WO2014112452A1

WO2014112452A1 - Cured-film-forming resin composition

Info

Publication number: WO2014112452A1
Application number: PCT/JP2014/050397
Authority: WO
Inventors: 隼人服部; 智久山田
Original assignee: 日産化学工業株式会社
Priority date: 2013-01-15
Filing date: 2014-01-14
Publication date: 2014-07-24
Also published as: TWI608021B; JPWO2014112452A1; CN104918965B; KR20150105378A; TW201443091A; CN104918965A; KR102128799B1; JP6225921B2

Abstract

This cured-film-forming resin composition contains (A) a (co)polymer containing repeating units represented by formulae (1) to (3), (B) a silane coupling agent, (C) a polyfunctional (meth)acrylate compound, and (D) a solvent. (In the formulae: R each independently represents a hydrogen atom or a methyl group; R¹ represents an alkyl group; R² to R⁶ each independently represent a hydrogen atom, a halogen atom, or an alkyl group; a, b, and c are integers each satisfying 40 ≤ a ≤ 100, 0 ≤ b ≤ 30, and 0 ≤ c ≤ 30; and 40 ≤ a + b + c ≤ 100.)

Description

Resin composition for forming cured film

The present invention relates to a resin composition for forming a cured film.

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 (Patent Document 1).

However, pattern processing by the photolithography method has a problem that not only the process is complicated but also costly. 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.

Also, due to demands for transportation and storage, the use of film substrates instead of glass substrates is increasing. The film substrate is stored in the form of a roll or the like at the time of storage. At this time, the substrate is curved, so that the material applied on the film substrate is required to have the same flexibility as the film.

Furthermore, in the case where an electrode is formed on a film such as an ITO film, when an adhesive is used for bonding the substrates, the silver wiring deteriorates due to the moisture of the adhesive, causing problems such as short-circuiting. There is a need for an overcoat material that protects the wiring.

On the other hand, the conventional overcoat material is intended for application on a glass substrate and contains inorganic fine particles to increase the hardness (Patent Document 2). However, the conventional method such as the inclusion of inorganic fine particles improves the hardness, but is not flexible, for example, it causes inconveniences such as cracking when bent, so it is applicable to application to a film substrate. The situation was impossible.

JP 2013-064973 A JP 2012-116975 A

The present invention has been made in view of the above problems, and can form a film on a necessary site by a simple method such as a printing method, and has high transmittance, high adhesion, and high hardness. Is intended to provide a composition capable of forming a cured film having high flexibility and long-term reliability.

As a result of intensive studies to solve the above problems, the present inventors have obtained a composition containing a specific (co) polymer, a silane coupling agent, a polyfunctional (meth) acrylate compound, and a solvent. The present inventors have found that the problem can be solved and completed the present invention.

That is, this invention provides the following resin composition for cured film formation.
1. (A) a (co) polymer containing repeating units represented by the following formulas (1) to (3),

(In the formula, each R independently represents a hydrogen atom or a methyl group. R ¹ represents an alkyl group. R ² to R ⁶ each independently represents a hydrogen atom, a halogen atom or an alkyl group. A, b And c are positive numbers that satisfy 40 ≦ a ≦ 100, 0 ≦ b ≦ 30, and 0 ≦ c ≦ 30, respectively, and 40 ≦ a + b + c ≦ 100.)
(B) a silane coupling agent,
A cured film-forming resin composition comprising (C) a polyfunctional (meth) acrylate compound and (D) a solvent.
2. (C) The polyfunctional (meth) acrylate compound is pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, 1 which is at least one selected from dipentaerythritol pentamethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate and ditrimethylolpropane tetramethacrylate Cured film Forming resin composition.
3. (C) The resin composition for 2 cured film formation whose polyfunctional (meth) acrylate compound is at least 1 sort (s) chosen from pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate.
4). (C) 2 cured film forming resins in which the polyfunctional (meth) acrylate compound is at least one selected from dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentamethacrylate Composition.
5. And (E) a cured film-forming resin composition according to any one of 1 to 4, further comprising an ion trapping agent.
6). (E) The cured film forming resin composition of 5, wherein the ion trapping agent is 5-methylbenzotriazole.
7).
The resin composition for forming a cured film according to any one of 1 to 6, having a viscosity at 25 ° C. of 1 to 10,000 mPa · s.
8). The resin composition for forming a cured film according to any one of 1 to 6, wherein the solvent has a boiling point of 150 ° C. or higher.
9. A cured film forming resin composition having a viscosity of 10.about.100,000 mPa · s at 9.25.degree.
10. (F) The resin composition for forming a cured film according to any one of 1 to 9, further comprising a radical polymerization initiator.
11. A method for producing a cured film comprising applying a cured resin composition for forming a cured film according to 11.10 to a substrate, irradiating with ultraviolet rays, and then baking at 80 ° C. to 120 ° C.
12. A cured film obtained using the cured film forming resin composition according to any one of 12.1 to 10.
13. A laminate obtained by laminating a cured film of 12.12 on a substrate.
14 13 laminates whose substrate is a film.
A touch panel including a cured film of 15.12.

The cured film obtained using the cured film forming resin composition of the present invention has high hardness and excellent adhesion. Therefore, it is useful as a material for forming a cured film such as a protective film, a planarizing film, an insulating film, an insulating film, etc. in various displays such as an organic electroluminescence (organic EL) element, a protective film, an insulating film, etc. in a touch panel. Moreover, since it is excellent also in a softness | flexibility, it is suitable also as an overcoat material for ITO films.

[Resin composition for forming cured film]
The resin composition for forming a cured film of the present invention contains (A) the following (co) polymer, (B) a silane coupling agent, (C) a polyfunctional (meth) acrylate compound, and (D) a solvent.

[(A) (Co) polymer]
The component (A) contained in the cured film forming resin composition of the present invention is a (co) polymer containing repeating units represented by the following formulas (1) to (3).

In said formula, R represents a hydrogen atom or a methyl group each independently, and a methyl group is preferable. R ¹ represents an alkyl group. R ² to R ⁶ each independently represents a hydrogen atom, a halogen atom or an alkyl group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
The alkyl group may be linear, branched or cyclic. The number of carbon atoms of the alkyl group is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, c-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and c-butyl group. In addition, some or all of the hydrogen atoms of the alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom, a hydroxy group, and an amino group. R ¹ to R ⁶ are preferably groups that do not react with the component (C) described later.

