TWI666274B - Resin composition for forming cured film - Google Patents

Abstract

Provided is a resin composition for forming a cured film, which comprises (A) a copolymer containing monomer units represented by formulae (1) and (2), (B) a melamine-based crosslinking agent, and (C) a thermal radical. Polymerization initiator, and (D) solvent,

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

Description

Resin composition for forming cured film

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

Conventionally, a protective film, an insulating film, and the like required for a touch panel and the like are formed at a required portion by pattern processing by a photolithography method using a photosensitive resin composition (Patent Document 1) .

However, in addition to the complicated steps, the pattern processing caused by photolithography has the problem of so-called cost. Therefore, there is a need for a composition that can form a protective film, an insulating film, and the like at a desired location in a simpler and cheaper way.

In addition, when an ITO film is sputter-formed on an insulating film as shown in Patent Document 2, cracks may occur due to a difference in stress between the insulating film and the ITO film. With regard to such protective films and insulating films, It must also have resistance to sputtering of ITO.

[Prior technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-064973

[Patent Document 2] Japanese Patent Laid-Open No. 2011-076386

The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide a composition capable of forming a film at a desired position by a simple method such as printing, and having high light transmittance and high adhesion. Properties, high hardness, and a hardened film that is resistant to ITO sputtering.

As a result of intensive research in order to solve the foregoing problems, the present inventors have found that the foregoing 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 thus completed the present invention .

That is, the present invention is to provide a resin composition for forming a cured film described below.

1. A resin composition for forming a cured film, comprising (A) a copolymer containing monomer units represented by formulae (1) and (2),

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

(B) a melamine-based crosslinking agent, (C) a thermal radical polymerization initiator, and (D) a solvent.

2. The resin composition for forming a cured film according to 1, wherein the (A) copolymer is a copolymer containing monomer units represented by the formulae (1), (2-1), and (2-2),

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

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

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

5. The resin composition for forming a cured film according to any one of 1 to 4, wherein (D) the solvent-based boiling point is 150 ° C or higher.

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

7. A laminated body, which is formed by laminating the hardened film of 6 on a substrate.

8. A touch panel comprising a hardened film of 6.

The cured film obtained by using the resin composition for forming a cured film of the present invention is excellent in hardness, adhesion, transparency, and resistance to ITO sputtering, and also has resistance to a resist release agent. Therefore, it is suitable as a material for forming a protective film, a flattening film, an insulating film, and the like in various displays such as an organic electroluminescence (EL) element, and a hardened film such as a protective film and an insulating film in a touch panel. Moreover, since it is excellent in flexibility, it is also suitable as a protective film material for ITO films.

[Best Mode for Implementing Invention]

[Resin composition for curing film formation]

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

[(A) Copolymer]

(A) A component is a copolymer containing the monomer unit represented by Formula (1) and (2).

In the formula, R ¹ each independently represents a hydrogen atom or a methyl group, and is preferably 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, and is preferably a hydrogen atom.

The alkyl group may be any of linear, branched, and cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, and isobutyl. , S-butyl, t-butyl, cyclobutyl, n-pentyl and the like. In addition, part or all of the hydrogen atoms of the alkyl group may be substituted with a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, and an amine group.

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

In the formula, R ¹ and R ³ are the same 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 are the same as those described above.

The copolymer of the component (A) preferably contains a monomer unit represented by the formula (1) in the all-monomer unit from the viewpoint that a cured film excellent in solvent resistance and hardness is obtained with good reproducibility. Molar% or more, and more preferably 10 Molar% or more.

The weight average molecular weight (Mw) of the aforementioned copolymer is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and more preferably 15,000 to 80,000 when operability and adhesion are considered. When the Mw exceeds 200,000, the solubility in a solvent may be reduced and the operability may be reduced. When the Mw is less than 5,000, the adhesion may be reduced.

When printing properties are taken into consideration, the 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 Mw exceeds 200,000, When the solubility is lowered and the operability is lowered, when the Mw is less than 10,000, the printability may be lowered.

