JPWO2016084828A1 - Cured film forming resin composition, cured film, conductive member, and method for inhibiting corrosion of metal electrode and / or metal wiring - Google Patents

Abstract

Provided a resin composition for forming a cured film comprising (meth) acrylate polymer (excluding those having a silane structure in the side chain and those having a carboxylic acid group in the side chain), an ion trap agent, and a solvent. To do.

Description

  The present invention relates to a cured film-forming resin composition, a cured film, a conductive member, and a method for inhibiting corrosion of metal electrodes and / or metal wirings.

  Conventionally, a protective film, an insulating film, and the like necessary for a touch panel and the like have been formed in a necessary portion by pattern processing by a photolithography method using a photosensitive resin composition (see, for example, Patent Document 1). However, pattern processing by the photolithography method has a problem that not only the process is complicated but also the cost is high. Therefore, there has been a demand for a composition that can form a protective film, an insulating film, and the like at a necessary site by a simpler method and at a lower cost.

  In recent years, metal materials such as silver, copper, and molybdenum have been proposed as an alternative to conventional transparent conductive materials made of metal oxides such as ITO (see, for example, Patent Document 2). It is generally known that materials corrode under the influence of oxygen and moisture in the atmosphere. Therefore, in a device having such an electrode, a member used together needs to be low corrosive from the viewpoint of improving reliability.

Special table 2009-505358 JP 2013-186632 A

  The present invention has been made in view of the above circumstances, and can be formed at a necessary site by a simple method such as a printing method, is excellent in light transmittance (transparency), and further suppresses metal corrosiveness. It is an object to provide a composition that gives a cured film, a cured film formed from the composition, a conductive member having the cured film, and a method for suppressing corrosion of metal electrodes and / or metal wirings And

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a composition containing a specific (meth) acrylate polymer, an ion trap agent and a solvent, and the present invention. Was completed.

（式中、Ｒ³は、メチル基又はエチル基を表す。Ｘは、加水分解性基を表す。Ｙは、反応性官能基を表す。ｍは、０〜３の整数である。ｎは、０〜３の整数である。）
１３．１〜１２のいずれかの硬化膜形成用樹脂組成物を用いて形成された硬化膜。
１４．金属の電極及び／又は金属の配線が形成された基材と、この基材上に前記電極及び／又は配線と接するように形成された１３の硬化膜とを備える導電性部材。
１５．金属の電極及び／又は金属の配線が形成された基材上に硬化膜を有する構造体の前記電極及び／又は配線の腐食を抑制する方法であって、
前記硬化膜を１〜１２のいずれかの硬化膜形成用樹脂組成物を用いて形成することを特徴とする方法。That is, the present invention provides the following cured film-forming resin composition, cured film, conductive member, and method for inhibiting corrosion of metal electrodes and / or metal wirings.
1. (Meth) acrylate polymer (excluding those having a silane structure in the side chain and those having a carboxylic acid group in the side chain), an ion trapping agent, and a solvent Resin composition.
2. The resin composition for 1 cured film formation in which the said ion trap agent contains the compound which has a nitrogen-type heterocyclic ring.
3. The resin composition for 1 or 2 cured film formation in which the said ion trap agent contains a benzo-1H-triazole compound.
4). The resin composition for forming a cured film according to any one of 1 to 3, wherein the solvent contains a solvent having a standard boiling point of 150 ° C. or higher.
5). The solvent is at least one selected from glycols, dialkylene glycol monoalkyl ethers, dialkylene glycol monoaralkyl ethers, dialkylene glycol monoaryl ethers, alkylene glycol monoalkyl ether acetates and alkylene glycol monoaralkyl ethers. The resin composition for cured film formation in any one of 1-3 containing a seed | species.
6). Furthermore, the resin composition for cured film formation in any one of 1-5 containing a polyfunctional (meth) acrylate compound.
7). The polyfunctional (meth) acrylate compound is at least one selected from a polyfunctional (meth) acrylate compound having three (meth) acryloyloxy groups and a polyfunctional (meth) acrylate compound having four (meth) acryloyloxy groups. 6. A resin composition for forming a cured film, comprising 6 seeds.
8). Furthermore, the resin composition for cured film formation in any one of 1-7 containing a radical polymerization initiator.
9. The resin composition for forming a cured film according to any one of 1 to 8, wherein the (meth) acrylate polymer has a weight average molecular weight of 5,000 to 200,000.
10. The resin composition for forming a cured film according to any one of 1 to 9, which is for screen printing or gravure offset printing.
11. Furthermore, the resin composition for cured film formation in any one of 1-10 containing a silane coupling agent.
12 11. The resin composition for 11 cured film formation in which the said silane coupling agent contains the silane compound represented by Formula (2).

(In the formula, R ³ represents a methyl group or an ethyl group. X represents a hydrolyzable group. Y represents a reactive functional group. M is an integer of 0 to ^3. n is It is an integer from 0 to 3.)
The cured film formed using the resin composition for cured film formation in any one of 13.1-12.
14 A conductive member comprising: a base material on which a metal electrode and / or metal wiring is formed; and 13 cured films formed on the base material so as to be in contact with the electrode and / or wiring.
15. A method of suppressing corrosion of the electrode and / or wiring of a structure having a cured film on a substrate on which a metal electrode and / or metal wiring is formed,
The said cured film is formed using the resin composition for cured film formation in any one of 1-12.

  A cured film obtained by using the resin composition for forming a cured film of the present invention can be easily formed by a simple method such as a printing method, and is excellent not only in light transmittance but also in suppressing metal corrosion. Can do. Therefore, the composition of the present invention is a material for forming a cured film such as a protective film, a planarizing film, an insulating film, etc. in various displays such as an organic electroluminescence (EL) element, a protective film in a touch panel, an insulating film, etc. Be expected.

  Moreover, the electroconductive member of this invention is equipped with the metal electrode and / or metal wiring, and the said cured film formed so that it may be contact | connected. The cured film not only has the property of high light transmittance required for cured films used in various displays such as organic EL elements, but also has reduced metal corrosivity. Corrosion of the metal electrode and / or the metal wiring is suppressed, and the durability is excellent.

  According to the method for suppressing corrosion of a metal electrode and / or metal wiring of the present invention, the cured film is formed so as to be in contact with the electrode and / or wiring. Corrosion can be effectively suppressed.

  The resin composition for forming a cured film of the present invention contains a (meth) acrylate polymer, an ion trap agent, and a solvent.

