Active energy ray curable composition

Abstract

The present invention provides an active energy ray curable composition that exhibits excellent scratch resistance, water resistance, and solvent resistance in the cured product, and that can reduce film warping. [Solution] An active energy ray curable composition is used, which contains at least one (meth)acrylate (A) selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, and pentaerythritol tetra(meth)acrylate; a 3-6 functional (meth)acrylate (B) having 1 to 15 divalent organic groups (a) represented by general formula (1) in its molecule; a compound (C) represented by chemical formula (2); a photopolymerization initiator (D); and an antistatic agent (E).

Description

[Technical Field]

[0001] This invention relates to an active energy ray curable composition. [Background technology]

[0002] Conventionally, active energy ray curable compositions have been used in a wide range of applications, such as film components, coatings, and adhesives, in products like flat panel displays, including liquid crystal displays and organic EL displays. In recent years, development for mobile devices such as smartphones and tablets has become active, and since these applications are used outdoors, waterproofing is necessary. Film components used in liquid crystal displays and organic EL displays are required to have scratch resistance, water resistance, and solvent resistance. Furthermore, these displays are constructed by bonding various film components with optical properties together, and film components coated with cured active energy ray curable compositions are required to have minimal warping caused by curing shrinkage. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 6022861 [Patent Document 2] Japanese Patent Publication No. 2008-094987 [Disclosure of the Invention] [Problems that the invention aims to solve]

[0004] However, conventional active energy ray curable compositions have problems such as not being able to accommodate lamination coating on cured products and not meeting high levels of scratch resistance, water resistance, and solvent resistance. The object of the present invention is to provide an active energy ray curable composition that has excellent scratch resistance, water resistance, and solvent resistance, and can reduce film warping. [Means for solving the problem]

[0005] As a result of intensive studies to solve the above problems, the inventors of the present invention have reached the present invention. That is, an active energy ray-curable composition containing at least one (meth)acrylate (A) selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, and pentaerythritol tetra(meth)acrylate, a 3- to 6-functional (meth)acrylate (B) having 1 to 15 divalent organic groups (a) represented by the general formula (1) in the molecule, a compound (C) represented by the following chemical formula (X), and a photopolymerization initiator (D): A cured product of the active energy ray-curable composition.

[0006] [Chemical formula] [In formula (1), R 1 represents a linear or branched alkylene group having 3 to 10 carbon atoms. ]

[0007] [Chemical formula] [Advantages of the Invention]

[0008] The active energy ray-curable composition of the present invention and the cured product of the composition exhibit the following effects. (1) Excellent scratch resistance. (2) Excellent water resistance. (3) Excellent solvent resistance. (4) Can reduce film warping. [Modes for Carrying Out the Invention]

[0009] The active energy ray curable composition of the present invention contains at least one (meth)acrylate (A) selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, and pentaerythritol tetra(meth)acrylate, a 3-6 functional (meth)acrylate (B) having 1 to 15 divalent organic groups (a) represented by general formula (1) in the molecule, a compound (C) represented by chemical formula (2), and a photopolymerization initiator (D).

[0010] The first essential component of the active energy ray curable resin composition of the present invention, (meth)acrylate (A), is, as described above, at least one (meth)acrylate selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Of the (meth)acrylates (A) mentioned above, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred from the viewpoint of scratch resistance, and dipentaerythritol hexa(meth)acrylate is even more preferred. In this invention, "(meth)acrylate" means "acrylate and / or methacrylate," "(meth)acrylic" means "acrylic and / or methacrylic," and "(meth)acryloyl" means "acryloyl and / or methacryloyl."

[0011] From the viewpoint of scratch resistance and coating properties, the content of (meth)acrylate (A) is preferably 5 to 80% by weight, more preferably 10 to 75% by weight, and even more preferably 15 to 55% by weight, based on the total weight of (A) to (C). If it is 5% by weight or more, scratch resistance is good, and if it is 80% by weight or less, coating properties are good.

[0012] The second essential component of the active energy ray curable resin composition of the present invention, (meth)acrylate (B), is a 3-6 functional (meth)acrylate having 1 to 15 divalent organic groups (a) represented by the following general formula (1) in its molecule.

