KR102128799B1 - Cured-film-forming resin composition - Google Patents

Abstract

(A) (co)polymer containing repeating units represented by the following formulas (1) to (3), (B) silane coupling agent, (C) polyfunctional (meth)acrylate compound and (D) solvent The resin composition for forming a cured film containing. (In the formula, R each independently represents a hydrogen atom or a methyl group. R ¹ represents an alkyl group. R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. a, b and c each represent 40 It is a positive number satisfying ≤a≤100, 0≤b≤30, 0≤c≤30, and 40≤a+b+c≤100.)

Description

Resin composition for forming a cured film {CURED-FILM-FORMING RESIN COMPOSITION}

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

Conventionally, a protective film, an insulating film, and the like required for a touch panel and the like have been formed at a site required 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 the process is not only complicated, but also expensive. For this reason, a composition that can form a protective film, an insulating film, and the like in a more convenient method and at a lower cost is desired.

In addition, the use of film substrates has been increasing in place of glass substrates from requests for transportation and storage. The film substrate is preserved in a roll shape or the like at the time of storage, but since the substrate is curved at that time, the material applied on the film substrate also requires flexibility such as a film.

In addition, in a substrate on which an electrode is formed on a film such as an ITO film, when an adhesive is used for bonding the substrate, the silver wiring is deteriorated due to the moisture of the adhesive, resulting in problems such as shorting. There is a need for protective overcoat materials.

On the other hand, the conventional overcoat material is intended to be applied onto a glass substrate, and contains inorganic fine particles to increase hardness (Patent Document 2). However, in the conventional method such as incorporation of inorganic fine particles, the hardness is improved, but there is no flexibility and, for example, cracks may occur when folded, and therefore, it cannot be applied to application to a film substrate. It was a situation.

Japanese Patent Publication No. 2013-064973 Japanese Patent Publication No. 2012-116975

The present invention has been made in view of the above problems, and it is possible to form a film on a required part by a simple method by a printing method or the like, and further forms a cured film having high transmittance, high adhesion, high hardness, and also high flexibility and long-term reliability. The aim is to provide a possible composition.

As a result of repeated studies of the inventors in order to solve the above problems, 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. It was found that the present invention was completed.

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

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

(In the formula, R each independently represents a hydrogen atom or a methyl group. R ¹ represents an alkyl group. R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. a, b and c each represent 40 It is a positive number satisfying ≤a≤100, 0≤b≤30, 0≤c≤30, and 40≤a+b+c≤100.)

(B) silane coupling agent,

(C) a polyfunctional (meth)acrylate compound and

(D) Solvent

It characterized in that it comprises a resin composition for forming a cured film.

2. (C) The polyfunctional (meth)acrylate compound is pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylic Rate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane Resin acrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate and ditrimethylolpropane tetramethacrylate at least one selected from the cured film forming resin composition.

3. (C) The polyfunctional (meth)acrylate compound is at least one selected from pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate 2 Resin composition for forming a cured film.

4. (C) The polyfunctional (meth)acrylate compound is selected from dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentamethacrylate A resin composition for forming at least one cured film of two.

5. In addition, (E) Resin composition for forming a cured film in any one of 1 to 4 containing an ion trap agent.

6. (E) A resin composition for forming a cured film of 5 wherein the ion trap 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 of any one of 1 to 6, wherein the solvent has a boiling point of 150°C or higher.

9. A resin composition for forming a cured film of 8 having a viscosity at 25°C of 10 to 100,000 mPa·s.

10. Moreover, (F) The resin composition for forming a cured film in any one of 1 to 9 containing a radical polymerization initiator.

11. A method for producing a cured film comprising applying the resin composition for forming a cured film of 10 to a substrate, irradiating with ultraviolet rays, and then firing at 80°C to 120°C.

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

13. A laminate formed by laminating 12 cured films on a substrate.

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

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

The cured film obtained 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 protective film in various displays such as organic electroluminescent (organic EL) elements, a planarizing film, an insulating film, an insulating film, and a protective film in a touch panel, and a cured film such as an insulating film. Moreover, since it is excellent also in flexibility, it is suitable also as an overcoat material for ITO films.

[Resin composition for curing film formation]

The resin composition for forming a cured film of the present invention contains (A) the following (co)polymer, (B) silane coupling agent, (C) polyfunctional (meth)acrylate compound, and (D) 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 repeating units represented by the following formulas (1) to (3).

In the above formula, R each 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 linear, branched or cyclic. Moreover, the number of carbon atoms of the alkyl group is preferably 1 to 4, more preferably 1 to 3, and even 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, c-butyl group, and the like. Can be lifted. Moreover, a part or all of the hydrogen atom of the said alkyl group may be substituted by the substituent, and a halogen atom, a hydroxyl group, an amino group, etc. are mentioned as said substituent. In addition, the R ¹ ~ R ⁶ are preferably caused to be described later does not react with the component (C).