The (co) polymer essentially comprises the repeating unit represented by the formula (1), and if necessary, the repeating unit represented by the formula (2) and / or the repeating unit represented by the formula (3). Containing. By containing the repeating unit represented by the formula (2), improvement in adhesion can be expected, and by containing the repeating unit represented by the formula (3), adhesion and hydrophobicity (low water absorption) The characteristic can be imparted.

A, b and c in the above formulas represent the content (mol%) of each repeating unit, and are positive numbers satisfying 40 ≦ a ≦ 100, 0 ≦ b ≦ 30, 0 ≦ c ≦ 30, respectively, 40 ≦ a + b + c ≦ 100. Preferably, 60 ≦ a ≦ 96, 2 ≦ b ≦ 20, 2 ≦ c ≦ 20, more preferably 70 ≦ a ≦ 90, 5 ≦ b ≦ 15, and 5 ≦ c ≦ 15.

The above (co) polymer preferably has a weight average molecular weight (Mw) of 5,000 to 200,000, more preferably 10,000 to 100,000, in consideration of handling properties and adhesion. More preferably, it is 15,000 to 80,000. When Mw exceeds 200,000, the solubility with respect to a solvent may fall and handling property may fall, and when Mw is less than 5,000, adhesiveness may fall.

In consideration of printability, the Mw of the (co) polymer is preferably 10,000 to 200,000, more preferably 30,000 to 180,000, and 40,000 to 170,000. More preferably, it is 000. When Mw exceeds 200,000, solubility in a solvent may be reduced and handling properties may be reduced. When Mw is less than 10,000, printability may be reduced.

In addition, Mw is a polystyrene conversion measured value by gel permeation chromatography (GPC).

When the component (A) is a copolymer, the copolymer may be a random copolymer, an alternating copolymer, or a block copolymer.

The (co) polymer of the component (A) is a monomer that gives a repeating unit represented by the formula (1), and a monomer that gives a repeating unit represented by the formula (2), if necessary, a formula (3) It is produced by (co) polymerizing a monomer or the like that gives the represented repeating unit.

As the polymerization method, radical polymerization, anionic polymerization, cationic polymerization and the like can be employed. Of these, radical polymerization is particularly preferred. Specifically, the above monomer may be heated and polymerized in a solvent in the presence of a polymerization initiator.

Monomers that give the repeating unit represented by the above formula (1) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, 2,2,2 -Trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl acrylate, tert-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 and the like. Of these, methyl methacrylate, ethyl methacrylate and the like are particularly preferable.

The monomer giving the repeating unit represented by the above formula (2) is acrylic acid or methacrylic acid.

Examples of the monomer that gives the repeating unit represented by the above formula (3) include styrene compounds such as styrene, methylstyrene, chlorostyrene, bromostyrene, and 4-tert-butylstyrene.

The above (co) polymer may contain other repeating units in addition to the repeating units represented by the above formulas (1) to (3) as long as the effects of the present invention are not impaired. Examples of the monomer that gives other repeating units include vinyl compounds, maleimide compounds, acrylonitrile, and maleic anhydride.

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

The polymerization initiator can be appropriately selected from conventionally known ones. For example, peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; azobisisobutyronitrile, azobismethylbutyrate And azo compounds such as nitrile, azobisisovaleronitrile, and 2,2′-azobis (isobutyric acid) dimethyl. These can be used alone or in combination of two or more.

The amount of the polymerization initiator used is preferably about 0.005 to 0.05 mol with respect to 1 mol of the monomer. The reaction temperature during the polymerization may be appropriately set from 0 ° C. to the boiling point of the solvent used, but is preferably about 20 to 100 ° C. The reaction time is preferably about 0.1 to 30 hours.

The solvent used in the polymerization reaction is not particularly limited, and may be appropriately selected from various solvents generally used in the polymerization reaction. Specifically, water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, alcohols such as i-pentanol, t-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, cyclohexanol; diethyl ether , Ethers such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride; methyl cellosolve, ethyl cellosolve Ether alcohols such as isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate; n-pentane, n -Aliphatic or aromatic hydrocarbons such as hexane, n-heptane, n-octane, n-nonane, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, anisole Acetals such as methylal and diethyl acetal; fatty acids such as formic acid, acetic acid and propionic acid; nitropropane, nitrobenzene, dimethylamine, monoethanol Emissions, pyridine, N- methyl-2-pyrrolidone, N, N- dimethylformamide, dimethyl sulfoxide, acetonitrile and the like. These can be used individually by 1 type or in mixture of 2 or more types.

[(B) Silane coupling agent]
Component (B) in the composition of the present invention is a silane coupling agent. As said silane coupling agent, the silane compound represented by following formula (4) is preferable.

In formula (4), R ⁷ 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.

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 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, such as an amino group, a ureido group, and a (meth) acryloxy group. preferable. Particularly preferred is an amino group or a ureido group.

Specific examples of the silane coupling agent include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane. 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Methoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, Examples include 3-mercaptopropylmethyldiethoxysilane.

Of these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Triethoxysilane and the like are particularly preferable. A commercial item can be used as said silane coupling agent.

The content of the component (B) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the component (A). . If it is less than 0.001 part by mass, the adhesion may be lowered, and if it exceeds 10 parts by mass, the hardness may be lowered.

[(C) Polyfunctional (meth) acrylate compound]
(C) component in the composition of this invention is a polyfunctional (meth) acrylate compound. The polyfunctional (meth) acrylate compound is a compound having at least 2, preferably at least 3 (meth) acryloxy groups in the molecule. Specifically, urethane acrylate, epoxy acrylate, polyhydric alcohol, Examples include ester compounds obtained from (meth) acrylic acid. Among these, an ester compound obtained from a polyhydric alcohol and (meth) acrylic acid is preferable in consideration of compatibility between the adhesion to the substrate and the surface hardness. The number of (meth) acryloxy groups in one molecule is 2 to 10, preferably 3 to 6, and more preferably 3 or 4.

