JP4911661B2 - Cationic polymerizable resin composition, coating agent, and coating layer surface processing method - Google Patents

Description

  The present invention relates to a cationic polymerizable resin composition, a coating agent using the same, and a processing method using the same. Specifically, cationic polymerization that can be used as a coating agent with excellent solvent resistance, long time for post-processing such as foil stamping and printing on the coating surface after application of coating agent, and good post-processing property The present invention relates to a resin composition, a coating agent using the same, and a coating layer surface processing method using the same.

Conventionally, the surface of a plastic product is coated with a cationic polymerizable resin composition. For example, Patent Document 1 discloses a technique using a dimer acid-modified epoxy resin as a cationic polymerizable resin. Patent Document 2 discloses a flexible coating agent mainly composed of a polybutadiene acrylonitrile-modified epoxy resin.
JP 2003-192762 A JP 2001-329045 A

  Although the coating agent described in Patent Document 1 has some post-processability, the post-processability cannot be maintained for a sufficient time during which industrial processing can be performed. In addition, the coating agent described in Patent Document 2 is not described for post-processability, and the coating agent used here does not have post-processability.

  Therefore, the object of the present invention is to provide a coating agent having excellent solvent resistance, a long time for post-processing such as foil stamping and printing on the coating surface after application of the coating agent, and good post-processing property. It is to provide a cationic polymerizable resin composition that can be produced, a coating agent using the same, and a processing method using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by adding a functional group having acid trapping property or proton trapping property to the cationic polymerizable resin composition, The present invention has been completed.

That is, the cationically polymerizable resin composition of the present invention contains (1) a cationically polymerizable organic substance and (2) at least a stoichiometric amount of an energy ray-sensitive cationic polymerization initiator as essential components. A cationically polymerizable resin composition comprising (1) 0.1 to 20 mmol of a nitrile group with respect to 100 g of the cationically polymerizable organic substance.

Moreover, it is preferable that the nitrile group according to the present invention is introduced into at least a part of the (1) cationic polymerizable organic substance, and further the (1) cationic polymerizable organic substance into which the nitrile group is introduced. Is more preferably an epoxy compound. Furthermore, it is preferable that 1 to 50% by mass of the (1) cationically polymerizable organic substance is an oxetane compound. Further, (3) any one or more of a surface conditioner, a fluidity conditioner and a solvent can be suitably contained.

  The coating agent of the present invention is characterized by using the cationic polymerizable resin composition of the present invention.

The processing method of the coating layer surface of the present invention is characterized in that after forming a coating layer using the coating agent of the present invention, foil pressing or printing is performed on the surface of the obtained coating layer.

  The effect of the present invention is a cationic polymerization that is excellent in solvent resistance, has a long time for post-processing such as foil stamping and printing on the coating surface after application of the coating agent, and can be used as a coating agent with good post-processing property It is in being able to provide a conductive resin composition, a coating agent using the same, and a processing method using the same.

  (1) The cationically polymerizable organic substance used in the present invention may be any substance as long as it is a substance that is polymerized or cross-linked by a cationic polymerization initiator activated by energy ray irradiation or the like. Although not given, an example is as follows.

  For example, an epoxy compound, an oxetane compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiroorthoester compound, a vinyl compound, and the like, and one or more of these can be used. Among them, an epoxy compound that is easy to obtain and convenient for handling is suitable. As the epoxy compound, aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds and the like are suitable.

  Specific examples of the alicyclic epoxy resin include cyclohexene oxide obtained by epoxidizing a polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. A cyclopentene oxide containing compound is mentioned. For example, hydrogenated bisphenol A diglycidyl ether, 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-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane Metageo Sun, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene bis (3,4 Epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-4-epoxyethylcyclohexane, 3, Examples include 4-epoxycyclohexylmethyl acrylate and 3,4-epoxycyclohexylmethyl methacrylate.

  Examples of commercially available products that can be suitably used as the alicyclic epoxy resin include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200 (manufactured by Union Carbide), Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolide GT-301, Epolide GT-302, Epolide 401, Epolide 403, ETHB, Epolide HD300 (above, Daicel Chemical Industries, Ltd.), KRM-2110, KRM-2199 (above, manufactured by Asahi Denka Kogyo Co., Ltd.) and the like.

