KR20150105378A - Cured-film-forming resin composition - Google Patents

Abstract

(A) a (co) polymer containing repeating units represented by the following formulas (1) to (3), (B) a silane coupling agent, (C) a polyfunctional (meth) By weight based on the total weight of the resin composition. (Wherein, R represents a hydrogen atom or a methyl group independently, respectively. R ¹ represents an alkyl group. R ² ~ R ⁶ represents a hydrogen atom, a halogen atom or an alkyl group independently, respectively. A, b, and c are 40 each A? 100, 0? B? 30, 0? C? 30, and 40? A + b + c? 100.

Description

CURED-FILM-FORMING RESIN COMPOSITION [0002]

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

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 required portion by pattern processing by photolithography using a photosensitive resin composition (Patent Document 1).

However, patterning by photolithography has a problem in that the process is complicated and costly. For this reason, a composition that can form a protective film, an insulating film, and the like at a necessary portion at a low cost with a simpler method has been demanded.

In addition, the use of a film substrate in place of a glass substrate has been increasing due to requests for transportation and storage. The film substrate is preserved in a roll shape or the like at the time of storage, but at that time, since the substrate is curved, the material to be coated on the film substrate is required to have flexibility such as film.

Further, in the case where an adhesive is used for bonding the substrates on a substrate on which electrodes are formed on a film such as an ITO film, the silver wire is deteriorated by the moisture of the adhesive to cause a problem such as short- A protective overcoat material is required.

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 2). However, in the conventional methods such as the incorporation of inorganic fine particles, the hardness is improved, but there is no flexibility and, for example, a problem such as a crack is introduced when the substrate is bent, and therefore, It was a situation.

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

SUMMARY OF THE INVENTION 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 transmittance, high adhesion, hardness and high flexibility and long-term reliability And to provide a possible composition.

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

That is, the present invention provides the following resin composition for forming a cured film.

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

(Wherein, R represents a hydrogen atom or a methyl group independently, respectively. R ¹ represents an alkyl group. R ² ~ R ⁶ represents a hydrogen atom, a halogen atom or an alkyl group independently, respectively. A, b, and c are 40 each A? 100, 0? B? 30, 0? C? 30, and 40? A + b + c? 100.

(B) a silane coupling agent,

(C) a polyfunctional (meth) acrylate compound and

(D) Solvent

And a curing accelerator.

2. The composition of claim 1 wherein (C) the polyfunctional (meth) acrylate compound is selected from the group consisting of pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Acrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, trimethylol ethane triacrylate, trimethylolethane trimethacrylate, trimethylol propane paint, dipentaerythritol pentaacrylate, Wherein the resin composition is at least one selected from the group consisting of acrylate, methacrylate, triacrylate, triacrylate, triacrylate, triacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate and ditrimethylolpropane tetramethacrylate.

3. The composition according to claim 1, wherein the (C) polyfunctional (meth) acrylate compound is at least one selected from pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate and pentaerythritol trimethacrylate By weight based on the total weight of the cured film.

4. The composition according to claim 1, wherein (C) the polyfunctional (meth) acrylate compound is selected from dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate and dipentaerythritol penta methacrylate At least one curable resin composition for forming a cured film.

5. The resin composition for forming a cured film according to any one of (1) to (4), which further comprises (E) an ion trap agent.

6. The resin composition for forming a cured film of (5), wherein the (E) ion trapping agent is 5-methylbenzotriazole.

7. The resin composition for forming a cured film according to any one of 1 to 6, wherein the viscosity at 25 占 폚 is 1 to 10,000 mPa 占 퐏.

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 deg.

9. A resin composition for forming a cured film of 8 having a viscosity at 25 占 폚 of 10 to 100,000 mPa 占 퐏.

10. The resin composition for forming a cured film according to any one of (1) to (9), further comprising (F) a radical polymerization initiator.

11. A process for producing a cured film, which comprises applying a resin composition for forming a cured film on a substrate, irradiating the substrate with ultraviolet rays, and then firing at 80 to 120 deg.

12. A cured film obtained by using the resin composition for forming a cured film according to any one of 1 to 10.

13. A laminate obtained by laminating a cured film of 12 on a substrate.

14. A laminate of 13 wherein the substrate is a film.

15. A touch panel comprising a cured film of 12.

The cured film obtained by using the resin composition for forming a cured film 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, an insulating film, and the like in a touch panel such as a protective film, a planarizing film, an insulating film, and an insulating film in various displays such as organic electroluminescence (organic EL) In addition, it is also suitable as an overcoat material for an ITO film because of its excellent flexibility.

[Resin composition for forming a cured film]

The resin composition for forming a cured film of the present invention contains (A) a (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 resin composition for forming a cured film of the present invention is a (co) polymer containing the repeating units represented by the following formulas (1) to (3).

