KR102149165B1 - Resin composition for forming cured film - Google Patents

Abstract

(식 중, R¹은, 각각 독립적으로, 수소 원자 또는 메틸기를 나타낸다. R²는 수소 원자 또는 탄소수 1∼5의 알킬기를 나타낸다. R³은 수소 원자 또는 메틸기를 나타낸다.)(A) A copolymer containing the monomer units represented by formulas (1) and (2), (B) a melamine-based crosslinking agent, (C) a thermal radical polymerization initiator, and (D) a resin for forming a cured film containing a solvent The composition is provided.

(In the formula, R ¹ each independently represents a hydrogen atom or a methyl group. R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ³ represents a hydrogen atom or a methyl group.)

Description

Resin composition for forming a cured film TECHNICAL FIELD [RESIN COMPOSITION FOR FORMING CURED FILM}

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

Conventionally, a protective film, an insulating film, etc. required for a touch panel or the like have been formed at a required site by pattern processing by a photolithography method using a photosensitive resin composition (Patent Document 1).

However, pattern processing by the photolithography method has a problem that not only the process is complicated, but also the cost is high. Therefore, there has been a demand for a composition capable of forming a protective film, an insulating film, or the like at a required site by a simpler method and at low cost.

In addition, as disclosed in Patent Document 2, when the ITO film is formed on the insulating film by sputtering, cracks and the like are generated due to the difference in stress between the insulating film and the ITO film. For this type of protective film and insulating film, the resistance to sputtering of ITO is also need.

Japanese Unexamined Patent Publication No. 2013-064973 Japanese Unexamined Patent Publication No. 2011-076386

The present invention has been made in view of the above circumstances, and it is possible to form a film on a required part by a simple method such as a printing method, and further, a cured film having high light transmittance, high adhesion, high hardness, and resistance to ITO sputtering is formed. It aims to provide a possible composition.

As a result of repeated intensive examination in order to solve the above problems, the inventors of the present invention discovered that the above problems can be solved by a composition containing a specific copolymer, a melamine-based crosslinking agent, a thermal radical polymerization initiator, and a solvent, and the present invention Completed.

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

1.(A) a copolymer containing monomer units represented by formulas (1) and (2),

(In the formula, R ¹ each independently represents a hydrogen atom or a methyl group. R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ³ represents a hydrogen atom or a methyl group.)

(B) melamine-based crosslinking agent,

(C) a thermal radical polymerization initiator, and

(D) solvent

A resin composition for forming a cured film comprising a.

2. (A) The resin composition for cured film formation of 1, wherein the copolymer is a copolymer containing monomer units represented by formulas (1), (2-1) and (2-2).

(In the formula, R ¹ and R ³ are as described above. R ⁴ represents an alkyl group having 1 to 5 carbon atoms.)

3. (E) The resin composition for forming a cured film of 1 or 2 further comprising a silane coupling agent.

4. (F) The resin composition for forming a cured film in any one of 1 to 3 further comprising a polyfunctional (meth)acrylate compound.

5. (D) The resin composition for cured film formation in any one of 1 to 4 in which the solvent has a boiling point of 150°C or higher.

6. A cured film obtained by using the resin composition for forming a cured film in any one of 1 to 5.

7. A laminate formed by laminating the cured film of 6 on a substrate.

8. A touch panel including the cured film of 6.

The cured film obtained by using the resin composition for forming a cured film of the present invention has high hardness, excellent adhesion, transparency, and resistance to ITO sputtering, and also has resistance to a resist stripper. Therefore, it is useful as a material for forming cured films such as protective films and insulating films in touch panels, such as protective films, planarization films, and insulating films in various displays such as organic electroluminescence (EL) elements. Moreover, since it is also excellent in flexibility, it is suitable also as an overcoat material for ITO films.

[Resin composition for forming a cured film]

The composition of the present invention contains (A) the following copolymer, (B) a melamine-based crosslinking agent, (C) a thermal radical polymerization initiator, and (D) a solvent.

