JP6251894B2 - Energy ray sensitive composition - Google Patents

Description

  The present invention relates to an energy ray sensitive composition and a cured product obtained by irradiating the energy ray sensitive composition with active energy rays. The energy ray sensitive composition is particularly useful for adhesives.

  Energy ray sensitive compositions are used in the fields of inks, paints, various coating agents, adhesives, optical members and the like.

  For example, the following Patent Documents 1 to 3 disclose various energy ray sensitive compositions.

JP 2008-007694 A JP 2010-250020 A JP 2013-068797 A

  An object of the present invention is to provide an energy ray-sensitive composition that is excellent in coatability, curability and adhesiveness.

  The present invention has been made on the basis of the above knowledge, and is a cationic polymerizable monomer mixture (1) and an energy ray-sensitive acid generator (2) having a bifunctional or higher symmetrical cationic polymerizable monomer (1A) as essential components. The above-mentioned object is achieved by providing an energy ray sensitive composition characterized by containing.

  The present invention also provides an adhesive comprising the above energy ray sensitive composition.

  Since the energy ray sensitive composition of the present invention is excellent in coating property, curability and adhesiveness, it is particularly useful as an adhesive application.

  Hereinafter, the energy ray sensitive composition of this invention and the adhesive agent which consists of this energy ray sensitive composition are demonstrated in detail.

  In the cationic polymerizable monomer mixture (1) used in the present invention, the cationic polymerizable monomer constituting the mixture is polymerized or causes a crosslinking reaction by an energy ray sensitive cationic polymerization initiator activated by light irradiation. An epoxy compound, an oxetane compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiroorthoester compound, a vinyl ether, or the like can be used, but a bifunctional or higher symmetric cationic polymerizable monomer (1A) is used. It is an essential ingredient. The cationic polymerizable monomer mixture (1) includes a bifunctional or higher symmetric cationic polymerizable monomer (1A), an asymmetric epoxycycloalkyl compound (1B), a monofunctional cationic polymerizable monomer ( 1C) is preferably used.

As the bifunctional or higher symmetric cationic polymerizable monomer (1A), a compound having two or more cationic polymerizable groups can be used. Examples of the cationic polymerizable group include an epoxy group, an oxetane group, a cyclic thioether group, A vinyl ether group etc. are mentioned. Examples of the bifunctional or higher symmetric cationic polymerizable monomer (1A) include 1,4-butanediol diglycidyl ether, 1,5-pentanediol glycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl. Glycol diglycidyl ether, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl- Bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, ethylenebis (3,4-epoxycyclohexanecarboxylate), 1,1,2,2-tetrakis (glycidyloxy) Phenyl) ethane, pentaerythritol Epoxy compounds such as traglycidyl ether, bis (3,4-epoxycyclohexylmethyl) adipate, 1,2,8,9-diepoxylimonene, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1 , 4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl- 3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3 -Oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanyl) Toxi) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether Dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) Ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanyl mel) ether, PO-modified bisphenol A Bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether And oxetane compounds such as EO-modified bisphenol F bis (3-ethyl-3-oxetanylmethyl) ether, and vinyl ether compounds such as ethylene glycol divinyl ether and triethylene glycol divinyl ether. From the viewpoint, an epoxy compound is more preferable, and a molecular weight of 500 or less is more preferable.
In addition, the molecular weight here shows the chemical formula amount of the compound as the main component.
These can be used alone or in combination of two or more.

  As the bifunctional or higher symmetric cationic polymerizable monomer (1A), a commercially available product mainly composed of a bifunctional or higher symmetric cationic polymerizable monomer (1A) can be used. For example, Epolite 40E, 1500NP, 1600, 80MF, 4000, 3002 (manufactured by Kyoeisha Chemical Co., Ltd.), Adekaglycil ED-503, ED-503D, ED-523T, ED-513, Adeka Resin EP-4000, EP-4005, EP-4080, EP-4085 ( ADEKA), Denacol EX-201, EX-203, EX-211, EX-212, EX-221, EX-251, EX-252, EX-711, EX-721 (manufactured by Nagase ChemteX), Aaron Oxetane OXT-121, OXT-221 (manufactured by Toagosei Co., Ltd.), Etanacol OXBP OXTP (manufactured by Ube Industries, Ltd.) oxetane compounds such like.

