KR20170033813A - Resin composition for forming cured film, cured film, electrically conductive member, and method for preventing migration - Google Patents

Abstract

(A) a migration inhibitor and ion trap agent comprising a (meth) acrylate polymer having a weight average molecular weight of 5,000 to 200,000 (provided that the side chain has no silane structure), (B) a benzotriazole compound, and (C) a solvent for forming a cured film.

Description

TECHNICAL FIELD [0001] The present invention relates to a resin composition for forming a cured film, a cured film, a conductive member, and a method of suppressing migration,

The present invention relates to a resin composition for forming a cured film, a cured film, a conductive member, and a method of inhibiting migration.

BACKGROUND ART [0002] Conventionally, a protective film, an insulating film, and the like necessary for a touch panel and the like have been formed at a necessary portion by pattern processing by a photolithography method using a photosensitive resin composition (Patent Document 1).

However, there has been a problem that pattern processing by the photolithography method is not only complicated in process but also is costly. For this reason, a composition capable of forming a protective film, an insulating film, and the like at a necessary site with a simpler method and at a lower cost has been desired.

In addition, the use of film substrates in place of glass substrates is increasing due to demands on transportation and storage. The film substrate is preserved in a roll shape or the like at the time of storage. At this time, since the substrate is curved, flexibility of the material to be coated on the film substrate is required.

In addition, although various developments have been made with respect to touch panels using metal nanowires as a substitute for ITO (Patent Document 2, etc.), there is a problem in that such a touch panel causes migration of metal, Therefore, there is a demand for an overcoat material for protecting electrodes, wiring, and the like, which can suppress migration.

On the other hand, the conventional overcoat material is intended to be coated on a glass substrate and contains inorganic fine particles in order to increase the hardness (Patent Document 3). However, in the conventional methods such as the incorporation of the inorganic fine particles, the hardness is improved, but there is a problem in that there is no flexibility and, for example, cracking occurs when bent, so that it can be applied to a film substrate There was no situation.

Japanese Patent Laid-Open Publication No. 2013-064973 Japanese Patent Application Laid-Open No. 2013-225296 Japanese Patent Laid-Open Publication No. 121-116975

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a cured film having a high light transmittance, high adhesion, hardness and high flexibility, A curable film formed from the composition, a conductive member having the cured film, and a migration inhibiting method.

As a result of intensive investigations to solve the above problems, the present inventors have found that a composition containing a (meth) acrylate polymer having a weight average molecular weight of 5,000 to 200,000, a migration inhibitor / ion trap agent comprising a benzotriazole compound and a solvent , The present inventors have found that the above problems can be solved and the present invention has been accomplished.

That is, the present invention provides the following resin composition for forming a cured film, a cured film, a conductive member, and a method of inhibiting migration.

1. (A) a (meth) acrylate polymer having a weight average molecular weight of 5,000 to 200,000 (except those having a silane structure in the side chain),

(B) a migration inhibitor / ion trap agent comprising a benzotriazole compound and

(C) Solvent

And a curing accelerator.

2. A resin composition for forming a cured film, which further comprises (D) a silane coupling agent.

3. A resin composition for forming a cured film of 1 or 2 further containing (E) a polyfunctional (meth) acrylate compound.

4. A resin composition for forming a cured film 3 further containing (F) a radical polymerization initiator.

5. The resin composition for forming a cured film according to any one of 1 to 4, wherein the benzotriazole compound (B) is contained in an amount of 0.1 to 50 parts by mass based on 100 parts by mass of the component (A).

6. A cured film formed by using any one of the resin compositions for forming a cured film.

7. A conductive member comprising a substrate on which electrodes and / or wires are formed, and a cured film of 6 formed on the substrate so as to contact the electrodes and / or wires.

8. A method for suppressing migration of a structure having a cured film formed from a resin composition for forming a cured film on a substrate on which electrodes and / or wires are formed from the electrodes and /

Wherein the resin composition for forming a cured film is one of the resin compositions for forming a cured film.

9. A method for suppressing migration of a structure having a cured film formed from a resin composition containing a (meth) acrylate polymer and a solvent, from the electrode and / or wiring on a substrate on which electrodes and / or wires are formed,

Wherein the benzotriazole compound is added to the composition.

The cured film obtained by using the resin composition for forming a cured film of the present invention has excellent light transmittance, adhesion, and hardness, and also has a metal migration inhibiting ability. Therefore, it is useful as a material for forming a cured film such as a protective film, an insulating film, etc. in a touch panel such as a protective film, a planarizing film, and an insulating film in various displays such as an organic electroluminescence (EL) device. And is also suitable as an overcoat material for an ITO film.