[0013] [ka]

[0014] In formula (1), R 1 represents a linear or branched alkylene group having 3 to 10 (preferably 4 to 8) carbon atoms.

[0015] Examples of the (meth)acrylate (B) mentioned above include compounds obtained by adding 1 to 15 moles of a lactone having 4 to 11 carbon atoms to a 3 to 8-valent alcohol, and then esterifying it with 3 to 6 moles of (meth)acrylic acid.

[0016] Examples of trivalent to octavalent alcohols include pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol. Examples of lactones with 4 to 11 carbon atoms include butyrolactone, valerolactone, caprolactone, and undecalactone.

[0017] Of these (meth)acrylates (B), those preferred from the viewpoint of water resistance are tetra(meth)acrylate, a 4-mol adduct of δ-valerolactone to pentaerythritol; penta(meth)acrylate, a 6-mol adduct of ε-caprolactone to dipentaerythritol; hexa(meth)acrylate, a 6-mol adduct of ε-caprolactone to dipentaerythritol; and hexa(meth)acrylate, a 12-mol adduct of ε-caprolactone to dipentaerythritol. The (meth)acrylate (B) mentioned above may be used alone or in combination of two or more types.

[0018] From the viewpoint of water resistance, solvent resistance, and coating properties, the content of (meth)acrylate (B) is preferably 10 to 85% by weight, more preferably 15 to 80% by weight, and even more preferably 20 to 60% by weight, based on the total weight of (A) to (C). If the content is 10% by weight or more, water resistance and solvent resistance will be good, and if it is 85% by weight or less, coating properties will be good.

[0019] The third essential component of the active energy ray-curable resin composition of the present invention, compound (C), is compound (C) represented by the following chemical formula (2).

[0020] [ka]

[0021] The above compound (C) can be obtained, for example, by a Michael addition reaction between dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate.

[0022] From the viewpoint of scratch resistance and coating properties, the content of compound (C) is preferably 1 to 30% by weight, more preferably 2 to 25% by weight, and even more preferably 5 to 20% by weight, based on the total weight of (A) to (C). If it is 1% by weight or more, scratch resistance is good, and if it is 30% by weight or less, coating properties are good.

[0023] The active energy ray curable resin composition of the present invention may contain (meth)acrylates other than those listed above (A) to (C), for example, di(meth)acrylate, tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate.

[0024] Among (meth)acrylates other than (A) to (C), di(meth)acrylates include di(meth)acrylates of alkylene oxide adducts (hereinafter, alkylene oxide may be abbreviated as "AO") of di(meth)acrylates containing aromatic ring skeletons {for example, divalent phenol compounds [monocyclic phenols (catechol, resorcinol, and hydroquinone, etc.), condensed polycyclic phenols (dihydroxynaphthalene, etc.), bisphenol compounds (bisphenol A, bisphenol F, and bisphenol S, etc.)] (for example, ethoxylated bis Examples include phenol A diacrylate, acrylic-modified bisphenoxyethanol fluorene, bis(4-(meth)acryloylthiophenyl) sulfide, polyalkylene glycol di(meth)acrylate (dipropylene glycol diacrylate, etc.), alicyclic skeleton-containing di(meth)acrylate {e.g., dimethylol-tricyclodecane di(meth)acrylate}, neopentyl glycol diacrylate, 1,4-butanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate. Specific examples of di(meth)acrylates of AO adducts of divalent phenol compounds include the di(meth)acrylate of the 4-mol adduct of resorcinol to ethylene oxide (hereinafter, ethylene oxide may be abbreviated as "EO"), the di(meth)acrylate of the 4-mol adduct of dihydroxynaphthalene to propylene oxide (hereinafter, propylene oxide may be abbreviated as "PO"), the di(meth)acrylate of the 4-mol adduct of bisphenol A to EO, the di(meth)acrylate of the 10-mol adduct of bisphenol A to EO, and the di(meth)acrylate of the 20-mol adduct of bisphenol A to EO.

