JP6284721B2 - 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 photocurable compositions.

JP 2002-037855 A JP-A-2005-350546 JP 2011-132487 A

  An object of the present invention is to provide an energy ray sensitive composition having excellent curability and adhesiveness.

The present invention has been made based on the above knowledge, and is an energy ray sensitive composition containing a cationically polymerizable monomer mixture (1),
The cationic polymerizable monomer mixture (1) is composed of 1 to 50 parts by mass of a cationic polymerizable monomer (1A) having a molecular weight of 500 or less and having no oxirane ring and an oxirane ring-containing cationic polymerizable monomer (100 parts by mass). The object is achieved by providing an energy ray-sensitive composition characterized by containing 1 to 50 parts by mass of 1B).

  Moreover, this invention has a cation polymerizable functional group with respect to 100 mass parts of said cation polymerizable monomer mixtures (1), and the polymer (2) whose mass with respect to 1 equivalent of cation polymerizable functional groups is 100-1000. Preferably, the energy ray-sensitive composition as described above is characterized by comprising 1 to 50 parts by mass of a polymer (2 ′) having an oxirane ring and having a mass of 100 to 1000 with respect to 1 equivalent of the oxirane ring. It is.

  Moreover, this invention contains 0.1-20 mass parts of energy-ray sensitive acid generators (3) with respect to 100 mass parts of said cation polymerizable monomer mixtures (1), The said energy sensitive composition characterized by the above-mentioned. Is to provide.

  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 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. A cationically polymerizable monomer having a molecular weight of 500 or less that does not have an oxirane ring, but can be an epoxy compound, an oxetane compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester compound, a vinyl ether, or the like. It is essential to contain (1A) and an oxirane ring-containing cationic polymerizable monomer (1B).

  Examples of the cationic polymerizable monomer (1A) having a molecular weight of 500 or less having no oxirane ring include 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-oxetanylmethoxy) butane, 1,6-bis (3-ethyl- -Oxetanylmethoxy) hexane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3 Oxetane compounds such as ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 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, 2-hydroxyethyl vinyl ether , 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, 1,4-butanediol divinyl ether, 1,6-cyclohexanedimethanol divinyl ether, and the like. From the viewpoint of properties, those having one cationic polymerizable functional group such as a vinyl ether group in the molecule, particularly those having one cationic polymerizable functional group and one hydroxyl group in the molecule are preferable. These can be used alone or in combination of two or more.

  As the cationic polymerizable monomer (1A) having a molecular weight of 500 or less that does not have an oxirane ring, commercially available products having a cationic polymerizable monomer as a main component can be used. For example, Aron oxetane OXT-121, OXT- 221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.), etanacol OXBP, OXTP (manufactured by Ube Industries); 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxy And butyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.).

  Specific examples of the oxirane ring-containing cationic polymerizable monomer (1B) include, for example, 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 glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether , Phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, 4-phenylphenol Ricidyl ether, cresyl glycidyl ether, dibromocresyl glycidyl ether, decyl glycidyl ether, methoxypolyethylene glycol monoglycidyl ether, ethoxypolyethylene glycol monoglycidyl ether, butoxypolyethylene glycol monoglycidyl ether, phenoxypolyethyleneglycol monoglycidyl ether, dibromophenylglycidyl ether Ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2,2-tetrakis (glycidyl Glycidyl ethers such as oxyphenyl) ethane and pentaerythritol tetraglycidyl ether Tellurides; glycidyl esters such as glycidyl acetate and glycidyl stearate; 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, ethylene bis (3,4-epoxycyclohexanecarboxylate), bis ( 3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6 -Mechi -3,4-epoxycyclohexylmethyl 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, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, dicyclopentadiene diepoxide, 3 , 4-epoxy-6-methylcyclohexylcarboxylate, α-pinene oxide, styrene oxide, cyclohexene oxide, cyclopentene oxide, and other epoxy cycloalkyl type compounds; N-glycidylphthalimid Etc. The. Among these, from the viewpoint of curability, a compound having two or more oxirane rings, particularly a compound having two or more epoxycyclohexane structures is preferable. These can be used alone or in combination of two or more.