  The (meth) acrylate polymer contained in the composition of the present invention is composed of at least one monomer selected from an acrylate compound and a methacrylate compound (hereinafter sometimes collectively referred to as “(meth) acrylate compound”). A polymer having derived monomer units. However, the (meth) acrylate polymer does not contain a silane structure in the side chain from the viewpoint of storage stability. In addition, the (meth) acrylate polymer does not include those having a carboxylic acid group in the side chain from the viewpoint of suppressing metal corrosion.

In the present invention, suitable (meth) acrylate compounds include those represented by the formula (1).

In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxy group, an epoxy group, an acryloyl group, a methacryloyl group or an isocyanato group.

  The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s- Linear or branched having 1 to 20 carbon atoms such as butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group Alkyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group , A cyclic alkyl group having 3 to 20 carbon atoms such as a bicyclononyl group and a bicyclodecyl group.

  Examples of the (meth) acrylate compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, 2,2,2-trifluoroethyl acrylate, and 2,2. , 2-trifluoroethyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, etc. That. Among these, in consideration of the balance between high light transmittance and low metal corrosivity of the obtained thin film, the monomer preferably contains one kind selected from methyl methacrylate and ethyl methacrylate, and more preferably contains methyl methacrylate.

  In the present invention, the (meth) acrylate polymer may contain other monomer units other than the monomer units derived from the (meth) acrylate compound. Typical examples of monomers that give other monomer units include styrenes, vinyl compounds, maleimides, acrylonitrile, and maleic anhydride.

  Examples of styrenes include styrene, methylstyrene, chlorostyrene, bromostyrene, 4-t-butylstyrene and the like.

  Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether and the like.

  Examples of maleimides include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

  Among these, considering the hydrophobicity (low water absorption) of the obtained thin film, the monomer that gives other monomer units preferably contains styrenes, and more preferably contains styrene.

  In the present invention, considering the balance between high light transmittance and low metal corrosivity of the thin film obtained, the content of the monomer unit derived from the (meth) acrylate compound in the (meth) acrylate polymer is preferably 50 mol%. Above, more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more.

  A commercially available product may be used as the (meth) acrylate polymer, but a polymer produced by polymerizing the above-described monomers may be used.

  As the polymerization method, radical polymerization, anionic polymerization, cationic polymerization and the like can be adopted. However, since a (meth) acrylate polymer having a weight average molecular weight (Mw) necessary in the present invention can be produced relatively easily, radical polymerization can be performed. preferable.

  Initiators include peroxides such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; azobisisobutyronitrile, azobismethyl Examples include azo compounds such as butyronitrile, azobisisovaleronitrile, 2,2′-azobis (isobutyric acid) dimethyl, and the like. The amount of such an initiator used varies depending on the type and amount of the monomer and the reaction temperature, and thus cannot be defined unconditionally, but is usually about 0.005 to 0.05 mol with respect to 1 mol of the monomer. Although the reaction temperature at the time of superposition | polymerization should just set suitably from 0 degreeC to the boiling point of the solvent to be used, it is about 20-100 degreeC normally. The reaction time is about 0.1 to 30 hours.

  The polymerization is preferably performed in a solvent, and a solvent generally used in this kind of reaction can be used as the solvent used in the polymerization reaction. Specifically, water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2- Pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1- Alcohols such as hexanol, benzyl alcohol, cyclohexanol; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane; halogenation such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride Hydrocarbons; ether alcohols such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate Esters such as: n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, anisole Aliphatic or aromatic hydrocarbons such as: acetals such as methylal and diethyl acetal; fatty acids such as formic acid, acetic acid and propionic acid; nitropropane, Nitro compounds such as lobenzene; Amines such as dimethylamine, monoethanolamine and pyridine; Amides such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; Sulfoxides such as dimethyl sulfoxide; Nitriles such as acetonitrile Etc. From these, the solvent to be used is appropriately selected in consideration of the type and amount of the monomer and initiator, the reaction temperature, and the like.

  In the present invention, the Mw of the (meth) acrylate polymer is preferably 5,000 to 200,000 from the viewpoint of preparing a composition that ensures the solubility of the polymer and gives a suitable cured film. In particular, in consideration of suppressing an excessive increase in the viscosity of the composition, the upper limit value of the Mw of the polymer is preferably 180,000, more preferably 150,000, still more preferably 100,000, still more preferably. Is 80,000, and considering the suppression of an excessive decrease in the viscosity of the composition, the lower limit is preferably 10,000, more preferably 15,000, still more preferably 30,000, Preferably it is 40,000. In addition, Mw is a polystyrene conversion measured value by gel permeation chromatography (GPC).

  When the (meth) acrylate polymer is produced using two or more monomers, the (meth) acrylate polymer may be any of a random copolymer, an alternating copolymer, and a block copolymer.

  The ion trapping agent contained in the composition of the present invention migrates when the metal wiring or the like comes into contact with water, particularly when the substrate is made of metal or a metal wiring is formed on the substrate. It also has a function of preventing the occurrence of corrosion and assists the function of suppressing corrosion of the metal wiring and the like of the cured film of the present invention.

  Considering improvement of migration suppression ability of the obtained cured film and reduction of metal corrosiveness, a preferred example of the ion trapping agent is a compound having a nitrogen-based heterocyclic ring in the structure. The nitrogen-based heterocycle has a cyclic structure having a 3-membered ring or more having a saturated or unsaturated bond, and one or more nitrogen elements in the cyclic structure.

  Examples of the nitrogen-based heterocycle include those having a saturated bond, such as aziridine (ethyleneimine), azetidine (azacyclobutane), azolidine (pyrrolidine), azinan (piperidine), azepane (hexamethyleneimine), and the like. As those having a saturated bond, azirine (1H-azirine, 2H-azirine), azeto (azacyclobutadiene), azole (1H-pyrrole, 2H-pyrrole, imidazole, pyrazole, 1,2,3-triazole, 1,2 , 4-triazole, 1H-tetrazole), pyridine, azepine (azatropylidene), imidazoline, pyrazine, triazine (1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine) and the like. In addition, porphyrin, choline, which is bonded with a plurality of nitrogen-based heterocycles, Examples include phthalocyanine.

  Furthermore, it may be condensed with nitrogen-based heterocycles or aromatic ring hydrocarbon compounds (benzene ring, naphthalene ring, etc.), for example, benzotriazole, indole, isoindole, benzimidazole, quinoline, isoquinoline, quinoxaline, cinnoline, purine , Pteridine, acridine, carbazole and the like.