[(A) Copolymer]

The component (A) is a copolymer containing monomer units represented by formulas (1) and (2).

In the formula, R ¹ each independently represents a hydrogen atom or a methyl group, and a methyl group is preferable. R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ³ represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred.

The alkyl group may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl. And a butyl group, a t-butyl group, a cyclobutyl group, and an n-pentyl group. Further, some or all of the hydrogen atoms of the alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom, a hydroxy group, and an amino group.

It is preferable that the said copolymer contains a monomer unit represented by Formula (1), (2-1), and (2-2) from a viewpoint of adhesive improvement.

In the formula, R ¹ and R ³ are as described above. R ⁴ represents an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include those similar to those described above.

The copolymer of component (A) is preferably 5 mol% or more, more preferably 10 mol% or more of the monomer unit represented by formula (1) among all monomer units from the viewpoint of obtaining a cured film having excellent solvent resistance and hardness with good reproducibility. It contains more than mol%.

The weight average molecular weight (Mw) of the copolymer is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and even more preferably 15,000 to 80,000 in consideration of handling properties and adhesion. When Mw exceeds 200,000, the solubility in a solvent decreases and handling property may fall, and when Mw is less than 5,000, the adhesiveness may fall.

In consideration of printability, Mw of the copolymer 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 the solvent may decrease and the handling property may decrease. When the Mw is less than 10,000, the printability may decrease.

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

The copolymer may be any of a random copolymer, an alternating copolymer, and a block copolymer.

The copolymer of component (A) is prepared by synthesizing poly(meth)acrylic acid, poly(meth)acrylic acid ester or (meth)acrylic acid-(meth)acrylic acid ester copolymer by a conventionally known method. It can be synthesized by ring-opening addition of ,4-epoxycyclohexylmethyl (meth)acrylate. The ring-opening addition reaction can be specifically performed according to the method described in Japanese Unexamined Patent Application Publication No. Hei 10-087725 or the like.

The copolymer of the component (A) can be obtained as a commercial product, for example, cyclomer P(ACA)Z200M, cyclomer P(ACA)Z230AA, cyclomer P(ACA)Z250, cyclomer P(ACA)Z251, Cyclomer P(ACA)Z300, Cyclomer P(ACA)Z320, Cyclomer P(ACA)Z254F (above, Daicel Allnex Co., Ltd. product), etc. are mentioned.

[(B) Melamine-based crosslinking agent]

The component (B) is a melamine-based crosslinking agent and contributes to the crosslinking of the component (A). Examples of the melamine-based crosslinking agent include melamine-based compounds having a crosslinking substituent such as a methylol group and a methoxymethyl group. Examples of the melamine-based crosslinking agent include CYMEL (registered trademark) 303 (hexamethoxymethylmelamine), 1170 (tetrabutoxymethylglycoluril), 1123 (tetramethoxymethylbenzo) manufactured by Nippon Cytec Industries, Ltd. Cymel series, such as guanamine); Nikalak (registered trademark) MW-30HM, MW-390, MW-100LM, MX-750LM, methylated melamine resin manufactured by Sanwa Chemical Co., Ltd., MX-270, MX-280, MX-290, etc. Nikalak series, etc. are mentioned.

The upper limit of the content of the component (B) is preferably 200 parts by mass, more preferably 100 parts by mass, and the lower limit is, with respect to 100 parts by mass of the component (A), from the viewpoint of suppressing the decrease in storage stability. From the viewpoint of obtaining a cured film having excellent solvent resistance with good reproducibility, it is preferably 30 parts by mass, more preferably 50 parts by mass with respect to 100 parts by mass of the component (A).

[(C) Thermal radical polymerization initiator]

Component (C) is a thermal radical polymerization initiator, and contributes to the initiation or acceleration of polymerization of component (A). As a thermal radical polymerization initiator, for example, acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butylper Oxide, dicumyl peroxide, dilauroyl peroxide, t-butylperoxyacetate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate (t-butyl2-ethylhexaneper Peroxides such as oxoate); 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, 2,2'- Azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl2,2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis(1-cyclohexanecarbonitrile), 2-(carbamoylazo)isobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), Azo compounds such as 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile and 2,2'-azobis (2-methylpropane); And persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, but are not limited to these.