  Among the alicyclic epoxy resins, an epoxy resin having a cyclohexene oxide structure is preferable in terms of the effects of the present invention and curability (curing speed).

  Specific examples of the aromatic epoxy resin include polyhydric phenol having at least one aromatic ring or polyglycidyl ether of an alkylene oxide adduct thereof, such as bisphenol A, bisphenol F, or further alkylene oxide added thereto. Examples thereof include glycidyl ethers and epoxy novolac resins of the above compounds.

  Specific examples of the aliphatic epoxy resin include polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, polyglycidyl ester of an aliphatic long-chain polybasic acid, vinyl polymerization of glycidyl acrylate or glycidyl methacrylate. And homopolymers, copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and other vinyl monomers. As typical compounds, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, dipentaerythritol One or more glycidyl ethers of polyhydric alcohols such as hexaglycidyl ether, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin Polyglycidyl ether of polyether polyol, diglycidyl ester of aliphatic long-chain dibasic acid obtained by adding an alkylene oxide of And the like. In addition, monoglycidyl ethers of higher aliphatic alcohols, phenols, cresols, butylphenols, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy Examples include octyl stearate, butyl epoxy stearate, epoxidized soybean oil, and epoxidized polybutadiene.

  Commercially available products that can be suitably used as the aromatic and aliphatic epoxy resins include Epicoat 801, Epicoat 828, Epicoat YX-4000, YDE-305, 871, and 872 (manufactured by Japan Epoxy Resin Co., Ltd.), PY-306 and 0163. DY-022 (above, manufactured by Ciba Geigy), KRM-2720, EP-4100, EP-4000, EP-4080, EP-4088, EP-4900, ED-505, ED-506 (above, Asahi Denka Kogyo ( Epolite M-1230, Epolite EHDG-L, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Polite 100MF, Epolite 4000, Epolite 3002, Epolite FR-1500 (above, manufactured by Kyoeisha Chemical Co., Ltd.), Santo Tote ST0000, YD-716, YH-300, PG-202, PG-207, YD-172, YDPN638 (above Manufactured by Toto Kasei Co., Ltd.), Denacol EX321, Denacol EX313, Denacol 314, Denacol EX-411, EM-150 (Nagase Kasei Kogyo), EPPN-201, EOCN-1020, EPPN-501H (Nippon Kayaku), Bremer G (Japanese fats and oils), Epo blend (Daicel Chemical Industry), EHPE-3150 (Daicel Chemical Industry), etc. can be mentioned.

  Specific examples of the oxetane compound include the following compounds. 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3 -Oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl- 3-Oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl ( 3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3- Ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl) -3- Xetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromo Phenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1 , 3- (2-Methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bi [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane Tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-Echi -3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3- Oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3- Til-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) 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, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, etc. It comes out.

  Specific examples of commercial products that can be suitably used as the oxetane compound include Aron Oxetane OXT-101, OXT-121, OXT-221, OXT-212, OXT-211 (above, manufactured by Toagosei Co., Ltd.) ), Etanacol EHO, OXBP, OXTP, OXMA (above Ube Industries, Ltd.). These can be used alone or in combination of two or more.

  Other cationically polymerizable organic materials include oxolane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran, cyclic acetal compounds such as trioxane, 1,3-dioxolane and 1,3,6-trioxane cyclooctane, and β-propio Lactones, cyclic lactone compounds such as ε-caprolactone, thiirane compounds such as ethylene sulfide and thioepichlorohydrin, thietane compounds such as 1,3-propyne sulfide and 3,3-dimethylthietane, cyclic thioether compounds such as tetrahydrothiophene derivatives, Ethylene glycol divinyl ether, alkyl vinyl ether, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, triethylene glycol divinyl ether, 1,4-cyclohex Vinyl ether compounds such as sandimethanol divinyl ether, hydroxybutyl vinyl ether, propenyl ether of propylene glycol, spiro ortho ester compounds obtained by reaction of epoxy compounds with lactones, ethylenically unsaturated compounds such as styrene, vinylcyclohexene, isobutylene, polybutadiene and the above Derivatives and the like.

  In the present invention, one or two or more of the above-mentioned cationic organic compounds can be blended and used as the cationic polymerizable organic substance.