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

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

In consideration of handling properties and adhesion, 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. When Mw exceeds 200,000, solubility in a solvent may fall and handling property may fall, and when Mw is less than 5,000, adhesiveness may fall.

Further, considering 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 Mw exceeds 200,000, solubility in a solvent may fall and handling property may fall. When Mw is less than 10,000, printability may fall.

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

(A) When a component is a copolymer, the said copolymer may be any of a random copolymer, an alternating copolymer, and a block copolymer.

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

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

As a monomer that gives the repeating unit represented by the formula (1), methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylic Rate, 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-dihydroxypropylacrylate, 2,3-dihydroxy And propyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate. Among them, methyl methacrylate and ethyl methacrylate are particularly preferred.

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

As a monomer which gives the repeating unit represented by said formula (3), styrene compounds, such as styrene, methylstyrene, chlorostyrene, bromostyrene, and 4-tert-butylstyrene, are mentioned, for example.

In addition to the repeating units represented by the formulas (1) to (3), the (co)polymer may include other repeating units within a range not impairing the effects of the present invention. Vinyl monomer, maleimide compound, acrylonitrile, maleic anhydride, etc. are mentioned as a monomer which gives another repeating unit.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether. Can be mentioned. Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The polymerization initiator may be appropriately selected from conventionally known ones and used. For example, peroxides, such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide; Persulfate salts such as sodium persulfate, potassium persulfate and ammonium persulfate; And azo-based compounds such as azobisisobutyronitrile, azobismethylbutyronitrile, 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 is preferably 0.005 to 0.05 mol per 1 mol of the monomer. The reaction temperature during polymerization may be appropriately set from 0°C to the boiling point of the solvent to be used, but 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 commonly 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, i-pentane Alcohols such as all, 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-nonane, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, Aliphatic or aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and anisole; Acetals such as methylal and diethyl acetal; Fatty acids such as formic acid, acetic acid and propionic acid; Nitropropane, nitrobenzene, dimethylamine, monoethanolamine, pyridine, N-methyl-2-pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, etc. Can. These can be used individually by 1 type or in mixture of 2 or more types.

[(B) Silane coupling agent]

(B) component in the composition of this 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 0-3. n is an integer of 0-3.

Examples of the hydrolyzable group represented by X include a halogen atom, an alkoxy group having 1 to 3 carbon atoms, an alkoxy alkoxy group having 2 to 4 carbon atoms, and the like. A chlorine atom, a bromine atom, etc. are mentioned as said halogen atom. The alkoxy group having 1 to 3 carbon atoms is preferably linear or branched, specifically, a methoxy group, an ethoxy group, an n-propoxy group and an i-propoxy group. Moreover, as a C2-C4 alkoxyalkoxy group, it is a methoxymethoxy group, 2-methoxyethoxy group, ethoxymethoxy group, and 2-ethoxyethoxy group specifically.

Examples of the reactive functional group represented by Y include an amino group, an oil group, a (meth)acryloxy group, a vinyl group, an epoxy group, and a mercapto group, and an amino group, an oil group, and a (meth)acryloxy group are preferable. Especially preferably, it is an amino group or an uraid group.

Specifically as the silane coupling agent, 3-aminopropyl trichlorosilane, 3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyl methyl diethoxysilane, 3-ureidpropyl trimethoxysilane, 3-ureidpropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropyl tri Ethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, allyl Trichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane And phosphorus.

Of these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidpropyltrimethoxysilane, 3-ureidpropyltriethoxysilane, 3-methacryloxy Particularly preferred is propyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, and the like. Commercially available products can be used as the 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 even more preferably 0.05 to 1 part by mass relative to 100 parts by mass of the component (A). If it is less than 0.001 part by mass, adhesiveness may decrease, and if it exceeds 10 parts by mass, hardness may decrease.

[(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 two, preferably at least three (meth)acryloxy groups in the molecule, specifically, urea acrylate, epoxy acrylate, polyhydric alcohol and (meth) And ester compounds obtained from acrylic acid. Among these, considering the compatibility of the substrate with adhesiveness and surface hardness, an ester compound obtained from a polyhydric alcohol and (meth)acrylic acid is preferable. Moreover, the number of (meth)acryloxy groups in 1 molecule is 2-10, Preferably it is 3-6, More preferably, it is 3 or 4.

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

The polyisocyanate may be any of aliphatic, aromatic and alicyclic polyisocyanates, for example, methylenediisocyanate, tetramethylenediisocyanate, and hexamethylenediisocyanate. Nate, 2,2,4-trimethylhexamethylenediisocyanate, isophoronediisocyanate, xylenediisocyanate, dicyclohexylmethanediisocyanate, tolylenediisocylate An acrylate, phenylene diisocyanate, methylene bisphenyl diisocyanate, etc. are mentioned. These polyisocyanates can be used alone or in combination of two or more. Among these polyisocyanates, it is suitable to be a yellowing-free urethane.