  It may also contain other elements other than nitrogen, such as thiazole containing sulfur element, isothiazole, thiazine, etc., oxazole containing oxygen element, isoxazole, furazane, morpholine, 3-pyrazolone, 5-pyrazolone, Examples thereof include benzoxazole.

  Furthermore, an addition compound of a nitrogen-based heterocycle in which another nitrogen-based heterocycle such as isocyanuric acid is added to these nitrogen-based heterocycles may be used. In the present invention, these nitrogen-based heterocycles can be used alone or in combination.

  Specific examples of the compound having a nitrogen-based heterocyclic ring in the structure include 2,4-diamino-6-vinyl-1,3,5-triazine, 2,4-diamino-6-vinyl-1,3,5- Triazine isocyanuric acid adduct salt, 2,4-diamino-6- (2-methacryloyloxyethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (hexyloxy) phenyl] -4,6 -Diphenyl-1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- ( 2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxy Propyloxy] phenyl] -4,6-bis (2,4-dimethyl) Enyl) -1,3,5-triazine, 2- [4- [2-hydroxy-3- (dodecyloxy) propyloxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Triazine compounds such as -1,3,5-triazine, 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine; N '-T-butyl-N-cyclopropyl-6- (methylthio) -1,3,5-triazine-2,4-diamine, 1,2,3-benzotriazole, 1,2,3-benzotriazole sodium salt 3-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, carboxybenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazo 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole, 2,2 ′-[[(methyl-1H-benzotriazol-1-yl) methyl] imino] bisethanol, 6 -(2-Benzotriazolyl) -4-t-octyl-6'-t-butyl-4'-methyl-2,2'-methylenebisphenol, 2- (5-methyl-2-hydroxyphenyl) benzotriazole 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5 Chlorobenzotriazole, 2- (2-hydroxy-3,5-di-t-pentylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole, 2- (3- Dodecyl 2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) -5 Chlorobenzotriazole, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4-tert-octylphenol], 2- (3-s-butyl-5-tert-butyl-2-hydroxyphenyl) ) Benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2-benzotriazole, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl)- Benzotriazols such as 4- (1,1,3,3-tetramethylbutyl) phenol and 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole Examples of such compounds include, but are not limited to.

  Among these, the ion trapping agent preferably includes a 1H-benzotriazole compound, more preferably includes 1H-benzotriazole which may be substituted with an alkyl group having 1 to 3 carbon atoms, and 5-methyl-1H-benzo It is even more preferable to include triazole.

  A compound having a nitrogen-based heterocycle in the structure can be synthesized by a known method or can be obtained as a commercial product. Specific examples of commercial products include Tinuvin (registered trademark) 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 571, Tinuvin 928, Tinuvin 1577, Tinuvin P, Tinuvin PS, UVITEX ( (Registered Trademark) OB, IRGAGUARD (Registered Trademark) D 1071 (above, manufactured by BASF), SB-UVA 6164, SB-UVA 6577, EVERSORB 70, EVERSORB 75 (above, manufactured by Sotte Co., Ltd.), Curazole (registered trademark) VT, Curesol VT-OK, Curesol MAVT (above, manufactured by Shikoku Kasei Kogyo Co., Ltd.), BT-120, JCL-400, CBT-1, BT-LX, TT-LX, TT-LYX, JAST-500, JF -832 (manufactured by Johoku Chemical Industry Co., Ltd.), 5MBT (manufactured by Chemipro Chemical Co., Ltd.), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.), 5-methyl-1H-benzotriazole (Tokyo Chemical Industry Co., Ltd.) ) Made)

  Other preferable examples of the ion trapping agent include hydrazide derivatives and sulfur-containing phosphites. Specific examples thereof include decamethylene dicarboxylic acid disalicyloyl hydrazide, N, N′-bis [3- [3,5-di-t-butyl-4-hydroxyphenyl] propionyl] hydrazine, 2,2′-. Oxamidobis [ethyl 3- (3,5-t-butyl-4-hydroxyphenyl) propionate], bisbenzylidene hydrazide oxalate, bis (2-phenoxypropionyl hydrazide) isophthalate, tris [2-tert-butyl-4- ( 2'-methyl-4'-hydroxy-5'-t-butylphenylthio) -5-methylphenyl] phosphite. These may be used alone or in combination of two or more.

  Hydrazide derivatives and sulfur-containing phosphites can be synthesized by known methods, and can also be obtained as commercial products. Specific examples of commercially available products include Inhibitor OABH (manufactured by Eastman), Adekastab (registered trademark) CDA-6 (manufactured by ADEKA), Irganox (registered trademark) MD 1024 (manufactured by BASF), and the like.

  The content of the ion trapping agent in the present invention is preferably 20 parts by mass or less, more preferably 10 parts from the viewpoint of obtaining a reproducible thin film excellent in hardness, adhesion and the like with respect to 100 parts by mass of the (meth) acrylate polymer. From the viewpoint of obtaining a reproducible thin film having an excellent ability to suppress migration and having reduced metal corrosivity, it is preferably 0.001 part by weight or more, more preferably 0.005 part by weight or more, and much more. Preferably it is 0.01 mass part or more.

  The composition of the present invention is a solution in which components other than the solvent are dissolved in the solvent. This solvent can dissolve the above-mentioned (meth) acrylate polymer and ion trapping agent, and further contains a polyfunctional (meth) acrylate compound, a radical polymerization initiator, a silane coupling agent, a polymerization inhibitor, other additives, etc. described later. In the case of inclusion, there is no particular limitation as long as these can be dissolved.