  In order to obtain the effect of the present invention more remarkably as the above cationic polymerizable organic substance, preferably (1) 1 to 50% by mass, more preferably 5 to 35% by mass of the cationic polymerizable organic substance is combined with the oxetane compound. It is good to do. The other cationically polymerizable organic substance component may be an epoxy resin or a cationically polymerizable organic substance other than the epoxy compound.

The energy beam sensitive cationic polymerization initiator (2) used in the present invention is a compound capable of releasing a substance that initiates cationic polymerization by irradiation with energy beam, and is particularly preferable. It is a double salt that is an onium salt that releases a Lewis acid upon irradiation, or a derivative thereof. Typical examples of such compounds include cation and anion salts represented by the general formula [A] ^{m +} [B] ^m- .

Here, the cation [A] ^{m +} is preferably onium, and the structure thereof can be represented by, for example, [(R ⁷ ) _a Q] ^{m +} . Further, R ⁷ is an organic group having 1 to 60 carbon atoms and optionally containing any number of atoms other than carbon atoms. a is an integer of 1 to 5. The a R ^{7 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] ^{m +} is q, it is necessary that the relationship m = a−q holds. However, N = N is treated as a valence of zero.

The anion [B] ^m− is preferably a halide complex, and its structure can be represented by, for example, [LX _b ] ^m− . 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] ^m− is p, it is necessary that the relationship m = b−p holds.

Specific examples of the anion [LX _b ] ^m− of the general formula include tetrafluoroborate (BF ₄ ) ⁻ , tetrakis (pentafluorophenyl) borate (B (C ₆ F ₅ ) ₄ ) ⁻ , hexafluorophosphate ( PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ^{− and the} like.

As the anion [B] ^m− , _one having a structure represented by [LX _b-1 (OH)] ^m− can be preferably used. L, X, and b are the same as described above.

Furthermore, other anions that can be used include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , and toluenesulfonate anion. , Trinitrobenzenesulfonic acid anion, tetrakis (pentafluorophenyl) borate and the like.

In the present invention, among these onium salts, it is particularly effective and preferable to use the following aromatic onium salts (a) to (c). Among these, one of them can be used alone, or two or more of them can be mixed and used.
(I) Phenyldiazonium hexafluorophosphate, phenyldiazonium tetrakis (pentafluorophenyl) borate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methoxyphenyldiazonium tetrakis (pentafluorophenyl) borate, 4-methylphenyldiazonium hexafluorophosphate Aryldiazonium salts such as 4-methylphenyldiazonium tetrakis (pentafluorophenyl) borate (ro) diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrakis (pentafluorophenyl) borate, di (4-methylphenyl) iodonium hexafluorophosphate, Di (4-methylphenyl) iodonium tetrakis (pentaful Diaryls such as orophenyl) borate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, tricumyliodonium tetrakis (pentafluorophenyl) borate Iodonium salts (c) triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, tris (4-methoxyphenyl) sulfonium tetrakis (pentafluorophenyl) Borate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl- 4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4 '-Bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4,4'-bis (diphenylsulfonio) phenyl sulfide-bis-tetrakis (pentafluorophenyl) borate, 4,4'-bis [di ( β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexa Fluorophosphate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-tetrakis (pentafluorophenyl) borate, 4- [4 ′-(benzoyl) phenylthio] phenyl-bis- (4-Fluorophenyl) sulfonium hexafluoroantimonate, 4- [4 ′-(benzoyl) phenylthio] phenyl-bis- (4-fluorophenyl) sulfonium hexafluorophosphate, 4- [4 ′-(benzoyl) phenylthio] phenyl -Bis- (4-fluorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-c B-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium tetrakis (pentafluorophenyl) Triarylsulfonium salts such as borates

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.

  Of these, aromatic iodonium salts, aromatic sulfonium salts, and iron-arene complexes are preferably used from the viewpoints of practical use and photosensitivity.