Specific examples of the asymmetric epoxycycloalkyl compound (1B) include polyglycidyl etherified products of polyhydric alcohols having at least one alicyclic ring and having a hydroxyl group directly bonded to the alicyclic ring. For example, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxy Cyclohexylmethyl 6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl 3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, bis (3,4-epoxycyclohexylmethyl) A Pies, 1,2-epoxy-2-epoxy ethylcyclohexane, dicyclopentadiene diepoxide, and the like. Among these, from the viewpoint of adhesion, a compound having two or more functional groups is preferable, and a compound having two epoxycycloalkyl structures in the molecule is more preferable.
These can be used alone or in combination of two or more.

  A commercial item can be used as said epoxy cycloalkyl type compound (1B), for example, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (made by Daicel) etc. are mentioned.

The monofunctional cationically polymerizable monomer (1C) is obtained, for example, by epoxidizing a cyclohexene or cyclopentene ring-containing compound such as α-pinene oxide, styrene oxide, cyclohexene oxide, or cyclopentene oxide with an oxidizing agent. Compound: methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, phenyl-2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, p-sec-butylphenyl Glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycyl Dil ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, n-butylphenyl glycidyl ether, phenylphenol glycidyl ether, cresyl glycidyl ether, dibromocresyl glycidyl ether, glycidyl acetate, glycidyl stearate, decyl glycidyl Ether, methoxy polyethylene glycol monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, etc., glycidyl etherified products of alcohols, phenols or alkylene oxide adducts thereof , Carvone Glycidyl esterified acid; monofunctional vinyl ethers such as n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether; 3-ethyl-3-[(phenoxy ) Methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl- Monofunctional oxetane compounds such as 3- (chloromethyl) oxetane; 3,4-epoxy-6-methylcyclohexylcarboxylate, N-glycidylphthalimide and the like.
Among these, an epoxy compound is preferable from the viewpoint of reactivity and coatability, and an epoxy compound having a molecular weight of 300 or less is more preferable.
The molecular weight referred to here indicates the chemical formula amount of the main compound.
These can be used alone or in combination of two or more.

  As the monofunctional cation polymerizable monomer (1C), commercially available products can be used. For example, Denacol EX-111, EX-121, EX-141, EX-142, EX-145, EX-146 , EX-147, EX-171, EX-192, EX-731 (manufactured by Nagase ChemteX Corporation); Epiol M, EH, L-41, SK, SB, TB, OH (manufactured by NOF Corporation); Epolite M- 1230, 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adekaglycilol ED-501, ED-502, ED-509, ED-518, ED-529 (manufactured by ADEKA); Aron Oxetane EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.) and the like.

  In the cationic polymerizable monomer mixture (A), the mixing ratio of the bifunctional or higher symmetric cationic polymerizable monomer (1A), the asymmetric epoxycycloalkyl compound (1B) and the monofunctional cationic polymerizable monomer (1C) Is 5 to 50 parts by mass of the bifunctional or higher symmetric cationic polymerizable monomer (1A) with respect to 100 parts by mass of the cationic polymerizable monomer mixture (A), and the asymmetric epoxycycloalkyl compound (1B). ) Is preferably 50 to 90 parts by mass, and the monofunctional cation polymerizable monomer (1C) is preferably 0.5 to 20 parts by mass, and the bifunctional or higher symmetric cationic polymerizable monomer (1A) is 10-40 parts by mass, the asymmetric epoxycycloalkyl type compound (1B) is 60-90 parts by mass, the monofunctional cationic polymerizable Nomar (1C) is more preferably 1 to 15 parts by weight.

The energy ray-sensitive acid generator (2) used in the present invention may be any compound that can generate an acid upon irradiation with energy rays, but preferably irradiation with energy rays. Is a double salt that is an onium salt that releases a Lewis acid, or a derivative thereof. Representative examples of such compounds include the following general formula:
[A] ^{r +} [B] ^r-
(However, A represents a cationic species, B represents an anionic species, and r represents the valence of the ion)
And cation and anion salts represented by the formula:

Here, the cation [A] ^{r +} is preferably onium, and the structure thereof is, for example, the following general formula:
[(R ¹ ) _a Q] ^{r +}
It can be expressed as

Further, here, R ¹ is an organic group having ¹ to 60 carbon atoms, and may contain any number of atoms other than carbon atoms. a is an integer of 1 to 5. The a R ^{1 s} are independent and may be the same or different. Further, at least one is preferably an organic group as described above having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] ^{r +} is q, the relationship r = a−q needs to be satisfied (however, N = N is treated as a valence of 0).