[0025] Among (meth)acrylates other than (A) to (C), examples of tri(meth)acrylates include trimethylolpropane tri(meth)acrylate, trimethylolpropane AO ​​adducts [trimethylolpropane EO6 molar adduct, EO9 molar adduct, EO15 molar adduct, EO20 molar adduct, and PO9 molar adduct, etc.], pentaerythritol tri(meth)acrylate, pentaerythritol AO adducts [pentaerythritol EO6 molar adduct, etc.], and glycerin AO adducts [glycerin EO6 molar adduct and PO3 molar adduct, etc.].

[0026] Among (meth)acrylates other than (A) to (C), examples of tetra(meth)acrylate include tetra(meth)acrylate of pentaerythritol AO adducts [such as EO2 molar adducts, EO4 molar adducts, EO10 molar adducts, EO15 molar adducts and EO35 molar adducts of pentaerythritol] and tetra(meth)acrylate of ditrimethylolpropane AO ​​adducts [such as EO10 molar adducts of ditrimethylolpropane].

[0027] Among (meth)acrylates other than (A) to (C), penta(meth)acrylates include penta(meth)acrylates of dipentaerythritol AO adducts [such as EO2 molar adducts, EO4 molar adducts, EO10 molar adducts, and EO15 molar adducts of dipentaerythritol].

[0028] Among (meth)acrylates other than (A) to (C), examples of hexa(meth)acrylates include hexa(meth)acrylates of dipentaerythritol AO adducts [such as EO2 molar adducts, EO4 molar adducts, EO10 molar adducts, and EO15 molar adducts of dipentaerythritol].

[0029] The fourth essential component of the active energy ray curable resin composition of the present invention, the photopolymerization initiator (D), includes phosphine oxide compounds (D1), benzoyl formate compounds (D2), thioxanthone compounds (D3), oxime ester compounds (D4), hydroxybenzoyl compounds (D5), benzophenone compounds (D6), ketal compounds (D7), and 1,3α-aminoalkylphenone compounds (D8). The photopolymerization initiator (D) may be used alone or in combination of two or more.

[0030] Examples of phosphine oxide compounds (D1) include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0031] Examples of benzoylformate compounds (D2) include methylbenzoylformate.

[0032] Examples of thioxanthone compounds (D3) include isopropylthioxanthone.

[0033] Examples of oxime ester compounds (D4) include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime)).

[0034] Examples of hydroxybenzoyl compounds (D5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, and benzoin alkyl ethers.

[0035] Examples of benzophenone compounds (D6) include benzophenone, among others.

[0036] Examples of ketal compounds (D7) include benzyldimethyl ketal.

[0037] Examples of 1,3α-aminoalkylphenone compounds (D8) include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

[0038] Of these photopolymerization initiators (D), those preferred from the viewpoint of curability and coloration of the cured product are phosphine oxide compounds (D1), hydroxybenzoyl compounds (D5), and 1,3α-aminoalkylphenone compounds (D8), and more preferably 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0039] From the viewpoint of curability and transparency, the content of the photopolymerization initiator (D) of the present invention is preferably 0.1 to 10% by weight, and more preferably 0.2 to 7% by weight, based on the total weight of the resin composition.

[0040] The active energy ray curable resin composition of the present invention is preferably further containing an antistatic agent (E) from the viewpoint of antistatic properties. Examples of the antistatic agent (E) include a salt composed of an anionic component and a cationic component.

[0041] The above anionic components include halogen ions (F - Cl - , Br - and I - (etc.), carboxylate anions {mono or dicarboxylic acids with 1 to 7 carbon atoms (ions such as formic acid, acetic acid, propionic acid, oxalic acid and succinic acid (-COO - )}, sulfonate ions {sulfonic acids with 1 to 20 carbon atoms (methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid, etc. ions (-SO3 -)}, phosphate ion {ion of phosphoric acid or a compound containing a phosphate group having 1 to 10 carbon atoms (-OPO3 2- )}, thiocyanate ion, perchlorate ion, sulfate ion, nitrate ion, BF4 - , PF6 - , SbF6 - , AsF6 - , TlF6 - , BF3Cl - , PF5Cl - , SbF5Cl - , AsF5Cl - , TlF5Cl - , BF3Br - , PF5Br - , SbF5Br - , AsF5Br - , TlF5Br - , BF3I - , PF5I - , SbF5I - , AsF5I - and TlF5I - ; and other anions, such as OH - , ClO4 - , bis(trifluoromethanesulfonyl)imide anion, and the like.