  The energy ray-sensitive cationic polymerization initiator as described above may be used in a stoichiometric amount with respect to (1) the cationic polymerizable organic material used in the present invention. It is preferable to use 0.05 to 10 parts by mass with respect to 100 parts by mass of the organic material. However, the amount of the energy ray-sensitive cationic polymerization initiator is determined according to the present invention depending on factors such as the nature of the cationically polymerizable organic substance, the irradiation intensity of energy rays such as light, the desired curing time, the physical properties of the cured product, and the cost. It is also possible to use by increasing / decreasing the above range within a range not departing from the purpose.

  The cationically polymerizable resin composition of the present invention needs to contain a functional group having acid trapping properties or proton trapping properties, and the content thereof is 0.1 to 100 g of (1) cationically polymerizable organic material. -20 mmol, preferably 0.1-10 mmol. If the functional group having acid trapping property or proton trapping property is less than the above, the post-processability which is the effect of the present invention cannot be sufficiently obtained, and if it exceeds the above, the solvent resistance becomes inferior.

  The form in which the functional group having acid trapping property or proton trapping property is contained in the cationic polymerizable resin composition of the present invention is not limited at all. For example, (1) in the cationic polymerizable organic substance which is an essential constituent component It may be contained as a functional group, and separately from this, a compound containing a functional group having acid trapping property or proton trapping property may be blended. Or both may be sufficient.

  The functional group having acid trapping property or proton trapping property is not particularly limited as long as it has acid trapping property or proton trapping property. For example, nitrile group, amino group, urethane bonding group, etc. Can be mentioned.

  When the functional group having acid trapping property or proton trapping property is contained in (1) the cationically polymerizable organic material, all compounds that can be used as the component (1) can be used as the cationically polymerizable organic material. However, it is preferable to use an epoxy compound from the viewpoint of remarkably obtaining the effects of the present invention, and an alicyclic epoxy resin is particularly suitable.

  The method for introducing these functional groups having acid trapping properties or proton trapping properties into the cationically polymerizable organic substance is not limited at all, and can be carried out by a conventional method. In the case of using an epoxy resin as the cationically polymerizable organic substance, for example, the terminal of a copolymer such as olefin and acrylonitrile such as butadiene is a group having reactivity with an epoxy resin such as a carboxyl group. What is necessary is just to make a compound react with an epoxy resin. Further, p-cyanobenzoic acid, cyanoacetic acid or the like may be reacted with the epoxy resin.

  In addition, urethane-modified epoxy resin obtained by urethane modification of an epoxy resin, for example, tetraglycidyldiaminodiphenylmethane obtained by reacting an amino compound with, for example, glycidyl ether can also be used.

  In addition, as a compound containing a functional group having acid trapping property or proton trapping property different from this, a low molecular weight compound such as acetonitrile can be used.

  The cationically polymerizable resin composition of the present invention can further contain any one or more of (3) a surface modifier, a fluidity modifier and a solvent, and the cationically polymerizable resin composition of the present invention is used as a coating. In this case, the coated object surface is preferably smoothed, the objects do not adhere to each other, and so-called slip property can be imparted.

  The surface conditioner has a function of smoothing the surface of the cured product of the cationic polymerizable resin composition of the present invention, and may be a compound known as a leveling agent or an antifoaming agent in paints and inks, An example is silicon oil. The surface conditioner is preferably used in an amount of about 0.01 to 5% by mass in the cationic polymerizable resin composition of the present invention.

  The fluidity modifier has a function of filling a fine recess on the surface of the cured product of the cationic polymerizable resin composition of the present invention and smoothing the surface, for example, silica fine powder, mineral fine powder, polymer fine powder. The known fine particle filler can be raised. The fluidity adjusting agent is preferably used in an amount of about 0.5 to 10% by mass in the cationic polymerizable resin composition of the present invention.

  The solvent has a function of lowering the viscosity of the cationic polymerizable resin composition of the present invention to smooth the surface of the cured product, for example, hydrocarbon solvents such as toluene and xylene, ethyl acetate, butyl acetate, isobutyl acetate, Examples thereof include ester solvents such as ethylene glycol monomethyl ether acetate, ether solvents such as ethylene glycol monoethyl ether, and aromatic petroleum solvents. The amount of solvent used can be arbitrarily selected according to the working environment.

  The coating agent of the present invention comprises the above-described cationic polymerizable resin composition of the present invention. The coating agent of the present invention is particularly useful for coating the surface of plastic products such as synthetic resins. In particular, the coating agent of the present invention is capable of forming a coating with good post-processability because the coating surface after application of the coating agent has a long time for post-processing such as foil stamping and printing.