As a commercially available thermal radical polymerization initiator, for example, Nichiyu Corporation Peroyl (registered trademark) IB, NPP, IPP, SBP, TCP, OPP, SA, 355, L, Perbutyl (registered trademark) ND, NHP, MA, PV, 355, A, C, D, E, L, I, O, P, Z, Perhexyl (registered trademark) ND, PV, D, I, O, Z, Perocta (registered trademark) ND, Niper (registered trademark) PMB, BMT, BW, Pertetra (registered trademark) A, Perhexa (registered trademark) MC, TMH, HC, 250, 25B, C, 25Z, 22, V, Perocta (registered trademark) ) O, Percumyl (registered trademark) ND, D, Permenta (registered trademark) H, Norfmer (registered trademark) BC; Wako Pure Chemical Industries, 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; BASF's IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, TPO, DAROCUR (registered trademark) 1116, 1173; UVECRYL (registered trademark) P36 manufactured by Cytec Surface Specialty's; Lamberti Esacure (registered trademark) KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B, etc. are mentioned, but are not limited to these.

The upper limit of the content of the component (C) is preferably 20 parts by mass, more preferably 10 parts by mass, and the lower limit is, with respect to 100 parts by mass of the component (A), from the viewpoint of suppressing the decrease in storage stability. From the viewpoint of obtaining a cured film having excellent solvent resistance and hardness with good reproducibility, it is preferably 0.01 parts by mass, more preferably 0.1 parts by mass with respect to 100 parts by mass of the component (A).

[(D) Solvent]

The component (D) is a solvent, and can dissolve the components (A) to (C), and when the composition of the present invention contains the components (E) to (I) and other additives described below, these are also dissolved. It is not particularly limited as long as it can be done. That is, the composition of the present invention is a solution in which components other than component (D) are dissolved in component (D).

Specific examples of the solvent include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol isopropyl ether, ethylene glycol mono Butyl ether, ethylene glycol dibutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, ethylene glycol monoacetate, ethylene glycol Call Diacetate, Ethylene Glycol Monomethyl Ether Acetate, Ethylene Glycol Monoethyl Ether Acetate, Ethylene Glycol Monobutyl Ether Acetate, Diethylene Glycol, Diethylene Glycol Monomethyl Ether, Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, Diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, diethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, diethylene glycol acetate, diethylene glycol Lycol Monoethyl Ether Acetate, Diethylene Glycol Monobutyl Ether Acetate, Triethylene Glycol Monomethyl Ether, Triethylene Glycol Monobutyl Ether, Propylene Glycol, Propylene Glycol Monomethyl Ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Lycol monobutyl ether, tripropylene glycol monomethyl ether, trimethylene glycol, hexylene glycol, octylene glycol, methoxymethoxyethanol, 1-butoxyethoxypropanol, isoacetic acid Butyl, methoxybutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, isoamyl acetate, n-butyl propionic acid, isobutyl lactate, n-butyl lactate, n-amyl lactate, isolactic acid Amyl, isoamyl isobalerate, ethyl acetobutyrate, butyl stearate, dibutyl oxalate, diethyl malonate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, methylphenyl ether, ethylbenzyl ether, ethylphenyle Ter, dichloroethyl ether, diisoamyl ether, n-hexyl ether, 1,4-dioxane, diethylacetal, cineol, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl n-butyl ketone, di-n -Propyl ketone, acetoneyl acetone, poron, isophorone, acetophenone, glycerin, butanol, 2-butanol, 1,3-butanediol, 2,3-butanediol, isoamyl alcohol, 1, 5-pentanediol, 2-methylcyclohexanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, 1-octanol, 2-octanol, nonanol, n-decanol, tri Methylnonyl alcohol, benzyl alcohol, α-terpineol, tetrahydrofurfuryl alcohol, furfuryl alcohol, abietinol, triglycol dichloride, trichloroacetic acid, lactic acid, valeric acid, isovaleric acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, butyric anhydride, decane, dipentene, p-mentane, dodecane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, hexachloroethane, toluene, xylene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, o -Dibromobenzene, benzonitrile, nitrobenzene, α-tolunitrile (phenylacetonitrile), N-methylformamide, N-methylacetamide, 2-pyrrolidone, and the like.