In the formula, each R independently represents a hydrogen atom or a methyl group, and a methyl group is preferable. R ¹ represents an alkyl group. R ² to R ⁶ each independently represent 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 any of linear, branched, and cyclic. The number of carbon atoms in 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 a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a c-propyl group, a n-butyl group, an i-butyl group, a s- . 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 hydroxyl group, and an amino group. It is preferable that R ¹ to R ⁶ are groups which do not react with the component (C) to be described later.

The (co) polymer contains a repeating unit represented by the formula (1) and, if necessary, a repeating unit represented by the formula (2) and / or a repeating unit represented by the formula (3). By containing the repeating unit represented by the formula (2), improvement of the adhesion can be expected, and by including the repeating unit represented by the formula (3), the characteristics of adhesion and hydrophobicity (low water absorption) can be imparted.

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

The (co) polymer preferably has a weight average molecular weight (Mw) of 5,000 to 200,000, more preferably 10,000 to 100,000, and even more preferably 15,000 to 80,000, from the viewpoints of handling and adhesion. When the Mw exceeds 200,000, the solubility in a solvent is lowered and the handling property is lowered. When the Mw is less than 5,000, the adhesion may be lowered.

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 even more preferably 40,000 to 170,000. When the Mw exceeds 200,000, the solubility in a solvent is lowered and the handling property is lowered. On the other hand, if the Mw is less than 10,000, the printability may be lowered.

Mw is measured value by polystyrene conversion 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 obtained by copolymerizing a monomer giving the repeating unit represented by the formula (1) and, if necessary, a monomer giving the repeating unit represented by the formula (2) (Co) polymerizing the monomer to give a polymerizable monomer.

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

Examples of the monomer giving the repeating unit represented by the formula (1) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, Tert-butyl acrylate, tert-butyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert- Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxy Propyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and the like. Of these, particularly preferred are methyl methacrylate, ethyl methacrylate and the like.

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

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

The (co) polymer may contain, in addition to the repeating units represented by the above formulas (1) to (3), other repeating units within the range not impairing the effects of the present invention. Examples of the monomer giving 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, . Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide.

As the polymerization initiator, conventionally known ones can be appropriately selected and used. Peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide and the like; 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. These may be used singly or in combination of two or more.

The amount of the polymerization initiator used is preferably about 0.005 to 0.05 mol based on 1 mol of the monomer. The reaction temperature at the time of polymerization may suitably be set from 0 占 폚 to the boiling point of the solvent used, but is preferably about 20 to 100 占 폚. The reaction time is preferably about 0.1 to 30 hours.

The solvent used in the polymerization reaction is not particularly limited, and it may be suitably selected from various solvents generally used in the polymerization reaction. Specifically, water; But are not limited to, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, There may be mentioned alcohols such as t-butanol, t-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol and cyclohexanol Ryu; Ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran and 1,4-dioxane; 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-hexane, n-heptane, n-octane, n-nonene, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, Aliphatic or aromatic hydrocarbons such as toluene, xylene, ethylbenzene and anisole; Acetals such as methylal, diethyl acetal and the like; Fatty acids such as formic acid, acetic acid and propionic acid; N, N-dimethylformamide, dimethylsulfoxide, acetonitrile and the like may be added to the reaction mixture in the presence of a base such as N, N-dimethylformamide, N, N-dimethylformamide, . These may be used alone or in combination of two or more.

[(B) Silane coupling agent]

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

In the 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 a straight chain or branched group, 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, an ureido group, a (meth) acryloyl group, a vinyl group, an epoxy group and a mercapto group, and an amino group, an ureide group and a (meth) acryloyl group are preferable. Particularly preferably an amino group or an ethyl group.

Specific examples of the silane coupling agent include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ethylidene propyltrimethoxysilane, 3-ethylidene propyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltri Methacryloxypropyltrimethoxysilane, vinyltriclorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Try Etiquette Mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, .

Of these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethylidopropyltrimethoxysilane, 3-ethylidopropyltriethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and the like are particularly preferable. As the silane coupling agent, a commercially available product can be used.

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

[(C) Multifunctional (meth) acrylate compound]

The component (C) in the composition of the present invention is a polyfunctional (meth) acrylate compound. The polyfunctional (meth) acrylate compound is a compound having at least two, preferably at least three, (meth) acryloxy groups in the molecule, specifically, a urethane acrylate, epoxy acrylate, polyhydric alcohol, And ester compounds obtained from acrylic acid. Of these, an ester compound obtained from a polyhydric alcohol and (meth) acrylic acid is preferable in view of compatibility between a substrate and a surface hardness. The number of (meth) acrylate 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 a compound obtained by reacting a hydroxyl 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, (Meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, trimethylolpropane diacrylate, and the like. These hydroxy group-containing (meth) acrylates may be used alone or in combination of two or more.

The polyisocyanate may be any of aliphatic, aromatic and alicyclic polyisocyanates. Examples of the polyisocyanate include methylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, Naphthalene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate Aniline, phenylene diisocyanate, and methylenebisphenyldiisocyanate. These polyisocyanates may be used singly or in combination of two or more. Of these polyisocyanates, it is preferable to be a non-yellowing urethane.