Further, the anion [B] ^r- is preferably a halide complex, and the structure thereof is, for example, the following general formula:
[LX _b ] ^r-
It can be expressed as

Further, here, L is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is a halogen atom. b is an integer of 3-7. Further, when the valence of L in the anion [B] ^r− is p, it is necessary that the relationship r = b−p be established.

Specific examples of the anion [LX _b ] ^{r− in} the above general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄ ) ⁻ , Examples include hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ^{− and the} like.

Further, the anion [B] ^r− is represented by the following general formula:
[LX _b-1 (OH)] ^r-
The thing of the structure represented by can also be used preferably. L, X, and b are the same as described above. Other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , and toluenesulfonate anion. , Trinitrobenzenesulfonic acid anion, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.

  In the present invention, among these onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). Among these, one of them can be used alone, or two or more can be mixed and used.

(I) Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate

(B) Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, tolylcumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt

(C) sulfonium salts such as sulfonium cations represented by the following group I or group II, hexafluoroantimony ions, tetrakis (pentafluorophenyl) borate ions, etc.

Other preferable examples include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Iron-arene complexes such as hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and silanols such as triphenylsilanol The mixture of these can also be mentioned.

  Among these, from the viewpoint of practical use and photosensitivity, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex.

  The use ratio of the energy ray sensitive acid generator (2) with respect to the cationic polymerizable monomer mixture (1) is not particularly limited, and may be used at a generally normal use ratio within a range not impairing the object of the present invention. For example, the energy ray sensitive acid generator may be 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the cationic polymerizable monomer mixture (1). If the amount is too small, curing tends to be insufficient, and if the amount is too large, various physical properties such as the water absorption rate and the strength of the cured product may be adversely affected.

In the energy ray sensitive composition of the present invention, a silane coupling agent can be used as necessary.
Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ Epoxy functional alkoxysilanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) -γ Aminofunctional alkoxysilanes such as aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium Titanium alkoxides such as tetraisopropoxide and titanium tetranormal butoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), zirconi Arm tetraacetyl acetonate, zirconium chelates such as zirconium tributoxy monoacetylacetonate, zirconium acylates such as zirconium tributoxy monostearate, an isocyanate silane such as methyl triisocyanate silane.

  Although the usage-amount of the said silane coupling agent is not specifically limited, Usually, it is the range of 1-20 mass parts with respect to 100 mass parts of whole quantity of the solid substance in an energy-ray sensitive composition.

In the energy ray sensitive composition of the present invention, a thermal polymerization initiator can be used as necessary.
The thermal polymerization initiator is a compound that generates a cationic species or a Lewis acid by heating, and is, for example, a salt such as sulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt; diethylenetriamine, triethylenetriamine , Polyalkylpolyamines such as tetraethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine; m-xylylenediamine, diaminodiphenylmethane Aromatic polyamines such as diaminodiphenylsulfone; the above polyamines, phenylglycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether Polyepoxy addition-modified products produced by reacting various epoxy resins such as glycidyl ethers such as terresidues or glycidyl esters of carboxylic acids by conventional methods; the above organic polyamines, phthalic acid, isophthalic acid, dimer acid Amidation-modified products produced by reacting carboxylic acids such as aldehydes by a conventional method; aldehydes such as polyamines and formaldehyde, and at least one aldehyde in the nucleus such as phenol, cresol, xylenol, tert-butylphenol, resorcin Mannich-modified products produced by reacting phenols having a reactive site with a conventional method; polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid , Azelaic acid, seba Acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7 -Aliphatic dicarboxylic acids such as dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Tricarboxylic acids such as trimellitic acid, trimesic acid and castor oil fatty acid trimer; acid anhydrides of tetracarboxylic acids such as pyromellitic acid; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides, etc. be able to.

  A commercial item can also be used as said thermal polymerization initiator, for example, Adeka Opton CP77, Adeka Opton CP66 (made by ADEKA), CI-2638, CI-2624 (made by Nippon Soda Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI -80L, Sun-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.