Specific examples of the solvent include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol (hexylene glycol), 1,3-octylene Glycols such as glycol and 3,6-octylene glycol;
Triols such as glycerin;
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, propylene glycol Propylene glycol monoalkyl ethers such as monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol monohexyl ether Alkylene glycol monoalkyl ethers;
Alkylene glycol monoaryl ethers such as ethylene glycol monoaryl ethers such as ethylene glycol monophenyl ether, propylene glycol monoaryl ethers such as propylene glycol monophenyl ether;
Alkylene glycol monoaralkyl ethers such as ethylene glycol monoaralkyl ethers such as ethylene glycol monobenzyl ether and propylene glycol monoaralkyl ethers such as propylene glycol monobenzyl ether;
Alkylene glycol alkoxyalkyl ethers such as ethylene glycol alkoxyalkyl ethers such as ethylene glycol butoxyethyl ether, propylene glycol alkoxyalkyl ethers such as propylene glycol butoxyethyl ether;
Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol diisopropyl Alkylene glycol dialkyl ethers such as ether, propylene glycol dialkyl ethers such as propylene glycol dibutyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Alkylene glycol monoalkyl ether acetates such as propylene glycol monoalkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate Over door like;
Alkylene glycol monoacetates such as ethylene glycol monoacetates such as ethylene glycol monoacetate, propylene glycol monoacetates such as propylene glycol monoacetate;
Alkylene glycol diacetates such as ethylene glycol diacetates such as ethylene glycol diacetate and propylene glycol diacetates such as propylene glycol diacetate;
Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono Dipropylene such as ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol monohexyl ether Dialkylene glycol monoalkyl ethers such as recall monoalkyl ethers;
Dialkylene glycol monoaralkyl ethers such as diethylene glycol monobenzyl ether;
Dialkylene glycol monoaryl ethers such as diethylene glycol monoaryl ethers such as diethylene glycol monophenyl ether, dipropylene glycol monoaryl ethers such as dipropylene glycol monophenyl ether;
Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol diisopropyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol diisopropyl ether, Dialkylene glycol dialkyl ethers such as dipropylene glycol dialkyl ethers such as dipropylene glycol dibutyl ether;
Diethylene glycol monoalkyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoisopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoisobutyl ether acetate, diethylene glycol monohexyl ether acetate and other diethylene glycol monoalkyl ether acetates, dipropylene Glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monoisopropyl ether acetate, dipropylene glycol monobutyl Ether acetate, dipropylene glycol monoisobutyl ether acetate, dipropylene glycol monoalkyl ether acetates dialkylene glycol monoalkyl ether acetates such as such as dipropylene glycol monohexyl ether acetate;
Trialkylene glycol monoalkyl ethers such as triethylene glycol monoalkyl ethers such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, and tripropylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether Ethers;
Trialkylene glycol dialkyl ethers such as triethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether and triethylene glycol diethyl ether; and tripropylene glycol dialkyl ethers such as tripropylene glycol dimethyl ether and tripropylene glycol diethyl ether;
1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tetradecanol Aliphatic alcohols such as linear aliphatic alcohols such as cycloaliphatic alcohols such as cyclohexanol and 2-methylcyclohexanol;
Phenols such as phenol;
Aromatic alcohols such as benzyl alcohol;
Heterocycle-containing alcohols such as furfuryl alcohol;
Hydrogenated heterocycle-containing alcohols such as tetrahydrofurfuryl alcohol;
Dialkyl ethers such as diisopropyl ether, di-n-butyl ether, di-n-hexyl ether;
Methyl phenyl ether, ethyl phenyl ether, n-butyl phenyl ether, benzyl (3-methylbutyl) ether, (2-methylphenyl) methyl ether, (3-methylphenyl) methyl ether, (4-methylphenyl) methyl ether, etc. Alkyl aryl ethers;
Alkyl aralkyl ethers such as ethyl benzyl ether;
Cyclic alkyl monoethers such as 2-methylfuran, tetrahydrofuran, tetrahydropyran;
Cyclic alkyl diethers such as 1,4-dioxane;
Cyclic alkyl triethers such as trioxane;
Diepoxyalkyl ethers such as diglycidyl ether;
Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, s-butyl acetate, t-butyl acetate, n-pentyl acetate, (3-methylbutyl) acetate, n-hexyl acetate, (2-ethylbutyl ) Alkyl acetates such as linear or branched alkyl acetates such as acetate and (2-ethylhexyl) acetate, cyclic alkyl acetates such as cyclohexyl acetate and 2-methylcyclohexyl acetate; ethyl propionate, n-propyl Pionate, isopropylpropionate, n-butylpropionate, isobutylpropionate, s-butylpropionate, t-butylpropionate, n-pentylpropionate, (3-me Linear or branched alkyl propionates such as (tilbutyl) propionate, n-hexylpropionate, (2-ethylbutyl) propionate, (2-ethylhexyl) propionate, cyclohexylpropionate, 2-methylcyclohexylpropionate Alkyl propionates such as cyclic alkyl propionates such as: ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, s-butyl butyrate, t-butyl butyrate Linear or branched alkyl butyrates such as acrylate, n-pentyl butyrate, (3-methylbutyl) butyrate, n-hexyl butyrate, (2-ethylbutyl) butyrate, (2-ethylhexyl) butyrate, cyclohexyl butyrate , 2- Alkyl butyrates such as cyclic alkyl butyrates such as tilcyclohexyl butyrate; ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, s-butyl lactate, t-butyl lactate, n-pentyl Linear or branched alkyl lactates such as lactate, (3-methylbutyl) lactate, n-hexyl lactate, (2-ethylbutyl) lactate, (2-ethylhexyl) lactate, cyclic such as cyclohexyl lactate, 2-methylcyclohexyl lactate Alkyl esters such as alkyl lactates such as alkyl lactates;
Aralkyl acetates such as aralkyl acetates such as benzyl acetate, aralkylpropionates such as benzylpropionate, aralkylbutyrates such as benzylbutyrate, aralkyllactates such as benzyllactate;
Dialkyl ketones such as diethyl ketone, diisobutyl ketone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-propyl ketone, methyl n-hexyl ketone, ethyl n-butyl ketone, di-n-propyl ketone Kind;
Cyclic alkenyl ketones such as isophorone;
Cyclic alkyl ketones such as cyclohexanone;
Hydroxydialkyl ketones such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol);
Heterocycle-containing aldehydes such as furfural;
Linear or branched alkanes such as heptane, octane, 2,2,3-trimethylhexane, decane, dodecane;
Alkylbenzenes such as toluene, xylene, o-xylene, m-xylene, p-xylene, mesitylene, tetralin, cyclohexylbenzene;
Examples include, but are not limited to, cyclic alkanes such as cyclohexane, methylcyclohexane, and ethylcyclohexane. These solvents can be used alone or in combination of two or more.

  The composition of the present invention is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, even more preferably 200 ° C. or higher, from the viewpoint of obtaining a suitable film with good reproducibility when the composition is applied by a printing method. Includes a solvent having a normal boiling point. By including a solvent having such a boiling point, a suitable liquid film state can be realized with good reproducibility.

  Under these circumstances, when the printing method is adopted as the coating method, the composition of the present invention is a solvent having characteristics of dissolving the (meth) acrylate polymer well, specifically, glycols, dialkylene glycol. It is preferable to contain at least one selected from monoalkyl ethers, dialkylene glycol monoaralkyl ethers, dialkylene glycol monoaryl ethers, alkylene glycol monoalkyl ether acetates and alkylene glycol monoaralkyl ethers.