Specific examples of the urethane acrylate include compounds obtained by reacting a hydroxy group-containing (meth) acrylate with a polyisocyanate. Examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, pentaerythritol triacrylate, Examples include dipentaerythritol pentaacrylate and trimethylolpropane diacrylate. These hydroxy group-containing (meth) acrylates can be used alone or in combination of two or more.

The polyisocyanate may be any of aliphatic, aromatic and alicyclic polyisocyanates, such as methylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone. Examples include diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and methylene bisphenyl diisocyanate. These polyisocyanates can be used singly or in combination of two or more. Of these polyisocyanates, those that are non-yellowing urethanes are preferred.

Commercially available urethane oligomers include EB2ECRYL220 (manufactured by Daicel Cytec); Art Resin UN-3320HA, UN-3320HB, UN-3320HC, UN-330, UN-901T (above, manufactured by Negami Industrial Co., Ltd.) ); NK Oligo U-4HA, U-6HA, U-324A, U-15HA, U-108A, U-200AX, U-122P, U-5201, U-340AX, U -511, U-512, U-311, UA-W1, UA-W2, UA-W3, UA-W4, UA-4000, UA-100 (above, Shin-Nakamura Chemical Co., Ltd. )); Purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7605B, UV- 610B, UV-7620EA, UV-7630B, UV-7640B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3000B, UV-3200B, UV- 3210EA, UV-3310B, UV-3500BA, UV-3520TL, UV-3700B, UV-6100B, UV-6640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

As the above-mentioned epoxy acrylate, generally, those obtained by esterifying a polyepoxy compound (or epoxy resin) and acrylic acid can be mentioned. Specific examples of epoxy acrylate include bisphenol type epoxy acrylate synthesized by reaction of various bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.), epichlorohydrin and acrylic acid, and synthesis by reaction of phenol novolac, epichlorohydrin and acrylic acid. And phenol novolac type epoxy acrylate.

Examples of the polyhydric alcohol include glycerol, erythritol, pentaerythritol, trimethylolethane, trimethylolpropane, dipentaerythritol, ditrimethylolpropane, and the like.

Specific examples of the ester compound obtained from the polyhydric alcohol and (meth) acrylic acid include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipenta Erythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetraacrylate Methacrylate And the like.

The ester compound obtained from the above polyhydric alcohol and (meth) acrylic acid can be easily obtained as a commercial product, and specific examples thereof include, for example, KAYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (Nippon Kayaku Co., Ltd.); Aronix M-210, -240, M-6200, M-309, M-400, M-402, M-405, M-405, M-450, M-7100, M-8030, M-8060, M -1310, M-1600, M-1960, M-8100, M-8530, M-8530, M-8560, M-9050 (manufactured by Toagosei Co., Ltd.); Biscote 295, 300, 360, the same GPT, the same 3PA, the same 400, the same 260, the same 312 and the same 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

The content of component (C) is preferably 10 to 300 parts by weight, more preferably 20 to 200 parts by weight, and still more preferably 50 to 150 parts by weight with respect to 100 parts by weight of component (A). When this content is too small, the hardness characteristics of the cured film are lowered, and when this content is too large, the adhesion and flexibility characteristics are lowered, and cracks are likely to occur. A polyfunctional (meth) acrylate compound can be used individually by 1 type or in combination of 2 or more types.

[(D) Solvent]
The composition of the present invention is used in a solution state dissolved in a solvent. The solvent used at that time can dissolve the above components (A) to (C), and further contains the following components (E), (F), (G), (H) and other additives. When doing, it will not specifically limit if these can also melt | dissolve.

Specific examples of the solvent include toluene, xylene, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol isopropyl ether, ethylene glycol mono Acetate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, methylphenyl Ether, 1,4-dioxane, diethyl acetal, butanol, 2-butanol, iso Mil alcohol, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, isobutyl acetate, n-butyl propionate, decane, dodecane, p-menthane, dipentene, Ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monohexyl ether, methoxymethoxyethanol, ethylene glycol diacetate, diethylene glycol, 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, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol acetate, triethylene glycol monomethyl ether, Triglycol dichloride, propylene glycol, propylene glycol monobutyl ether, 1-butoxyethoxypropanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether Ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, hexylene glycol, octyl Lenglycol, glycerin, hexachloroethane, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, o-dibromobenzene, dichloroethyl ether, diisoamyl ether, n-hexyl ether, Ethyl phenyl ether, ethyl benzyl ether, cineol, 1-octanol, 2-octanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, nonanol, -Decanol, trimethylnonyl alcohol, 2-methylcyclohexanol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, α-terpineol, abiethinol, acetonylacetone, phorone, isophorone, acetophenone, methoxybutyl acetate, 2-ethyl acetate Xylyl, cyclohexyl acetate, methyl cyclohexyl acetate, benzyl acetate, isoamyl acetate, butyl stearate, ethyl acetobutyrate, isoamyl isovalerate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate, methyl benzoate, benzoic acid Ethyl, propyl benzoate, methyl salicylate, dibutyl oxalate, diethyl malonate, butyric anhydride, valeric acid, isovaleric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, Examples include lichloroacetic acid, lactic acid, nitrobenzene, benzonitrile, α-trinitrile, N-methylformamide, N-methylacetamide, 2-pyrrolidone and the like.

The above solvents can be used singly or in combination of two or more. Moreover, the solvent at the time of superposing | polymerizing (A) component can also be used as it is.

From the viewpoint of printability, 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. 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 monobenzyl ether Le, diethylene glycol benzyl ether or the like are particularly preferable.

When two or more solvents are used in combination, at least one boiling point is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher.

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, An amount such that the concentration is 10 to 85% by mass is more preferable. Here, solid content removes (D) solvent from all the components of the resin composition for cured film formation of this invention.

The resin composition for forming a cured film of the present invention contains the above components (A) to (D), and if necessary, (E) an ion trap agent,
(F) radical polymerization initiator (G) polyfunctional thiol compound and / or (H) polymerization inhibitor may be included.