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

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

The copolymer of the component (A) can be synthesized by a conventionally known method. After synthesizing poly (meth) acrylic acid, poly (meth) acrylate, or (meth) acrylic acid- (meth) acrylate copolymer, the copolymerization is performed. 3,4-epoxycyclohexylmethyl (meth) acrylate is synthesized by ring-opening addition. The ring-opening addition reaction can be specifically performed according to a method described in, for example, Japanese Patent Application Laid-Open No. 10-087725.

The copolymer of the component (A) is commercially available, and examples thereof include 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 (the above is made by Daicel-Allnex (shares)) and so on.

[(B) Melamine-based crosslinking agent]

The component (B) is a melamine-based crosslinking agent, which contributes to the crosslinking of the component (A). Examples of the melamine-based cross-linking agent include a melamine-based compound having a methyl group, a methoxymethyl group, or the like to form a substituent. Regarding the melamine-based cross-linking agent, for example, CYMEL (registered trademark) 303 (hexamethoxymethyl melamine), 1170 (four CYMEL series such as butoxymethyl acetylene urea), 1123 (tetramethoxymethylbenzoguanamine); (share) Nikalac (registered trademark) MW-30HM, MW of methylated melamine resin made by SANWA Chemical -390, MW-100LM, MX-750LM, Nikalac series of methylated urea resin MX-270, MX-280, MX-290, etc.

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

[(C) Thermal radical polymerization initiator]

The component (C) is a thermal radical polymerization initiator, which contributes to the start or promotion of the polymerization of the component (A). Examples of the thermal radical polymerization initiator include acetamidine peroxide, benzamidine peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, tertiary butyl hydrogen peroxide, and cumene peroxide. Hydrogen oxide, di (tertiary butyl) peroxide, dicumyl peroxide, dilauryl peroxide, tertiary butyl peroxyacetate, tertiary butyl peroxytrimethyl acetate , Tertiary butyl peroxy-2-ethylhexanoate (tertiary butyl 2-ethylhexane peroxyester) and the like; 2,2'-azobisisobutyronitrile, 2 , 2'-Azobis (2,4-dimethylvaleronitrile), (1-phenylethyl) azobisphenylmethane, 2,2'-azobis (4-methoxy-2 , 4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azo Bis (1-cyclohexanecarbonyl Nitrile), 2- (aminomethylamidoazo) isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4- Azo compounds such as dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane); persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate Etc., but it is not limited to this.

As a commercially available thermal radical polymerization initiator, for example, Peroyl (registered trademark) IB, NPP, IPP, SBP, TCP, OPP, SA, 355, L, Perbutyl (registered trademark) ND manufactured by Nippon Oil Co., Ltd. may be mentioned. , 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 , Nyper (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, Nofuma (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; IRGACURE (registered trademark) made by BASF Corporation 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, TPO, DAROCUR (registered trademark) 1116, 1173; Cytec Surface Specialties company UVECRYL (registered trademark) P36; Lamberti company Esacure (registered trademark) KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46 KIP75 / B, but are not limited thereto.

(C) The upper limit of the content of the component suppresses storage stability From the viewpoint of reducing the property, it is preferably 20 parts by mass, and more preferably 10 parts by mass with respect to 100 parts by mass of the component (A). This lower limit value gives solvent resistance and hardness with good reproducibility as From the viewpoint of an excellent cured film, it is preferably 0.01 parts by mass, and 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 the composition of the present invention includes the components (E) to (I) described below and other additives, so long as they are soluble. It is not particularly limited. That is, in the composition of the present invention, components other than the (D) component are solutions dissolved in the (D) component.