As a commercially available urethane oligomer, EB2ECRYL220 (made by Daicel-Sytech); Art resin UN-3320HA, East UN-3320HB, East UN-3320HC, East UN-330, East UN-901T (above, manufactured by Negami Kogyo Co., Ltd.); NK Oligo U-4HA, Copper U-6HA, Copper U-324A, Copper U-15HA, Copper U-108A, Copper U-200AX, Copper U-122P, Copper U-5201, Copper U-340AX, Copper U-511 , East U-512, East U-311, East UA-W1, East UA-W2, East UA-W3, East UA-W4, East UA-4000, East UA-100 (above, Shinnakamura Kagaku Co., Ltd.) My); Cisco UV-1400B, Copper UV-1700B, Copper UV-6300B, Copper UV-7550B, Copper UV-7600B, Copper UV-7605B, Copper UV-7610B, Copper UV-7620EA, Copper UV-7630B, Copper UV-7640B, Copper UV-6630B, Copper UV-7000B, Copper UV-7510B, Copper UV-7461TE, Copper UV-3000B, Copper UV-3200B, Copper UV-3210EA, Copper UV-3310B, Copper UV-3500BA, Copper UV-3520TL, Copper UV-3700B, copper UV-6100B, copper UV-6640B (above, Nippon Kosei Chemical Co., Ltd. product) etc. are mentioned.

As said epoxy acrylate, what is obtained by esterifying a polyepoxy compound (or epoxy resin) and acrylic acid generally is mentioned. As a specific example of the epoxy acrylate, various bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.), bisphenol-type epoxy acrylate synthesized by the reaction of epichlorhydrin and acrylic acid, reaction of phenol novolak with epichlorhydrin and acrylic acid And phenol novolac-type epoxy acrylates synthesized therefrom.

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

As a specific example of the ester compound obtained from the said polyhydric alcohol and (meth)acrylic acid, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol Hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylol Propane triacrylate, trimethylol propane trimethacrylate, ditrimethylol propane tetraacrylate, ditrimethylol propane tetramethacrylate, and the like.

The ester compound obtained from the polyhydric alcohol and (meth)acrylic acid is readily available as a commercial product, and specific examples thereof include KAYARAD T-1420, copper DPHA, copper DPHA-2C, copper D-310, copper D-330 , Copper DPCA-20, Copper DPCA-30, Copper DPCA-60, Copper DPCA-120, Copper DN-0075, Copper DN-2475, Copper R-526, Copper NPGDA, Copper PEG400DA, Copper MANDA, Copper R-167, Copper HX-220, Copper HX620, Copper R-551, Copper R-712, Copper R-604, Copper R-684, Copper GPO-303, Copper TMPTA, Copper THE-330, Copper TPA-320, Copper TPA-330 , Copper PET-30, Copper RP-1040 (above, manufactured by Nippon Kayaku Co., Ltd.); Aaronix M-210, Copper M-240, Copper M-6200, Copper M-309, Copper M-400, Copper M-402, Copper M-405, Copper M-450, Copper M-7100, Copper M-8030 , East M-8060, East M-1310, East M-1600, East M-1960, East M-8100, East M-8530, East M-8560, East M-9050 (above, manufactured by Toagosei Co., Ltd.) ; Biscot 295, copper 300, copper 360, copper GPT, copper 3PA, copper 400, copper 260, copper 312, copper 335HP (above, manufactured by Osaka Yuki Chemical 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 even more preferably 50 to 150 parts by mass relative to 100 parts by mass of the component (A). When the content is too small, the hardness properties of the cured film are lowered. When the content is excessive, the properties of adhesion and flexibility are reduced, and cracks are likely to occur. The polyfunctional (meth)acrylate compound can be used alone 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 used at that time can dissolve the components (A) to (C), and further contains the components (E), (F), (G), (H) and other additives described later. The case is not particularly limited as long as these are also soluble.

Specific examples of the solvent include toluene, xylene, methyl ethyl ketone, ethylene glycol monomethyl ether, hetylene glycol 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 acetal, butanol, 2-butanol, isoamyl alcohol, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, isobutyl acetate, N-butyl propane, 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, 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, triethylene glycol monobutyl ether, tripropylene glycol monomethyl Group, dipropylene glycol monobutyl ether, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, hexylene glycol , Octylene gla Ecole, glycerin, hexachloroethane, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, o-dibromobenzene, dichloroethyl ether, diiso Amyl ether, n-hexyl ether, ethylphenyl ether, ethyl benzyl ether, cineol, 1-octanol, 2-octanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, Nonanol, n-decanol, trimethylnonyl alcohol, 2-methylcyclohexanol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, α-terpineol, abietinol, acetonyl acetone, foron, iso Foron, acetophenone, methoxybutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, isoamyl acetate, butyl stearate, ethyl acetobutyrate, isoamyl valate, n-lactic acid Butyl, isobutyl lactate, n-amyl lactate, isoamyl lactate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, dibutyl oxalate, diethyl malonate, butyric anhydride, valeric acid, isovaleric acid, capric acid, ka And prylic acid, 2-ethylhexaneic acid, trichloroacetic acid, lactic acid, nitrobenzene, benzonitrile, α-trinitrile, N-methylformamide, N-methylacetoamide, 2-pyrrolidone, and the like. have.