Commercially available urethane oligomers include EB2ECRYL220 (manufactured by Daicel-Cytec); Art Resin UN-3320HA, UN-3320HB, UN-3320HC, UN-330, and UN-901T (manufactured by Negami Kogyo Co., Ltd.); NK Oligo U-4HA, U-6HA, U-324A, U-15HA, U-108A, U-200AX, U-122P, U-5201, U-340AX, U-511 UA-W4, UA-W4, UA-4000, UA-100 (above, Shin Nakamura Kagaku Co., Ltd.) My); UV-7600B, Copper UV-7600B, Copper UV-7600B, Copper UV-7600B, Copper UV-7610B, Copper UV-7600B, Copper UV-7600B, Copper UV- UV-3310B, UV-3500BA, UV-3520TL, UV-3510B, UV-3510B, UV-3610B, UV-3700B, UV-6100B, and UV-6640B (manufactured by Nippon Gohsei Kaikakogyo Co., Ltd.).

As the epoxy acrylate, those generally obtained by esterifying a polyepoxy compound (or an epoxy resin) and acrylic acid can be cited. Specific examples of the epoxy acrylate include bisphenol-type epoxy acrylates synthesized by reaction of various bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.) with epichlorohydrin and acrylic acid, reaction of phenol novolak, epichlorohydrin and acrylic acid And phenol novolak type epoxy acrylate synthesized by the following method.

Examples of the polyhydric alcohol include glycerol, erythritol, pentaerythritol, trimethylolethane, trimethylol propane, dipentaerythritol, ditrimethylol propane 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, hexaacrylate, hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, trimethylol ethane triacrylate, trimethylolethane trimethacrylate, trimethylol Propyl methacrylate, propyl methacrylate, propyl methacrylate, propyl methacrylate, propyl methacrylate, propyl methacrylate, propyl methacrylate, propyl methacrylate,

Examples thereof include KAYARAD T-1420, Copper DPHA, Copper DPHA-2C, Copper D-310, Copper D-330 (trade name) , DPCA-20, DPCA-30, DPCA-60, DPCA-120, Copper DN-0075, Copper DN-2475, Copper R-526, Copper NPGDA Copper PEG400DA Copper Manda Copper R- 330, TPA-320, TPA-330, TP-320, TP-330, TP-320, TP-320 , Copper PET-30, copper RP-1040 (manufactured by Nippon Kayaku Co., Ltd.); ARONIX M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100 and M-8030 (Manufactured by Toa Kosei Co., Ltd.), M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M- ; Viscoat 295, 300, 360, GPT, 3PA, 400, 260, 312 and 335HP (manufactured by Osaka Yuki Kagakukogyo Co., Ltd.).

The content of the component (C) is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, and still more preferably 50 to 150 parts by mass, per 100 parts by mass of the component (A). When the content is too small, the hardness characteristics of the cured film are deteriorated. When the content is excessive, the adhesiveness and flexibility properties are deteriorated, and cracks are likely to occur. The polyfunctional (meth) acrylate compounds may be used singly or in combination of two or more.

[(D) Solvent]

The composition of the present invention is used in the form of a solution dissolved in a solvent. The solvent to be used at this time is a solvent which can dissolve the above components (A) to (C) and contains the component (E), the component (F), the component (G) Is not particularly limited as far as they can dissolve.

Specific examples of the solvent include toluene, xylene, methyl ethyl ketone, ethylene glycol monomethyl ether, hexyleneglycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, Ethylene glycol monoethyl ether acetate, ethylene glycol isopropyl ether, ethylene glycol monoacetate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, methylphenyl ether, 1,4-dioxane, di Ethyl acetate, isobutanol, isobutanol, isoamyl alcohol, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl n-butyl ketone, N-butyl propionate, decane, dodecane, p-methane, 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, methoxymethoxy ethanol, ethylene glycol diacetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Diethylene glycol monohexyl ether, diethylene glycol monobenzyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, Ethylene glycol Propylene glycol monobutyl ether, 1-butoxyethoxypropanol, dipropylene glycol, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol dichloride, propylene glycol, propylene glycol monobutyl ether, Diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, trimethylene glycol, 1, 1,3-butanediol, 1,5-pentanediol, hexylene glycol, octyleneglycol, glycerin, hexachloroethane, o-dichlorobenzene, m- Dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, o-dibromobenzene, dichloroethylether, diisobutylether, n-hexylether, ethylphenylether, ethyl Benzyl ether, cineol, 1-octanol, 2-octanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, Benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, alpha-terpineol, avietinol, acetonyl acetone, poron, isophorone, acetophenone, acetic acid, acetic acid, Butyl acetate, isobutyl isoamyl, n-butyl lactate, isobutyl lactate, isobutyl lactate, isobutyl lactate, isobutyl lactate, isobutyl lactate, isobutyl lactate, isobutyl lactate, isobutyl lactate, isobutyl lactate, Amyl lactate, isoamyl lactate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, dibutyl oxalate, diethyl malonate, butyric anhydride, valeric acid, isovaleric acid, caproic acid, Hexanoic acid, trichloroacetic acid, lactic acid, nitrobenzene, benzonitrile, alpha-trinitrilyl, N-methylformamide, N-methylacetoamide, 2- Pyrrolidone and the like.