[0042] Examples of the cation component include lithium cation, ammonium cation, amidinium cation, pyridinium cation, and the like.

[0043] Examples of the ammonium cation include the following. [1] Aliphatic quaternary ammonium having an alkyl and / or alkenyl group having 4 to 30 or more carbon atoms Tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, trimethylethylammonium, tetraethylammonium, trimethylpropylammonium, dimethyldipropylammonium, ethylmethyldipropylammonium, butyltrimethylammonium, dimethyldibutylammonium, tetrabutylammonium, tetrahexylammonium, trimethyldecylammonium, dimethyldidecylammonium, etc. [2] Aromatic quaternary ammonium compounds with 6 to 30 or more carbon atoms. Trimethylphenylammonium, dimethylethylphenylammonium, triethylphenylammonium, etc. [3] Alicyclic quaternary ammonium compounds with 3 to 30 or more carbon atoms. N,N-dimethylpyrrodinium, N-ethyl-N-methylpyrrodinium, N,N-diethylpyrrodinium, N,N-dimethylmorpholinium, N-ethyl-N-methylmorpholinium, N,N-diethylmorpholinium, N,N-dimethylpiperidinium, N, N-diethylpiperidinium, etc.

[0044] Examples of amidinium cations include the following: [1] Imidazolinium cation C5-C15, for example, 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium, 1,3-dimethyl-2,4-diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-2,3,4-triethylimidazolinium, 1,2,3,4-tetraethylimidazolinium, 1,2,3-trimethylimidazolinium, 1,3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium, 1,2,3-triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 3-cyanomethyl-1,2-dimethylimidazolinium, 2-cyanomethyl-1,3 -Dimethylimidazolinium, 4-acetyl-1,2,3-trimethylimidazolinium, 3-acetylmethyl-1,2-dimethylimidazolinium, 4-methylcarboxymethyl-1,2,3-trimethylimidazolinium, 3-methylcarboxymethyl-1,2-dimethylimidazolinium, 4-methoxy-1,2,3-trimethylimidazolinium, 3-methoxymethyl-1,2-dimethylimidazolinium, 4-formyl-1,2,3-trimethylimidazolinium, 3-formylmethyl-1,2-dimethylimidazolinium, 3-hydroxyethyl-1,2-dimethylimidazolinium, 4-hydroxymethyl-1,2,3-trimethylimidazolinium, 2-hydroxyethyl-1,3-dimethylimidazolinium;

[0045] [2] imidazolium cation C5-C15, for example, 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1,2,3-trimethylimidazolium, 1,2,3,4-tetramethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1,3-dimethyl-2-ethylimidazolium, 1,2-dimethyl-3-ethylimidazolium, 1,2,3-triethylimidazolium, 1,2,3,4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 1-benzyl-2,3-dimethylimidazolium, 4-cyano-1,2,3-trimethylimidazolium, 3-cyanomethyl-1,2-dimethylimidazolium Tylimidazolium, 2-cyanomethyl-1,3-dimethylimidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2-dimethylimidazolium, 4-methylcarboxymethyl-1,2,3-trimethylimidazolium, 3-methylcarboxymethyl-1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 3-methoxymethyl-1,2-dimethylimidazolium, 4-formyl-1,2,3-trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 3-hydroxyethyl-1,2-dimethylimidazolium, 4-hydroxymethyl-1,2,3-trimethylimidazolium, 2-hydroxyethyl-1,3-dimethylimidazolium;

[0046] [3] Tetrahydropyrimidinium cation C6-C15, e.g., 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,8-diazabicyclo[5,4,0]-7-undecenium, 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium, 1 ,5-diazabicyclo[4,3,0]-5-nonenium, 5-methyl-1,5-diazabicyclo[4,3,0]-5-nonenium, 4-cyano-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-cyanomethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-cyanomethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-acetyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium Nium, 3-acetylmethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-methylcarboxymethyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methylcarboxymethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-methoxy-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methoxymethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium Midinium, 4-formyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-formylmethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 3-hydroxyethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-hydroxymethyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-hydroxyethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium;