The said solvent can be used individually by 1 type or in mixture of 2 or more types. 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 has a boiling point of preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. As such a solvent, 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 preferred.

When two or more types of solvents are mixed and used, at least one boiling point 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 an amount such that the solid content concentration in the composition of the present invention is 1 to 95 mass%, an amount such that the solid content concentration is 5 to 90 mass%, more preferably, the solid content concentration is 10 to 85 It is more preferable that the amount becomes mass%. Here, the solid content is obtained by removing the (D) solvent from all 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-mentioned (A) to (D) components.

(E) ion trap agent,

(F) radical polymerization initiator

(G) polyfunctional thiol compounds and/or

(H) polymerization inhibitor

You may include.

[(E) Ion trap agent]

(E) A component is an ion trap agent, and when a metal wiring is formed on a board|substrate, it has an effect which prevents migration by causing this metal wiring to contact with water. As such an ion trapping agent, a compound having a chelate-forming 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), bisoxalate (benzylidene hydrazide) (Eastman Inhibitor OABH, manufactured by Eastman Chemical), benzotriazole, 5-methylbenzotriazole, and the like. These can be obtained as a commercial item. In addition, as other commercial products, Adekastave CDA-1 (manufactured by Asahidenka Co., Ltd.), Adekastave CDA-6 (manufactured by Asahidenka Co., Ltd.), Qunox (manufactured by Mitsui Totsu Fine Co., Ltd.), Naugard XL-1 (made by Uni Royal Co., Ltd.), etc. are mentioned. Of these, 5-methylbenzotriazole is particularly preferred.

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

[(F) Radial polymerization initiator]

The component (F) is a radical polymerization initiator, and contributes to the initiation or acceleration of polymerization of the component (C). (C) The component spontaneously polymerizes by treating at a high temperature, but when a high temperature curing treatment such as the substrate is denatured is not possible, a low temperature curing treatment or photocuring treatment is possible by adding the (F) component.

The radical polymerization initiator may be capable of releasing a substance that initiates radical polymerization by light irradiation and/or heating. For example, as a photo radical polymerization initiator, benzophenone derivatives, imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azide compounds, titanocene compounds, aluminate complexes, organic peroxides, and N-alkoxypyridinium salts And thioxanthone derivatives. Also, specifically, 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-diphenylethan-1-one( Irgacure 651, manufactured by BASF), 1-hydroxycyclohexylphenylketone (Irgacure 184, manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane -1-one (Irgacure 369, manufactured by BASF), bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole) 1-yl)-phenyl)titanium) (Irgacure 784, manufactured by BASF), and the like.

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, Irga manufactured by BASF. Garcure 250, Irgacure 1800, Irgacure 1870, Irgacure OXE01, DAROCUR TPO, DAROCUR1173; Lambson's Speedcure MBB, Speedcure PBZ, Speedcure ITX, Speedcure CTX, Speedcure EDB, Esacure ONE, Esacure KIP150, Esacure KTO46; Nippon Kayaku Co., Ltd.KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE DMBI, etc. Can be lifted.

Moreover, as a thermal radical polymerization initiator, for example, acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ditert-butylper Peroxides such as oxide, dicumyl peroxide, dilauroyl peroxide, tert-butyl peroxy acetate, tert-butyl peroxy pivalate, and tert-butyl peroxy-2-ethylhexanoate; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), (1-phenylethyl)azodiphenylmethane, 2,2'- Azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl2,2'-azobisisobutylate, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis (1-cyclohexane carbonitrile), 2-(carbamoyl azo) isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), Azo-based compounds such as 2-phenyl azo-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 to these.

As commercially available thermal radical polymerization initiators, for example, perroyl IB, percumyl ND, perroyl NPP, perroyl IPP, perroyl SBP, perocta ND, perroyl TCP, perroyl OPP, perhexyl ND, perbutyl ND, Perbutyl NHP, Perhexyl PV, Perbutyl PV, Perroyl 355, Perroyl L, Perocta O, Perroyl SA, Perhexa 250, Perhexyl O, Naper PMB, Perbutyl O, Naper BMT, Naper 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, Per Hexa 25Z, Perbutyl A, Perhexa 22, Perbutyl Z, Perhexaper V, Perbutyl P, Percumyl D, Perhexyl D, Perhexa 25B, Perbutyl C, Perbutyl D, Permenta H, Norphmer BC (above, manufactured by Nichiyu Co., Ltd.); 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 (above, manufactured by Wako Pure Chemical Industries, Ltd.); Irgacure (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocure 1116, 1173, Lucirin TPO (above BASF); Ubecryl P36 (above, manufactured by UCB); Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, and KIP75/B (above, manufactured by Prattesri-Lamberti), and the like, but are not limited to these.