  Specific examples of such solvents include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, Triethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monophenyl ether, ethylene glycol monoben Ether, diethylene glycol benzyl ether, and the like, without limitation.

  The amount of the solvent is preferably such that the solid content concentration in the composition of the present invention is 1 to 95% by mass, more preferably the solid content concentration is 5 to 90% by mass, and the solid content concentration is 10%. An amount that is ˜85 mass% is even more preferred. Here, solid content means what remove | excluded the solvent from all the components of the resin composition for cured film formation of this invention.

  As described above, the composition of the present invention contains a (meth) acrylate polymer, an ion trap agent and a solvent, but for the purpose of adjusting the adhesion and hardness of the cured film, etc., a polyfunctional (meth) acrylate compound, radical polymerization An initiator, a silane coupling agent, a polymerization inhibitor, and the like may be included.

  The composition of the present invention may contain a polyfunctional (meth) acrylate compound from the viewpoint of improving hardness. The polyfunctional (meth) acrylate compound is a compound having at least three (meth) acryloyloxy groups in the molecule, and specifically includes an ester of a polyhydric alcohol and (meth) acrylic acid. . The number of (meth) acryloyloxy groups in one molecule of the polyfunctional (meth) acrylate compound is 3 to 6, preferably 3 or 4. Examples of such polyhydric alcohols include glycerol, erythritol, pentaerythritol, trimethylolethane, trimethylolpropane, dipentaerythritol, ditrimethylolpropane, and the like.

  Specific examples of the polyfunctional (meth) acrylate compound include pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and the like. Polyfunctional (meth) acrylate compound having four (meth) acryloyl groups, polyfunctional (meth) acrylate compound, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, etc. (Meth) acrylate compound, dipentaerythritol hexaacrylate, dipentaerythritol hexame Examples include, but are not limited to, polyfunctional (meth) acrylate compounds having five or six (meth) acryloyl groups, such as tacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and the like. A polyfunctional (meth) acrylate compound can be used individually by 1 type or in combination of 2 or more types.

  The polyfunctional (meth) acrylate compound can be easily obtained as a commercial product. Specific examples thereof include, for example, KAYARAD (registered trademark) T-1420, DPHA, DPHA-2C manufactured by Nippon Kayaku Co., Ltd. , D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, MANDA, GPO-303, TMPTA, THE-330, TPA -320, TPA-330, PET-30, RP-1040; Aronix (registered trademark) M-6200, M-309, M-400, M-402, M-405, M-450, manufactured by Toagosei Co., Ltd. M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050; Biscoat 295 manufactured by Osaka Organic Chemical Industry Co., Ltd. , 300, 360, GPT, 3PA, 400, 312; Shin Nakamura Chemical Co., Ltd. NK ester A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3 A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, and the like.

  According to a preferred embodiment of the present invention, the polyfunctional (meth) acrylate compound contained in the composition of the present invention comprises at least one polyfunctional (meth) acrylate compound having 3 or 4 (meth) acryloyloxy groups. Including.

  10-300 mass parts is preferable with respect to 100 mass parts of (meth) acrylate polymers, as for content of a polyfunctional (meth) acrylate compound, 20-200 mass parts is more preferable, and 50-150 mass parts is still more preferable. When the content is less than 10 parts by mass, the effect of improving the hardness of the cured film may not be obtained, and when it exceeds 300 parts by mass, cracks may easily occur.

  The composition of the present invention may contain a radical polymerization initiator in order to promote polymerization of the polymerizable component contained in the composition. For example, when there is a situation in which high-temperature curing treatment cannot be performed, for example, the substrate is denatured by treatment at a high temperature, but the substrate is denatured, a low-temperature curing treatment or a photo-curing treatment can be performed by the radical polymerization initiator.

The radical polymerization initiator may be any substance that can release a substance that initiates radical polymerization by light irradiation and / or heating. For example, photo radical polymerization initiators include benzophenone derivatives, imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocene compounds, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives. Etc. More specifically, benzophenone, 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone, 3-phenyl-5 Isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) butan-1-one, bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrole) Examples include, but are not limited to, 1-yl) phenyl) titanium and the like.

  Commercially available products can also be used as the photo radical polymerization initiator, and examples thereof include IRGACURE (registered trademark) 651, 184, 369, and 784 manufactured by BASF. Commercial products other than those described above can also be used. Specifically, IRGACURE 500, 907, 379, 819, 127, 500, 754, 250, 1800, 1870, OXE01, TPO, DAROCUR (registered trademark) 1173 manufactured by BASF Lambson Speedcure (registered trademark) MBB, PBZ, ITX, CTX, EDB; Lamberti Esacure (registered trademark) ONE, KIP150, KTO46; Nippon Kayaku Co., Ltd. KAKACURE (registered trademark) DETX-S, CTX , BMS, DMBI and the like.

  Examples of the thermal radical polymerization initiator include acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, Peroxides such as lauroyl peroxide, t-butylperoxyacetate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate (t-butyl-2-ethylhexaneperoxoate); 2,2′-azo Bisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) , Dimethyl 2,2 ' -Azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile, 2,2 Azo compounds such as' -azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane); ammonium persulfate Persulfates such as sodium persulfate and potassium persulfate, but are not limited thereto.

  Examples of commercially available thermal radical polymerization initiators include, for example, NOF Corporation Parroyl (registered trademark) IB, NPP, IPP, SBP, TCP, OPP, SA, 355, L, perbutyl (registered trademark) ND, NHP, MA, PV, 355, A, C, D, E, L, I, O, P, Z, Perhexyl (registered trademark) ND, PV, D, I, O, Z, Perocta (registered trademark) ND, Nyper ( (Registered trademark) PMB, BMT, BW, pertetra (registered trademark) A, perhexa (registered trademark) MC, TMH, HC, 250, 25B, C, 25Z, 22, V, perocta (registered trademark) O, park mill (registered trademark) ) ND, D, Permenta (registered trademark) H, NOFMER (registered trademark) BC; V-70, V-65, V-59, V-40, V-30, VA-044 manufactured by Wako Pure Chemical Industries, Ltd. , VA-046B, VA-061, V-50, VA-057, VA-086, VF-096, VAm-110, V-601, V-501; IRGACURE 184, 369, 651, 500, 819 manufactured by BASF 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, TPO, DAROCUR 1116, 1173; Yarutizu Co. UVECRYL (registered trademark) P36; Lamberti Co. Esacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / but B, and the like, without limitation.