  Although it does not specifically limit as a base material to which the coating agent of this invention is applied, For example, polyolefin resins, such as polyethylene and a polypropylene, a polyethylene terephthalate, a polycarbonate, ABS, a polystyrene etc. can be mentioned suitably.

  The processing method of the present invention is a processing method of the surface of the coating layer, in which after the coating layer is formed using the coating agent of the present invention, the surface of the obtained coating layer is processed.

  First, the process of forming the coating layer will be described in detail. The above-mentioned base material can be used as the base material for forming the coating layer. The coating agent of the present invention is applied to the surface of the substrate. The application method is not limited at all, and known methods such as brush coating, spraying, dipping, and spin coating can be used. In addition, although the usage-amount of a coating agent is not specifically limited, What is necessary is just to use the quantity used as about 0.5-100 micrometers in thickness as a stable coating layer after hardening, Preferably it is about 1-10 micrometers.

  Since the coating agent of the present invention consists of the cationic polymerizable resin composition of the present invention, it can be cured by irradiation with energy rays. Curing may be performed by a method of curing a conventionally known energy ray curable resin composition, and is not particularly limited. For example, irradiation with energy rays such as ultraviolet rays, visible rays, electron beams, X rays, and gamma rays is performed. In particular, ultraviolet rays are preferable. The method for generating ultraviolet rays is not particularly limited, and a known method such as a mercury lamp or an ultraviolet laser can be used. Thus, a coating layer can be formed by hardening | curing a coating agent.

  Next, the process of processing the coating layer surface will be described in detail. The processing applied to the surface of the coating layer is not particularly limited, but the surface of the coating layer by the above-described coating agent of the present invention is particularly suitable for processing such as foil pressing or printing with ink. In detail, after the coating agent is sufficiently cured, that is, without touching with a finger, it may be subjected to foil stamping or ink printing by a conventional method. By using the coating agent of the present invention, it is possible to maintain workability for a sufficient time for industrially performing foil stamping or ink printing after curing, and therefore, favorable processing can be performed.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.
Examples 1 to 11 and Comparative Examples The following cationically polymerizable organic materials, nitrile group-containing modified epoxy resins, other cationically polymerizable organic materials having functional groups having acid trapping properties or proton trapping properties, acid trapping properties or protons A compound having a trapping functional group, a cationic polymerization initiator, and other optional components were blended as shown in Table 1 to prepare various cationic polymerizable resin compositions. In addition, the numerical value in the table | surface of each component represents the mass%.
[Cationically polymerizable organic substance A]
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate [cationically polymerizable organic substance B]
Bisphenol A diglycidyl ether (trade name: EP-4100, manufactured by Asahi Denka Kogyo Co., Ltd.)
[Cationically polymerizable organic substance C]
3-ethyl-3-hydroxymethyloxetane

A cationically polymerizable resin into which a functional group having acid trapping property or proton trapping property was introduced was synthesized or obtained according to the following procedure.
[Functional group-containing resin A]
Both terminal carboxylated butadiene-acrylonitrile copolymer (trade name: HYCAR CTBN 1300 × 13, Ube Industries, Ltd., average molecular weight: 3500, nitrile group content with respect to 100 parts by mass of the above cationic polymerizable organic substance A : 0.509 mol / 100 g) 10 parts by mass were charged and reacted at 100 ° C. for 5 hours to obtain a nitrile group-containing modified epoxy resin. This was designated as functional group-containing resin A.
[Functional group-containing resin B]
Both terminal carboxylated butadiene-acrylonitrile copolymer (trade name: HYCAR CTBNX 1300 × 9, manufactured by Ube Industries, average molecular weight: 3500, nitrile group content with respect to 100 parts by mass of the above cationic polymerizable organic substance A : 0.321 mol / 100 g) 25 parts by mass were charged and reacted at 100 ° C. for 5 hours to obtain a nitrile group-containing modified epoxy resin. This was designated as functional group-containing resin B.
[Functional group-containing resin C]
With respect to 100 parts by mass of the above cationic polymerizable organic substance A, 0.5 part by mass of p-cyanobenzoic acid (molecular weight: 147.13) is charged and reacted at 100 ° C. for 5 hours to obtain a nitrile group-containing modified epoxy resin. It was. This was designated as functional group-containing resin C.
[Functional group-containing resin D]
With respect to 100 parts by mass of the above cationic polymerizable organic substance A, 0.2 part by mass of cyanoacetic acid (molecular weight: 85.06) was charged and reacted at 100 ° C. for 5 hours to obtain a nitrile group-containing modified epoxy resin. This was designated as functional group-containing resin D.
[Functional group-containing resin E]
Urethane-modified epoxy resin (trade name: EPU-1395, manufactured by Asahi Denka Kogyo Co., Ltd., urethane bond content: 31.2 mmol / 100 g)
[Functional group-containing resin F]
Tetraglycidyldiaminodiphenylmethane (molecular weight: 422.5)