The content of the component (F) is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass relative to 100 parts by mass of the component (A).

[(G) Polyfunctional thiol compound]

If necessary, the composition of the present invention may contain a polyfunctional thiol compound (G) component. 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. As specific compounds, 1,3,5-tris(3-mercaptopropionyloxyethyl)-isocyanurate, 1,3,5-tris(3-mercaptobutylyloxyethyl)-isocyanurate (show Trifunctional thiol compounds such as Wadenco Co., Ltd., Carens MT (registered trademark) NR1), and trimethylol propri tris (3-mercaptopropionate); Pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutylate) (manufactured by Showa Denko Corporation, Carens MT (registered trademark) PEI) Thiol compounds; And six-functional thiol compounds such as dipentaerythritol hexakis (3-propionate).

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

[(H) polymerization inhibitor]

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

(H) The content rate of the polymerization inhibitor which is a component is preferably 1% by mass or less, and more preferably 0.5% by mass or less, among the total solids. When the content is more than 1% by mass, curing failure may occur, and the reaction may be insufficient.

[Other additives]

The composition of the present invention may contain a surfactant, an antifoaming agent, a rheology modifier, a pigment, a dye, a storage stabilizer, a dissolution accelerator such as a polyhydric phenol or a polyhydric carboxylic acid, and the like, as long as the effects of the present invention are not impaired.

Although it does not specifically limit as surfactant, For example, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. As this kind of surfactant, commercial products, such as Sumitomo 3M Co., Ltd. product, DIC Co., Ltd. product, Asahi Glass Co., Ltd. product, etc. can be used, for example. As specific examples, F-top EF301, EF303, EF352 (Mitsubishi Material Denshi Kasei Co., Ltd.), Megapak F171, F173 (DIC Co., Ltd.), Fluorad FC430, FC431 (Sumitomo 3M Co., Ltd.), And fluorine-based surfactants such as Asahi Guard AG710, Suplon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.).

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. , Not limited to these. When performing screen printing, it is preferable that the composition of the present invention contains an antifoaming agent.

[Preparation of composition]

The method for preparing the composition of the present invention is not particularly limited. As an example, the method of dissolving (A) component in (D) solvent, mixing (B) component and (C) component in this solution at a predetermined ratio, and making it a uniform solution is mentioned. Moreover, in the appropriate step of this preparation method, the preparation method which adds and mixes (E) component, (F) component, (G) component, (H) component, and/or other components further as needed is mentioned. have.

In the preparation of the composition of the present invention, a solution of the component (A) obtained by polymerization reaction in a solvent can be used as it is. In this case, concentration is adjusted when the solution of the component (A) is added to the solution of the component (B), the component (C), the component (E), the component (F), and the like as described above, to obtain a uniform solution. For the purpose of this, the solvent (D) may be further added. At this time, the solvent used in the process of synthesizing the component (A) and the solvent (D) used for concentration adjustment when preparing the composition may be the same or different.

It is preferable to use the resin composition for forming a cured film in a solution state prepared in this way after filtering with a filter having a pore size of about 0.2 μm or the like.

From the viewpoint of coatability, 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 even more preferably 1 to 1,000 mPa·s. Do. If the viscosity is too low, the intended film thickness may not be obtained, and if the viscosity is too high, the coatability may decrease.

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 even more preferably 1,000 to 100,000 mPa·s. Do. If the viscosity is too low, the composition may diffuse after application, so that a desired pattern may not be formed. If the viscosity is too high, a load on the process such as lowering of ejection properties may occur, or transferability of the composition to the substrate This may decrease.

In the case where a fine structure such as an insulating film for constructing a bridge structure is formed at a portion where X-axis electrodes and Y-axis electrodes are orthogonal to the touch panel by a printing method such as screen printing or gravure offset printing, the present invention The composition has a viscosity at 25°C of 10 to 100,000 mPa·s, more preferably 5,000 to 100,000 mPa·s, and even more preferably 20,000 to 100,000 mPa·s. If the viscosity is too low, the composition may diffuse after application, so that a desired pattern may not be formed. If the viscosity is too high, a load on the process such as lowering of ejection properties may occur, or transferability of the composition to the substrate This may decrease.

In addition, in this invention, viscosity is a measured value by an E-type viscometer.

[Coating film 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; TAC film, polyester film, resin film substrate such as acrylic film), etc., rotation coating, flow coating, roll coating, slit coating, rotation coating followed by slit, inkjet coating, screen printing, gravure offset printing, etc. The coating film can be formed by coating by a printing method or the like, and then preliminarily drying (prebaking) in a hot plate or an oven. The composition of the present invention is particularly suitable for printing methods such as screen printing and gravure offset printing.

The pre-baking method is generally 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. Is adopted.

Next, post-baking for heat curing is performed. Specifically, it is heated using a hot plate, an oven, or the like. The method of post-baking is generally performed at 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 adopted.