[0047] [4] Dihydropyrimidinium cation C6-20, for example, 1,3-dimethyl-1,4- or 1,3-dimethyl-1,6-dihydropyrimidinium [these will be written as 1,3-dimethyl-1,4(6)-dihydropyrimidinium, and the same notation will be used hereafter.] 1,2,3-trimethyl-1,4(6)-dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4(6)-dihydropyrimidinium, 1,2,3,5-tetramethyl-1,4(6)-dihydropyrimidinium, 8-methyl-1,8-diazabicyclo[5,4,0]-7,9(10)-undecadienium, 5-methyl-1,5-diazabicyclo[4,3,0]-5,7(8)-nonadienium , 4-cyano-1,2,3-trimethyl-1,4(6)-dihydropyrimidinium, 3-cyanomethyl-1,2-dimethyl-1,4(6)-dihydropyrimidinium, 2-cyanomethyl-1,3-dimethyl-1,4(6)-dihydropyrimidinium, 4-acetyl-1,2,3-trimethyl-1,4(6)-dihydropyrimidinium, 3-acetylmethyl-1,2-dimethyl-1,4(6)-dihydropyrimidinium Dinium, 4-methylcarbooxymethyl-1,2,3-trimethyl-1,4(6)-dihydropyrimidinium, 3-methylcarbooxymethyl-1,2-dimethyl-1,4(6)-dihydropyrimidinium, 4-methoxy-1,2,3-trimethyl-1,4(6)-dihydropyrimidinium, 3-methoxymethyl-1,2-dimethyl-1,4(6)-dihydropyrimidinium, 4-formyl-1,2,3 -Trimethyl-1,4(6)-dihydropyrimidinium, 3-formylmethyl-1,2-dimethyl-1,4(6)-dihydropyrimidinium, 3-hydroxyethyl-1,2-dimethyl-1,4(6)-dihydropyrimidinium, 4-hydroxymethyl-1,2,3-trimethyl-1,4(6)-dihydropyrimidinium, 2-hydroxyethyl-1,3-dimethyl-1,4(6)-hydropyrimidinium.

[0048] Examples of pyridinium cations include those with 6 to 20 carbon atoms, such as 3-methyl-1-propylpyridinium, 1-propyl-3-methylpyridinium, 1-butyl-3-methylpyridinium, 1-butyl-4-methylpyridinium, 1-butyl-3,4-dimethylpyridinium, and 1-butyl-3,5-dimethylpyridinium.

[0049] From the viewpoint of yield, preferred salts composed of anionic and cationic components include 1-hexyl-4-methylpyridinium hexafluorophosphate, bisfluorosulfonylimide lithium, and bis(trifluoromethanesulfonyl)imide lithium.

[0050] When an antistatic agent (E) is included, the content of the antistatic agent (E) of the present invention is preferably 0.1 to 5% by weight, and more preferably 0.1 to 1% by weight, based on the total weight of the resin composition.

[0051] The active energy ray curable composition of the present invention may contain various additives as needed, as long as they do not inhibit the effects of the present invention. Examples of additives include plasticizers, organic solvents, dispersants, defoamers, thixotropic agents (thickeners), slip agents, antioxidants, hindered amine light stabilizers, and ultraviolet absorbers.

[0052] The active energy ray curable composition of the present invention can be produced by uniformly mixing, for example, the above-mentioned (meth)acrylate (A), the above-mentioned (meth)acrylate (B), the above-mentioned compound (C), the above-mentioned photopolymerization initiator (D), and optionally (meth)acrylates other than (A) to (C), an antistatic agent (E), and the above-mentioned additives using a known mechanical mixing method (a method using a mechanical stirrer and a magnetic stirrer, etc.).