  The amount of the thermal polymerization initiator used is not particularly limited, but is usually in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of solids in the energy ray sensitive composition. When using an initiator, it is preferable to heat at 130 to 180 ° C. for 20 minutes to 1 hour when curing the energy ray sensitive composition of the present invention.

  In the energy ray-sensitive composition of the present invention, the properties of the cured product can be improved by using a thermoplastic organic polymer as necessary. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

  The energy ray-sensitive composition of the present invention is not particularly limited, and a solvent that can dissolve or disperse the components (A) and (B) that are usually used can be used. For example, methyl ethyl ketone, methyl amyl ketone, Ketones such as diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether, Ether solvents such as dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; Cellosolve solvents such as tylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol mono Ether ester solvents such as ethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; benzene, toluene, xylene, etc. BTX solvents; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpenes such as terpine oil, D-limonene and pinene Hydrocarbon oils; paraffinic solvents such as mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2- Halogenated aliphatic hydrocarbon solvents such as dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N- Examples thereof include dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like, and these solvents can be used as one or a mixture of two or more.

  The energy ray sensitive composition of the present invention is preferably one having a viscosity of 1 to 200 mPa · s because it is excellent in curability and coating properties.

  The energy ray sensitive composition of the present invention is applied onto a supporting substrate by a known means such as a roll coater, a curtain coater, various types of printing, and immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

The material for the support substrate is not particularly limited and may be any commonly used material, such as inorganic materials such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl. Cellulose esters such as cellulose and nitrocellulose; Polyamide; Polyimide; Polyurethane; Epoxy resin; Polycarbonate; Polyethylene terephthalate, Polyethylene naphthalate, Polybutylene terephthalate, Poly-1,4-cyclohexanedimethylene terephthalate, Polyethylene-1,2-diphenoxy Polyester such as ethane-4,4′-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene, polypropylene, polymethylpentene, etc. Polyolefins; polyvinyl compounds such as polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; Imide; polymer materials such as polyoxyethylene, norbornene resin, and cycloolefin polymer (COP) can be used.
Note that the support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment and the like.

  Further, as long as the effects of the present invention are not impaired, other monomers, other energy ray-sensitive polymerization initiators, inorganic fillers, organic fillers, pigments, coloring agents such as pigments, dyes, photosensitizers, antifoaming agents as necessary. , Thickener, surfactant, leveling agent, flame retardant, thixotropic agent, diluent, plasticizer, stabilizer, polymerization inhibitor, ultraviolet absorber, antioxidant, antistatic agent, flow regulator, Various resin additives such as an adhesion promoter can be added.

  The energy ray-sensitive composition of the present invention is cured by irradiation with active energy rays. Examples of active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are most preferable economically. . Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.

  Specific applications of the energy ray-sensitive composition of the present invention include glasses, optical materials represented by imaging lenses, paints, coating agents, lining agents, inks, resists, liquid resists, adhesives, printing plates, and insulation. Varnish, insulating sheet, laminate, printed circuit board, sealing agent for molding of semiconductor devices, LED packages, liquid crystal inlets, organic EL, optical elements, electrical insulation, electronic components, separation membranes, etc. Materials, putty, glass fiber impregnating agent, sealant, semiconductor / solar cell passivation film, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display, screen for projection TV, etc. The lens portion of a lens sheet such as a Fresnel lens sheet or a lenticular lens sheet used in Examples include light, optical lenses such as microlenses, optical elements, optical connectors, optical waveguides, optical molding casting agents, etc. Examples of substrates that can be used as coating agents include metals, wood, rubber, and plastics. , Glass, ceramic products and the like.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

  Hereinafter, the energy ray sensitive composition of the present invention and the cured product obtained by curing the energy ray sensitive composition will be specifically described with reference to Examples, Evaluation Examples, and Comparative Examples. In Examples and Comparative Examples, “part” means “part by mass”.

[Examples 1-7 and Comparative Examples 1-3]
Each component was fully mixed by the mixing | blending shown in the following [Table 1]-[Table 2], and the implementation compositions 1-7 and the comparative compositions 1-3 were obtained, respectively.

