KR102170935B1 - A curable resin composition and an electronic device comprising a cured layer formed therefrom - Google Patents

Abstract

The present invention relates to a curable resin composition and an electronic device comprising a cured layer formed therefrom. More particularly, the present invention relates to: a curable resin composition which includes, as a binder resin, a copolymer of a specific structure including a hydroxyl-terminated ester group-containing monomer, a maleimide group-containing monomer, and an epoxy group-containing monomer as a polymerization unit, and by including an acid anhydride having a specific structure as a curing agent, allows sufficient thermal cure at low temperatures (e.g., a temperature of 130°C or lower) and exhibits improved storage stability, and can provide a cured film having excellent flexibility and improved adhesion, pattern development, residual film rate, chemical resistance, heat resistance, mechanical properties, and the like applicable to a flexible device; and an electronic device comprising a cured layer formed therefrom.

Description

An electronic device comprising a curable resin composition and an electronic device comprising a cured layer formed therefrom

The present invention relates to an electronic device comprising a curable resin composition and a cured layer formed therefrom, and more particularly, a hydroxy-terminated ester group-containing monomer, a maleimide group-containing monomer, and an epoxy group-containing monomer as a polymerization unit. By including a copolymer of a specific structure as a binder resin, and by including an acid anhydride of a specific structure as a curing agent, it is possible to sufficiently heat cure at low temperature (eg, a temperature of 130° C. or lower) and exhibits improved storage stability, Electronics including a curable resin composition and a cured layer formed therefrom, capable of providing a cured film having excellent flexibility and improved adhesion, pattern development, residual film rate, chemical resistance, heat resistance, and mechanical properties as applicable to flexible devices It relates to the device.

Recently, a flexible organic electroluminescent material is being used for premium mobile displays because of the advantages of bezel-less and high color gamut. In addition, when a flexible organic electroluminescent material is applied, it is not limited to the existing form factor, and various types of displays can be implemented due to its thin and bendable characteristics.

As displays using flexible organic electroluminescent materials are in the spotlight, flexible touch panels suitable for them are also being actively studied. A low-temperature process is essential for an organic insulating film applied to a flexible organic electroluminescent material or a flexible touch panel. In the case of organic electroluminescent materials, there is a limitation to constructing an organic film by a low-temperature process of 130°C or less due to heat resistance problems such as a light-emitting material and a film substrate in the case of a touch panel. It also needs resistance to withstand repeated bending. In more detail, the low-temperature-fired organic film is mainly required to have resistance to withstand the deposition process, photo process, wet etching process in the post process, characteristics without deformation even in repeated bending, high transmittance, high adhesion, high resolution, etc. have.

Accordingly, various thermosetting resin compositions have been suggested (related prior art documents: Korean Patent Registration No. 10-0848196, 10-1336305), but thermosetting is possible under low temperature conditions of 130°C or lower, and the cured film is applicable to flexible devices. A curable resin composition having an excellent level of flexibility and excellent other physical properties has not yet been developed.

It is an object of the present invention to sufficiently heat cure at low temperature (eg, a temperature of 130° C. or lower), exhibit improved storage stability, and excellent flexibility and improved adhesion, pattern development at a level applicable to flexible devices, It is to provide an electronic device including a curable resin composition and a cured layer formed therefrom that can provide a cured film having a residual film rate, chemical resistance, heat resistance, mechanical properties, and the like.

In order to solve the above-described technical problem, the present invention includes (A) a binder resin which is a copolymer containing a hydroxy-terminated ester group-containing monomer, a maleimide group-containing monomer, and an epoxy group-containing monomer as a polymerization unit; (B) a curing agent which is an anhydride of a substituted or unsubstituted alicyclic dicarboxylic acid having 6 to 12 carbon atoms; (C) polyfunctional monomer; And (D) an organic solvent; and, based on the total 100% by weight of the composition, the content of the binder resin is 3 to 40% by weight, and the content of the curing agent is 0.1 to 11.5% by weight, providing a curable resin composition do.