[(E) Ion trap agent]
The component (E) is an ion trapping agent, and has an action of preventing migration when the metal wiring is in contact with water when the metal wiring is formed on the substrate. As such an ion trapping agent, a compound having a chelating ability having an unpaired electron in the structure is preferable. For example, N, N′-bis [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyl] hydrazine (Irganox MD1024, manufactured by BASF), bis (benzylidene hydrazide) oxalate (Eastman Inhibitor OABH, manufactured by Eastman Chemical), benzotriazole, 5-methylbenzotriazole and the like. These are available as commercial products. Other commercially available products include Adecataps CDA-1 (Asahi Denka Co., Ltd.), Adekapuas CDA-6 (Asahi Denka Co., Ltd.), Quunox (Mitsui Toatsu Fine Co., Ltd.), Naugard XL-1 (Manufactured by Uniroyal Corporation). Of these, 5-methylbenzotriazole is particularly preferable.

The addition amount of the ion trapping agent is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the component (A). If the amount is less than 0.0001 parts by mass, the effect of protecting the metal wiring may not be obtained. If the amount exceeds 20 parts by mass, characteristics such as hardness and adhesion as a cured film may be deteriorated. May also be disadvantageous.

[(F) radical polymerization initiator]
Component (F) is a radical polymerization initiator and contributes to the initiation or promotion of polymerization of component (C). The component (C) is polymerized spontaneously by processing at a high temperature, but when a high temperature curing process such as a substrate modification is not possible, a low temperature curing process or a photocuring process can be performed by adding the component (F). Become.

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 (tert-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5 Isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651, manufactured by BASF), 1-hydroxy Cyclohexylphenyl ketone (Irgacure 184, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure 369, manufactured by BASF), bis (η ^5- 2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3 -(1H-pyrrol-1-yl) -phenyl) titanium) (Irgacure 784, manufactured by BASF), and the like, but is not limited thereto.

In addition to the above, commercially available products can be used. Specifically, Irgacure 500, Irgacure 907, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800, Irgacure 1870, Irgacure manufactured by BASF OXE01, DAROCUR TPO, DAROCUR 1173; Speedcure MBB, Speedcure PBZ, Speedcure ITX, Speedcure ACX, Speedcure EDX, Speed ｕｒEK , KAYACURE BM , KAYACURE DMBI, and the like.

Examples of the thermal radical polymerization initiator include acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ditert-butyl peroxide, dicumyl peroxide, dilauroyl Peroxides such as peroxide, tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate; 2,2′-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-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); Examples thereof include, but are not limited to, persulfates such as ammonium sulfate, sodium persulfate, and potassium persulfate.

Examples of commercially available thermal radical polymerization initiators include Parroyl IB, Parkmill ND, Parroyl NPP, Parroyl IPP, Parroyl SBP, Perocta ND, Parroyl TCP, Parroyl OPP, Perhexyl ND, Perbutyl ND, Perbutyl NHP, Parhexyl PV, Perbutyl PV , Parroyl 355, Parroyl L, Paroctyl O, Parroyl SA, Parhexa 250, Perhexyl O, Nipper PMB, Perbutyl O, Nipper BMT, Nipper BW, Perhexa MC, Perhexa TMH, Perhexa HC, Perhexa C, Pertetra A, Perhexyl I, Perbutyl MA, perbutyl 355, perbutyl L, perbutyl I, perbutyl E, perhexyl Z, perhexa 25Z, perbutyl A, perhexa 22, perb Z, Perhexaper V, Perbutyl P, Parkyl D, Perhexyl D, Perhexa 25B, Perbutyl C, Perbutyl D, Permenta H, NOFMER BC (above, NOF Corporation); V-70, V-65, V- 59, V-40, V-30, VA-044, VA-046B, VA-061, V-50, VA-057, VA-086, VF-096, VAm-110, V-601, V-501 ( (Wako Pure Chemical Industries, Ltd.); Irgacure (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur 1116, 1173, Lucyrin TPO ( Above, manufactured by BASF); Ubekrill P36 (above, manufactured by UCB); Ezacure KIP150, KI 65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B (or, Furatetsuri-Lamberti Co., Ltd.) include, but are not limited to.

The content of the component (F) 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 component (A).

[(G) polyfunctional thiol compound]
The composition of this invention may contain the polyfunctional thiol compound which is (G) component as needed. The polyfunctional thiol compound used in the composition of the present invention is preferably a trifunctional or higher functional thiol compound. 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 (3-mercaptopropionyloxyethyl) -isocyanurate, 1,3,5-tris (3-mercaptobutyryloxyethyl) -isocyanurate (Showa Denko K.K. , Manufactured by Karenz MT (registered trademark) NR1), trifunctional thiol compounds such as trimethylolpropane tris (3-mercaptopropionate); pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto) Butyrate) (made by Showa Denko KK, Karenz MT (registered trademark) PEI) and the like; and hexafunctional thiol compounds such as dipentaerythritol hexakis (3-propionate).

The content of the polyfunctional thiol compound in the composition of the present invention is preferably 0.1 to 8% by mass, more preferably 0.8 to 5% by mass in the total solid content. If the content is too large, the stability, odor, adhesion and the like of the composition may deteriorate.

[(H) Polymerization inhibitor]
The composition of this invention may contain a polymerization inhibitor as (H) component as needed. Examples of the polymerization inhibitor 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.

The content of the polymerization inhibitor that is the component (H) is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total solid content. If the content exceeds 1% by mass, poor curing may occur and the reaction may become insufficient.

[Other additives]
The composition of the present invention may further comprise a surfactant, an antifoaming agent, a rheology modifier, a pigment, a dye, a storage stabilizer, a polyhydric phenol or a polycarboxylic acid as long as the effects of the present invention are not impaired. A dissolution accelerator such as an acid can be contained.

The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant. As this type of surfactant, for example, commercially available products such as those manufactured by Sumitomo 3M Co., Ltd., DIC Corporation, and Asahi Glass Co., Ltd. can be used. Specific examples include F-top EF301, EF303, EF352 (Mitsubishi Materials Electronics Chemical Co., Ltd.), MegaFuck F171, F173 (DIC Corporation), Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), Fluorine surfactants such as Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (Asahi Glass Co., Ltd.) can be used.