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 pre-baking conditions are the same as above, but the post-baking 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 an optical radical polymerization initiator, photocuring can be performed by irradiating an ultraviolet-ray to the said coating film after prebaking. Ultraviolet rays are in the range of 200 to 500 nm in wavelength, and the exposure amount is preferably 100 to 5,000 mJ/cm ² .

After photo-curing, post-baking for thermal curing is performed. Specifically, it is heated using a hot plate, an oven, or the like. The post-baking process is generally performed at 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 adopted.

By curing the composition of the present invention under the above conditions, the level difference 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 required level of flatness, hardness, and adhesion, it can be applied to a touch panel, such as a protective film, a planarizing film, an insulating film, etc. in various displays such as thin film transistor (TFT) type liquid crystal display devices and organic EL devices. It is also useful as a material for forming a cured film such as a protective film and an insulating film. Moreover, since it is also excellent in flexibility, it is suitable as an overcoat material for ITO films.

(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. In addition, the weight average molecular weight (Mw) of the copolymer obtained in Synthesis Example is GPC apparatus (Shodex GPC-101) manufactured by Showa Denko Corporation (column: Shodex (registered trademark) KF803L and KF804L (Showa Denko Corporation) It was measured under the condition that elution solvent tetrahydrofuran was eluted by flowing in a column (column temperature 40°C) at a flow rate of 1 mL/min. Mw is expressed in terms of polystyrene.

In addition, 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-butyl styrene, manufactured by Tokyo Kaseiko Co., Ltd.

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

MAIB: 2,2'-azobis (isobutyric acid) dimethyl, manufactured by Tokyo Chemical Industry Co., Ltd.

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

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 from BASF.

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

UPS:3-ureid propyl triethoxysilane, Dore Corning Co., Ltd. AY43-031.

MPMS: 3-methacryloxypropyl trimethoxysilane, Momentive Performance Material Japan Corporation A-174.

AGITAN771: Antifoaming agent, manufactured by MUNZING.

Stirring device: ARE-310 from Akitori Renta Co., Ltd., Shinki Co., Ltd.

Z320: Cyclomer P. manufactured by Daicel Cytech Co., Ltd.

[1] synthesis of polymers (resins)

[Synthesis Example 1]

DEGMEA was added to 532.0 g of a 1,000 mL four-neck flask, and while stirring at 70°C (temperature) under a nitrogen atmosphere, a mixture of MMA 280.0g, MAA 30.1g, ST 36.5g, and MAIB 8.1g was added over 2 hours. Dropped slowly. After dropping, the mixture was further reacted at 70°C for 20 hours to obtain a resin solution P1. Mw=about 50,000.

[Synthesis Example 2]

DEGMEA was added to 537.1 g of a 1,000 mL four-neck flask, and a mixture of MMA 350.0 g and MAIB 8.1 g was slowly added dropwise over 2 hours while stirring at 70° C. (temperature) under a nitrogen atmosphere. After dropping, the mixture was further reacted at 70°C for 20 hours to obtain a resin solution P2. Mw=about 50,000.

[Synthesis Example 3]

DEGMHE was put in a 1,000 mL 4-neck flask, 571.0 g of DEGMHE was stirred under a nitrogen atmosphere at 70° C. (temperature), and a mixture of MMA 240.0 g, MAA 25.8 g, ST 31.3 g, and MAIB 10.4 g was added over 2 hours. Dropped slowly. After dropping, the mixture was further reacted at 70°C for 20 hours to obtain a resin solution P3. Mw = about 40,000.

[Synthesis Example 4]

Put 694.8 g of TEGMBuE in a 1,000 mL four-neck flask, and while stirring at 70° C. (temperature) under a nitrogen atmosphere, a mixture of 140.0 g of MMA, 15.0 g of MAA, 18.3 g of ST, and 0.4 g of MAIB was added over 2 hours. Dropped slowly. After dropping, the mixture was further reacted at 80°C for 20 hours to obtain a resin solution P4. Mw=about 170,000.

[Synthesis Example 5]

577.4 g of MEK was added to a 1,000 mL four-neck flask, and while stirring at 70° C. (temperature) under a nitrogen atmosphere, a mixture of 250.0 g MMA, 26.9 g MAA, 32.6 g ST, and 1.4 g MAIB was added over 2 hours. Dropped slowly. After dropping, the mixture was further reacted at 80°C for 20 hours to obtain a resin solution P5. Mw=about 80,000.

[Synthesis Example 6]

DEGMEA was added to a 1,000 mL 4-neck flask, 570.0 g of DEGMEA, and while stirring at 80° C. (temperature) under a nitrogen atmosphere, a mixture of 300.0 g of MMA, 32.2 g of MAA, 39.2 g of ST, and 8.6 g of MAIB was added over 2 hours. Dropped slowly. After dropping, the mixture was further reacted at 80°C for 20 hours to obtain a resin solution P6. Mw=about 30,000.