  As said oxirane ring containing cationically polymerizable monomer (1B), a commercially available thing can be used, for example, Epolite 40E, 1500NP, 1600, 80MF, 4000, 3002 (made by Kyoeisha Chemical Co., Ltd.), Adeka glycilol ED- 503, ED-503D, ED-503G, ED-523T, ED-513, ED-501, ED-502, ED-509, ED-518, ED-529, Adeka Resin EP-4000, EP-4005, EP-4080 , EP-4085 (manufactured by ADEKA), Denacol EX-201, EX-203, EX-211, EX-212, EX-221, EX-251, EX-252, EX-711, EX-721, Denacol EX- 111, EX-121, EX-141, EX-142, EX-145, E -146, EX-147, EX-171, EX-192, EX-731 (manufactured by Nagase ChemteX); Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (manufactured by Daicel); Epiol M, EH, L- 41, SK, SB, TB, OH (manufactured by NOF Corporation); Epolite M-1230, 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

  In the cationic polymerizable monomer mixture (1), the mixing ratio of the cationic polymerizable monomer (1A) having no molecular weight of 500 or less and the oxirane ring-containing cationic polymerizable monomer (1B) is the above cationic polymerizable monomer. In 100 parts by mass of the mixture (1), the cationic polymerizable monomer (1A) having a molecular weight of 500 or less having no oxirane ring is 1 to 50 parts by mass, and the oxirane ring-containing cationic polymerizable monomer (1B) is 50 to 50%. The cationic polymerizable monomer (1A) having a molecular weight of 500 or less and having no oxirane ring is 5 to 25 parts by mass, and the oxirane ring-containing cationic polymerizable monomer (1B) is 75 to 95 parts by mass. It is preferable that

  The energy ray sensitive composition of the present invention has a cationically polymerizable functional group from the viewpoint of curability and adhesiveness, and has a polymer (2) (100) having a mass per 100 equivalents of the cationically polymerizable functional group ( Hereinafter, it is preferable to contain a polymer (also referred to as a polymer (2)) having a mass of 100 to 1000 with respect to 1 equivalent of the cationically polymerizable functional group. Examples of the polymer (2) having a mass of 100 to 1000 with respect to 1 equivalent of the cationic polymerizable functional group include a polymer obtained by radical polymerization, and an ethylenically unsaturated monomer having a cationic polymerizable functional group is used. A homopolymerized polymer or an ethylenically unsaturated monomer having a cationic polymerizable functional group and a polymer copolymerized with an ethylenically unsaturated monomer having no cationic polymerizable functional group, in particular, an oxirane ring And a polymer (2 ′) having a mass per 100 equivalent of the oxirane ring (hereinafter also referred to as a polymer having an epoxy equivalent of 100 to 1000) is preferable.

  The ethylenically unsaturated monomer constituting the polymer (2) having a mass of 100 to 1000 with respect to 1 equivalent of the cationic polymerizable functional group is not particularly limited, and a known one can be used. It has a structure substituted with a cationically polymerizable functional group such as an oxetane group or a vinyl ether group, preferably contains 10 to 80% by weight of an ethylenically unsaturated monomer having an oxirane ring, and is substituted with a cationically polymerizable functional group An ethylenic group substituted with an unsubstituted methyl group or a linear or branched alkyl group having 2 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms. What contains 20 to 90% of a saturated monomer and is a total of 100 parts by weight together with other ethylenically unsaturated monomers is preferred.

  The polymer (2) having a mass of 100 to 1000 with respect to 1 equivalent of the cationic polymerizable functional group preferably has a weight average molecular weight of 5000 to 100,000, more preferably 7000 to 70000.

  In the present invention, a polymer refers to a compound formed by combining one or more monomers into a chain or network, and includes oligomers, further polymerizable compounds such as prepolymers and macromonomers. Including.