[Compound having a functional group having acid trapping property or proton trapping property (functional group-containing compound)]
Acetonitrile (Molecular weight: 41.05)
[Cationic polymerization initiator]
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluorophosphate [fluidity modifier]
Silica fine powder (trade name: TS-100, manufactured by Degussa)

Furthermore, using these cationic polymerizable resin compositions as coating agents, the curability, slip property, post-workability, and alcohol resistance were tested by the methods described below. The obtained results are also shown in Table 1.
(1) Curability Each cationically polymerizable resin composition was applied on a polyethylene substrate at a thickness of about 5 μm, irradiated with about 200 mJ / cm ² of ultraviolet light using a high-pressure mercury lamp, and the surface condition was observed. Evaluation based on the criteria.
◎: No touch tack immediately after UV irradiation ○: Touch touch immediately after UV irradiation, but no touch tack within 1 minute Δ: Touch touch after UV irradiation, 1 to 10 minutes within 10 minutes Loss x: 10 minutes after UV irradiation but there is a finger touch (2) Post-processability Write the letter "A" with a line width of 2mm on the film cured by the above method with an oil-based felt pen. The repellency was observed and evaluated according to the following criteria. The evaluation was performed immediately after curing, at 25 ° C., and after one week and two weeks.
◎: Characters could be written neatly and ink was not repelled ○: Part of characters was thin, but ink was slightly repelled △: Characters could be read but some were missing and ink was repelled X: Characters could not be read, and ink repelling was remarkable. (3) Slip property The films cured by the above method were rubbed together, and the slip property was evaluated according to the following criteria based on their slip condition. .
◎: Slip smoothly, good slip property ○: Slight resistance but slip property △: Slip but considerable resistance, no slip property ×: Non-slip, no slip property (4) Alcohol resistance The cured film was post-cured at 80 ° C. for 1 hour and then rubbed 10 times with a 99.5% ethanol-impregnated cotton swab to observe the state of the film and evaluated according to the following criteria.
◎: No appearance abnormality ○: The film is not scraped, but rubbing marks remain Δ: The film is scraped, but the base is not exposed ×: The film falls off and the base is exposed

Claims (6)

An essential constituent component is a cationically polymerizable resin composition containing (1) a cationically polymerizable organic material and (2) at least a stoichiometric amount of an energy ray-sensitive cationic polymerization initiator, ) 0.1 to 20 mmol of nitrile group per 100 g of cationically polymerizable organic substance, and the nitrile group is introduced into at least a part of the (1) cationically polymerizable organic substance A cationically polymerizable resin composition for a coating agent . Wherein (1) the cationically polymerizable organic substance according to claim 1 for a coating agent cationically polymerizable resin composition wherein the epoxy compound wherein the nitrile group is introduced. The cationically polymerizable resin composition for a coating agent according to claim 1 or 2, wherein 1 to 50% by mass of the (1) cationically polymerizable organic substance is an oxetane compound. Furthermore, (3) The cationically polymerizable resin composition for coating agents as described in any one of Claims 1-3 containing any one or more of a surface modifier, a fluidity modifier, and a solvent. A coating agent comprising the cationic polymerizable resin composition for a coating agent according to any one of claims 1 to 4 . 6. A method for processing a coating layer surface, comprising forming a coating layer using the coating agent according to claim 5 and then subjecting the obtained coating layer surface to foil pressing or printing.