[Synthesis Example 7]

DEGMEA was placed in a 1,000 mL 4-neck flask, 540.2 g of DEGMEA was stirred at 80° C. (temperature) under a nitrogen atmosphere, and a mixture of 300.0 g of MMA, 15.2 g of MAA, 36.8 g of ST, and 7.7 g of MAIB was added over 2 hours. Dropped slowly. After dropping, the mixture was further reacted at 80°C for 20 hours to obtain a resin solution P7. Mw=about 30,000.

[Synthesis Example 8]

460.3 g of DEGMEA was placed in a 1,000 mL four-neck flask, and a mixture of 300.0 g of MMA and 6.8 g of MAIB was slowly added dropwise over 2 hours while stirring at 80°C (temperature) under a nitrogen atmosphere. After dropping, the mixture was further reacted at 80°C for 20 hours to obtain a resin solution P8. Mw=about 30,000.

[Synthesis Example 9]

DEGMEA was placed in a 1,000 mL four-necked flask and 452.1 g of DEGMEA was stirred at 80° C. (temperature) under a nitrogen atmosphere, and a mixture of 200.0 g of MMA, 49.1 g of MAA, 45.7 g of tBuST and 6.6 g of MAIB was added over 2 hours. Dropped slowly. After dropping, 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 (resin composition for curing film formation)

[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 were placed in a stirring device, and stirred at 2,000 rpm for 10 minutes 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 were placed in a stirring device, and stirred at 2,000 rpm for 10 minutes to prepare a varnish. .

[Example 3]

In a 200 mL plastic container, 67.7 g of 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 stirring device, and stirred at 2,000 rpm for 10 minutes 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 were placed in a stirring device, and stirred at 2,000 rpm for 10 minutes 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 were placed in a stirring device, and the varnish was prepared by stirring at 2,000 rpm for 10 minutes. .

[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 were placed in a stirring device, and stirred at 2,000 rpm for 10 minutes 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 were placed in a stirring device, and the varnish was produced by stirring at 2,000 rpm for 10 minutes. .

[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 were added to the stirring device, and the varnish was prepared by stirring at 2,000 rpm for 10 minutes. .

[Example 9]

In a 200 mL plastic container, 53.8 g of 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 It was put into a stirring device, 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, 0.04 g of AGITAN771, and 18.8 g of DEGMEA It was put into a stirring device, and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 11]

In a 200 mL plastic container, 53.9 g of 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 It was put into a stirring device, 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 It was put into a stirring device, 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 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 It was put into a stirring device, 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 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 It was put into a stirring device, 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 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 It was put into a stirring device, 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, 0.04 g of AGITAN771, and 18.7 g of DEGMEA It was put into a stirring device, 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 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 It was put into a stirring device, and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 18]

In a 200 mL plastic container, 55.6 g of 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 It was put into a stirring device, and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Example 19]

In a 200 mL plastic container, 58.9 g of 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, This was put in a stirring device, and stirred at 2,000 rpm for 10 minutes 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, 0.04 g of AGITAN771, and 18.8 g of DEGMEA, This was put in a stirring device, 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 resin solution P1 obtained in Synthesis Example 1, 0.40 g of UPS, and 0.59 g of DEGMEA were placed in a stirring device, and stirred at 2,000 rpm for 10 minutes to prepare a varnish.

[Comparative Example 2]

In a 200 mL plastic container, 53.9 g of 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 are added, and this is a stirring device. And stirred at 2,000 rpm for 10 minutes to produce a varnish.

[Comparative Example 3]

In a 200 mL plastic container, put 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, and put this in a stirring device. The varnish was prepared by stirring at 2,000 rpm for 10 minutes.

[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, placed in a stirring device, stirred at 2,000 rpm for 10 minutes. To produce a varnish.

[Comparative Example 5]

In a 200 mL plastic container, 78.7 g of PET-30, 9.5 g of IRG500, 3.9 g of 5-MBT, and 0.08 g of APS were added to the stirring device, and the varnish was prepared by stirring at 2,000 rpm for 10 minutes.

[Comparative Example 6]

In a 200 mL plastic container, 93.5 g of 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 are added to the stirring device, The varnish was produced by stirring at 2,000 rpm for 10 minutes.

The composition of the varnishes produced in Examples 1 to 8 and Comparative Example 1 are collectively shown in Table 2. In addition, the composition of the varnishes produced in Examples 9 to 20 and Comparative Examples 2 to 6 are collectively shown in Table 3.

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

[Production of hard film]

The varnishes of Examples 1 to 8 and Comparative Example 1 were respectively coated on a glass with ITO to have a thickness of about 3 to 10 μm, followed by pre-baking at 110°C for 2 minutes. Subsequently, 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. Moreover, the viscosity of the varnishes of Examples 3 to 5 was measured, and the printability was evaluated for the varnishes of Examples 3 to 5 and 8, respectively, by the following method. Table 4 shows the results.