  The use ratio of the polymer (2) having a mass of 100 to 1000 with respect to 1 equivalent of the cationic polymerizable functional group to the cationic polymerizable monomer mixture (1) is not particularly limited, and does not impair the object of the present invention. What is necessary is just to use it in a normal use ratio, for example, the polymer (2) whose mass with respect to 1 equivalent of said cation polymerizable functional groups is 100-1000 with respect to 100 mass parts of cation polymerizable monomer mixtures (1). It can be 1-50 mass parts. If the amount is too small, the adhesiveness 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.

The energy ray-sensitive acid generator (3) used in the energy ray-sensitive composition of the present invention may be any compound that can generate an acid upon irradiation with energy rays, but is preferably Is a double salt that is an onium salt that releases a Lewis acid upon irradiation with energy rays, or a derivative thereof. Representative examples of such compounds include the following general formula:
[A] ^{r +} [B] ^r-
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 holds.

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 (3) 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, with respect to 100 parts by mass of the cationic polymerizable monomer mixture (1), the energy ray sensitive acid generator (3) can be 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass. 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.
Thermal polymerization initiator is a compound that generates a cationic species or Lewis acid by heating, such as a salt of sulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt; diethylenetriamine, triethylenetriamine, tetraethylenepenta Polyalkylpolyamines such as min; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine; m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone Aromatic polyamines such as: the above polyamines, phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, etc. Polyepoxy addition-modified products produced by reacting various kinds of epoxy resins such as glycidyl ethers or glycidyl esters of carboxylic acids by conventional methods; the above organic polyamines, phthalic acid, isophthalic acid, dimer acid, etc. Amidation-modified product produced by reacting carboxylic acids with a conventional method; at least one aldehyde reaction in the above polyamines and aldehydes such as formaldehyde and nuclei such as phenol, cresol, xylenol, tert-butylphenol, and resorcin Mannich-modified products produced by reacting phenols having sex sites by a conventional method; polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelain Acid, sebacic acid, do Candiic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecane Aliphatic dicarboxylic acids such as diacids, hydrogenated dimer acids and dimer acids; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid , Tricarboxylic acids such as trimesic acid and trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid) acid anhydrides; dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides, etc. .

  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, 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 (1) to (3) that are usually used can be used. For example, methyl ethyl ketone, methyl amyl ketone , Diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like ketones; 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, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and 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”. In addition, Examples 1, 2, 4, 5, 9, 11, and 14 are reference examples and are outside the scope of the present invention.

[Examples 1 to 17 and Comparative Examples 1 to 3]
Each component was fully mixed by the mixing | blending shown to the following [Table 1]-[Table 3], and the implementation compositions 1-17 and the comparative compositions 1-3 were obtained, respectively.

The following compounds (1A-1) to (1A- 7 ) and (1B-1) to (1B-3) are used as the cationic polymerizable monomer, and the following compound (2) is used as the polymer having an epoxy equivalent of 100 to 1000. -1) to (2-2) were used. Compound 1A-1: 2-hydroxyethyl vinyl ether compound 1A-2: 4-hydroxybutyl vinyl ether compound 1A-3: diethylene glycol monovinyl ether compound 1A-4: 1,4-butanediol divinyl ether compound 1A-5: to 2-ethyl Xyl vinyl ether compound 1A-6: Aron oxetane OXT-211 (manufactured by Toagosei Co., Ltd.) Compound 1A-7: Aron oxetane OXT-101 (manufactured by Toagosei Co., Ltd.) Compound 1B-1: Celoxide 2021P (manufactured by Daicel) Compound 1B-2 : Adekaglycilol ED-503G (manufactured by ADEKA) Compound 1B-3: Denacol EX-201 (manufactured by Nagase ChemteX) Compound 2-1: copolymer of glycidyl methacrylate and methyl methacrylate (epoxy equivalent: 580, Mw) : 7000 Compound 2-2: copolymer of glycidyl methacrylate and methyl methacrylate (epoxy equivalent 700, Mw: 20000)