Further, the electroconductive member of the present invention comprises an electrode and / or a wiring and the cured film formed in contact with the electrode and / or the wiring. Since the cured film not only has characteristics of high light transmittance, high adhesion and hardness required for a cured film used for various displays such as organic EL elements, but also has a migration inhibiting ability, the conductive member of the present invention is excellent in migration of metals So that durability is excellent. Further, since the cured film is also excellent in flexibility, the conductive member of the present invention can be suitably employed also in a display having an ITO film.

According to the migration inhibiting method of the present invention, migration of the metal can be suppressed while maintaining the light transmittance, adhesion and hardness of the cured film by using the benzotriazole compound.

1 is a plan view of a sample for internal migration evaluation used in Examples and Comparative Examples.
2 is a cross-sectional view of a sample for internal migration evaluation used in Examples and Comparative Examples.
3 is a diagram showing a silver pattern before the test of the migration evaluation.
Fig. 4 is a diagram showing a silver pattern after the migration evaluation test according to Example 1. Fig.
5 is a diagram showing a silver pattern after the migration evaluation test according to Comparative Example 1. Fig.

[Resin composition for forming a cured film]

The resin composition for forming a cured film of the present invention comprises (A) a (meth) acrylate polymer having a weight average molecular weight of 5,000 to 200,000, (B) a migration inhibitor and ion trap agent comprising a benzotriazole compound, and (C) do.

[(A) (meth) acrylate polymer]

The component (A) contained in the composition of the present invention is a (meth) acrylate polymer having a weight average molecular weight of 5,000 to 200,000. (Meth) acrylate polymer is a polymer having a monomer unit derived from at least one monomer selected from an acrylate compound and a methacrylate compound. However, the (meth) acrylate polymer in the present invention does not contain a silane structure in the side chain in terms of storage stability.

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

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

The alkyl group having 1 to 20 carbon atoms may be any of linear, branched and cyclic, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n- butyl group, isobutyl group, a linear or branched alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, A cyclohexyl group, a bicyclohexyl group, a bicyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclopentyl group, A cyclic alkyl group having 3 to 20 carbon atoms such as a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group,

(Meth) acrylate compounds include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, Propyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2- Acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and the like. Among them, in consideration of balance of high light transmittance, high adhesion and high hardness, the monomer preferably includes one selected from methyl methacrylate and ethyl methacrylate.

In the present invention, the (meth) acrylate polymer may contain other monomer units other than the monomer units derived from acrylate and methacrylate. Monomers providing other monomer units are typically styrene compounds, vinyl compounds, maleimide compounds, acrylonitrile, and maleic anhydride.

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

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 and propyl vinyl ether .

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

Of these, a styrene compound is preferable and styrene is more preferable from the viewpoint of hydrophobicity (low water absorption) of the obtained thin film.

In the present invention, the content of the monomer unit derived from the (meth) acrylate compound in the (meth) acrylate polymer is preferably at least 50 mol%, more preferably at least 50 mol% , Preferably not less than 60 mol%, further preferably not less than 70 mol%, more preferably not less than 80 mol%.

As the (meth) acrylate polymer, a commercially available product may be used, but a polymer produced by polymerizing the above-mentioned monomer may be used.

As the polymerization method, radical polymerization, anionic polymerization, cationic polymerization and the like can be employed. Radical polymerization is preferable in that a (meth) acrylate polymer having a weight average molecular weight required in the present invention can be relatively easily produced.

Examples of the initiator include peroxides such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide; Persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; Azo compounds such as azobisisobutyronitrile, azobismethylbutyronitrile, azobisisovaleronitrile, 2,2'-azobis (isobutyrate) dimethyl, and the like can be given. The amount of such an initiator to be used can not be uniformly defined because it varies depending on the type and amount of the monomer and the reaction temperature, but is usually about 0.005 to 0.05 mol per 1 mol of the monomer. The reaction temperature at the time of polymerization may suitably be set from 0 ° C to the boiling point of the solvent to be used, but is usually about 20 to 100 ° C. The reaction time is about 0.1 to 30 hours.

The polymerization is preferably carried out in a solvent, and as the solvent used in the polymerization reaction, a solvent generally used in this kind of reaction can be used. Specifically, water; Propanol, 1-butanol, 2-butanol, i-butyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, i-pentyl Alcohols such as alcohol, t-pentyl alcohol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol and cyclohexanol ; Ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane and the like; Halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane and carbon tetrachloride; Ether alcohols such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve and diethylene glycol monobutyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl propionate, and cellosolve acetate; n-pentane, n-pentane, n-hexane, n-heptane, n-octane, Aliphatic or aromatic hydrocarbons such as toluene, xylene, ethylbenzene and anisole; Acetal such as methylal, diethyl acetal; Fatty acids such as formic acid, acetic acid and propionic acid; N, N-dimethylformamide, dimethylsulfoxide, acetonitrile, and the like can be given as examples of the organic solvent have. From these, the solvent to be used is appropriately selected in consideration of the kind and amount of the monomer and the initiator, the reaction temperature, and the like.

