferred.

  Furthermore, among the condensates, a condensate obtained by condensation in a range where the condensation rate is 20 to 99% is more preferable.

  A condensate obtained by condensing a compound represented by the following structural formula (1);

（式中、Ｒ_１は炭素数１〜１０のアルキル基、Ｒ_２、Ｒ_３は水素原子又は炭素数１〜１０のアルキル基、ａは０〜２の整数を示す。）

(In the formula, _{R 1} represents an alkyl group having 1 to 10 carbon _atoms, R 2, _{R 3} is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 2.)

  Compound represented by the following general formula (2) or general formula (2)

〔一般式（２）中、Ｒ_１、Ｒ_２はそれぞれ炭素原子数１〜２０の直鎖状、分岐状または環状の炭化水素基を表す。ｎは２〜６の整数である。一般式（３）中、Ｒは水素原子または下記一般式（４）で表される基である。〕

[Represented in the general formula _{(2), R 1, R} 2 each having 1 to 20 carbon atoms of straight, branched or cyclic hydrocarbon group. n is an integer of 2-6. In general formula (3), R represents a hydrogen atom or a group represented by the following general formula ( 4 ). ]

〔一般式（３）中、Ｒ_１は炭素原子数１〜２０の直鎖状、分岐状または環状の炭化水素基を表す。〕等が挙げられる。これらは１種で又は２種以上を併用して使用できる。

[In General Formula (3), R ₁ represents a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. ] Etc. are mentioned. These can be used alone or in combination of two or more.

  Examples of the condensate obtained by condensing the compound represented by the structural formula (1) include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3- Examples include mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane.

  In the silane compound having a mercapto group, a mercapto group bonded to a silicon atom is hydrolyzed to form a silanol group, and condensed by a condensation reaction. The silane compound having a mercapto group may have a hydrolyzable group bonded to a silicon atom in addition to the mercapto group.

  Examples of the hydrolyzable group bonded to the silicon atom include, for example, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, an amino group, an amide group, an aminooxy group, and an iminooxy group bonded to the silicon atom, respectively. Or the group etc. which hydrolyze and produce | generate a silanol group, such as an alkenyloxy group, are mentioned.

  The condensate can be obtained, for example, by adding water to a silane compound having a mercapto group and hydrolyzing alkoxy groups that are hydrolyzable groups, and simultaneously or later performing a condensation reaction (hydrolytic condensation). it can.

  In preparing the condensate, 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, preferably 0 The range is from 8 to 2 mol.

  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.

  In obtaining the condensate, a silane compound other than a silane compound having a mercapto group may be used as long as the effects of the present invention are not impaired. 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.

Examples of the compound represented by the general formula (2) include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris [(3-mercaptopropionyloxy). ) -Ethyl] isocyanurate and the like.

  Examples of the compound represented by the general formula (3) include dipentaerythritol hexakis (3-mercaptopropionate).

  Among the compounds (B) containing a mercapto group, a condensate obtained by condensing a compound represented by the structural formula (1), a compound represented by the general formula (2) or the general formula (3) is more preferable.

  As content of the unsaturated polyester resin (A) and the compound (B) having a mercapto group in the active energy ray-curable resin composition of the present invention, the unsaturated polyester resin (A) and the compound having a mercapto group (B ) By weight ratio [(A) / (B)] = 60/40 to 80/20 is preferable, and 65/35 to 75/25 is more preferable.

  The active energy ray-curable resin composition of the present invention can contain a compound having an unsaturated group other than the unsaturated polyester resin (A) as long as the effects of the present invention are not impaired.

  Examples of the compound having an unsaturated group other than the unsaturated polyester resin (A) include diene compounds, allyl alcohol derivatives, vinyl ethers, (meth) acrylates, (meth) acrylamides, olefins, styrenes, and others. These vinyl monomers are mentioned.

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

  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.

  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 [Synthesis of polyester resin (A1)]
A flask having a stir bar, a temperature sensor, and a rectifying tube was charged with 472.7 g of linseed oil, and then 99.0 g of pentaerythritol was charged. The temperature was raised to 190 ° C. over 2 hours while flowing dry nitrogen from the inside of the 10 ml / min flask and stirring, and 0.07 g of lithium hydroxide was added. Then, transesterification was performed at 240 ° C. After the transesterification reaction, the temperature was lowered to 160 ° C., 6.7 g of glycerin and 192.0 g of phthalic anhydride were charged, and the esterification reaction was performed at 230 ° C. When this was diluted to 70% with NV (nonvolatile content) with toluene, an unsaturated polyester resin having an acid value of 7.1 and a Gardner viscosity of Z1-Z2 was obtained. This is abbreviated as polyester resin (A1). The number average molecular weight of the polyester resin (A1) by gel permeation chromatography (GPC) was 4513. The oil length of the polyester resin (A1) is 65 (wt%).

Synthesis example 2 (same as above)
A flask having a stir bar, temperature sensor, and rectifying tube was charged with 304.5 g of linseed oil and 16.0 g of soybean oil, and then with 74.0 g of pentaerythritol. Dry nitrogen was allowed to flow from the inside of the 10 ml / min amount flask while stirring and the temperature was raised to 190 ° C. over 2 hours, and 0.06 g of lithium hydroxide was added. Then, transesterification was performed at 240 ° C. After the transesterification reaction, the temperature was lowered to 160 ° C., 16.0 g of glycerin and 201.0 g of phthalic anhydride were charged, and the esterification reaction was performed at 230 ° C. When this was diluted with toluene to NV 60%, a polyester resin having an acid value of 5.2 and a Gardner viscosity ST was obtained. This is abbreviated as polyester resin (A2). The number average molecular weight of the polyester resin (A2) by gel permeation chromatography (GPC) was 5,500. The oil length of the polyester resin (A2) is 50 (wt%).