Specific examples of the solvent include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol isopropyl ether, and ethylene glycol monobutyl ether. Ether, ethylene glycol dibutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethyl ether 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 monoethyl ether acetate, diethylene glycol Alcohol 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 monobutyl ether, tripropylene glycol monomethyl ether, trimethylene glycol, hexanediol, octanediol, methoxymethoxyethanol, 1-butoxyethoxypropanol, isobutyl acetate, methoxybutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, isoamyl acetate Ester, n-butyl propionate, isobutyl lactate, n-butyl lactate, n-amyl lactate, isoamyl lactate, isoamyl isoxalate, ethyl acetobutyrate, butyl stearate, dioxalate Butyl ester, diethyl malonate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, methylphenyl ether, ethyl benzyl ether, ethylphenyl ether, di Chloroethyl ether, diisoamyl ether, n-hexyl ether, 1,4-dioxane, diethyl acetal, eucalyptol, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, Methyl isobutyl ketone, diethyl ketone, ethyl n-butyl ketone, di-n-propyl ketone, acetone, phorone, isophorone, acetophenone, glycerol, butanol, 2-butanol, 1,3-butanediol, 2,3-butanediol, Amyl alcohol, 1,5-pentanediol, 2-methylcyclohexanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, 1-octanol, 2-octanol, nonanol , N-decanol, trimethylnonanol, benzyl alcohol, α-terpineol, tetrahydrofurfuryl alcohol, furfuryl alcohol, pinoresinol, triethylene glycol dichloride, trichloroacetic acid, lactic acid, erythrin, isoglycylic acid, hexane Acid, 2-ethylhexaneic acid, octanoic acid, butyric anhydride, decane, dipentene, p-menthane, dodecane, 1,1,2-trichloroethane, 1,1,1,2-tetra Ethyl chloride, 1,1,2,2-tetrachloroethane, hexachloroethane, toluene, xylene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichloro Benzene, o-dibromobenzene, benzonitrile, nitrobenzene, α-toluenenitrile (phenylacetonitrile), N-methylformamide, N-methylacetamide, 2-pyrrolidone, and the like.

Solvents can be used alone or in combination of two or more. use. Moreover, you may use the solvent used at the time of superposing | polymerizing (A) component 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 more preferably 200 ° C or higher. Examples of such solvents include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, and diethylene glycol. Monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, triethylene glycol monobutyl Ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether Waiting is especially good.

When two or more solvents are used in combination, the boiling point of at least one of them is preferably 150 ° C or higher, more preferably 180 ° C or higher, and 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 becomes 1 to 95% by mass, and an amount such that the solid content concentration becomes 5 to 90% by mass is further preferable. The amount is preferably such that the concentration becomes 10 to 85% by mass. Here, the "solid content" is obtained by removing the solvent (D) from all the components of the composition of the present invention.

The composition of the present invention may further include (E) a silane coupling agent, (F) a polyfunctional (meth) acrylate compound, (G) an ion trapping agent, (H) a polyfunctional thiol compound, (I) Polymerization inhibitors and the like.

[(E) Silane coupling agent]

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

In formula (3), R ⁵ represents methyl or ethyl, X represents hydrolyzable group, Y represents reactive functional group, m is an integer of 0 to 3, n is an integer of 0 to 3, and 0 to An integer of 2 is preferred.

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

Examples of the reactive functional group represented by Y include amine, ureido, (meth) acrylfluorenyl, vinyl, epoxy, and mercapto, and amine, urea, and (meth) acrylfluorene Oxygen and the like are preferred. Particularly preferred is amine or urea.

As a specific example of the silane coupling agent, for example, 3-amine Propyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyl Methyldiethoxysilane, 3-Ureapropyltrimethoxysilane, 3-Ureapropyltriethoxysilane, 3-Acryloxypropyltrimethoxysilane, 3-Acryloxypropyl Triethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, ethylene Triethoxysilane, allyl trichlorosilane, allyl trimethoxysilane, allyl triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidyl Oxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3- Mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and the like.

Among these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureapropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 3-Methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane are particularly preferred. As the silane coupling agent, a commercially available product can be used.