In the present invention, the weight average molecular weight (Mw) of the (meth) acrylate polymer is from 5,000 to 200,000 from the viewpoint of securing the solubility of the polymer and preparing a composition providing a suitable cured film, but suppressing an excessive increase in viscosity of the composition , The upper limit value is preferably 180,000, more preferably 150,000, still more preferably 100,000, still more preferably 80,000, and in consideration of suppressing excessive decrease of the viscosity of the composition, Is preferably 10,000, more preferably 15,000, even more preferably 30,000, still more preferably 40,000. Mw is a polystyrene reduced value measured by gel permeation chromatography (GPC).

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

[(B) Migration inhibitor and ion trap agent]

The component (B) contained in the composition of the present invention is a migration inhibitor and ion trap agent comprising a benzotriazole compound. Examples of such benzotriazole compounds include benzotriazole derivatives substituted with alkyl groups having 1 to 3 carbon atoms such as benzotriazole, 4-methylbenzotriazole, and 5-methylbenzotriazole. Among them, 5-methylbenzotriazole .

The content of the component (B) is preferably about 0.1 to 50 parts by mass based on 100 parts by mass of the component (A). However, it is preferable that the cured film having excellent migration inhibiting ability is formed with good reproducibility while maintaining high light transmittance, high adhesion, More preferably from 1 to 30 parts by mass, still more preferably from 2 to 25 parts by mass, from the viewpoint of production.

Since the composition of the present invention contains a benzotriazole compound, excellent migration inhibition can be realized without impairing high transparency, high adhesion, and hardness of the cured film.

[(C) Solvent]

The composition of the present invention is used in a solution state dissolved in a solvent. The solvent to be used at this time is not particularly limited as long as it can dissolve the above components (A) and (B) and contains the components (D) to (H) It is not limited.

Specific examples of the solvent include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol isopropyl ether, ethylene glycol mono Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, Ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol, diethylene glycol monomethylether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, Diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, die Ethylene glycol dibutyl ether, diethylene glycol monohexyl ether, diethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, diethylene glycol acetate, diethylene glycol Diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Propylene glycol monomethyl ether, trimethylene glycol, hexylene glycol, octyleneglycol, methoxymethoxyethanol, 1-butoxyethoxypropanol, acetic acid Butyl acetate, n-butyl lactate, n-amyl lactate, lactic acid amide, n-amyl lactate, isobutyl acetate, methoxybutyl acetate, acetic acid 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, isoamyl acetate, n-butyl propionate, Isoamyl, isoamyl, isoamyl isovalerate, ethyl acetobutyrate, butyl stearate, dibutyl oxalate, diethyl malonate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, methylphenyl ether, ethyl benzyl ether, ethyl phenyl But are not limited to, ether, dichloroethylether, diisobutylether, n-hexylether, 1,4-dioxane, diethyl acetal, cineol, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone , Diethyl ketone, ethyl n-butyl ketone, di-n-propyl ketone, acetone diacetone, poron, isophorone, acetophenone, glycerin, Diol, 2,3-butanediol, isoamyl alcohol, 1,5-pentanediol, 2-methylcyclohexanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, 1 But are not limited to, aliphatic alcohols such as aliphatic alcohol, aliphatic alcohol, aliphatic alcohol, aliphatic alcohol, aliphatic alcohol, aliphatic alcohol, aliphatic alcohols, aliphatic alcohols, But are not limited to, chlorides, trichloroacetic acid, lactic acid, valeric acid, isovaleric acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, anhydrous butyric acid, decane, dipentene, p- Tetrachloroethane, 1,1,2,2-tetrachloroethane, hexachloroethane, toluene, xylene, o-dichlorobenzene, m-dichlorobenzene , p-dichlorobenzene, 1,2,4-trichlorobenzene, o-dibromobenzene, benzonitrile, nitrobenzene, alpha -tolunitril (phenylacetonitrile) Polyimide and the like, N- dimethylacetamide, 2-pyrrolidone.

These solvents may be used alone or in combination of two or more. The solvent used for polymerizing the component (A) may be used as it is.

The solvent preferably has a boiling point of 150 ° C or higher, more preferably 180 ° C or higher, and even more preferably 200 ° C or higher. Examples of such a solvent include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol mono Butyl 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 monobenzyl ether, diethylene glycol monobenzyl ether and the like are particularly preferable.

When a mixture of two or more solvents is used, the boiling point of at least one species is preferably 150 ° C or higher, more preferably 180 ° C or higher, and even more preferably 200 ° C or higher.