According to another aspect of the present invention, an electronic device including a cured layer formed from the curable resin composition of the present invention is provided.

The curable resin composition of the present invention can be sufficiently thermally cured under low temperature (eg, a temperature of 130° C. or lower) and exhibits improved storage stability, and the cured film formed therefrom has excellent flexibility and improved adhesion at a level applicable to flexible devices. , Pattern development, residual film rate, chemical resistance, heat resistance, mechanical properties, etc. can be shown, it is useful as an organic insulating film for a flexible organic light emitting device or an overcoat material for a flexible touch panel.

In particular, the cured film formed from the curable resin composition of the present invention serves to insulate and protect the metal electrode of the flexible organic light emitting device or the flexible touch panel, that is, selectively present on or under the metal through patterning at a desired position. Thus, it plays the role of an insulating film, and has excellent resistance to wet chemicals such as organic solvents, acids, and alkalis used during the manufacturing process, and functions to protect the metal electrode from it. In addition, it has a flexible characteristic suitable for the characteristic of a flexible device, so when the device is repeatedly bent, the material does not break and maintains its original characteristics.

Further, the curable resin composition of the present invention can provide a negative resist film having a pattern resolution of 20 micrometers or less and excellent in transmittance and adhesion, since the development speed of the non-exposed portion is high.

1 is a comparison of Fourier transform infrared spectroscopy spectra before/after thermosetting of the curable composition prepared in Example 1 of the present invention.
2 is a result of measuring the weight change by temperature using a thermogravimetric analyzer for the cured film of the curable composition prepared in Example 1 of the present invention.
3 is a result of measuring outgassing using ATD GC-MS for cured films of curable compositions prepared in Examples 1, 4, 5 and Comparative Example 5 of the present invention.
4 is a result of measuring the Vickers hardness of the cured film of the curable composition prepared in Examples 1, 6 and 7 and Comparative Example 4 of the present invention.

Hereinafter, the present invention will be described in detail.

The curable resin composition of the present invention comprises (A) a binder resin; (B) curing agent; (C) polyfunctional monomer; And (D) an organic solvent.

(A) binder resin

The binder resin contained in the curable resin composition of the present invention is a copolymer containing a hydroxy-terminated ester group-containing monomer, a maleimide group-containing monomer, and an epoxy group-containing monomer as polymerization units.

In one embodiment, in the copolymer, which is the binder resin, the hydroxy-terminated ester group-containing monomer is 1 part by weight or more, 3 parts by weight or more, 5 parts by weight, based on a total of 100 parts by weight of monomers for forming the copolymer. It may be included in an amount of more than, 7 parts by weight or more, or 10 parts by weight or more, and may be included in an amount of 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, or 30 parts by weight or less.

In one embodiment, in the copolymer as the binder resin, the maleimide group-containing monomer is 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 7 It may be included in an amount of 40 parts by weight or more or 10 parts by weight or more, and may be included in an amount of 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less, or 20 parts by weight or less.

In one embodiment, in the copolymer, which is a binder resin, the epoxy group-containing monomer is 1 part by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight, based on a total of 100 parts by weight of monomers for forming the copolymer. It may be included in an amount of more than or 20 parts by weight or more, and may be included in an amount of 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, or 40 parts by weight or less.

In one embodiment, the binder resin may be a copolymer represented by Formula 1:

[Formula 1]

In Formula 1,

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or a methyl group,

R ₆ is an alkylene group, a cycloalkylene group or an arylene group,

R ₇ is hydrogen, an alkyl group, a cycloalkyl group or an aryl group,

R ₈ is an alkyl group, a cycloalkyl group or an aryl group including an epoxy group,

x, y and z are the molar ratios of each polymerization unit, where x is 0.01 to 0.5, y is 0.01 to 0.4, and z is 0.01 to 0.8.