When the composition of the present invention contains the component (E), the content of the component (E) is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass, with respect to 100 parts by mass of the component (A). It is preferably 0.05 to 1 part by mass. When the content is less than 0.001 parts by mass, the effect of improving the adhesion may not be obtained. When it exceeds 10 parts by mass, the hardness may be reduced.

[(F) Multifunctional (meth) acrylate compound]

From the viewpoint of improving the hardness, the composition of the present invention preferably contains a polyfunctional (meth) acrylate compound as the (F) component. The so-called polyfunctional (meth) acrylate compound is a compound having at least three (meth) acryloxy groups in the molecule, and specific examples thereof include esters obtained from a polyhydric alcohol and (meth) acrylic acid. The number of (meth) acrylic fluorenyloxy groups in one molecule is 3 to 6, preferably 3 or 4.

Examples of the polyhydric alcohol include glycerol, erythritol, neopentaerythritol, trimethylolethane, trimethylolpropane, dinepentaerythritol, and ditrimethylolpropane.

Specific examples of the polyfunctional (meth) acrylate compound include neopentaerythritol tetraacrylate, neopentaerythritol tetramethacrylate, neopentaerythritol triacrylate, and neopentaerythritol trimethyl. Acrylate, Dipentaerythritol hexaacrylate, Dipentaerythritol hexamethacrylate, Dipentaerythritol pentaacrylate, Dipentaerythritol pentamethacrylate, Trimethylolethane three Acrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, bistrimethylolpropane tetraacrylate, bistrimethylol Propane tetramethacrylate and the like.

The polyfunctional (meth) acrylate compound is commercially available and can be easily obtained. In this specific example, for example, 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; Aronix (registered trademark) made by East Asia Synthesis ) 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; Viscoat 295, 300, 360, GPT, 3PA, 400, 260, 312, 335HP made by Osaka Organic Chemical Industry Co., Ltd .; NK esters 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.

When the composition of the present invention contains the component (F), the content of the component (F) is preferably 10 to 300 parts by mass, and more preferably 20 to 200 parts by mass with respect to 100 parts by mass of the component (A). It is preferably 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. When it exceeds 300 parts by mass, the characteristics of adhesion and softness may be reduced, and cracks may easily occur. A polyfunctional (meth) acrylate compound can be used individually by 1 type or in combination of 2 or more types.

[(G) Ion trapping agent]

The composition of the present invention preferably contains an ion trapping agent from the viewpoint of suppressing migration of metal wiring and the like in contact with the cured film. As such an ion trapping agent, a compound having a chelating energy having an unpaired electron in the structure is preferable, and for example, N, N'-bis [3- (3,5-di-t-butyl- 4-hydroxybenzene (Propyl) propanyl] hydrazine (Irganox MD1024, manufactured by BASF), bis (benzylidenehydrazine) oxalate (Eastman Inhibitor OABH, manufactured by Eastman Chemical), benzotriazole, 5-methylbenzotriazole, etc. . These can be obtained from commercial products. In addition, as other commercially available products, for example, Adeka Stab CDA-1 ((share) ADEKA), Adeka Stab CDA-6 ((share) ADEKA), Qunox (Mitsui Toatsu Fine (share)), Naugard XL- 1 (Uniroyal). Among these, 5-methylbenzotriazole is particularly preferred.

When the composition of the present invention contains the (G) component, the content of the (G) component is preferably 0.0001 to 20 parts by mass, and more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the component (A). When it is less than 0.0001 parts by mass, the effect of protecting the metal wiring may not be obtained. When it exceeds 20 parts by mass, characteristics such as the hardness and adhesion of the cured film may be reduced, and the cost is also disadvantageous. .

[(H) Polyfunctional thiol compound]

The composition of the present invention may contain a polyfunctional thiol compound as needed. 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, for example, 1,3,5-tris (3-mercaptopropionyloxyethyl) -isocyanate, and 1,3,5-tris (3-mercaptobutyryloxyethyl) -isocyanate (Showa Made by Electric Engineering Co., Ltd., Karenz MT (registered trademark) NR1), trimethylolpropane tri (3-mercaptopropionate), etc. Thiol compounds; neopentaerythritol tetrakis (3-mercaptopropionate), neopentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko, Karenz MT (registered trademark) PEI), etc. 4-functional thiol compounds; 6-functional thiol compounds such as dipentaerythritol hexa (3-propionate) and the like.