The amount of the solvent is preferably such an amount that the solid content concentration in the composition of the present invention is 1 to 95 mass%, more preferably the amount such that the solid content concentration is 5 to 90 mass%, and the solid content concentration is 10 to 85 The same amount as that in the case of the mass% is further preferable. Here, the solid content is obtained by excluding the solvent (C) from the entire components of the composition of the present invention.

The composition of the present invention contains the above components (A) to (C), but in terms of improving the overcoat function,

(D) a silane coupling agent,

(E) a polyfunctional (meth) acrylate compound,

(F) a radical polymerization initiator,

(G) a polymerization inhibitor,

(H) benzotriazole compounds other than ion trap agents

And the like.

[(D) Silane coupling agent]

The composition of the present invention preferably contains a silane coupling agent as the component (D) from the viewpoint of improving the adhesion. A preferred example of the silane coupling agent is a silane compound represented by the formula (2).

In the 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 to 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 a linear or branched one, specifically a methoxy group, an ethoxy group, an n-propoxy group and an i-propoxy 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) acryloxy group, a vinyl group, an epoxy group, a mercapto group and the like, and an amino group, a ureido group and a (meth) acryloxy group are preferable. Particularly preferably an amino group or a ureido group.

Specific examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane 3-acryloylpropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloylpropyltrimethoxysilane, 3-acryloylpropyltriethoxysilane, 3- Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltriclorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltri But are not limited to, chlorosilane, allyltrimethoxysilane, allyl triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidyl jade 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Propoxysilane, and the like.

Of these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxy Propyl trimethoxysilane, 3-methacryloxypropyltriethoxysilane and the like are particularly preferable.

As the silane coupling agent, a commercially available product can be used.

When the composition of the present invention contains the component (D), the content thereof is preferably from 0.001 to 10 parts by mass, more preferably from 0.01 to 5 parts by mass, still more preferably from 0.05 to 1 part by mass, per 100 parts by mass of the component (A) Do. 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 be lowered.

[(E) Multifunctional (meth) acrylate compound]

The composition of the present invention preferably contains a polyfunctional (meth) acrylate compound as the component (E) from the viewpoint of improving the hardness. The polyfunctional (meth) acrylate compound is a compound having at least three (meth) acryloxy groups in the molecule, and specifically includes an ester of a polyhydric alcohol and (meth) acrylic acid. The number of (meth) acryloxy groups in one molecule is 3 to 6, preferably 3 or 4.

Examples of the polyhydric alcohol include glycerol, erythritol, pentaerythritol, trimethylolethane, trimethylol propane, dipentaerythritol, ditrimethylol propane and the like.

Specific examples of the polyfunctional (meth) acrylate compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, Dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, trimethylol ethane triacrylate, trimethylolethane trimethacrylate, trimethylol propyl acrylate, trimethylol propane trimethacrylate, Trimethylol propane trimethacrylate, ditrimethylol propane tetraacrylate, and ditrimethylol propane tetramethacrylate. [0035] The term "

Specific examples of the polyfunctional (meth) acrylate compound include commercially available products such as KAYARAD (registered trademark) T-1420, DPHA, DPHA-2C, D (manufactured by Nippon Kayaku Co., DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX620, DPCA-30, DPCA-30, DPCA-60 , R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040; M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M- 8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050; 295, 300, 360, GPT, 3PA, 400, 260, 312, 335HP manufactured by Osaka Yuki Kagaku Kogyo; A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM (trade name) manufactured by Shin Nakamura Kagaku Kogyo Co., -N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH and TMPT.

When the composition of the present invention contains the component (E), the content thereof is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, further preferably 50 to 150 parts by mass per 100 parts by mass of the component (A) The addition is further 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. When the content is more than 300 parts by mass, the properties of adhesion and flexibility are lowered, and cracks are likely to occur. The polyfunctional (meth) acrylate compound may be used alone or in combination of two or more.

[(F) Radical polymerization initiator]

The composition of the present invention preferably contains a radical polymerization initiator as the component (F) in terms of initiation or promotion of polymerization of the component (E). The component (E) is spontaneously polymerized by treatment at a high temperature. However, when the high-temperature curing treatment such as denaturation of the substrate can not be performed, a low-temperature curing treatment or a photo-curing treatment can be performed by adding the component (F).

The radical polymerization initiator should be capable of emitting a substance that initiates radical polymerization by light irradiation and / or heating. Examples of the photo radical polymerization initiator include benzophenone derivatives, imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azide compounds, titanocene compounds, aluminate complexes, organic peroxides, N-alkoxypyridinium salts , Thioxanthone derivatives, and the like. More specifically, there can be mentioned benzophenone, 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethan-1-one , 1-hydroxychlorohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butaine-1-one, bis (η5-2,4-cyclopentadien- 1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like.