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

[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 in which the component (A) is dissolved in the solvent (D) and the components (B) and (C) are mixed in this solution at a predetermined ratio to obtain a uniform solution. In addition, in an appropriate stage of this preparation method, there is a preparation method in which (E) component, (F) component, (G) component, (H) component and / or other components are further added and mixed as necessary. Can be mentioned.

In preparing 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, when the (B) component, the (C) component, and the (E) component, (F) component, and the like are added to the solution of the (A) component as described above to make a uniform solution as described above, For the purpose of adjusting the concentration, (D) a solvent may be additionally added. At this time, the solvent used in the synthesis process of the component (A) and the solvent (D) used for concentration adjustment at the time of preparing the composition may be the same or different.

The resin composition for forming a cured film in a solution state thus prepared is preferably used after being filtered using a filter or the like having a pore diameter of about 0.2 μm.

From the viewpoint of applicability, the composition of the present invention preferably has a viscosity at 25 ° C. of 1 to 10,000 mPa · s, more preferably 1 to 5,000 mPa · s, and more preferably 1 to 1, More preferably, it is 000 mPa · s. 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.

From the viewpoint of printability, the composition of the present invention preferably has a viscosity at 25 ° C. of 10 to 100,000 mPa · s, more preferably 500 to 100,000 mPa · s, and more preferably 1,000 to More preferably, it is 100,000 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 may be reduced.

In addition, when a fine structure such as an insulating film for forming a bridge structure is formed at a portion where the X-axis electrode and the Y-axis electrode of the touch panel are orthogonal to each other by a printing method such as screen printing or gravure offset printing, The viscosity of the composition of the invention at 25 ° C. is preferably 10 to 100,000 mPa · s, more preferably 5,000 to 100,000 mPa · s, and 20,000 to 100,000 mPa · s. More preferably. 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 may be reduced.

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

[Coating and cured film]
The resin composition for forming a cured film of the present invention is a substrate (for example, a silicon / silicon dioxide-coated substrate; a silicon nitride substrate; a substrate coated with a metal such as aluminum, molybdenum, or chromium; a glass substrate; a quartz substrate; an ITO substrate; ITO film substrate (resin film substrate such as TAC film, polyester film, acrylic film, etc.) etc., spin coating, flow coating, roll coating, slit coating, rotary coating following slit, inkjet coating, screen printing, gravure offset A coating film can be formed by applying by a printing method such as printing, and then pre-drying (pre-baking) with a hot plate or oven. The composition of the present invention is particularly suitable for printing methods such as screen printing and gravure offset printing.

The pre-bake is generally preferably performed at 60 ° C. to 150 ° C., more preferably 80 ° C. 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 of doing is taken.

Next, post-baking for thermosetting is performed. Specifically, heating is performed using a hot plate, an oven, or the like. The post-baking is generally performed at a temperature of preferably 150 ° C. to 300 ° C., more preferably 200 ° C. to 250 ° C. for 1 to 30 minutes when using a hot plate, and 1 to 90 minutes when using an oven. Is taken.

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

Moreover, when the resin composition for cured film formation of this invention contains radical photopolymerization initiator, photocuring can be performed by irradiating an ultraviolet-ray to the said coating film after prebaking. The ultraviolet ray preferably 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 thermal curing is performed. Specifically, heating is performed using a hot plate, an oven, or the like. The post-bake 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 when using a hot plate, and 1 to 90 minutes when using an oven. Is taken.

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 transparency can be formed.

Since the cured film of the present invention has at least the necessary level of flatness, hardness and adhesion, the protective film, flattening film, and insulating film in various displays such as thin film transistor (TFT) type liquid crystal display elements and organic EL elements. It is also useful as a material for forming a cured film such as a protective film or an insulating film in a touch panel. Moreover, since it is excellent also in a softness | flexibility, it is suitable also as an overcoat material for ITO films.

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 these examples. In addition, the weight average molecular weight (Mw) of the copolymer obtained in the synthesis example was measured by Showa Denko Co., Ltd. GPC apparatus (Shodex GPC-101) (column: Shodex (registered trademark) KF803L and KF804L (Showa Denko Co., Ltd.). ))), And the elution solvent tetrahydrofuran was allowed to flow through the column (column temperature 40 ° C.) at a flow rate of 1 mL / min for elution. Mw was expressed in terms of polystyrene.

The reagents and devices used in the following synthesis examples, examples, and comparative examples are as follows.
DEGMEA: Diethylene glycol monoethyl ether acetate, DEGMHE: diethylene glycol monohexyl ether, MEK: methyl ethyl ketone, MMA: methyl methacrylate, MAA: methacrylic acid, ST: styrene, tBuST: 4-t-butylstyrene, Tokyo Chemical Industry Co., Ltd. Made.
-TEGMBuE: Triethylene glycol monobutyl ether, manufactured by Wako Pure Chemical Industries, 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.
DPHA: dipentaerythritol (hexa / penta) acrylate, manufactured by Nippon Kayaku Co., Ltd.
-5-MBT: 5-methylbenzotriazole, manufactured by Tokyo Chemical Industry Co., Ltd.
IRG500: Photopolymerization initiator, Irgacure 500 manufactured by BASF
IRG651: photopolymerization initiator, Irgacure 651 manufactured by BASF
APS: 3-aminopropyltriethoxysilane, LS-3150 manufactured by Shin-Etsu Chemical Co., Ltd.
UPS: 3-ureidopropyltriethoxysilane, AY43-031 manufactured by Toray Dow Corning Co., Ltd.
MPMS: 3-methacryloxypropyltrimethoxysilane, A-174 manufactured by Momentive Performance Materials Japan.
-AGITAN 771: Antifoam, manufactured by MUNZING.
-Stirrer: Shintaro Awatori ARE-310 manufactured by Shinky Corporation.
-Z320: Daicel Cytec Co., Ltd. cyclomer P.

[1] Synthesis of polymer (resin) [Synthesis Example 1]
In a 1,000 mL four-necked flask, 532.0 g of DEGMEA was added 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 The mixture was slowly added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 70 ° C. for 20 hours to obtain a resin solution P1. Mw = about 50,000.