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

[(I) Polymerization inhibitor]

The composition of the present invention may contain a polymerization inhibitor as needed. Specific examples of the polymerization inhibitor include 2,6-diisobutylphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcresol, hydroquinone, and hydroquinone monomer. Methyl ether, pyrogallol, t-butylcatechol, 4-methoxy-1-naphthol, etc.

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

[Other additives]

The composition of the present invention may further include a surfactant, a defoaming agent, a rheology modifier, a pigment, a dye, a storage stabilizer, a polyphenol, or a polycarboxylic acid, etc., without impairing the effects of the present invention. Dissolution accelerator and so on.

The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant. For such surfactants, for example, EF Top (registered trademark) EF301, EF303, EF352 made by Mitsubishi Materials Electronic Chemicals (stock); Megafac (registered trademark) F171, F173 made by DIC (stock); FLUORAD (registered by 3M) (Trademarks) FC430, FC431; Asahi Guard (registered trademark) AG710 manufactured by Asahi Glass, and Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106, etc.

Examples of defoamers include acetylene glycols, polysiloxane fluids and emulsions, ethoxylated or propoxylated polysiloxanes, hydrocarbons, fatty acid ester derivatives, acetylated polyfluorene imines, poly ( Alkylene oxide) polymers, copolymers, and the like, but are not limited to these. When screen printing is performed, the composition of the present invention preferably contains a defoamer.

From the viewpoint of coating properties, the composition of the present invention preferably has a viscosity at 25 ° C of 1 to 10,000 mPa · s, more preferably 1 to 5,000 mPa · s, and more preferably 1 to 1,000 mPa · s. . When the viscosity is too low, the intended film thickness may not be obtained, and when the viscosity is too high, the coatability may be reduced.

From the viewpoint of printability, the composition of the present invention has a viscosity at 25 ° C of preferably 10 to 100,000 mPa‧s, more preferably 500 to 100,000 mPa‧s, and more preferably 1,000 to 100,000 mPa‧ s. When the viscosity is too low, the composition may spread after coating, and the desired pattern may not be formed. When the viscosity is too high, the ejection property is reduced, etc. This may cause a load, or the transferability of the composition to the substrate may decrease.

When a fine structure like an insulating film constituting a bridge structure is formed in a portion where the X-axis electrode and the Y-axis electrode are orthogonal to each other by a printing method such as screen printing or gravure printing, the present invention The viscosity of the composition at 25 ° C is preferably 10 to 100,000 mPa‧s, more preferably 5,000 to 100,000 mPa‧s, and more preferably 20,000 to 100,000 mPa‧s. When the viscosity is too low, the composition may spread after coating, and the desired pattern may not be formed. When the viscosity is too high, the ejection property may be reduced, etc., which may cause a load on the step, or the composition may be transferred to the substrate. The transferability may be reduced.

In the present invention, the viscosity is a measurement value based on an E-type viscometer.

[Method for preparing composition]

The method for preparing the composition of the present invention is not particularly limited. As one example, a method of dissolving the component (A) in the solvent (D), and mixing the components (B) and (C) with the solution in an arbitrary order at a specified ratio to form a uniform solution can be mentioned. Further, in a suitable stage of the preparation method, a preparation method in which components (E) to (I) or other components can be added and mixed as required can also be mentioned. The resin composition for forming a cured film in a solution state prepared in such a manner is preferably used after being filtered using a filter having a pore size of about 0.2 μm or the like.