As the photo radical polymerization initiator, commercially available products may be used. Examples thereof include IRGACURE (registered trademark) 651, 184, 369, 784 manufactured by BASF. Specific examples thereof include IRGACURE (registered trademark) 500, 907, 379, 819, 127, 500, 754, 250, 1800, 1870, OXE01, TPO, DAROCUR (registered trademark) 1173; Speedcure (registered trademark) MBB, PBZ, ITX, CTX, EDB manufactured by Lambson; Esacure (registered trademark) ONE, KIP150, KTO46 manufactured by Lamberti; KAYACURE (registered trademark) DETX-S manufactured by Nippon Kayaku Co., Ltd., 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, T-butylperoxy-2-ethylhexanoate (t-butyl 2-ethylhexane (t-butyl 2-ethylhexane), t-butylperoxide Peroxoate); Azobisisobutyronitrile, 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-methylbutyrononitrile) Azobis (2-cyclohexanecarbonitrile), 2- (carbamoyl azo) isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), Azo compounds such as 2-phenylazo-2,4-dimethyl-4-methoxy valeronitrile and 2,2'-azobis (2-methylpropane); And persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. However, the present invention is not limited thereto.

Examples of commercially available thermal radical polymerization initiators include perfluoro (registered trademark) IB, NPP, IPP, SBP, TCP, OPP, SA, 355, L, Perbutyl TM ND, NHP, MA, PV, 355, A, C, D, E, L, I, O, P, Z, Perhexyl ND, PV, D, I, O, Z, ND, NIPER (registered trademark) PMB, BMT, BW, Fetetra (registered trademark) A, PERHEXA (registered trademark) MC, TMH, HC, 250, 25B, C, 25Z, 22, V, ) O, PERCUMIL TM ND, D, PERMENTA TM H, NOFMER TM BC; V-70, V-65, V-59, V-40, V-30, VA-044, VA-046B, VA-061, V- 086, VF-096, VAm-110, V-601, V-501; IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, TPO, DAROCUR (registered trademark) 1116, 1173, UVECRYL (registered trademark) P36 manufactured by Saitec Surface Specialties; But are not limited to, Esacure (registered trademark) KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46 and KIP75 / B manufactured by Lamberti.

When the composition of the present invention contains the component (F), its content is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the component (A).

[(G) Polymerization inhibitor]

The composition of the present invention may contain a polymerization inhibitor as a component (G), if necessary. Examples of the polymerization inhibitor include 2,6-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-t- butylcresol, hydroquinone, hydroquinone monomethyl ether , Pyrogallol, t-butylcatechol, 4-methoxy-1-naphthol, and the like.

When the composition of the present invention contains the component (G), its content is preferably 1% by mass or less, more preferably 0.5% by mass or less, of the total solid content. If the content is more than 1% by mass, the curing may be defective and the reaction may be insufficient.

[(H) ion trap agent other than benzotriazole compound]

The composition of the present invention may contain an ion trap agent other than the benzotriazole compound as the component (H). Examples of such an ion trap agent include N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine (Irganox TM MD1024, ), Oxalic acid bis (benzylidene hydrazide) (Eastman Inhibitor OABH, manufactured by Eastman Chemical Company), and the like.

When the composition of the present invention contains the component (H), the content thereof is about 0.0001 to 20 parts by mass based on 100 parts by mass of the component (A). However, as described above, the benzotriazole compound may also be used as an ion trap It is preferable that it does not contain any other ion trap agent.

[Other additives]

The composition of the present invention may contain a surfactant, a crosslinking agent, a defoaming agent, a rheology modifier, a pigment, a dye, a storage stabilizer, a dissolution accelerator such as a polyhydric phenol or a polyvalent carboxylic acid, etc., . ≪ / RTI >

The surfactant is not particularly limited, and examples thereof include a fluorine surfactant, a silicone surfactant, and a nonionic surfactant. Examples of the surfactant of this type include FEPTOT (registered trademark) EF301, EF303, and EF352 manufactured by Mitsubishi Materials Denshikasei; F171, F173 manufactured by DIC Corporation, Megapack (registered trademark); FLUORAD (registered trademark) FC430, FC431 manufactured by 3M; SC101, SC102, SC103, SC104, SC105, SC106, and the like, available from Asahi Glass Co., Ltd., Asahi Guard (registered trademark) AG710 manufactured by Asahi Kasei Corporation, and Sulfuron (registered trademark) S-382,

Examples of the crosslinking agent include a polyfunctional epoxy compound, a polyfunctional isocyanate compound, a polyfunctional thiol compound, and a melamine crosslinking agent. When the component (E) is contained, a trifunctional or higher 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 examples of the compound include 1,3,5-tris (3-mercaptopropionyloxyethyl) isocyanurate, 1,3,5-tris (3-mercaptobutyryloxyethyl) isocyanurate Trifunctional thiol compounds such as Carlens MT (registered trademark) NR1), trimethylol propanol (3-mercaptopropionate), and the like; (4-mercaptoethanol), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko KK, Thiol compounds; Dipentaerythritol hexaquis (3-propionate), and the like.