These solvents may be used singly or in combination of two or more. The solvent used when the component (A) is polymerized may be used as it is.

The solvent preferably has a boiling point of 150 캜 or higher, more preferably 180 캜 or higher, and still more preferably 200 캜 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 that the solid content concentration in the composition of the present invention is 1 to 95 mass%, more preferably the solid content concentration is 5 to 90 mass%, the solid content concentration is 10 to 85 And more preferably in such an amount as to be in a mass%. Herein, the solid content is obtained by excluding the solvent (D) from the total components of the resin composition for forming a cured film of the present invention.

The resin composition for forming a cured film of the present invention contains the above components (A) to (D), and if necessary,

(E) ion trap agent,

(F) Radical polymerization initiator

(G) a polyfunctional thiol compound and / or

(H) polymerization inhibitor

.

[(E) ion trap agent]

The component (E) is an ion trap agent, and when the metal wiring is formed on the substrate, the metal wiring has an action of preventing the migration due to contact with water. As such an ion trapping agent, a compound having a chelate-forming ability having an auxiliary electron in the structure is preferable, and for example, N, N'-bis [3- (3,5-di-tert- Propionyl] hydrazine (Irganox MD1024, manufactured by BASF), oxalic acid bis (benzylidene hydrazide) (Eastman Inhibitor OABH, manufactured by Eastman Chemical), benzotriazole, and 5-methylbenzotriazole. These are available as commercial products. Other commercially available products include Adekastab CDA-1 (manufactured by Asahi Denka Co., Ltd.), Adekastab CDA-6 (manufactured by Asahi Denka Co., Ltd.), Qunox (manufactured by Mitsui Toatsu Fine Chemical Co., Ltd.) XL-1 (manufactured by Uni Royal Co., Ltd.) and the like. Of these, 5-methylbenzotriazole is particularly preferable.

The amount of the ion trap agent to be added is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass, per 100 parts by mass of the component (A). If the amount is less than 0.0001 part by mass, the effect of protecting the metal wiring may not be obtained. If the amount is more than 20 parts by mass, properties such as hardness and adhesion of the cured film may be deteriorated and the cost may be deteriorated.

[(F) Radical polymerization initiator]

The component (F) is a radical polymerization initiator and contributes to initiation or promotion of polymerization of the component (C). The component (C) is spontaneously polymerized by treatment at a high temperature. When the high-temperature curing treatment such as denaturation of the substrate is not possible, a low-temperature curing treatment or a photo-curing treatment can be performed by adding the component (F).

The radical polymerization initiator is required to be capable of emitting a substance that initiates radical polymerization by light irradiation and / or heating. Examples of the photoradical polymerization initiator include a benzophenone derivative, an imidazole derivative, a bisimidazole derivative, an N-arylglycine derivative, an organic azide compound, a titanocene compound, an aluminate complex, an organic peroxide, an N-alkoxypyridinium salt , Thioxanthone derivatives, and the like. Specific examples include benzophenone, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3 ', 4,4'-tetrakis (tert- butyldioxycarbonyl) benzophenone, 3- Phenyl-5-isooxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane- 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 1-one (IRGACURE 369, BASF Corp.), bis (η ⁵ -2,4- cyclopentadienyl-1-yl) -bis (2,6-difluoro -3- (1H- pyrrol- 1-yl) -phenyl) titanium) (Irgacure 784, manufactured by BASF), and the like.

Specific examples thereof include Irgacure 500, Irgacure 907, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 500 available from BASF. Cure 250, Irgacure 1800, Irgacure 1870, Irgacure OXE01, DAROCUR TPO, DAROCUR1173; KAYACURE DETX-S, KAYACURE BX, and KAYACURE DMBI manufactured by Nippon Kayaku Co., Ltd., and the like, such as Speedcure MBB, Speedcure PBZ, Speedcure ITX, Speedcure CTX, Speedcure EDB, Esacure ONE, Esacure KIP150, .

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, Peroxides such as oxides, dicumylperoxides, diaryloyl peroxides, tert-butylperoxyacetate, tert-butylperoxy pivalate and tert-butylperoxy-2-ethylhexanoate; Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, 2,2'- Azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutylate, 2,2'-azobis (2-methylbutyrononitrile) Azobis (2-cyclohexanecarbonitrile), 2- (carbamoyl azo) isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), Azo-based 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, but are not limited thereto.