Solvents can be used alone or in combination of two or more. Further, the solvent used when polymerizing the component (A) can also be used as it is.

From the viewpoint of printability, the solvent preferably has a boiling point of 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. Such solvents include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, and diethylene glycol monoethyl ether. 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 solvents are mixed and used, at least one boiling point is preferably 150°C or higher, more preferably 180°C or higher, and still 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%, more preferably an amount such that the solid content concentration becomes 5 to 90 mass%, and the solid content concentration is 10 to 85 mass%. An amount such as% is even more preferable. Here, the solid content excludes the (D) solvent from all components of the composition of the present invention.

The composition of the present invention

(E) a silane coupling agent,

(F) polyfunctional (meth)acrylate compound,

(G) an ion trap agent,

(H) polyfunctional thiol compounds,

(I) polymerization inhibitor

You may further include, etc.

[(E) Silane coupling agent]

The composition of the present invention preferably contains a silane coupling agent as the component (E) from the viewpoint of improving adhesion. As a preferable example of a silane coupling agent, a silane compound represented by Formula (3) is mentioned.

In formula (3), R ⁵ 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, and an integer of 0-2 is preferable.

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

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

Specific examples of the silane coupling agent include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3- Aminopropylmethyldiethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichloro Silane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxy Silane, etc. are mentioned.

Among these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-methacryloxy Especially preferred are propyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane and the like. As the silane coupling agent, a commercial item can be used.

When the composition of the present invention contains the component (E), the content is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, further preferably, based on 100 parts by mass of the component (A). Is 0.05 to 1 part by mass. If the content is less than 0.001 parts by mass, the effect of improving adhesion may not be obtained, and if the content is more than 10 parts by mass, the hardness may decrease.

[(F) polyfunctional (meth)acrylate compound]

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

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

Specific examples of the polyfunctional (meth)acrylate compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, Dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacryl Rate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, and the like.

The polyfunctional (meth)acrylate compound is readily available as a commercial item, and specific examples thereof include, for example, Nippon Kayaku Co., Ltd. KAYARAD (registered trademark) T-1420, DPHA, DPHA-2C, D -310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX620 , R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040; Doagose Co., Ltd. (registered trademark) M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M- 8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050; Osaka Yuki Chemical Co., Ltd. Viscoat 295, 300, 360, GPT, 3PA, 400, 260, 312, 335HP; Shin Nakamura Kagaku High School NK ester A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM -N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, etc. are mentioned.

When the composition of the present invention contains the component (F), the content is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, further preferably, based on 100 parts by mass of the component (A). Is 50 to 150 parts by mass. When the content is less than 10 parts by mass, the effect of improving the hardness of the cured film may not be obtained, and when it exceeds 300 parts by mass, the properties of adhesion and flexibility are deteriorated, and cracks may easily occur. Polyfunctional (meth)acrylate compounds may be used alone or in combination of two or more.

[(G) Ion trap agent]

The composition of the present invention preferably contains an ion trapping agent from the viewpoint of suppressing migration of metal wiring in contact with the cured film. 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), oxalic acid bis (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, Adecastave CDA-1 (made by ADEKA Co., Ltd.), Adecastave CDA-6 (made by ADEKA Co., Ltd.), Qunox (made by Mitsuito Arts Fine Co., Ltd.), Naugard XL-1 ( Uniloy R Co., Ltd. product) etc. are mentioned. Among these, 5-methylbenzotriazole is particularly preferred.

When the composition of the present invention contains the component (G), the content is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass, based on 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 it may be disadvantageous in terms of cost. .