Examples of antifoaming agents include acetylene glycol, silicone fluids and emulsions, ethoxylated or propoxylated silicones, hydrocarbons, fatty acid ester derivatives, acetylated polyamides, poly (alkylene oxide) polymers and copolymers, It is not limited. In the case of performing screen printing, the composition of the present invention preferably contains a defoaming agent.

The viscosity of the composition of the present invention at 25 占 폚 is preferably from 1 to 10,000 mPa 占 퐏, more preferably from 1 to 5,000 mPa 占 퐏, still more preferably from 1 to 1,000 mPa 占 퐏, from the viewpoint of coatability. If the viscosity is too low, the intended film thickness may not be obtained. If the viscosity is too high, the coating property may be lowered.

The viscosity of the composition of the present invention at 25 占 폚 is preferably 10 to 100,000 mPa 占 퐏, more preferably 500 to 100,000 mPa 占 퐏, still more preferably 1,000 to 100,000 mPa 占 퐏 . If the viscosity is too low, the composition may spread after application and a desired pattern may not be formed. If the viscosity is too high, a load may be applied to the step such as lowering the dischargeability, May be deteriorated.

In the case where a fine structure such as an insulating film for constituting a bridge structure is formed by a printing method such as screen printing or gravure offset printing at a portion where the X-axis electrode and the Y-axis electrode in the touch panel are orthogonal to each other, Is preferably 10 to 100,000 mPa · s, more preferably 5,000 to 100,000 mPa · s, still more preferably 20,000 to 100,000 mPa · s at 25 ° C. If the viscosity is too low, the composition may spread after application and a desired pattern may not be formed. If the viscosity is too high, a load may be applied to the step such as lowering the dischargeability, May be deteriorated.

In the present invention, the viscosity is a value measured by an E-type viscometer.

[Preparation of composition]

The method for preparing the composition of the present invention is not particularly limited. As an example, there may be mentioned a method of dissolving the component (A) in a solvent (C) and mixing the component (B) in a predetermined ratio to prepare a homogeneous solution. In addition, a preparation method of adding (D) to (H) components and other components at an appropriate stage of the preparation method and adding them as required may be mentioned.

In the preparation of the composition of the present invention, the solution of the component (A) obtained by the polymerization reaction in a solvent can be used as it is. In this case, as described above, the component (B) is added to the solution of the component (A) to obtain a homogeneous solution. Further, a solvent (C) may be further added for the purpose of adjusting the concentration.

The thus prepared solution composition is preferably used after being filtered using a filter having a pore diameter of about 0.2 mu m or the like.

[Coating film and cured film]

The composition of the present invention may be applied to a substrate having electrodes and / or wirings (e.g., silicon / silicon dioxide coated substrate, silicon nitride substrate, metal such as aluminum, molybdenum, chromium, Metal nanoparticles such as silver nanoparticles, metal nanowires, silver nanoparticles, and copper nanoparticles, poly (3,4-ethylene dioxythiophene) / poly (styrene sulfonate) (PEDOT / PSS), graphene, A resin film substrate such as a glass substrate, a quartz substrate, an ITO substrate, an ITO film substrate, a TAC film, a polyester film, an acrylic film and a cycloolefin (COP) film) By a printing method such as coating, roll coating, slit coating, rotary coating after slit, inkjet coating, screen printing, flexographic printing, gravure printing, offset printing, gravure offset printing, (Prebake) in an oven or the like to form a coating film. The composition of the present invention is particularly suitable for printing methods such as inkjet application, screen printing, flexographic printing and gravure offset printing.

The prebake is generally treated at a temperature of preferably 60 ° C. to 150 ° C., more preferably 80 ° C. to 120 ° C., for 0.5 to 30 minutes when using a hot plate, and for 0.5 to 90 minutes when using an oven Is adopted.

Subsequently, post-baking for thermosetting is performed. Specifically, it is heated using a hot plate, an oven, or the like. The postbake is generally treated at a temperature of preferably 150 to 300 DEG C, more preferably 200 to 250 DEG C, for 1 to 30 minutes when a hot plate is used, and for 1 to 90 minutes when using an oven Is adopted.

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

When the composition of the present invention contains a photo radical polymerization initiator, photo-curing can be performed by irradiating the coating film with ultraviolet rays after pre-baking. The ultraviolet rays preferably have a wavelength of 200 to 500 nm and an exposure amount of 100 to 5,000 mJ / cm ² .

Post-baking for thermal curing is performed after photo-curing. Specifically, it is heated using a hot plate, an oven, or the like. The post-baking is generally performed at a temperature of preferably 60 ° C to 150 ° C, more preferably 80 ° C to 120 ° C, for 1 to 30 minutes in the case of using a hot plate, for 1 to 90 minutes in the case of using an oven Is adopted.