  The content of the radical polymerization initiator is preferably 1 to 20 parts by mass and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the (meth) acrylate polymer.

  The composition of the present invention may contain a silane coupling agent from the viewpoint of improving the adhesion of the resulting cured film to the substrate, and according to a preferred embodiment, the silane coupling agent is represented by the formula (2). The silane compound represented by these is included.

In formula (2), R ³ represents a methyl group or an ethyl group. X represents a hydrolyzable group. Y represents a reactive functional group. m is an integer of 0-3. n is an integer of 0 to 3, preferably an integer of 0 to 2.

  Examples of the hydrolyzable group represented by X include a halogen atom, an alkoxy group having 1 to 3 carbon atoms, and an alkoxyalkoxy group having 2 to 4 carbon atoms. Examples of the halogen atom include a chlorine atom and a bromine atom. The alkoxy group having 1 to 3 carbon atoms is preferably linear or branched, and specifically includes a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. Specific examples of the alkoxyalkoxy group having 2 to 4 carbon atoms include a methoxymethoxy group, a 2-methoxyethoxy group, an ethoxymethoxy group, and a 2-ethoxyethoxy group.

  Examples of the reactive functional group represented by Y include an amino group, a ureido group, a (meth) acryloyloxy group, a vinyl group, an epoxy group, a mercapto group, etc. Among them, an amino group, a ureido group, and a (meth) acryloyl group. An oxy group is preferred. An amino group or a ureido group is more preferable.

  Specific examples of the silane coupling agent include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl (methyl) (dimethoxy) silane, 3-aminopropyl ( Methyl) (diethoxy) silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3 -Mercaptopropyl (methyl) (dimethoxy) silane, 3-mercaptopropyl (methyl) (diethoxy) silane, etc. are mentioned.

  Among them, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxy Silane and the like are preferable.

  The silane coupling agent can be synthesized by a known method or can be obtained as a commercial product. Moreover, a silane coupling agent can be used 1 type or in combination of 2 or more types.

  The content of the silane coupling agent is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the (meth) acrylate polymer. Even more preferred. If the content is less than 0.001 part by mass, the effect of improving the adhesion may not be obtained, and if it exceeds 10 parts by mass, the hardness may decrease.

  The composition of this invention may contain the polymerization inhibitor as needed. Specific examples of the polymerization initiator include 2,6-diisobutylphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, 4-methoxy-1-naphthol and the like can be mentioned. The content of the polymerization inhibitor is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total solid content. When the content exceeds 1% by mass, the reaction may be insufficient and may not be cured sufficiently.

  The composition of the present invention may further comprise a surfactant, a crosslinking agent, an antifoaming agent, a rheology modifier, a pigment, a dye, a storage stabilizer, a polyhydric phenol, A dissolution accelerator such as a polyvalent carboxylic acid can be included.

  Although it does not specifically limit as surfactant, For example, a fluorine-type surfactant, a silicon-type surfactant, a nonionic surfactant, etc. are mentioned. Examples of this type of surfactant include, for example, F-top (registered trademark) EF301, EF303, EF352 manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd .; Mega-Fac® (registered trademark) F171, F173 manufactured by DIC Corporation; FLUORAD manufactured by 3M (Registered trademark) FC430, FC431; Asahi Guard Co., Ltd. Asahi Guard (registered trademark) AG710, AGC Seimi Chemical Co., Ltd. Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106, etc. Can be mentioned.

  Examples of the crosslinking agent include a polyfunctional epoxy compound, a polyfunctional isocyanate compound, a polyfunctional thiol compound, and a melamine-based crosslinking agent. When a polyfunctional (meth) acrylate compound is included, a trifunctional or higher functional thiol compound is preferable. The polyfunctional thiol compound can be obtained as an addition reaction product of a polyhydric alcohol and a monofunctional and / or polyfunctional thiol compound. Specific compounds include 1,3,5-tris (2- (3-mercaptopropionyloxy) ethyl) isocyanurate, 1,3,5-tris (2- (3-mercaptobutyryloxy) ethyl) isocyanate. Trifunctional thiol compounds such as nurate (manufactured by Showa Denko KK, Karenz MT (registered trademark) NR1), trimethylolpropane tris (3-mercaptopropionate); pentaerythritol tetrakis (3-mercaptopropionate), penta Tetrafunctional thiol compounds such as erythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko KK, Karenz MT PEI); hexafunctional thiol compounds such as dipentaerythritol hexakis (3-mercaptopropionate) It is done.

  Antifoaming agents include, but are not limited to, acetylene glycol, silicone fluids and emulsions, ethoxylated or propoxylated silicones, hydrocarbons, fatty acid ester derivatives, acetylated polyamides, poly (alkylene oxide) polymers and copolymers, and the like. . When screen printing is performed, the composition of the present invention preferably contains an antifoaming agent.

  The viscosity at 25 ° C. of the composition of the present invention is preferably 1 to 10,000 mPa · s, more preferably 1 to 5,000 mPa · s, and still more preferably 1 to 1,000 mPa · s from the viewpoint of applicability. It is. If the viscosity is too low, the desired film thickness may not be obtained, and if the viscosity is too high, the coatability may deteriorate.

  In addition, the viscosity at 25 ° C. of the composition of the present invention is preferably 10 to 100,000 mPa · s, more preferably 500 to 100,000 mPa · s, and still more preferably 1,000 to 100 from the viewpoint of printability. 1,000 mPa · s. If the viscosity is too low, the composition may diffuse after application, and a desired pattern may not be formed. If the viscosity is too high, the discharge performance may be reduced, and a load on the process may occur. Transferability to the surface may be reduced.

  Printing methods such as screen printing and gravure offset printing are used when forming a hardened film with a fine structure, such as an insulating film to form a bridge structure, in the touch panel where the X-axis electrode and Y-axis electrode intersect at right angles. The viscosity at 25 ° C. of the composition of the present invention is preferably 10 to 100,000 mPa · s, more preferably 5,000 to 100,000 mPa · s, and even more preferably 20,000 to 100,000 mPa · s. -S. If the viscosity is too low, the composition may diffuse after application, and a desired pattern may not be formed. If the viscosity is too high, the discharge performance may be reduced, and a load on the process may occur. Transferability to the surface may be reduced. In the present invention, the viscosity is a value measured with an E-type viscometer.