[(H) polyfunctional thiol compound]

The composition of the present invention contains a polyfunctional thiol compound, 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 compounds include 1,3,5-tris(3-mercaptopropionyloxyethyl)isocyanurate, 1,3,5-tris(3-mercaptobutyryloxyethyl)isocyanurate (Showa Denko Trifunctional thiol compounds, such as the company's product, Karenz MT (registered trademark) NR1) and trimethylolpropanetris (3-mercaptopropionate); Four functions such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) (made by Showa Denko Co., Ltd., Karenz MT (registered trademark) PEI), etc. Thiol compounds; 6-functional thiol compounds, such as dipentaerythritol hexakis (3-propionate), etc. are mentioned.

When the composition of the present invention contains the component (H), the content is preferably 0.1 to 8% by mass, more preferably 0.8 to 5% by mass, based on the total solid content. If the content is too high, the stability, odor, adhesion, and the like of the composition may deteriorate.

[(I) polymerization inhibitor]

The composition of the present invention, if necessary, contains a polymerization inhibitor. Specific examples of the polymerization inhibitor include 2,6-diisobutylphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyro Gallol, t-butylcatechol, 4-methoxy-1-naphthol, etc. are mentioned.

When the composition of the present invention contains the component (I), the content is preferably 1% by mass or less, and more preferably 0.5% by mass or less based on the total solid content. If the content exceeds 1% by mass, curing failure may occur, and the reaction may become insufficient.

[Other additives]

The composition of the present invention further contains a surfactant, an antifoaming agent, a rheology modifier, a pigment, a dye, a storage stabilizer, and a dissolution accelerator such as polyhydric phenol or polycarboxylic acid, if necessary, as long as the effect of the present invention is not impaired You can do it.

Although it does not specifically limit as surfactant, For example, a fluorine type surfactant, a silicone type surfactant, a nonionic surfactant, etc. are mentioned. As this kind of surfactant, Mitsubishi Material Denshi Kasei Co., Ltd. Ftop (registered trademark) EF301, EF303, EF352; Megapac (registered trademark) F171, F173 manufactured by DIC Corporation; FLUORAD (registered trademark) FC430, FC431 manufactured by 3M; Asahi Glass Co., Ltd. Asahigard (registered trademark) AG710, AGC Semichemical Co., Ltd. Suflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106, and the like.

Defoamers include acetylene glycol, silicone fluids and emulsions, ethoxylated or propoxylated silicones, hydrocarbons, fatty acid ester derivatives, acetylated polyamides, poly(alkylene oxide) polymers and copolymers. Not limited. In the case of screen printing, it is preferable that the composition of the present invention contains a defoaming agent.

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

In addition, the viscosity at 25° C. of the composition of the present invention is preferably 10 to 100,000 mPa·s, more preferably 500 to 100,000 mPa·s, and even more preferably 1,000 to 100,000 mPa·s from the viewpoint of printability. . If the viscosity is too low, the composition may diffuse after application and a desired pattern may not be formed. If the viscosity is too high, a load on the process, such as lower discharge properties, occurs, or transferability of the composition to the substrate This may decrease.

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

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

[How to prepare the composition]

The method for preparing the composition of the present invention is not particularly limited. As an example, a method of dissolving the component (A) in the solvent (D) and mixing the component (B) and the component (C) in an arbitrary order in a predetermined ratio to obtain a uniform solution is mentioned. In addition, a preparation method in which components (E) to (I) or other components are further added and mixed as necessary in an appropriate step of this preparation method may be mentioned. It is preferable to use the resin composition for forming a cured film in a solution state thus prepared after filtering with a filter or the like having a pore diameter of about 0.2 µm.