Examples of the commercially available thermal radical polymerization initiator include peryl IL, peryl ILP, peryl ILP, peryl ILP, peroyl SBP, perocta ND, peroyl TCP, peroyl OPP, perheyl ND, ND, perbutyl NHP, perhexyl PV, perbutyl PV, peroyl 355, peroyl L, perocta O, peroyl SA, perhexa 250, perhexyl O, nippers PMB, perbutyl O, , Perhexa MC, Perhexa TMH, Perhexa HC, Perhexa C, Per tetra A, Perhexyl I, Perbutyl MA, Perbutyl 355, Perbutyl L, Perbutyl I, Perbutyl E, Hexa 25Z, perbuta A, perhexa 22, perbutyl Z, perhexapar V, perbutyl P, percumyl D, perhexyl D, perhexa 25B, perbutyl C, perbutyl D, permha H, BC (above, manufactured by Nichiyu Corporation); V-70, V-65, V-59, V-40, V-30, VA-044, VA-046B, VA-061, V- 110, V-601, V-501 (manufactured by Wako Pure Chemical Industries, Ltd.); IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, DARACURE 1116, 1173, lucylline TPO Ubecryl P36 (manufactured by UCB Co., Ltd.); But are not limited to, Echocuria KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B (manufactured by Prattsu Lambert).

The content of the component (F) 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) polyfunctional thiol compound]

The composition of the present invention may contain a polyfunctional thiol compound as component (G), if necessary. The polyfunctional thiol compound used in the composition of the present invention is preferably a trifunctional or higher 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 examples of the compound include 1,3,5-tris (3-mercaptopropionyloxyethyl) -isocyanurate, 1,3,5-tris (3-mercaptobutyryloxyethyl) -isocyanurate And trifunctional thiol compounds such as trimethylolpropane (3-mercaptopropionate), which are commercially available from Wako Pure Chemical Industries, Ltd., Carpens MT (registered trademark) NR1; 4-functional group such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutylate) (manufactured by Showa Denko KK, Carens MT (registered trademark) PEI) Thiol compounds; 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 mass%, more preferably 0.8 to 5 mass%, of the total solid content. If the content is too large, the stability, odor, and adhesion of the composition may deteriorate.

[(H) polymerization inhibitor]

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

The content of the polymerization inhibitor as the component (H) 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.

[Other additives]

The composition of the present invention may contain a surfactant, a defoaming agent, a rheology modifier, a pigment, a dye, a preservative stabilizer, a dissolution accelerator such as a polyhydric phenol or a polyvalent carboxylic acid, etc., if necessary, as long as the effect of the present invention is not impaired.

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

Examples of 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 , But are not limited thereto. In the case of performing screen printing, the composition of the present invention preferably contains a defoaming 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 of dissolving the component (A) in a solvent (D), mixing the component (B) and the component (C) in a predetermined ratio to prepare a homogeneous solution. A preparation method for further adding and mixing the components (E), (F), (G), (H) and / or other components at an appropriate stage of the preparation method have.

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, when a homogeneous solution is prepared by adding the component (B), the component (C), the component (E), the component (F) and the like to the solution of the component (A) (D) solvent may be further added for the purpose of reducing the amount of the solvent. At this time, the solvent used in the synthesis of the component (A) may be the same as or different from the solvent used for adjusting the concentration at the time of preparing the composition.

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

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, still more preferably 1 to 1,000 mPa · s Do. If the viscosity is too low, a desired film thickness may not be obtained. If the viscosity is too high, the coating property may be lowered.

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 even more preferably 1,000 to 100,000 mPa · s Do. 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 lowered.

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 at 25 ° C, more preferably 5,000 to 100,000 mPa · s, and even more preferably 20,000 to 100,000 mPa · s. 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 lowered.

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

[Coating film and curing film]

The resin composition for forming a cured film of the present invention may be applied to a substrate (e.g., 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, Such as spin coating, roll coating, slit coating, spin coating on the slit, inkjet coating, screen printing, gravure offset printing, etc. on an ITO film substrate, a resin film substrate such as a TAC film, a polyester film, (Pre-baking) in a hot plate, an oven or the like to form a coating film. The composition of the present invention is particularly suitable for printing methods such as screen printing and gravure offset printing.

The prebake is generally treated preferably at 60 ° C to 150 ° C, more preferably at 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 .

Next, post baking for thermosetting is performed. Specifically, it is heated using a hot plate, an oven, or the like. In general, post bake is preferably carried out at a temperature of 150 to 300 DEG C, more preferably 200 to 250 DEG C, for 1 to 30 minutes when using a hot plate, and for 1 to 90 minutes when using an oven .

When the resin composition for forming a cured film of the present invention contains a thermal radical polymerization initiator, curing at a low temperature is possible. In this case, the prebake condition is the same as described above, but the postbake temperature is preferably 60 to 200 占 폚, and more preferably 80 to 150 占 폚. The other conditions are the same as described above.

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

Post-baking for thermosetting is performed. Specifically, it is heated using a hot plate, an oven, or the like. The postbake is generally treated preferably at 60 ° C to 150 ° C, more preferably at 80 ° C to 120 ° C, for 1 to 30 minutes when using a hot plate, and for 1 to 90 minutes when using an oven .