[0053] The active energy ray curable composition of the invention becomes a cured product upon curing, and can be used to manufacture molded articles that can be used, for example, as optical components. The following describes a method for producing a molded article as a cured product by curing the active energy ray curable composition of the present invention. The method for manufacturing a molded article using the active energy ray curable composition of the present invention is not particularly limited, but for example, it can be coated and molded by the following method. That is, the composition of the present invention is preheated to 20 to 50°C, and the composition is coated (or filled) using a dispenser or the like into a mold (mold temperature preferably 20 to 50°C, more preferably 25 to 40°C) that can obtain a molded article shape (e.g., an optical lens shape) so that the thickness after curing is 50 to 150 μm. A transparent substrate (including a transparent film) is then pressure-laminated on top of the coating film so that no air is trapped inside. After curing the coating film by irradiating the transparent substrate with the active energy ray described below, the coating film is removed from the mold to obtain a molded article (e.g., a lens sheet).

[0054] Examples of the transparent substrate (including transparent film) mentioned above include those made using resins such as methyl methacrylate (co)polymer, polyethylene terephthalate, polycarbonate, polytriacetylcellulose, and polycycloolefin.

[0055] The active energy rays in this invention include ultraviolet rays, electron beams, X-rays, infrared rays, and visible light. Of these active energy rays, ultraviolet rays and electron beams are preferred from the viewpoint of curability and suppression of resin degradation.

[0056] When curing the active energy ray-curable composition of the present invention with ultraviolet light, various ultraviolet irradiation devices can be used (for example, an ultraviolet irradiation device [model number "VPS / I600", manufactured by Fusion UV Systems Co., Ltd.]). Examples of lamps that can be used include high-pressure mercury lamps and metal halide lamps. The amount of ultraviolet irradiation is preferably 10 to 10,000 mJ / cm² from the viewpoint of the curability of the composition and the flexibility of the cured product. 2 More preferably 100 to 5,000 mJ / cm² 2 That is the case.

[0057] The cured product of the active energy ray curable composition of the present invention has excellent mold release properties and is therefore useful as an optical component, electrical / electronic component, and the like. In particular, it is useful as an optical component such as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, and field-of-view enhancement lenses, etc.), optical compensation films, phase difference films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, and photosensitive optical waveguides. Furthermore, the cured product of the active energy ray curable composition of the present invention also exhibits excellent water resistance, making it useful as an optical component for mobile products such as smartphones and tablets, which are frequently used outdoors. [Examples]

[0058] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments. In the following, "parts" refers to parts by weight.

[0059] <Manufacturing Example 1> In a reaction vessel equipped with a stirrer, condenser, and thermometer, 579 parts of dipentaerythritol hexaacrylate [product name: Neomer DA-600, manufactured by Sanyo Chemical Industries, Ltd.], 350 parts of dipentaerythritol pentaacrylate [product name: Aronics M-403, manufactured by Toagosei Co., Ltd.] (dipentaerythritol hexaacrylate:dipentaerythritol pentaacrylate = 1.5:1 (molar ratio)), 600 parts of toluene, and 1.5 parts of p-toluenesulfonic acid as a catalyst were charged and reacted at 90°C for 2 hours. Next, the reaction solution was cooled to 30°C, neutralized with an aqueous sodium hydroxide solution (concentration: 30% by weight), and then, while stirring, 600g of water was added to dissolve the resulting salt. After stopping the stirring, the solution was allowed to stand at 30°C for 2 hours, and the lower layer (aqueous layer) was removed. Furthermore, 10g of "(Registered Trademark) Kyoward 1000" (manufactured by Kyowa Chemical Co., Ltd.) was added as an adsorbent, and the mixture was stirred at 90°C for 30 minutes, after which the contents were filtered. The obtained filtrate was charged into a stainless steel pressure-resistant reaction vessel, and while stirring, toluene and water were removed by distillation under reduced pressure at 90°C until the toluene and water content was 0.1% by weight or less to obtain composition (S-1) containing compound (C). The content of (C) in (S-1) was 75% by weight.

[0060] <Examples 1-20, Comparative Examples 1-5> The components and their proportions listed in Table 1 were combined in a single mixture and stirred in a disperser until homogeneous to obtain the activated energy ray curable compositions of Examples 1-20 and Comparative Examples 1-5.