[Coated film and cured film]

The composition for forming a cured film of the present invention is used as a substrate (for example, a silicon/silicon dioxide coated substrate; a silicon nitride substrate; a metal such as aluminum, molybdenum, chromium, copper, silver, or a metal nanowire such as silver nanowire. , Silver nanoparticles, metal nanoparticles such as copper nanoparticles, poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS), conductive polymers such as graphene, carbon nanotubes, etc. Coated substrate; glass substrate; quartz substrate; ITO substrate; ITO film substrate; resin film substrate such as TAC film, polyester film, acrylic film, cycloolefin (COP) film), etc., rotation coating, flow coating, roll Coating, slit coating, rotational coating following the slit, ink jet coating, screen printing, flexo printing, gravure printing, offset printing, gravure offset printing, etc., and then pre-drying in a hot plate or oven (free By baking), a coating film can be formed. The composition of the present invention is particularly suitable for printing methods such as inkjet application, screen printing, flexo printing, gravure offset printing, and the like.

Pre-baking is generally treated at preferably 60°C to 150°C, more preferably 80°C to 120°C, 0.5 to 30 minutes when using a hot plate, and 0.5 to 90 minutes when using an oven. The method to say is adopted.

Subsequently, post-baking for thermal curing is performed. Specifically, it heats using a hot plate or an oven. Post-baking is generally treated at preferably 150°C to 300°C, more preferably 200°C to 250°C, 1 to 30 minutes when using a hot plate, and 1 to 90 minutes when using an oven. The method to say is adopted.

By curing the composition of the present invention under the above-described conditions, the step 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 a necessary level of flatness, hardness and adhesion, it is used in touch panels such as protective films, planarization films, insulating films, 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 or an insulating film. Moreover, since it is excellent also in flexibility, it is suitable also as an overcoat material for ITO films.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

In addition, reagents and devices used in the examples are as follows.

<Reagent>

DEGEEA (diethylene glycol monoethyl ether acetate), DEGME (diethylene glycol monomethyl ether): manufactured by Tokyo Chemical Industry Co., Ltd.

MEA (2-aminoethanol): manufactured by Kanto Chemical Co., Ltd.

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

UPS: 3-ureidopropyl triethoxysilane, Toray Dow Corning Co., Ltd. AY43-031

CYCLOMER-P: Cyclomer P(ACA)Z250 manufactured by Daicel Allnex Co., Ltd.

CYMEL303: Melamine-based crosslinking agent, manufactured by Nippon Cytec Industries, Ltd.

Perbutyl L: Thermal radical polymerization initiator, manufactured by Nichiyu Corporation

<device>

・Stirring device: ARE-310 Awatori Rentaro, manufactured by Shinki Co., Ltd.

Ultraviolet visible near-infrared analysis photometer (ultraviolet visible absorption spectrum measurement): Shimadzu Corporation UV-3100PC

[1] Preparation of the composition

[Example 1]

In a 200 mL container, 41.5 g of CYCLOMER-P, 9.8 g of PET-30, 9.8 g of CYMEL 303, 0.6 g of Perbutyl L, 0.2 g of UPS, and 37.5 g of DEGEEA were placed. This was put in a stirring device, and stirred at 2,000 rpm for 10 minutes to prepare a composition (varnish).

[Example 2]

In a 200 mL container, 33.5 g of CYCLOMER-P, 11.8 g of PET-30, 11.8 g of CYMEL 303, 0.5 g of Perbutyl L, 0.2 g of UPS, and 42.2 g of DEGEEA were placed. This was put in a stirring device, and stirred at 2,000 rpm for 10 minutes to prepare a composition (varnish).

[2] Preparation of cured film and its evaluation

[2-1] Measurement of light transmittance

The varnishes of Examples 1 and 2 were applied on a quartz glass substrate by spin coating, respectively, and prebaked at 110°C for 2 minutes. Subsequently, it post-baked at 230 degreeC for 30 minutes, and produced the cured film of 2 micrometers in thickness.

And the light transmittance at a wavelength of 400 nm of each obtained cured film was measured. In addition, the light transmittance of the quartz glass substrate used was 93.8%.