[Synthesis Example 2]
In a 1,000 mL four-necked flask, 537.1 g of DEGMEA was added and stirred at 70 ° C. (internal temperature) under a nitrogen atmosphere, and a mixed solution of MMA 350.0 g and MAIB 8.1 g was slowly added over 2 hours. It was dripped. After the dropwise addition, the mixture was further reacted at 70 ° C. for 20 hours to obtain a resin solution P2. Mw = about 50,000.

[Synthesis Example 3]
In a 1,000 mL four-necked flask, 571.0 g of DEGMHE was added and stirred at 70 ° C. (internal temperature) under a nitrogen atmosphere, and MMA 240.0 g, MAA 25.8 g, ST 31.3 g and MAIB 10.4 g The mixture was slowly added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 70 ° C. for 20 hours to obtain a resin solution P3. Mw = about 40,000.

[Synthesis Example 4]
In a 1,000 mL four-necked flask, 694.8 g of TEGMBuE was added and stirred at 70 ° C. (internal temperature) under a nitrogen atmosphere, and MMA 140.0 g, MAA 15.0 g, ST18.3 g and MAIB 0.4 g were added thereto. The mixture was slowly added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 80 ° C. for 20 hours to obtain a resin solution P4. Mw = about 170,000.

[Synthesis Example 5]
In a 1,000 mL four-necked flask, 577.4 g of MEK was placed and stirred at 70 ° C. (internal temperature) under a nitrogen atmosphere, while MMA 250.0 g, MAA 26.9 g, ST 32.6 g and MAIB 1.4 g were mixed. The mixture was slowly added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 80 ° C. for 20 hours to obtain a resin solution P5. Mw = about 80,000.

[Synthesis Example 6]
In a 1,000 mL four-necked flask, 570.0 g of DEGMEA was placed and stirred at 80 ° C. (internal temperature) under a nitrogen atmosphere, and MMA 300.0 g, MAA 32.2 g, ST 39.2 g, and MAIB 8.6 g The mixture was slowly added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 80 ° C. for 20 hours to obtain a resin solution P6. Mw = about 30,000.

[Synthesis Example 7]
In a 1,000 mL four-necked flask, 540.2 g of DEGMEA was placed and stirred at 80 ° C. (internal temperature) under a nitrogen atmosphere, and MMA 300.0 g, MAA 15.2 g, ST 36.8 g and MAIB 7.7 g The mixture was slowly added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 80 ° C. for 20 hours to obtain a resin solution P7. Mw = about 30,000.

[Synthesis Example 8]
Place 460.3 g of DEGMEA in a 1,000 mL four-necked flask and stir at 80 ° C. (internal temperature) under a nitrogen atmosphere while slowly adding a mixture of MMA 300.0 g and MAIB 6.8 g over 2 hours. It was dripped. After the dropwise addition, the mixture was further reacted at 80 ° C. for 20 hours to obtain a resin solution P8. Mw = about 30,000.

[Synthesis Example 9]
In a 1,000 mL four-necked flask, 452.1 g of DEGMEA was added and stirred at 80 ° C. (internal temperature) under a nitrogen atmosphere, and 200.0 g of MMA, 49.1 g of MAA, 45.7 g of tBuST, and 6.6 g of MAIB were added thereto. The mixture was slowly added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 80 ° C. for 20 hours to obtain a resin solution P9. Mw = about 30,000.

Table 1 shows the composition ratio of each resin obtained in the above synthesis example.

[2] Preparation of varnish (cured film forming resin composition) [Example 1]
In a 200 mL plastic container, 58.0 g of the resin solution P1 obtained in Synthesis Example 1, 25.5 g of DPHA, 0.23 g of UPS, and 16.2 g of DEGMEA are put into a stirrer. Stirring was performed at 2,000 rpm to prepare a varnish.

[Example 2]
In a 200 mL plastic container, 58.0 g of the resin solution P2 obtained in Synthesis Example 2, 25.5 g of DPHA, 0.23 g of UPS, and 16.2 g of DEGMEA are placed in a stirrer. Stirring was performed at 2,000 rpm to prepare a varnish.

[Example 3]
In a 200 mL plastic container, 67.7 g of the resin solution P3 obtained in Synthesis Example 3, 26.1 g of DPHA, 0.24 g of UPS, and 6.0 g of DEGMHE are put into a stirrer, and this is placed for 10 minutes. Stirring was performed at 2,000 rpm to prepare a varnish.

[Example 4]
In a 200 mL plastic container, 58.2 g of the resin solution P3 obtained in Synthesis Example 3, 22.4 g of DPHA, 0.20 g of UPS, and 19.2 g of DEGMHE are placed in a stirrer. Stirring was performed at 2,000 rpm to prepare a varnish.

[Example 5]
In a 200 mL plastic container, 64.3 g of the resin solution P4 obtained in Synthesis Example 4, 14.1 g of DPHA, 0.13 g of UPS, and 21.4 g of TEGMBuE are placed in a stirrer. Stirring was performed at 2,000 rpm to prepare a varnish.

[Example 6]
In a 200 mL plastic container, 67.3 g of the resin solution P3 obtained in Synthesis Example 3, 21.2 g of DPHA, 0.24 g of UPS, and 11.3 g of DEGMHE are put into a stirrer. Stirring was performed at 2,000 rpm to prepare a varnish.

[Example 7]
In a 200 mL plastic container, 55.7 g of the resin solution P3 obtained in Synthesis Example 3, 25.3 g of DPHA, 0.19 g of UPS and 18.8 g of DEGMHE are put into a stirrer, and this is put into a stirrer for 10 minutes. Stirring was performed at 2,000 rpm to prepare a varnish.

[Example 8]
In a 200 mL plastic container, 58.0 g of the resin solution P5 obtained in Synthesis Example 5, 25.5 g of DPHA, 0.23 g of UPS, and 16.2 g of MEK are put into a stirrer. Stirring was performed at 2,000 rpm to prepare a varnish.

[Example 9]
In a 200 mL plastic container, 53.8 g of the resin solution P6 obtained in Synthesis Example 6, 23.7 g of PET-30, 2.6 g of IRG500, 1.1 g of 5-MBT, 0.11 g of APS, and AGITAN 771 0.04 g and DEGMEA 18.7 g were put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 10]
In a 200 mL plastic container, 53.7 g of the resin solution P6 obtained in Synthesis Example 6, 23.6 g of PET-30, 2.6 g of IRG500, 1.1 g of 5-MBT, 0.21 g of APS, and AGITAN 771 Of 0.04 g and 18.8 g of DEGMEA were put into a stirrer and stirred for 10 minutes at 2,000 rpm to prepare a varnish.