  The method for preparing the composition of the present invention is not particularly limited. An example is a method in which a (meth) acrylate polymer is dissolved in a solvent, and an ion trapping agent is mixed in this solution at a predetermined ratio to obtain a uniform solution. Moreover, the preparation method which mixes a radical polymerization initiator, a silane coupling agent, a polymerization inhibitor, another additive etc. as needed in the suitable step of this preparation method is mentioned.

  In preparing the composition of the present invention, a (meth) acrylate polymer-containing solution obtained by a polymerization reaction in a solvent can be used as it is. In this case, as described above, an ion trapping agent or the like may be added to the (meth) acrylate polymer-containing solution to make a uniform solution. Further, a solvent may be further added for the purpose of adjusting the concentration.

  From the viewpoint of obtaining a more uniform cured film, the composition thus prepared is preferably used after being filtered using a filter having a pore diameter of about 0.2 μm.

  The composition of the present invention is applied to a substrate having electrodes and / or wirings (for example, a silicon / silicon dioxide-coated substrate; a silicon nitride substrate; a metal such as aluminum, molybdenum, chromium, copper, or silver; a metal nanowire such as a silver nanowire; Metal nanoparticles such as silver nanoparticles and copper nanoparticles, poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonate) (PEDOT / PSS), conductive polymers such as graphene and carbon nanotubes are coated Glass substrate; quartz substrate; ITO substrate; ITO film substrate; TAC film, polyester film, acrylic film, resin film substrate such as cycloolefin (COP) film), etc., spin coating, flow coating, roll coating , Slit coating, spin coating following slit, ink jet coating, screen marking , Flexographic printing, gravure printing, offset printing, coated by a printing method such as gravure offset printing, followed by pre-drying (prebaking) on a hot plate or an oven or the like, it is possible to form a coating film. The composition of the present invention is particularly suitable for printing methods such as inkjet coating, screen printing, flexographic printing, and gravure offset printing.

  In general, the pre-baking is preferably performed at 60 to 150 ° C., more preferably 80 to 120 ° C., for 0.5 to 30 minutes when using a hot plate, and 0.5 to 90 minutes when using an oven. The method is taken.

  Next, post-baking for heat curing is performed. Specifically, heating is performed using a hot plate, an oven, or the like. In general, the post-bake is preferably performed at 150 to 300 ° C., more preferably 200 to 250 ° C., for 1 to 30 minutes when using a hot plate, and 1 to 90 minutes when using an oven. It is done.

  When the composition of the present invention contains a thermal radical polymerization initiator, curing at a low temperature is possible. In this case, the pre-bake conditions are the same as described above, but the post-bake temperature is preferably 60 to 200 ° C, more preferably 80 to 150 ° C. Other conditions are the same as described above.

Moreover, when the composition of this invention contains a radical photopolymerization initiator, photocuring can be performed by irradiating light, such as an ultraviolet-ray, to the said coating film after prebaking. Light such as ultraviolet rays has a wavelength in the range of 200 to 500 nm, and the exposure amount is preferably 100 to 5,000 mJ / cm ² .

  After photocuring, post-baking for heat curing may be performed. Specifically, heating is performed using a hot plate, an oven, or the like. In general, post-baking is preferably performed at 60 to 150 ° C., more preferably 80 to 120 ° C., for 1 to 30 minutes when using a hot plate, and 1 to 90 minutes when using an oven. It is done.

  By curing the composition of the present invention under the above conditions, the step of the substrate can be sufficiently flattened, and a cured film having high light transmittance can be formed.

  The cured film of the present invention can be easily formed by a simple method such as a printing method, and is excellent not only in light transmittance but also in suppressing metal corrosion, so that it is a protective film in various displays such as organic EL elements. It is expected as a material for forming a cured film such as a protective film or an insulating film in a touch panel, such as a planarizing film or an insulating film.

  The conductive member having the cured film of the present invention formed so as to be in contact with the electrode and / or the wiring on the substrate on which the metal electrode and / or the metal wiring is formed has the corrosion of the electrode and / or the wiring. Therefore, an increase in resistance in the electrodes and wiring, separation between the electrodes and metal and other members, and the like are suppressed, and as a result, durability is excellent.

  According to the method for inhibiting corrosion of an electrode and / or wiring of the present invention, the above-mentioned cured film is formed so as to be in contact with the metal electrode and / or the metal wiring. Wiring corrosion can be effectively suppressed. The method of the present invention is effective for inhibiting corrosion of metals such as silver, copper, gold, aluminum, nickel, tin, lead, and palladium.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated in more detail, this invention is not limited to the following Example. In addition, Mw of the copolymer obtained in the synthesis example used Showa Denko Co., Ltd. GPC apparatus (Shodex GPC-101, column: Shodex (trademark) KF803L and KF804L (Showa Denko Co., Ltd. product)). The elution solvent tetrahydrofuran was flowed through a column (column temperature: 40 ° C.) at a flow rate of 1 mL / min for elution. Mw was expressed in terms of polystyrene.

The abbreviations of the reagents used and the equipment used are as follows.
-DEGMEA (diethylene glycol monoethyl ether acetate), MMA (methyl methacrylate), MAA (methacrylic acid), ST (styrene), EMA (ethyl methacrylate): manufactured by Tokyo Chemical Industry Co., Ltd.-MAIB: 2,2'- Azobis (isobutyric acid) dimethyl, manufactured by Tokyo Chemical Industry Co., Ltd. PET-30: Pentaerythritol (tri / tetra) acrylate, manufactured by Nippon Kayaku Co., Ltd. 5-MBT: 5-methylbenzotriazole, Tokyo Chemical Industry ( IRG184: photopolymerization initiator, IRGACURE 184 manufactured by BASF
APS: 3-aminopropyltriethoxysilane, Shin-Etsu Chemical Co., Ltd. LS-3150
・ AGITAN 771: Antifoaming agent, manufactured by MUNZING ・ Stirrer: Shintaro Awatori Nertaro ARE-310
・ Viscosity measuring device: TVE-20LT, TVE-20HT manufactured by Toki Sangyo Co., Ltd.

[1] Synthesis of polymer [Synthesis Example 1]
In a 1,000 mL four-necked flask, 60,000 g of DEGMEA was added, and while stirring at 70 ° C. (internal temperature) under a nitrogen atmosphere, a mixed solution of EMA 392.1 g and MAIB 7.9 g was slowly added dropwise over 2 hours. did. After dripping, it was further reacted at 70 ° C. for 20 hours to obtain a polymer solution P1. Mw = about 50,000.