[2-2] Evaluation of pencil hardness and adhesion

The varnishes of Examples 1 and 2 were each applied onto a glass substrate with ITO using a bar coater, and prebaked at 110°C for 2 minutes. Subsequently, it post-baked at 230 degreeC for 30 minutes, and the cured film of about 2 micrometers in thickness was produced. And about the obtained cured film, hardness and adhesiveness were evaluated by the following method.

[Evaluation of pencil hardness]

In conformity with JIS K 5400, it measured with 1,000 g load.

[Evaluation of adhesion]

It evaluated by the crosscut test method. First, using a cutter guide, 100 checkers were created on the cured film. Next, a cellophane tape made by Nichiban Co., Ltd. was adhered to the checkered eye, and it was strongly rubbed with an eraser on the top to make it sufficiently close. And next, the cellophane tape was peeled off, and at that time, evaluation was performed by how many out of 100 checkers had peeled off.

0B: 66 or more peeled off

1B: 36-65 peeled

2B: 16-35 peeled

3B: 6 to 15 peeled

4B: 1 to 5 peeled off

5B: no peeling

[2-3] Evaluation of solvent resistance

The varnishes of Examples 1 and 2 were applied on a silicon wafer by spin coating, respectively, and prebaked at 110°C for 2 minutes. Subsequently, it post-baked at 230 degreeC for 30 minutes, and produced the cured film of 2 micrometers in thickness. Each obtained cured film was immersed in a mixed solvent (mass ratio) of MEA:DEGME=3:7 at 60°C for 2 minutes, rinsed with pure water for 30 seconds, and dried at 100°C for 1 minute. And solvent resistance was evaluated by measuring the film thickness of each thin film and confirming the film reduction.

[2-4] Evaluation of ITO sputter resistance

Using the varnishes of Examples 1 and 2, a beta film of 4 cm in width was printed by screen printing on an alkali-free glass substrate having a width of 10 cm, respectively, and prebaked at 110°C for 2 minutes. Subsequently, post-baking was performed at 230°C for 30 minutes to prepare a cured film. The obtained cured film was 5 µm. With respect to the obtained glass substrate with a cured film, ITO sputtering was performed at a substrate temperature of 200° C. and a sputtering time of 1.9 minutes to form an ITO film having a thickness of about 300 Å. The state after ITO sputtering was observed visually, and the presence or absence of abnormality was confirmed.

Table 1 shows the results of the above measurement and evaluation.

Varnish Pencil hardness Adhesion Light transmittance (%) Solvent resistance
(Film reduction) ITO sputter resistance Example 1 3H 5B 92.5 Less than 5% nothing strange Example 2 3H 5B 92.5 Less than 5% nothing strange

As is clear from Table 1, the cured film obtained from the composition (varnish) of the present invention has excellent hardness and adhesion, has a high light transmittance of 92% or more, and has excellent solvent resistance and ITO sputter resistance.

Claims (8)

(A) a copolymer containing a monomer unit represented by formulas (1) and (2),

(In the formula, R ¹ each independently represents a hydrogen atom or a methyl group. R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ³ represents a hydrogen atom or a methyl group.)
(B) melamine-based crosslinking agent,
(C) a thermal radical polymerization initiator, and
(D) solvent
A resin composition for forming a cured film comprising a. The method of claim 1,
(A) The resin composition for forming a cured film, wherein the copolymer is a copolymer containing monomer units represented by formulas (1), (2-1) and (2-2).

(In the formula, R ¹ and R ³ are as described above. R ⁴ represents an alkyl group having 1 to 5 carbon atoms.) The method according to claim 1 or 2,
(E) A resin composition for forming a cured film, further comprising a silane coupling agent. The method according to claim 1 or 2,
(F) A resin composition for forming a cured film, further comprising a polyfunctional (meth)acrylate compound. The method according to claim 1 or 2,
(D) A resin composition for forming a cured film, wherein the solvent has a boiling point of 150°C or higher. A cured film obtained using the resin composition for forming a cured film according to claim 1 or 2. A laminate obtained by laminating the cured film according to claim 6 on a substrate. A touch panel comprising the cured film according to claim 6.