By curing the composition of the present invention under the above-described conditions, the step of the substrate can be sufficiently planarized, and a cured film having high transparency can be formed.

Since the cured film of the present invention has at least a necessary level of planarizing property, hardness and adhesion, it is preferable to use a protective film, a flattening film, an insulating film and the like in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element It is also useful as a material for forming a cured film such as a protective film or an insulating film. It is also excellent as an overcoat material for ITO films because of its excellent flexibility.

The conductive member including the cured film of the present invention formed so as to contact the electrode and / or the wiring on the substrate having the electrode and / or wiring formed thereon is less likely to cause a short circuit between the electrode and the wiring because migration is suppressed, .

According to the migration inhibiting method of the present invention, since the benzotriazole compound is contained in the composition, excellent migration inhibition can be realized without impairing transparency, adhesion and hardness of the cured film. The method of the present invention is effective for inhibiting migration of silver, copper, gold, aluminum, nickel, tin, lead, palladium and the like, and is particularly effective for inhibiting migration of silver.

Example

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. The weight average molecular weight (Mw) of the copolymer obtained in Synthesis Example was measured using a Shodex GPC-101 (column: Shodex (registered trademark) KF803l and KF804l (manufactured by Showa Denko K.K.) ) Was used, and elution solvent tetrahydrofuran was eluted at a flow rate of 1 mL / min in a column (column temperature: 40 DEG C). Further, Mw was expressed in terms of polystyrene conversion value.

The reagents and devices used in the following Synthesis Examples, Examples and Comparative Examples are as follows.

, DEGMEA (diethylene glycol monoethyl ether acetate), MMA (methyl methacrylate), MAA (methacrylic acid), ST (styrene): manufactured by Tokyo Kasei Kogyo Co.,

MAIB: 2,2'-azobis (isobutyrate) dimethyl, manufactured by Tokyo Kasei Kogyo Co., Ltd.

PET-30: pentaerythritol (tri / tetra) acrylate, manufactured by Nippon Kayaku Co., Ltd.

5-MBT: 5-methylbenzotriazole, manufactured by Tokyo Kasei Kogyo Co., Ltd.

IRG184: Photopolymerization initiator, IRGACURE (registered trademark) 184 from BASF

APS: 3-aminopropyltriethoxysilane, LS-3150 manufactured by Shin-Etsu Chemical Co., Ltd.

· AGITAN771: antifoaming agent, manufactured by MUNZING

· Stirring apparatus: ARE-310 (Thin film)

[1] Synthesis of resin

[Synthesis Example 1]

A mixed solution of 280.0 g of MMA, 30.1 g of MAA, 36.5 g of ST and 8.1 g of MAIB was added to a 1,000 mL four-necked flask under stirring in a nitrogen atmosphere at 70 캜 (internal temperature) for 2 hours Over a long period. After the dropwise addition, the reaction was further carried out at 70 DEG C for 20 hours to obtain a resin solution P1. The molar ratio of the monomer units in the resin ((meth) acrylate polymer) contained in this resin solution was MMA unit: MAA unit: ST unit = 80: 10: 10, and Mw was about 50,000.

[2] Production of a resin composition for forming a cured film, production of a cured film and evaluation thereof

[Example 1]

55.1 g of the resin solution P1 obtained in Synthesis Example 1, 24.3 g of PET-30, 1.3 g of IRG 184, 1.3 g of 5-MBT, 0.02 g of APS, 0.03 g of AGITAN 771, Was placed in a stirrer, and the mixture was stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 2]

50.2 g of the resin solution P1 obtained in Synthesis Example 1, 25.1 g of PET-30, 1.4 g of IRG 184, 0.68 g of 5-MBT, 0.03 g of APS, 0.03 g of AGITAN 771, Was placed in a stirrer, and stirred for 10 minutes at 2,000 rpm to prepare a varnish.

[Example 3]

48.3 g of the resin solution P1 obtained in Synthesis Example 1, 24.1 g of PET-30, 1.3 g of IRG 184, 2.62 g of 5-MBT, 0.02 g of APS, 0.03 g of AGITAN 771, Was charged into a stirrer and stirred for 10 minutes at 2,000 rpm to prepare a varnish.

[Example 4]

45.9 g of the resin solution P1 obtained in Synthesis Example 1, 22.9 g of PET-30, 1.2 g of IRG 184, 5.00 g of 5-MBT, 0.02 g of APS, 0.03 g of AGITAN 771, Was placed in a stirrer, and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Comparative Example 1]

56.7 g of the resin solution P1 obtained in Synthesis Example 1, 24.9 g of PET-30, 1.4 g of IRG 184, 0.02 g of APS, 0.03 g of AGITAN 771 and 17.0 g of DEGMEA were placed in a 200 mL plastic container, And the mixture was stirred at 2,000 rpm for 10 minutes to prepare a varnish.