[0061] [Table 1]

[0062] The compound symbols listed in Table 1 represent the following compounds. (A-1): Dipentaerythritol hexaacrylate [Product name: Neomer DA-600, manufactured by Sanyo Chemical Industries, Ltd., hexafunctional] (A-2): Pentaerythritol tetraacrylate [Product name: Neomer EA-300, manufactured by Sanyo Chemical Industries, Ltd., tetrafunctional] (A-3): Dipentaerythritol pentaacrylate [Product name: Aronics M-403, Toagosei Co., Ltd., 5-functional] (B-1): Hexaacrylate of ε-caprolactone 12-mol adduct of dipentaerythritol [Product name: Kayarad DPCA-120, manufactured by Nippon Kayaku Co., Ltd.] (B-2): Hexaacrylate of the ε-caprolactone 6-mol adduct of dipentaerythritol [Product name: Kayarad DPCA-60, manufactured by Nippon Kayaku Co., Ltd.] (Ratio B-1): Phenoxyethyl acrylate [Product name: Light Acrylate PO-A, manufactured by Kyoeisha Chemical Co., Ltd.] (D-1): 2,4,6-Trimethylbenzoyldiphenylphosphine oxide [Trade name: Lucilin TPO, manufactured by BASF] (D-2): 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [Product name: Irgacure 907, manufactured by BASF] (D-3): 1-Hydroxycyclohexylphenyl ketone [Trade name: Irgacure 184, manufactured by BASF] (E-1): 1-Hexyl-4-methylpyridinium hexafluorophosphate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (E-2): Bis(trifluoromethanesulfonyl)imide lithium [manufactured by Fujifilm Wako Pure Chemical Corporation] (F-1): Dimethylol tricyclodecanediaacrylate [Product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., bifunctional] (F-2): Cyclohexanedimethanol diacrylate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., bifunctional] (F-3): PEG600 # Diacrylate [Product name: Light Acrylate 14EG-A, manufactured by Kyoeisha Chemical Co., Ltd., bifunctional] (F-4): 1,6-Hexanediol diacrylate [Product name: Light Acrylate 1.6HX-A, manufactured by Kyoeisha Chemical Co., Ltd., bifunctional] (G-1): Triacrylate of 15 molar trimethylolpropane EO adduct [Product name: SR-9035, manufactured by Arkema Co., Ltd., trifunctional]

[0063] Using an active energy ray-curable composition, scratch resistance, water resistance, solvent resistance, antistatic properties, and warping were evaluated using the following test methods. The results are shown in Table 1.

[0064] <Scratch resistance> Prepare a glass plate by wiping off surface dirt with a cloth soaked in acetone. Apply the active energy ray-curable composition to one side of the glass plate to a thickness of 10 μm using an applicator. Then, a 100 μm thick polyester film [product name "Cosmoshine A4360", manufactured by Toyobo Co., Ltd.] is bonded to the resin side, and a roller is rolled over it to push out the air. From the polyester film side, ultraviolet light is applied at a rate of 1000 mJ / cm² using an ultraviolet irradiation device [model number "VPS / I600", manufactured by Fusion UV Systems Co., Ltd.].2 The film was cured by irradiation, peeled off the glass plate, and a cured film was obtained on a polyester film. The surface of the hardened film was tested using a pencil fitted with a chrome cap in accordance with JIS K 5600-5-4. After standing for 10 minutes, it was visually inspected and its scratch resistance was evaluated according to the following criteria. ○: The pencil marks have completely disappeared. ×: Pencil marks remain

[0065] <Water resistance> Prepare a glass plate by wiping off surface dirt with a cloth soaked in acetone. Apply the active energy ray-curable composition to one side of the glass plate to a thickness of 50 μm using an applicator. Then, a 75 μm thick polypropylene film [product name "Trefan #60-2500", manufactured by Toray Industries, Inc.] is bonded to the resin side, and a roller is rolled over it to push out air. From the polypropylene film side, ultraviolet light at 1000 mJ / cm² is applied using an ultraviolet irradiation device [model number "VPS / I600", manufactured by Fusion UV Systems Co., Ltd.]. 2 The cured film was irradiated and cured, and the resulting cured film was peeled off the glass plate and polypropylene film. The resulting cured film was cut into 5cm x 5cm films on each side to form test specimens. The test specimens were immersed in 40°C water and left for 24 hours. After immersion, the surface of the cured film of the test specimens was wiped with Kimwipes (registered trademark) [S-200, manufactured by Nippon Paper Crecia Co., Ltd.], and the weight change before and after immersion was measured. The water swelling rate was calculated as follows, and the water resistance was evaluated according to the following criteria. Water swelling rate: (Weight after water immersion - Weight before water immersion) / Weight before water immersion × 100 (weight %) ◎: Less than 1.5% by weight ○: 1.5% by weight or more, less than 4.5% by weight ×: 4.5% by weight or more