The following compounds (1A-1) to (1A-4) (1B-1) to (1B-2) and (1C-1) were used as the cationic polymerizable monomer.
Compound 1A-1: Adekaglycilol ED-503G
(Adeka / epoxy resin based on 1,6-hexanediol glycidyl ether)
Compound 1A-2: DY-022
(Nepase ChemteX / epoxy resin based on 1,4-butanediol diglycidyl ether)
Compound 1A-3: Adekaglycilol ED-523T
(Made by ADEKA / epoxy resin mainly composed of neopentyl glycol diglycidyl ether)
Compound 1A-4: Aron oxetane OXT-221
(Toagosei Co., Ltd./di[1-ethyl(3-oxetanyl)]methyl ether)
Compound 1B-1: Celoxide 2021P
(Daicel / 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate)
Compound 1B-2: Celoxide 3000
(Daicel / 1,2,8,9-diepoxy limonene)
Compound 1C-1: Denacol EX-121
(Manufactured by Nagase ChemteX Corporation / 2-ethylhexyl glycidyl ether: molecular weight)

The following compounds (2-1) to (2-2) were used as the energy ray-sensitive acid generator (2).
Compound 2-1: Compound represented by [Chemical Formula 3] Compound 2-2: Compound represented by [Chemical Formula 4]

[Evaluation Examples 1 to 7 and Comparative Evaluation Examples 1 to 3]
The following evaluation was performed about the implementation composition obtained by the said Examples 1-7 and the comparison composition obtained by Comparative Examples 1-3. The results are shown in the above [Table 1] to [Table 2].
(Coating property)
Apply each of the working composition and comparative composition obtained on a 40 μm PET film, and check the state when laminated with another 40 μm PET film using a laminator. An evaluation was given as ◯ when there was no wrinkle or disorder, and x when there was a bubble between the films or when there was a wrinkle or disorder on the film.
(Curable)
Each of Examples 1 to 7 and Comparative Compositions 2 and 3 having good coatability were applied on a PET film with a bar coater to a thickness of 3 to 6 μm, and an electrodeless ultraviolet lamp was used. An energy of 800 mJ / cm ² was irradiated. Evaluation was made with ◯ indicating that the coated surface was tack-free 3 minutes after irradiation, and × indicating that the tack remained.
(Adhesiveness)
After apply | coating each of the obtained Example compositions 1-7 and 1-3 of a comparative composition to the TAC (triacetylcellulose) film which gave the corona discharge process of this sheet, this film was used for the laminator. A test piece was obtained by bonding to another COP (cycloolefin polymer) film that had been subjected to corona discharge treatment, and using an electrodeless ultraviolet lamp to irradiate with 1000 mJ / cm ² of energy. The obtained test piece was subjected to a 90-degree peel test, and a test piece having a value of 0.5 N / cm or more was evaluated as x and a test piece having a value of 0.5 N / cm or less was evaluated as x.

  From [Table 1] to [Table 2], it is clear that the energy ray sensitive composition of the present invention is excellent in coating property, curability and adhesiveness.

Claims (6)

An energy ray-sensitive composition comprising a cation polymerizable monomer mixture (1) having a bifunctional or higher symmetric cationic polymerizable monomer (1A) as essential components and an energy ray-sensitive acid generator (2). There,
The cationically polymerizable monomer mixture (1) relative to 100 parts by weight of difunctional or more symmetric cationically polymerizable monomer (1A) 35 to 50 parts by mass of bifunctional or more asymmetric epoxy cycloalkyl-type compound of (1B) energy-sensitive composition characterized by containing 65 parts by mass 50 to two or more.   2. The energy ray-sensitive composition according to claim 1, comprising 0.5 to 20 parts by mass of a monofunctional cation polymerizable monomer (1C) with respect to 100 parts by mass of the cation polymerizable monomer mixture (1). object.   The energy ray according to claim 1 or 2, comprising 0.5 to 10 parts by mass of the energy ray-sensitive acid generator (2) with respect to 100 parts by mass of the cationic polymerizable monomer mixture (1). Sensitive composition. The energy ray-sensitive acid generator is a cation or anion represented by [A] ^{r +} [B] ^r- (where A represents a cationic species, B represents an anionic species, and r represents the valence of an ion). The energy ray sensitive composition according to any one of claims 1 to 3, which is an ion salt.   The energy ray-sensitive composition according to any one of claims 1 to 4, wherein the viscosity is 1 to 200 mPa · s.   An adhesive comprising the energy ray sensitive composition according to any one of claims 1 to 5.