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 planarization property, hardness and adhesiveness, 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, It is also useful as a material for forming a cured film such as a protective film or an insulating film. In addition, since it is excellent in flexibility, it is also suitable as an overcoat material for an ITO film.

(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 these 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.) manufactured by Showa Denko K.K. And eluting solvent tetrahydrofuran was flowed in a column at a flow rate of 1 mL / min (column temperature: 40 캜) to be eluted. Mw was expressed as a 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, DEGMHE: diethylene glycol monohexyl ether, MEK: methyl ethyl ketone, MMA: methyl methacrylate, MAA: methacrylic acid, ST: styrene, tBuST : 4-t-butylstyrene, manufactured by Tokyo Kasei Corporation.

TEGMBuE: triethylene glycol monobutyl ether, manufactured by Wako Junyaku Co., Ltd.

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.

DPHA: Dipentaerythritol (hexa / penta) acrylate, manufactured by Nippon Kayaku Co., Ltd.

5-MBT: 5-methylbenzotriazole, manufactured by Tokyo Kasei Corporation.

IRG500: photopolymerization initiator, IRGACURE 500 from BASF.

IRG651: Photopolymerization initiator, Irgacure 651 from BASF.

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

· UPS: 3-Yreed propyltriethoxysilane, Dow Corning Co., Ltd. AY43-031.

MPMS: 3-methacryloxypropyltrimethoxysilane, A-174 manufactured by Momentive Performance Material Japan.

· AGITAN771: Anti-foaming agent, manufactured by MUNZING.

· Stirring apparatus: ARE-310 with Shinkie Awatori Rentero Co., Ltd.

Z320: manufactured by Daicel-Cytec Co., Ltd.

[1] Synthesis of polymer (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 1000 mL four-necked flask while stirring under nitrogen atmosphere at 70 캜 (at room temperature) Slowly dropped. After dropwise addition, the reaction was further carried out at 70 DEG C for 20 hours to obtain a resin solution P1. Mw = about 50,000.

[Synthesis Example 2]

537.1 g of DEGMEA was placed in a 1,000 mL four-necked flask, and a mixture of 350.0 g of MMA and 8.1 g of MAIB was slowly added dropwise over 2 hours while stirring at 70 DEG C (room temperature) in a nitrogen atmosphere. After dropwise addition, the reaction was further carried out at 70 DEG 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 placed, and a mixture of 240.0 g of MMA, 25.8 g of MAA, 31.3 g of ST, and 10.4 g of MAIB was added thereto over 2 hours while stirring at 70 캜 (room temperature) Slowly dropped. After dropwise addition, the reaction was further carried out at 70 DEG C for 20 hours to obtain a resin solution P3. Mw = about 40,000.

[Synthesis Example 4]

694.8 g of TEGMBuE was placed in a 1,000 mL four-necked flask, and a mixed solution of 140.0 g of MMA, 15.0 g of MAA, 18.3 g of ST and 0.4 g of MAIB was added thereto over 2 hours while stirring at 70 DEG C (room temperature) Slowly dropped. After dropwise addition, the reaction was further carried out at 80 DEG C for 20 hours to obtain a resin solution P4. Mw = about 170,000.

[Synthesis Example 5]

577.4 g of MEK was placed in a 1,000 mL four-necked flask, and a mixture of 250.0 g of MMA, 26.9 g of MAA, 32.6 g of ST and 1.4 g of MAIB was added thereto over 2 hours while stirring at 70 캜 (at room temperature) Slowly dropped. After the dropwise addition, the reaction was further carried out at 80 DEG C for 20 hours to obtain a resin solution P5. Mw = about 80,000.

[Synthesis Example 6]

570.0 g of DEGMEA was placed in a 1,000 ml four-necked flask, and a mixed solution of 300.0 g of MMA, 32.2 g of MAA, 39.2 g of ST and 8.6 g of MAIB was added thereto over a period of 2 hours while stirring at 80 캜 (room temperature) Slowly dropped. After the dropwise addition, the resin solution P6 was obtained by further reacting at 80 DEG C for 20 hours. Mw = about 3 million.

[Synthesis Example 7]

A mixed solution of 300.0 g of MMA, 15.2 g of MAA, 36.8 g of ST and 7.7 g of MAIB was added thereto over a period of 2 hours while stirring at 80 캜 (at room temperature) in a nitrogen atmosphere in a 1,000 mL four-necked flask, Slowly dropped. After dropwise addition, the reaction was further carried out at 80 DEG C for 20 hours to obtain a resin solution P7. Mw = about 3 million.

[Synthesis Example 8]

460.3 g of DEGMEA was placed in a 1,000 mL four-necked flask, and a mixed solution of 300.0 g of MMA and 6.8 g of MAIB was slowly added dropwise thereto over a period of 2 hours while stirring at 80 캜 (room temperature) in a nitrogen atmosphere. After dropwise addition, the reaction was further carried out at 80 DEG C for 20 hours to obtain a resin solution P8. Mw = about 3 million.