[Synthesis Example 2]
In a 1,000 mL four-necked flask, 60.000 g of DEGMEA was placed and stirred at 70 ° C. (internal temperature) under a nitrogen atmosphere, and a mixed solution of MMA 310.2 g, ST80.9 g and MAIB 8.9 g was added for 2 hours. The solution was slowly added dropwise. After dropping, the mixture was further reacted at 70 ° C. for 20 hours to obtain a polymer solution P2. Mw = about 50,000.

[Comparative Synthesis Example 1]
In a 1,000 mL four-necked flask, 532.0 g of DEGMEA was placed and stirred at 70 ° C. (internal temperature) under a nitrogen atmosphere, and MMA 280.0 g, MAA 30.1 g, ST 36.5 g and MAIB 8.1 g were mixed therein. The solution was slowly added dropwise over 2 hours. After the dropping, the reaction was further continued at 70 ° C. for 20 hours to obtain a polymer solution P3. Mw = about 50,000.

[2] Preparation of resin composition for forming cured film [Example 1]
In a 200 mL plastic container, 55.1 g of the polymer solution P1 obtained in Synthesis Example 1, 24.3 g of PET-30, 1.3 g of IRG184, 1.3 g of 5-MBT, 0.02 g of APS, AGITAN771 0.03 g and DEGMEA 17.9 g were put into a stirrer and stirred for 10 minutes at 2,000 rpm to prepare a varnish. The viscosity of the obtained varnish was 3,100 mPa · s.

[Example 2, Comparative Example 1]
The polymer solution P1 obtained in Synthesis Example 2 (Example 2) or the polymer solution P3 obtained in Comparative Synthesis Example 1 (Comparative Example 1) was used in place of the polymer solution P1 obtained in Synthesis Example 1. Prepared a varnish in the same manner as in Example 1. The viscosity of the obtained varnish of Example 2 was 3,900 mPa · s.

[3] Production of cured film and its evaluation The light transmittance was measured and the metal corrosivity was evaluated by the following methods.
[3-1] Measurement of Light Transmittance Each of the varnishes of Examples 1 and 2 and Comparative Example 1 was applied on a glass substrate by spin coating, and prebaked at 110 ° C. for 2 minutes. Subsequently, UV irradiation (800 mJ / cm ² ) was performed, and then post-baking was performed at 110 ° C. for 30 minutes to produce a cured film having a thickness of about 5 μm. The UV-visible absorption spectrum was measured for light transmittance at a wavelength of 400 nm of the cured film using UV-3100PC manufactured by Shimadzu Corporation. The results are shown in Table 1.

[3-2] Evaluation of metal corrosiveness The varnishes of Examples 1 and 2 and Comparative Example 1 were each applied by spin coating onto the MAM of a glass substrate (hereinafter referred to as MAM substrate) with MAM (Molybten / Aluminum / Molybten). First, pre-baking was performed at 110 ° C. for 2 minutes. Subsequently, UV irradiation (800 mJ / cm ² ) was performed, and then post-baking was performed at 110 ° C. for 30 minutes, and a cured film having a thickness of about 5 μm was formed on the MAM. And the resistance value of MAM in each of these MAM board | substrates with a cured film and the resistance value of MAM in a MAM board | substrate without cured film formation were measured, respectively, the difference was computed, and the metal corrosivity of each cured film was evaluated. The resistance value of MAM on the MAM substrate was 0.2388 (Ω / □). The results are shown in Table 1.

  As is clear from Table 1, the cured films obtained from the varnishes of Examples 1 and 2 were excellent in light transmittance. Moreover, the resistance value of the metal in the metal substrate having the cured film was lower than that of the metal in the metal substrate having the cured film obtained from the varnish of the comparative example. Specifically, the difference between the resistance of the metal in the metal substrate having no cured film and the resistance value of the metal in the metal substrate having the cured film obtained from the varnish of the example is the cured obtained from the varnish of the comparative example. When compared with that of the metal in the metal substrate having the film, it was 1/10 or less, and the metal corrosivity of the cured film according to the example was suppressed.

Claims (15)

  (Meth) acrylate polymer (excluding those having a silane structure in the side chain and those having a carboxylic acid group in the side chain), an ion trapping agent, and a solvent Resin composition.   The resin composition for forming a cured film according to claim 1, wherein the ion trapping agent contains a compound having a nitrogen-based heterocyclic ring.   The resin composition for forming a cured film according to claim 1 or 2, wherein the ion trapping agent contains a benzo-1H-triazole compound.   The resin composition for forming a cured film according to any one of claims 1 to 3, wherein the solvent contains a solvent having a normal boiling point of 150 ° C or higher.   The solvent is at least one selected from glycols, dialkylene glycol monoalkyl ethers, dialkylene glycol monoaralkyl ethers, dialkylene glycol monoaryl ethers, alkylene glycol monoalkyl ether acetates and alkylene glycol monoaralkyl ethers. The resin composition for cured film formation of any one of Claims 1-3 containing a seed | species.   Furthermore, the resin composition for cured film formation of any one of Claims 1-5 containing a polyfunctional (meth) acrylate compound.   The polyfunctional (meth) acrylate compound is at least one selected from a polyfunctional (meth) acrylate compound having three (meth) acryloyloxy groups and a polyfunctional (meth) acrylate compound having four (meth) acryloyloxy groups. The resin composition for cured film formation of Claim 6 containing a seed | species.   Furthermore, the resin composition for cured film formation of any one of Claims 1-7 containing a radical polymerization initiator.   The resin composition for forming a cured film according to any one of claims 1 to 8, wherein the (meth) acrylate polymer has a weight average molecular weight of 5,000 to 200,000.   The resin composition for forming a cured film according to any one of claims 1 to 9, which is used for a screen printing method or a gravure offset printing method.   Furthermore, the resin composition for cured film formation of any one of Claims 1-10 containing a silane coupling agent. The resin composition for forming a cured film according to claim 11, wherein the silane coupling agent contains a silane compound represented by the formula (2).

(In the formula, R ³ represents a methyl group or an ethyl group. X represents a hydrolyzable group. Y represents a reactive functional group. M is an integer of 0 to ^3. n is It is an integer from 0 to 3.)   The cured film formed using the resin composition for cured film formation of any one of Claims 1-12.   An electroconductive member provided with the base material in which the metal electrode and / or metal wiring were formed, and the cured film of Claim 13 formed so that it might contact | connect the said electrode and / or wiring on this base material. A method of suppressing corrosion of the electrode and / or wiring of a structure having a cured film on a substrate on which a metal electrode and / or metal wiring is formed,
The said cured film is formed using the resin composition for cured film formation of any one of Claims 1-12.