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

[Evaluation Examples 1 to 17 and Comparative Evaluation Examples 1 to 3]
The following evaluation was performed about the implementation composition obtained in the said Examples 1-17 and the comparison composition obtained in Comparative Examples 1-3. The results are shown in the above [Table 1] to [Table 3].
(Curable)
Each of Examples 1 to 17 and Comparative Compositions 1 to 3 having good coating properties was applied to a thickness of 3 to 6 μm on a PET film with a bar coater, 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 applying each of the obtained implementation compositions 1 to 17 and the comparative composition 1 to the base film described in [Table 1] to [Table 3], the film was corona-coated using a laminator. Bonded with another sheet of the base material film described in [Table 1] to [Table 3] that has been subjected to discharge treatment, and bonded by irradiating energy of 1000 mJ / cm ² using an electrodeless ultraviolet light lamp. I got a piece. A 90-degree peel test is performed on the obtained test piece. A specimen having a value of 0.8 N / cm or more is indicated by ◎, a specimen having a value of 0.4 to 0.8 N / cm is indicated by ◯, and a specimen having a value of 0.4 N / cm or less It evaluated as x.

  From the above [Table 1] to [Table 3], it is clear that the energy ray sensitive composition of the present invention is excellent in curability and excellent in adhesiveness regardless of the substrate.

Claims (5)

An energy ray sensitive composition comprising a cationic polymerizable monomer mixture (1) and 0.1 to 20 parts by mass of an energy ray sensitive acid generator (3) with respect to 100 parts by mass of the cationic polymerizable monomer mixture (1). Because
The cationic polymerizable monomer mixture (1) is prepared by adding 1 to 25 parts by mass of a cationic polymerizable monomer (1A) having a molecular weight of 500 or less and having no oxirane ring and an oxirane ring-containing cationic polymerizable monomer (100 parts by mass). 1B) is contained in an amount of 75 to 99 parts by mass,
The cationic polymerizable monomer (1A) having a molecular weight of 500 or less that does not have an oxirane ring is a vinyl ether compound,
The oxirane ring-containing cationic polymerizable monomer (1B) is 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 glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4 -N-butylphenyl glycidyl ether, 4-phenylphenol glycidyl ether, Diglycidyl ether, dibromocresyl glycidyl ether, decyl glycidyl ether, dibromophenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,1,2,2-tetrakis (glycidyloxyphenyl) ethane, pentaerythritol tetraglycidyl ether, glycidyl acetate, glycidyl stearate, 2- (3,4-epoxycyclohexyl-5,5-spiro -3,4-epoxy) cyclohexane-metadioxane, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane) Sun), 2,2-bis (3,4-epoxycyclohexyl) propane, ethylenebis (3,4-epoxycyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl 6-methyl-3,4 -Epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl 3,4-epoxy-5-methylcyclo Xanthcarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, dicyclopentadiene diepoxide, 3,4-epoxy-6-methylcyclohexyl carboxylate, α-pinene oxide, styrene oxide, cyclohexene oxide, at least one compound der selected from cyclopentene oxide and N- glycidylphthalimide is,
The weight which has a cation polymerizable functional group with respect to 100 mass parts of the said cation polymerizable monomer mixture (1), and the mass with respect to 1 equivalent of cation polymerizable functional groups is 100-1000, and a weight average molecular weight is 5000-100000. An energy ray sensitive composition containing 1 to 50 parts by mass of the coalescence (2) .   The energy-sensitive composition according to claim 1, wherein the cationic polymerizable monomer (1A) is a compound having one cationic polymerizable functional group in the molecule.   The energy ray-sensitive composition according to claim 2, wherein the compound having one cationic polymerizable functional group in the molecule is a compound having one cationic polymerizable functional group and one hydroxyl group in the molecule. . The energy ray-sensitive acid generator (3) is a cation represented by [A] ^{r +} [B] ^r- (where A is a cationic species, B is an anionic species, and r is a valence of an ion). The energy ray sensitive composition according to any one of claims 1 to 3 , which is a salt of an ion and an anion. An adhesive comprising the energy ray-sensitive composition according to any one of claims 1 to 4 .