[Coated film and hardened film]

By spin coating, flow coating, roll coating, slit coating, spin coating subsequent to slit coating, inkjet coating, screen printing, flexographic printing, gravure printing, lithography, gravure The resin composition for forming a cured film of the present invention is applied to a substrate (such as a silicon / silicon dioxide-coated substrate; a silicon nitride substrate; aluminum, molybdenum, chromium, copper, silver, etc.) by a printing method such as lithography. Metal nanowires such as metals, silver nanowires, metal nanoparticle such as silver nano particles, copper nano particles, poly (3,4-ethylenedioxythiophenol) / poly (styrene sulfonate) (PEDOT / PSS), substrates of conductive polymers such as graphene, carbon nanotubes; glass substrates; quartz substrates; ITO substrates; ITO film substrates; TAC films, polyester films, acrylic films, cyclic olefins (COP) A resin film substrate such as a film, etc.), and then a pre-drying (pre-baking) using a hot plate or a baking oven, etc., thereby forming a coating film. The composition of the present invention is particularly suitable for printing methods such as inkjet coating, screen printing, flexographic printing, and gravure lithography.

Pre-baking generally adopts the following methods, that is, preferably at 60 ° C to 150 ° C, and more preferably at 80 ° C to 120 ° C, for 0.5 to 30 minutes when using a heating plate, and 0.5 when using a baking oven ~ 90 minutes of processing.

It is then baked for post-hardening. Specifically, heating is performed using a hot plate, a baking oven, or the like. Post-baking generally adopts the following methods, that is, preferably at 150 ° C to 300 ° C, and more preferably at 200 ° C to 250 ° C, which is performed for 1 to 30 minutes when using a heating plate, and 1 when using a baking oven. ~ 90 minutes of processing.

The composition of the present invention is hardened under the aforementioned conditions, whereby the step of the substrate can be sufficiently flattened, and a cured film having high transparency can be formed.

Since the cured film of the present invention has at least the required level of flatness, hardness, and adhesion, it is useful as a protective film in various displays for forming a thin film transistor (TFT) type liquid crystal display element, an organic EL element, and the like. , Flattening film, insulating film, etc., as well as hardened films such as protective films and insulating films in touch panels. In addition, since it is also excellent in flexibility, it is also suitable as a protective film material for ITO films.

[Example]

The following series gives examples to explain the present invention in more detail, but the present invention is not limited to the following examples.

The 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): made by Kanto Chemical Co., Ltd.

‧PET-30: Neopentaerythritol (tris / tetra) acrylate, made by Nippon Kayaku Co., Ltd.

‧UPS: 3-ureapropyltriethoxysilane, AY43-031 manufactured by Toray Dow-Corning

‧CYCLOMER-P: Cyclomer P (ACA) Z250 by Daicel-Allnex

‧CYMEL303: Melamine-based crosslinking agent, manufactured by Nihon Cytec Industries

‧Perbutyl L: Thermal radical polymerization initiator, made by Nippon Oil & Gas Co., Ltd.

<Device>

‧Mixing device: THINKY MIXER ARE-310, manufactured by Thinky

‧Ultraviolet visible near infrared analysis photometer (UV visible absorption spectrometry): UV-3100PC manufactured by Shimadzu Corporation

[1] Production of composition

[Example 1]

In a 200 mL container, CYCLOMER-P 41.5g, PET-30 9.8g, CYMEL303 9.8g, Perbutyl L 0.6g, UPS 0.2g, and DEGEEA 37.5g 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, CYCLOMER-P 33.5g, PET-30 11.8g, CYMEL303 11.8g, Perbutyl L 0.5g, UPS 0.2g, and DEGEEA 42.2g were placed. This was put in a stirring device and stirred at 2,000 rpm for 10 minutes to prepare a composition (varnish).

[2] Production and evaluation of hardened film

[2-1] Measurement of light transmittance

The varnishes of Examples 1 and 2 were applied to a quartz glass substrate by a spin coater, and pre-baked at 110 ° C for 2 minutes. Next, post-bake at 230 ° C for 30 minutes to produce a cured film having a thickness of 2 µm.