In addition, the varnishes of Examples 9 to 20 and Comparative Examples 2 to 6 were manufactured by Sanyo Shinko Co., Ltd., respectively. ), a bar coater was applied to a thickness of about 3 to 10 μm, and pre-baking was performed at 110° C. for 10 minutes. Subsequently, UV irradiation (400 mJ/cm ² ) was performed, followed by post-baking at 110° C. for 50 minutes to prepare a cured film.

About the obtained film, pencil hardness, adhesiveness, and flexibility were evaluated by the following method. Table 5 shows the results.

[Evaluation of pencil hardness]

In accordance with JIS K 5400, it was measured under a 1,000 g load.

[Evaluation of adhesion]

It evaluated by the crosscut test method. First, 100 checkerboard scales were prepared on the coating film using a cutter guide. Next, a cellophane tape made by Nichiban Co., Ltd. was adhered on the checkerboard scale, and rubbed strongly from the top with an eraser to ensure sufficient adhesion. Then, the cellophane tape was peeled off, and the evaluation was made based on how many of the 100 checkerboard scales were peeled off at that time.

0B: more than 66 peeled

1B: 36~65 peels

2B: 16~35 peeled

3B: 6 to 15 peeled

4B: 1~5 peeled

5B: No peeling

[Evaluation of printability]

The varnish of Example 3 was printed on a glass substrate with ITO by a screen printing method using MT-320TVC manufactured by Micro-Tech. Further, 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. The obtained pattern on the glass substrate with ITO (20 μm in length and 20 μm in width) was observed with an optical microscope. The pattern printed out with or without the pattern protruding with the naked eye was set to ○. Table 4 shows the results.

[Measurement of viscosity]

About the varnishes of Examples 3-5, viscosity (mPa*s) was measured by TVE-20LT and TVE-20HT manufactured by Toki Sangyo Co., Ltd. Table 4 shows the results.

[Measurement of transmittance]

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

[Evaluation of flexibility]

The films obtained by using the varnishes of Examples 9 to 20 and Comparative Examples 2 to 6 were fixed for 15 seconds by following a cylinder having a diameter of 3 cm with the coat side outward. Changes in the appearance of the coating film were observed, and those with no changes were designated as ○ and those with cracks as ×.

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

As for Comparative Example 1, the pencil hardness was lower than B.

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

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

Claims (16)

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

(In the formula, R each independently represents a hydrogen atom or a methyl group. R ¹ represents an alkyl group. R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. a, b and c each represent 40 It is a positive number satisfying ≤a≤100, 0≤b≤30, 0≤c≤30, and also 40≤a+b+c≤100.)
(B) a silane coupling agent composed of a silane compound represented by the following formula (4),

(In the formula, R ⁷ represents a methyl group or an ethyl group. X represents a hydrolyzable group. Y represents a reactive functional group selected from an amino group, an ured group, a (meth)acryloxy group, a vinyl group, an epoxy group, and a mercapto group. m is an integer from 0 to 3. n is an integer from 0 to 3.)
(C) a polyfunctional (meth)acrylate compound and
(D) Solvent
It characterized in that it comprises a resin composition for forming a cured film. The polyfunctional (meth)acrylate compound according to claim 1, wherein the pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipenta Erythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, trimethylolethane triacrylate, trimethylolethanetrimethacrylate, tri Cured film, characterized in that it is at least one member selected from methylolpropane triacrylate, trimethylolpropanetrimethacrylate, ditrimethylolpropanetetraacrylate and ditrimethylolpropanetetramethacrylate. Resin composition for formation. The polyfunctional (meth)acrylate compound according to claim 2, which is selected from pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate and pentaerythritol trimethacrylate. A resin composition for forming a cured film, characterized in that it is at least one. The polyfunctional (meth)acrylate compound according to claim 2, wherein the dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate and dipentaerythritolpentamethacryl. A resin composition for forming a cured film, characterized in that it is at least one selected from rates. The resin composition for forming a cured film according to claim 1, further comprising (E) an ion trap agent. The resin composition for forming a cured film according to claim 5, wherein the ion trapping agent (E) is 5-methylbenzotriazole. The resin composition for forming a cured film according to claim 1, wherein the viscosity at 25°C is 1 to 10,000 mPa·s. The resin composition for forming a cured film according to claim 1, 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 claim 1, further comprising (F) a radical polymerization initiator. The resin composition for forming a cured film according to claim 1, wherein 60≤a≤96, 2≤b≤20, and 2≤c≤20. A method for producing a cured film, comprising applying the resin composition for forming a cured film according to any one of claims 1 to 11 to a substrate, irradiating with ultraviolet rays, and then firing at 80°C to 120°C. A cured film obtained by using the resin composition for forming a cured film according to any one of claims 1 to 11. A laminate obtained by laminating the cured film according to claim 13 on a substrate. 15. The laminate according to claim 14, wherein the substrate is a film. A touch panel comprising the cured film according to claim 13.