[Example 11]
In a 200 mL plastic container, 53.9 g of the resin solution P6 obtained in Synthesis Example 6, 23.7 g of PET-30, 2.6 g of IRG500, 1.1 g of 5-MBT, 0.02 g of UPS, AGITAN771 0.04 g and DEGMEA 18.7 g were put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 12]
In a 200 mL plastic container, 53.8 g of the resin solution P6 obtained in Synthesis Example 6, 23.7 g of PET-30, 2.6 g of IRG500, 1.1 g of 5-MBT, 0.11 g of UPS, 0.11 g of AGITAN771 0.04 g and DEGMEA 18.7 g were put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 13]
In a 200 mL plastic container, 53.9 g of the resin solution P6 obtained in Synthesis Example 6, 23.7 g of PET-30, 2.6 g of IRG500, 1.1 g of 5-MBT, 0.02 g of MPMS, AGITAN 771 0.04 g and DEGMEA 18.7 g were put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 14]
In a 200 mL plastic container, 53.8 g of the resin solution P6 obtained in Synthesis Example 6, 23.7 g of PET-30, 2.6 g of IRG500, 1.1 g of 5-MBT, 0.11 g of MPMS, AGITAN 771 0.04 g and DEGMEA 18.7 g were put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 15]
In a 200 mL plastic container, 53.9 g of the resin solution P7 obtained in Synthesis Example 7, 23.7 g of PET-30, 2.6 g of IRG500, 1.1 g of 5-MBT, 0.02 g of APS, AGITAN 771 0.04 g and DEGMEA 18.7 g were put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 16]
In a 200 mL plastic container, 53.9 g of the resin solution P8 obtained in Synthesis Example 8, 23.7 g of PET-30, 2.6 g of IRG500, 1.1 g of 5-MBT, 0.02 g of APS, and AGITAN771 0.04 g and DEGMEA 18.7 g were put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 17]
In a 200 mL plastic container, 55.1 g of the resin solution P6 obtained in Synthesis Example 6, 24.3 g of PET-30, 1.31 g of IRG651, 1.3 g of 5-MBT, 0.02 g of APS, and AGITAN771 0.04 g and DEGMEA 17.9 g were put into a stirrer and stirred for 10 minutes at 2,000 rpm to prepare a varnish.

[Example 18]
In a 200 mL plastic container, 55.6 g of the resin solution P6 obtained in Synthesis Example 6, 24.5 g of PET-30, 0.89 g of IRG651, 1.3 g of 5-MBT, 0.02 g of APS, AGITAN771 0.04 g and DEGMEA 17.6 g were put into a stirrer and stirred for 10 minutes at 2,000 rpm to prepare a varnish.

[Example 19]
In a 200 mL plastic container, 58.9 g of the resin solution P9 obtained in Synthesis Example 9, 21.2 g of DPHA, 2.83 g of IRG500, 1.2 g of 5-MBT, 0.24 g of APS, 0 of AGITAN771 .04 g and 15.7 g of DEGMEA were put into a stirrer and stirred for 10 minutes at 2,000 rpm to prepare a varnish.

[Example 20]
In a 200 mL plastic container, 53.7 g of the resin solution P9 obtained in Synthesis Example 9, 23.6 g of DPHA, 2.58 g of IRG500, 1.1 g of 5-MBT, 0.21 g of APS, and 0.21 g of AGITAN771 .04 g and 18.8 g of DEGMEA were put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Comparative Example 1]
In a 200 mL plastic container, 99.0 g of the resin solution P1 obtained in Synthesis Example 1, 0.40 g of UPS and 0.59 g of DEGMEA are placed, and this is placed in a stirrer and stirred at 2,000 rpm for 10 minutes. A varnish was prepared.

[Comparative Example 2]
In a 200 mL plastic container, 53.9 g of the resin solution P6 obtained in Synthesis Example 6, 23.7 g of PET-30, 2.6 g of IRG500, 1.1 g of 5-MBT, 0.04 g of AGITAN771, and DEGMEA Was put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Comparative Example 3]
In a 200 mL plastic container, 21.6 g of Z320, 23.7 g of PET-30, 2.6 g of IRG500, 1.1 g of 5-MBT, 0.02 g of APS, 0.04 g of AGITAN771, and 51. of DEGMEA. 0 g was put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Comparative Example 4]
In a 200 mL plastic container, 41.8 g of Z320, 5.0 g of IRG500, 2.1 g of 5-MBT, 0.04 g of APS, 0.04 g of AGITAN771, and 51.0 g of DEGMEA are placed in a stirring device. The mixture was stirred for 10 minutes at 2,000 rpm to prepare a varnish.

[Comparative Example 5]
In a 200 mL plastic container, put 78.7 g of PET-30, 9.5 g of IRG500, 3.9 g of 5-MBT, and 0.08 g of APS, put them in a stirrer, and stir at 2,000 rpm for 10 minutes. And varnish was produced.

[Comparative Example 6]
In a 200 mL plastic container, 93.5 g of the resin solution P6 obtained in Synthesis Example 6, 4.49 g of IRG500, 1.9 g of 5-MBT, 0.19 g of APS, 0.04 g of AGITAN771, and 0.1 g of DEGMEA This was put into a stirrer and stirred for 10 minutes at 2,000 rpm to prepare a varnish.

Table 2 summarizes the compositions of the varnishes produced in Examples 1 to 8 and Comparative Example 1. Table 3 summarizes the compositions of the varnishes produced in Examples 9 to 20 and Comparative Examples 2 to 6.

[3] Evaluation of printability of varnish and production and evaluation of cured film [Preparation of cured film]
The varnishes of Examples 1 to 8 and Comparative Example 1 were each coated on a glass with ITO so as to have a thickness of about 3 to 10 μm, and prebaked at 110 ° C. for 2 minutes. Next, post-baking was performed at 230 ° C. for 30 minutes to prepare a cured film.
About the obtained cured film, pencil hardness, adhesiveness, and transparency were evaluated by the following method. The varnishes of Examples 3 to 5 were measured for viscosity, and the varnishes of Examples 3 to 5 and 8 were evaluated for printability by the following methods. The results are shown in Table 4.