Then, the transmittance of each obtained cured film at a wavelength of 400 nm was measured. 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 coated on a glass substrate with ITO using a bar coater, and pre-baked at 110 ° C for 2 minutes. Next, post-bake at 230 ° C for 30 minutes to produce a cured film having a thickness of 2 µm. Then, the hardness and adhesion of the obtained cured film were evaluated by the following methods.

[Evaluation of pencil hardness]

The measurement was performed in accordance with JIS K 5400 under a load of 1,000 g.

[Assessment of adhesion]

Evaluated by cross-cut test method. First, using a tool guide, 100 checkerboard squares were made on the hardened film. Next, a cellophane tape made of Nichiban (strand) was adhered to the checkerboard square, and it was wiped strongly with an eraser from above to make it fully and closely contact. Then, the cellophane tape was peeled off, and the number of peeled out of 100 checkerboard squares was calculated for evaluation at this time.

0B: 66 or more peeled

1B: 36 ~ 65 peeled

2B: 16 ~ 35 peeled

3B: 6 to 15 peeled

4B: 1 to 5 peels

5B: No peeling

[2-3] Evaluation of solvent resistance

The varnishes of Examples 1 and 2 were coated on a silicon wafer by a spin coater, and pre-baked at 110 ° C for 2 minutes. Next, post-bake at 230 ° C for 30 minutes to produce a cured film having a thickness of 2 µm. Each obtained cured film was immersed in a mixed solvent (mass ratio) of MEA: DEGME = 3: 7 at 60 ° C, rinsed with pure water for 30 seconds, and dried at 100 ° C for 1 minute. Then, the film thickness of each thin film was measured, and the solvent resistance was evaluated by confirming the amount of film reduction.

[2-4] Evaluation of ITO sputtering resistance

The varnishes of Examples 1 and 2 were respectively printed on a 10 cm square alkali-free glass substrate by screen printing to form a 4 cm square flat film, and pre-baked at 110 ° C for 2 minutes. Next, post-bake at 230 ° C for 30 minutes to produce a cured film. Then, the obtained cured film was 5 μm. For 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, and an ITO film having a film thickness of about 300 Å was formed. The state after ITO sputtering was visually observed, and the presence or absence of abnormality was confirmed.

The measurement and evaluation results are shown in Table 1.

It is clear from Table 1 that the cured film obtained from the composition (varnish) of the present invention is excellent in hardness and adhesion, and has a light transmittance of 92% or more, and further has solvent resistance and ITO splash The plating resistance is also excellent.

Claims (12)

A resin composition for forming a cured film, comprising (A) a copolymer containing monomer units represented by formulae (1) and (2), (Wherein R ¹ represents a hydrogen atom or a methyl group independently, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents a hydrogen atom or a methyl group) (B) a melamine-based crosslinking agent , (C) a thermal radical polymerization initiator, and (D) a solvent. The resin composition for forming a cured film according to claim 1, wherein the (A) 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 the same as described above, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms). The resin composition for forming a cured film according to claim 1 or 2, further comprising (E) a silane coupling agent. The resin composition for forming a cured film according to claim 1 or 2, further comprising (F) a polyfunctional (meth) acrylate compound. The resin composition for forming a cured film according to claim 3, further comprising (F) a polyfunctional (meth) acrylate compound. The resin composition for forming a cured film according to claim 1 or 2, wherein the solvent-based boiling point of (D) is 150 ° C or higher. The resin composition for forming a cured film according to claim 3, wherein (D) the solvent-based boiling point is 150 ° C or higher. The resin composition for forming a cured film according to claim 4, wherein (D) the solvent-based boiling point is 150 ° C or higher. The resin composition for forming a cured film according to claim 5, wherein (D) the solvent-based boiling point is 150 ° C or higher. A cured film obtained by using the resin composition for forming a cured film according to any one of claims 1 to 9. A laminate comprising a cured film of claim 10 laminated on a substrate. A touch panel comprising a hardened film of claim 10.