Synthesis example 3 (same as above)
A flask having a stir bar, temperature sensor, and rectifying tube was charged with 221.8 g of linseed oil and 11.7 g of soybean oil, and then 153.8 g of pentaerythritol. Dry nitrogen was allowed to flow from the inside of the 10 ml / min flask to the temperature of 190 ° C. over 2 hours while stirring, and 0.09 g of lithium hydroxide was added. Then, transesterification was performed at 240 ° C. After the transesterification reaction, the temperature was lowered to 160 ° C., 153.7 g of phthalic anhydride was charged, and the esterification reaction was performed at 230 ° C. When this was diluted with xylene to NV50%, a polyester resin having an acid value of 5.5 and a Gardner viscosity W-X was obtained. This is abbreviated as polyester resin (A3). The number average molecular weight of the polyester resin (A3) by gel permeation chromatography (GPC) was 6814. The oil length of the polyester resin (A3) is 45 (wt%).

Synthesis Example 4 [Synthesis of Compound Having Mercapto Group]
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 1-7 and Comparative Examples 1'-4 '
A polyester resin (A), a compound (B) having a mercapto group, and a photoinitiator are blended in the formulations shown in Tables 1 and 2, and the active energy ray-curable resin compositions 1 to 7 of the present invention and comparison are made. Control active energy ray-curable resin compositions 1 'to 4' were prepared. The curability of these compositions and the water absorption and gel fraction of the compositions were evaluated. The method of each evaluation is shown below.

<Method of creating test piece for evaluation of curability>
The active energy ray-curable resin composition of the present invention and the comparative active energy ray-curable resin composition were dissolved in methyl ethyl ketone to obtain a solution of an active energy ray-curable composition having a nonvolatile content of 50%. 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 500 mJ / cm 2 to obtain a coated film having a cured coating film having a thickness of 3 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 creating test piece for evaluation of gel fraction and water absorption of cured product>
The active energy ray-curable resin composition of the present invention and the comparative active energy ray-curable resin composition were dissolved in methyl ethyl ketone to obtain a solution of an active energy ray-curable composition having a nonvolatile content of 50%. After applying this solution to a mirror-finished aluminum plate (A1050P manufactured by Engineering Test Service Co., Ltd.) with an applicator, it is left in an oven at 70 ° C. for 5 minutes to volatilize the solvent in the composition, and integrated light quantity using an 80W high-pressure mercury lamp The coating film was cured by irradiating with 500 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 (a1): polybutadiene glycol (number average molecular weight 1350)
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 In gel fraction--: A cured coating film could not be obtained and could not be tested.
In terms of water absorption rate: a test could not be performed because a cured coating film could not be obtained.

Claims (12)

An active energy ray-curable resin composition comprising an unsaturated polyester resin (A) obtained using an unsaturated fatty acid ester and a compound (B) having a mercapto group ,
The unsaturated fatty acid ester is a natural fat and oil, and the unsaturated polyester resin (A) and the compound (B) having a mercapto group in a weight ratio [(A) / (B)] = 80/20 to 20/80 the active energy ray curable resin composition characterized by containing in a ratio made. Wherein the natural fats and oils linseed oil, soybean oil, tung oil, the active energy ray curable resin composition according to claim 1, wherein the one or more fats selected from the group consisting of tall oil. The polyester resin (A) is an active energy ray curable resin composition of any one of claims 1-2 which is a polyester resin having an iodine value of 20 to 150. The active energy ray-curable resin composition according to any one of claims 1 to 3 , wherein the polyester resin (A) is a polyester resin having a number average molecular weight of 1,000 to 30,000.   The active energy ray-curable resin composition according to claim 1, wherein the compound (B) having a mercapto group is an alkoxysilane having a mercapto group or a condensate of an alkoxysilane having a mercapto group. The compound (B) having a mercapto group is a mixture of a condensate obtained by dealcoholizing an alkoxysilane having a mercapto group and then dehydrating, and an alkoxysilane having a mercapto group. the active energy ray curable resin composition according to claim 5, wherein the content of alkoxysilane is 5 to 80 parts by weight with respect condensate having. The active energy ray-curable resin composition according to claim 5 , wherein the condensate is a condensate obtained by condensation in a range where the condensation rate is 20 to 99%. The active energy ray-curable resin composition according to claim 5, wherein the condensate of alkoxysilane having a mercapto group is a condensate obtained by condensing a compound represented by the following structural formula (1).

(In the formula, _{R 1} represents an alkyl group having 1 to 10 carbon _atoms, R 2, _{R 3} is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a is an integer of 0 to 2.) The active energy ray-curable resin composition according to claim 1, wherein the compound (B) having the mercapto group is a compound represented by the following general formula (2) or general formula (3).

[Represented in the general formula _{(2), R 1, R} 2 each having 1 to 20 carbon atoms of straight, branched or cyclic hydrocarbon group. n is an integer of 2-6. In general formula (3), R represents a hydrogen atom or a group represented by the following general formula ( 4 ). ]

[In the general formula ( 4 ), R ₁ represents a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. ] The active energy ray-curable resin composition according to any one of claims 5 to 9 , wherein the compound (B) having a mercapto group has a number average molecular weight of 200 to 10,000.   Furthermore, a photoinitiator is contained, The active energy ray-curable resin composition of any one of Claims 1-10 characterized by the above-mentioned. The hardened | cured material obtained by hardening | curing the active energy ray-curable resin composition of any one of Claims 1-11.