[Synthesis Example 9]

452.1 g of DEGMEA was placed in a 1,000 mL four-necked flask, and a mixed solution of 200.0 g of MMA, 49.1 g of MAA, 45.7 g of tBuST and 6.6 g of MAIB was added thereto over 2 hours while stirring at 80 캜 (at room temperature) Slowly dropped. After dropwise addition, the reaction was further carried out at 80 DEG C for 20 hours to obtain a resin solution P9. Mw = about 3 million.

Table 1 shows the composition ratios of the respective resins obtained in the above Synthesis Examples.

[2] Production of varnish (resin composition for forming a cured film)

[Example 1]

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 were placed in a 200-mL plastic container, and the mixture was stirred at 2,000 rpm for 10 minutes to prepare a varnish .

[Example 2]

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 were placed in a 200 mL plastic container, and the mixture was stirred at 2,000 rpm for 10 minutes to prepare a varnish .

[Example 3]

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 were placed in a 200-mL plastic container, and the mixture was stirred at 2,000 rpm for 10 minutes to prepare a varnish .

[Example 4]

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 were placed in a 200 mL plastic container, and the mixture was stirred at 2,000 rpm for 10 minutes to prepare a varnish .

[Example 5]

64.3 g of the resin solution P4 obtained in Synthesis Example 4, 14.1 g of DPHA, 0.13 g of the UPS and 21.4 g of TEGMBuE were placed in a 200 mL plastic container, and the mixture was stirred at 2,000 rpm for 10 minutes to prepare a varnish .

[Example 6]

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 were placed in a 200-mL plastic container, and the mixture was stirred at 2,000 rpm for 10 minutes to prepare a varnish .

[Example 7]

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 were placed in a 200-mL plastic container, and the mixture was stirred at 2,000 rpm for 10 minutes to prepare a varnish .

[Example 8]

58.0 g of the resin solution P5 obtained in Synthesis Example 5, 25.5 g of DPHA, 0.23 g of the UPS and 16.2 g of MEK were placed in a 200-mL plastic container, and the mixture was stirred at 2,000 rpm for 10 minutes to prepare a varnish .

[Example 9]

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, 0.04 g of AGITAN771 and 18.7 g of DEGMEA This was put in a stirring apparatus and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 10]

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, 0.04 g of AGITAN771 and 18.8 g of DEGMEA This was put in a stirring apparatus and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 11]

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, 0.04 g of AGITAN771 and 18.7 g of DEGMEA This was put in a stirring apparatus 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, 0.04 g of AGITAN771 and 18.7 g of DEGMEA This was put in a stirring apparatus and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 13]

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, 0.04 g of AGITAN771 and 18.7 g of DEGMEA This was put in a stirring apparatus and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 14]

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, 0.04 g of AGITAN771 and 18.7 g of DEGMEA This was put in a stirring apparatus and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 15]

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, 0.04 g of AGITAN771 and 18.7 g of DEGMEA This was put in a stirring apparatus and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 16]

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, 0.04 g of AGITAN771 and 18.7 g This was put in a stirring apparatus and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 17]

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, 0.04 g of AGITAN771 and 17.9 g of DEGMEA were added to a 200- This was put in a stirring apparatus and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 18]

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, 0.04 g of AGITAN771 and 17.6 g of DEGMEA This was put in a stirring apparatus and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 19]

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, 0.04 g of AGITAN771 and 15.7 g of DEGMEA were placed in a 200- This was put in a stirring apparatus and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 20]

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, 0.04 g of AGITAN771 and 18.8 g of DEGMEA were placed in a 200- This was put in a stirring apparatus and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Comparative Example 1]

99.0 g of the resin solution P1 obtained in Synthesis Example 1, 0.40 g of the UPS, and 0.59 g of DEGMEA were placed in a 200 mL plastic container, which was put in a stirring device and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Comparative Example 2]

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 18.6 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.

[Comparative Example 3]

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 51.0 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.

[Comparative Example 4]

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 were put into a 200 mL plastic container and stirred at 2,000 rpm for 10 minutes To make a varnish.

[Comparative Example 5]

78.7 g of PET-30, 9.5 g of IRG500, 3.9 g of 5-MBT and 0.08 g of APS were placed in a 200 mL plastic container, and the mixture was stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Comparative Example 6]

93.5 g of the resin solution P6 obtained in Synthesis Example 6, 4.49 g of IRG500, 1.9 g of 5-MBT, 0.09 g of APIT, 0.04 g of AGITAN771 and 0.1 g of DEGMEA were placed in a 200 mL plastic container, 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 8 and Comparative Example 1 are summarized in Table 2. The compositions of the varnishes produced in Examples 9 to 20 and Comparative Examples 2 to 6 are summarized in Table 3.