[0066] <Solvent resistance> The cured film obtained by the same procedure as in the water resistance test described above was peeled off the glass plate and polyester film. The obtained cured film was cut into 5cm x 5cm films on one side to form test specimens. The test specimens were immersed in methyl ethyl ketone (hereinafter referred to as MEK) at 25°C and left for 24 hours. After immersion, the surface of the cured film of the test specimen was wiped with Kimwipes (registered trademark) [S-200, manufactured by Nippon Paper Crecia Co., Ltd.], and the weight change before and after immersion was measured. The MEK swelling rate was calculated as follows, and the water resistance was evaluated according to the following criteria. MEK swelling rate: (Weight after MEK immersion - Weight before MEK immersion) / Weight before MEK immersion × 100 (weight %) ◎: Less than 1% by weight ○: 1% by weight or more, less than 3% by weight ×: 3% by weight or more

[0067] <Antistatic properties> The cured film obtained by the same procedure as in the scratch resistance test described above was peeled off the glass plate to obtain a cured film on a polyester film. The obtained cured film with polyester film was cut into 10cm x 10cm films on each side to be used as test specimens. In accordance with ASTM D257, the test specimens were measured using the "DSM-8103" super-insulation meter [manufactured by Toa Denpa Kogyo Co., Ltd.] under conditions of 23°C and 50% RH humidity, and evaluated according to the following criteria. ◎: Less than 1E+14 Ω / sq ○: 1E+14 Ω / sq or more, less than 5E+14 Ω / sq ×: 5E+14 Ω / sq or greater

[0068] <curve> The cured film obtained by the same procedure as the scratch resistance test described above was peeled from the glass plate to obtain a cured film on a polyester film. The obtained polyester film-attached cured film was cut into 10cm x 10cm pieces to make test specimens. The specimens were placed on a horizontal table with the side with the cured film facing upwards, and the warping of the film due to curing shrinkage was measured at four points, from the top of the table to each corner, to serve as an indicator of warping due to curing shrinkage. ◎: The distance between the floating corner and the base is less than 0.5 cm on average. ○: The distance between the floating corner and the base is between 0.5cm and 1.5cm on average. ×: The distance between the floating corner and the base is 1.5 cm or more.

[0069] As can be seen from the results in Table 1, the active energy ray curable composition of the present invention and the cured product (film) obtained by curing the composition have good scratch resistance, water resistance, solvent resistance, antistatic properties, and warp resistance. [Industrial applicability]

[0070] The active energy ray curable composition of the present invention exhibits excellent mold release properties, as well as good scratch resistance, water resistance, solvent resistance, and antistatic properties, making it widely used in optical components (plastic lenses, optical fibers, circular polarizers, etc.), electrical and electronic components (anti-reflective films, anti-gray films), and various coating agents.

Claims

1. An active energy ray curable composition comprising at least one (meth)acrylate (A) selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, and pentaerythritol tetra(meth)acrylate; a 3-6 functional (meth)acrylate (B) having 1 to 15 divalent organic groups (a) represented by general formula (1) in its molecule; a compound (C) represented by the following chemical formula (2); and a photopolymerization initiator (D). 【Chemistry 1】 [In formula (1), R １ This represents a linear or branched alkylene group with 3 to 10 carbon atoms. 【Chemistry 2】

2. The active energy ray curable composition according to claim 1, wherein, based on the total weight of (A) to (C), the weight percentage of (A) is 5 to 80% by weight, the weight percentage of (B) is 10 to 85% by weight, and the weight percentage of (C) is 1 to 30% by weight.

3. The active energy ray curable composition according to claim 1, further comprising an antistatic agent (E).

4. A cured product of the active energy ray curable composition according to claims 1 to 3.

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