In addition, the varnishes of Examples 9 to 20 and Comparative Examples 2 to 6 were respectively made by Santo Vacuum Co., Ltd. ITO film (resistance film (high transmission) ITO film, resistance value: 400 ± 100 Ω / sq, total light transmittance :> 90%), a bar coater was applied to a thickness of about 3 to 10 μm, and prebaked at 110 ° C. for 10 minutes. Subsequently, UV irradiation (400 mJ / cm ² ) was performed, and then post-baking was performed at 110 ° C. for 50 minutes to prepare a cured film.
About the obtained film, pencil hardness, adhesiveness, and a softness | flexibility were evaluated by the following method. The results are shown in Table 5.

[Evaluation of pencil hardness]
Based on JIS K 5400, the measurement was performed under a load of 1,000 g.

[Evaluation of adhesion]
The cross-cut test method was used for evaluation. First, 100 grids were created on the coating film using a cutter guide. Next, a cellophane tape made by Nichiban Co., Ltd. was bonded onto the grid, and rubbed with an eraser from above to make it adhere sufficiently. Then, the cellophane tape was peeled off, and at that time, it was evaluated how many of the 100 grids were peeled off.
0B: 66 or more peeled 1B: 36 to 65 peeled 2B: 16 to 35 peeled 3B: 6 to 15 peeled 4B: 1 to 5 peeled 5B: No peeling

[Evaluation of printability]
The varnish of Example 3 was printed on a glass substrate with ITO by screen printing using MT-320TVC manufactured by Micro Tech Co., Ltd. In addition, the varnishes of Examples 4, 5 and 8 were printed on a glass substrate with ITO by a gravure offset printing method using Suma Labo-III manufactured by Komura Tech Co., Ltd. The pattern (vertical 20 μm, horizontal 20 μm) on the obtained glass substrate with ITO was observed with an optical microscope. A sample that did not protrude from the pattern and could be printed neatly by visual inspection was marked with a circle. The results are shown in Table 4.

[Measurement of viscosity]
For the varnishes of Examples 3 to 5, the viscosity (mPa · s) was measured by TVE-20LT and TVE-20HT manufactured by Toki Sangyo Co., Ltd. The results are shown in Table 4.

[Measurement of transmittance]
The UV-visible absorption spectra of the cured films prepared using the varnishes of Examples 1 to 7 and Comparative Example 1 were measured using UV-3100PC manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm was evaluated. The results are shown in Table 4.

[Evaluation of flexibility]
The above films obtained using the varnishes of Examples 9 to 20 and Comparative Examples 2 to 6 were placed on a 3 cm diameter cylinder with the coat side facing outward and fixed for 15 seconds. The change in the appearance of the coating film was observed.

As can be seen from the results shown in Table 4, all of the cured films obtained from the cured film forming resin compositions of Examples 1 to 8 had a high pencil hardness of H or higher and an adhesiveness of 4B or higher. Further, the cured film forming resin compositions of Examples 3 to 5 had a viscosity in a predetermined range and good printability. However, in Example 8, although the adhesion and hardness were good, the printability was low because a low boiling point solvent was used.

Comparative Example 1 had a low pencil hardness of less than B.

As can be seen from the results shown in Table 5, each of the cured films obtained from the cured film forming resin compositions of Examples 9 to 20 has a high pencil hardness of 2H or higher, an adhesiveness of 3B or higher, and flexibility. Was also good.

On the other hand, in Comparative Examples 2 to 6, the adhesion was as low as 1B or less, and in Comparative Examples 4 and 5, the flexibility was also low. Moreover, about the comparative example 6, pencil hardness was as low as less than H.

Claims

(A) a (co) polymer containing repeating units represented by the following formulas (1) to (3),

(In the formula, each R independently represents a hydrogen atom or a methyl group. R 1 represents an alkyl group. R 2 to R 6 each independently represents a hydrogen atom, a halogen atom or an alkyl group. A, b And c are positive numbers that satisfy 40 ≦ a ≦ 100, 0 ≦ b ≦ 30, and 0 ≦ c ≦ 30, respectively, and 40 ≦ a + b + c ≦ 100.)
(B) a silane coupling agent,
A cured film-forming resin composition comprising (C) a polyfunctional (meth) acrylate compound and (D) a solvent.
(C) The polyfunctional (meth) acrylate compound is pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, It is at least one selected from dipentaerythritol pentamethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate and ditrimethylolpropane tetramethacrylate Item 1 Cured film-forming resin composition of the mounting.
3. The resin composition for forming a cured film according to claim 2, wherein the polyfunctional (meth) acrylate compound is at least one selected from pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate and pentaerythritol trimethacrylate. object.
The cured film according to claim 2, wherein the polyfunctional (meth) acrylate compound is at least one selected from dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentamethacrylate. Resin composition for forming.
The resin composition for forming a cured film according to any one of claims 1 to 4, further comprising (E) an ion trapping agent.
(E) The resin composition for forming a cured film according to claim 5, wherein the ion trapping agent is 5-methylbenzotriazole.
The resin composition for forming a cured film according to any one of claims 1 to 6, wherein the viscosity at 25 ° C is 1 to 10,000 mPa · s.
The resin composition for forming a cured film according to any one of claims 1 to 6, wherein the solvent has a boiling point of 150 ° C or higher.
The resin composition for forming a cured film according to claim 8, wherein the viscosity at 25 ° C is 10 to 100,000 mPa · s.
The resin composition for forming a cured film according to any one of claims 1 to 9, further comprising (F) a radical polymerization initiator.
A method for producing a cured film, comprising applying the resin composition for forming a cured film according to claim 10 to a substrate, irradiating with ultraviolet rays, and baking at 80 ° C to 120 ° C.
A cured film obtained using the resin composition for forming a cured film according to any one of claims 1 to 10.
A laminate obtained by laminating the cured film according to claim 12 on a substrate.
The laminate according to claim 13, wherein the substrate is a film.
A touch panel including the cured film according to claim 12.