[3] Evaluation of printability of varnish and production and evaluation of cured film

[Production of a cured film]

The varnishes of Examples 1 to 8 and Comparative Example 1 were each applied to a glass with ITO on a bar coater so as to have a thickness of about 3 to 10 mu m and prebaked at 110 DEG C for 2 minutes. Subsequently, post-baking was performed at 230 캜 for 30 minutes to prepare a cured film.

The obtained cured film was evaluated for pencil hardness, adhesion, and transparency by the following method. The viscosities of the varnishes of Examples 3 to 5 were measured, 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.

The varnishes of Examples 9 to 20 and Comparative Examples 2 to 6 were applied to an ITO film (resistance film (high permeability) 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 mu m, and pre-baking was performed at 110 DEG C for 10 minutes. Subsequently, UV irradiation (400 mJ / cm < ² >) was performed, and post baking was performed at 110 DEG C for 50 minutes to prepare a cured film.

The resulting film was evaluated for pencil hardness, adhesion, and flexibility by the following method. The results are shown in Table 5.

[Evaluation of pencil hardness]

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

[Evaluation of adhesion]

And evaluated by the cross-cut test method. First, a checker grid of 100 pieces was formed on the coating film using a cutter guide. Next, a cellophane tape made by Nichiban Co., Ltd. was adhered on the checker scale and rubbed strongly from the top with an eraser, and sufficiently adhered. Then, the cellophane tape was peeled off, and at that time, evaluation was made as to whether or not some of the 100 checkerboard peels were peeled off.

0B: More than 66 pieces peeled off

1B: 36 to 65 peeled off

2B: 16 to 35 peeled off

3B: 6 to 15 peeling

4B: 1 to 5 peeling off

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. The varnishes of Examples 4, 5 and 8 were printed on a glass substrate with ITO by gravure offset printing using Suma Labo-III manufactured by Gomarate Co., Ltd. The obtained pattern (20 mu m in length and 20 mu m in width) on the ITO-adhered glass substrate was observed with an optical microscope. The pattern was clearly printed with naked eyes without protruding or protruding. The results are shown in Table 4.

[Measurement of viscosity]

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

[Measurement of transmittance]

The ultraviolet absorption spectrum of the cured film prepared using the varnish of Examples 1 to 7 and Comparative Example 1 was measured using UV-3100PC manufactured by Shimadzu Seisakusho Co., Ltd., and the transmittance at a wavelength of 400 nm was evaluated . The results are shown in Table 4.

[Evaluation of flexibility]

The films obtained using the varnishes of Examples 9 to 20 and Comparative Examples 2 to 6 were fixed for 15 seconds along a cylindrical cylinder having a diameter of 3 cm with the coat side outward. Changes in the external appearance of the coated film were observed, and those with no change were rated as & cir &

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

For Comparative Example 1, pencil hardness was as low as B and lower.

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

On the other hand, in Comparative Examples 2 to 6, the adhesiveness was as low as 1B or less, and in Comparative Examples 4 and 5, flexibility was low. In Comparative Example 6, the pencil hardness was as low as less than H.

Claims (15)

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

(Wherein, R represents a hydrogen atom or a methyl group independently, respectively. R ¹ represents an alkyl group. R ² ~ R ⁶ represents a hydrogen atom, a halogen atom or an alkyl group independently, respectively. A, b, and c are 40 each A? 100, 0? B? 30, 0? C? 30, and 40? A + b + c? 100.
(B) a silane coupling agent,
(C) a polyfunctional (meth) acrylate compound and
(D) Solvent
And a curing accelerator. The positive resist composition according to claim 1, wherein the (C) polyfunctional (meth) acrylate compound is at least one selected from the group consisting of pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, But are not limited to, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, Wherein the curing agent is at least one selected from the group consisting of methylol propyl acrylate, methylol propyl acrylate, trimethylol propyl methacrylate, ditrimethylol propane tetraacrylate and ditrimethylol propane tetramethacrylate. . 3. The composition of claim 2, wherein the (C) polyfunctional (meth) acrylate compound is selected from pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate and pentaerythritol trimethacrylate And at least one of them is at least one type. The composition according to claim 2, wherein the (C) polyfunctional (meth) acrylate compound is at least one compound selected from the group consisting of dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol penta methacrylate Wherein the resin composition is at least one selected from the group consisting of a fluorine-containing resin and a fluorine-containing resin. The resin composition for forming a cured film according to any one of claims 1 to 4, further comprising (E) an ion trap agent. The resin composition for forming a cured film according to claim 5, wherein the (E) ion trap agent is 5-methylbenzotriazole. The resin composition for forming a cured film according to any one of claims 1 to 6, wherein the resin has a viscosity of 1 to 10,000 mPa · s at 25 ° C. 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 캜 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. 10. 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 process for producing a cured film, which comprises applying the resin composition for forming a cured film according to claim 10 onto a substrate, and irradiating ultraviolet rays, followed by baking at 80 to 120 캜. A cured film obtained by 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. 14. The laminate according to claim 13, wherein the substrate is a film. A touch panel comprising the cured film according to claim 12.