The compositions of the varnishes produced in Examples 1 to 4 and Comparative Example 1 are summarized in Table 1.

[3] Production and evaluation of cured films

[Production of cured film for measuring light transmittance]

The varnishes of Examples 1 to 4 and Comparative Example 1 were respectively coated on a glass substrate by spin coating and prebaked at 110 DEG C for 2 minutes. Subsequently, UV irradiation (800 mJ / cm ² ) was performed, and post-baking was performed at 110 캜 for 30 minutes to prepare a cured film having a thickness of about 5 탆. The obtained cured film was evaluated for pencil hardness, adhesion, and transparency by the following method. The results are shown in Table 2.

[Measurement of light transmittance]

The ultraviolet visible absorption spectrum of the cured film was measured using UV-3100PC manufactured by Shimazu Seisakusho Co., Ltd., and the transmittance at a wavelength of 400 nm was evaluated.

[Evaluation of pencil hardness]

Measured according to JIS K 5400, at a load of 1,000 g.

[Evaluation of adhesion]

And evaluated by a crosscut test method. First, 100 pieces of checkerboards were formed on the cured film using a cutter guide. Next, a cellophane tape made by Nichiban Co., Ltd. was adhered to the checkerboard eye, and rubbed strongly with an eraser from above, and sufficiently adhered. Then, the cellophane tape was peeled off, and at that time, evaluation was made on how many of the 100 checkerboards were peeled off.

0B: More than 66 pieces peeled off

1B: 36 to 65 peeled off

2B: 16 to 35 peeling

3B: 6 to 15 peeling

4B: 1 to 5 peeling

5B: No peeling

[Create a sample for my migration evaluation]

A silver pattern 2 as shown in Fig. 1 was formed on the glass substrate 1 by sputter deposition. Each of the varnishes of Examples 1 to 4 and Comparative Example 1 was applied to the glass substrate with a silver pattern by a screen printing method and prebaked at 110 DEG C for 2 minutes. Subsequently, post-baking was performed at 110 占 폚 for 30 minutes to prepare a cured film (3) having a thickness of about 5 占 퐉 to obtain a sample for evaluation. Fig. 2 shows a sectional view of a silver pattern substrate on which a cured film is formed. With respect to the obtained sample, migration evaluation was carried out by the following method.

[My migration evaluation]

A test sample was subjected to a test in which a positive electrode and a negative electrode were connected to both ends of the silver pattern with a temperature of 60 캜 and a relative humidity of 90% RH and a voltage of 5 V was applied for 15 hours so that electric field concentration occurred at the tip of the pattern. To confirm whether or not the migration occurred. Whether the migration occurred or not was confirmed by observing the pattern before and after the test with a microscope. The patterns before and after the test are shown in Figs.

As is clear from the results shown in Table 2, the cured film obtained from the varnish (resin composition for forming a cured film) of the Example had a pencil hardness of H or more, a high adhesion of 4B or more, and excellent transparency. When these cured films were used, the occurrence of migration was not observed (Fig. 4). On the other hand, when the cured film obtained from the varnish of the comparative example was used, the occurrence of migration was confirmed (Fig. 5).

1 substrate
2 is a pattern
3 curing membrane

Claims (9)

(A) a (meth) acrylate polymer having a weight average molecular weight of 5,000 to 200,000 (excluding those having a silane structure in the side chain),
(B) a migration inhibitor / ion trap agent comprising a benzotriazole compound, and
(C) Solvent
And a curing accelerator. The method according to claim 1,
(D) a silane coupling agent. 3. The method according to claim 1 or 2,
(E) a polyfunctional (meth) acrylate compound. The method of claim 3,
(F) a radical polymerization initiator. 5. The method according to any one of claims 1 to 4,
(B) a benzotriazole compound is contained in an amount of 0.1 to 50 parts by mass based on 100 parts by mass of the component (A). A cured film formed by using the resin composition for forming a cured film according to any one of claims 1 to 5. 7. A conductive member comprising a substrate on which electrodes and / or wires are formed, and a cured film according to claim 6 formed on the substrate so as to contact the electrodes and / or wires. A method for suppressing migration of a structure having a cured film formed from a resin composition for forming a cured film on a substrate on which electrodes and / or wires are formed from the electrodes and / or wiring,
Wherein the resin composition for forming a cured film according to any one of claims 1 to 5 is used as the resin composition for forming a cured film. A method for suppressing migration of a structure having a cured film formed from a resin composition containing a (meth) acrylate polymer and a solvent from the electrode and / or wiring on a substrate on which electrodes and / or wires are formed,
Wherein the benzotriazole compound is added to the composition.

Images