The alkylene group, cycloalkylene group, arylene group, alkyl group, cycloalkyl group and aryl group are each unsubstituted or substituted with a hydroxy group, an alkyl group or an alkoxy group (e.g., an alkyl group or alkoxy group having 1 to 6 or 1 to 4 carbon atoms). I can.

In one embodiment, in the definition of R ₆ in Formula 1, the number of carbon atoms of the alkylene group may be 1 to 14, 1 to 10, 1 to 6, or 1 to 4; The number of carbon atoms of the cycloalkylene group may be 3 to 12, 3 to 10, 3 to 8, or 3 to 6; The number of carbon atoms of the arylene group may be 6-14, 6-10, or 6. More specifically, examples of R ₆ include methylene, ethylene, propylene, isopropylene, butylene, t-butylene, hexylene, cyclohexylene, octylene, decylene, dodecylene, tetradecylene, ethoxymethylene, Phenylene or benzylene may be mentioned, but the present invention is not limited thereto.

In one embodiment, in the definition of R ₇ in Formula 1, the number of carbon atoms of the alkyl group may be 1 to 14, 1 to 10, 1 to 6, or 1 to 4; The number of carbon atoms of the cycloalkyl group may be 3 to 12, 3 to 10, 3 to 8, or 3 to 6; The number of carbon atoms of the aryl group may be 6-14, 6-10, or 6. More specifically, examples of R ₇ include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, cyclohexyl, 2-ethylhexyl, decyl, dodecyl, dicyclopentanyl, adamane Tyl, phenyl, benzyl, naphthyl, 4-hydroxyphenyl, 4-methylphenyl, or 4-methoxyphenyl may be mentioned, but the present invention is not limited thereto.

In one embodiment, in the definition of R ₈ in Formula 1, the number of carbon atoms of the alkyl group may be 1 to 14, 1 to 10, 1 to 6, or 1 to 4; The number of carbon atoms of the cycloalkyl group may be 3 to 12, 3 to 10, 3 to 8, or 3 to 6; The number of carbon atoms of the aryl group may be 6-14, 6-10, or 6. More specifically, examples of R ₈ include glycidyl, glycidyl-alpha-methyl, glycidyl-alpha-ethyl, glycidyl-alpha-butyl, 3,4-epoxybutyl, 6,7-epoxyheptyl , 6,7-epoxyheptyl-alpha-methyl, 2,3-epoxycyclohexyl, 3,4-epoxycyclohexyl, 2-glycidyloxy-1-propyl, 3-methyloxetane-3-methyl or 3 -Ethyloxetane-3-methyl, but is not limited thereto.

In one embodiment, in Formula 1, x may be 0.01 or more, 0.03 or more, 0.05 or more, 0.07 or more, or 0.1 or more, and may be 0.5 or less, 0.45 or less, 0.4 or less, 0.35 or less, or 0.3 or less.

In one embodiment, y in Formula 1 may be 0.01 or more, 0.03 or more, 0.05 or more, 0.07 or more, or 0.1 or more, and may be 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, or 0.2 or less.

In one embodiment, z in Formula 1 may be 0.01 or more, 0.05 or more, 0.1 or more, 0.15 or more, or 0.2 or more, and may be 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, or 0.4 or less.

In one embodiment, the copolymer, in addition to the above-described monomers, within a range capable of achieving the object of the present invention, may further include one or more additional monomers as polymerization units.

In one embodiment, the additional monomer that may be further included in the copolymer is styrene, (meth)acrylic acid, alkyl (meth)acrylate, aryl (meth)acrylate, arylalkyl (meth)acrylate, or a combination thereof. I can.

In one embodiment, when the copolymer further includes an additional monomer, the additional monomer is 1 part by weight or more, 5 parts by weight or more, 7 parts by weight based on a total of 100 parts by weight of monomers for forming the copolymer. It may be included in an amount of at least 10 parts by weight or more, and may be included in an amount of 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, or 20 parts by weight or less.

In one embodiment, when the copolymer further contains styrene as an additional monomer, based on a total of 100 parts by weight of monomers for forming the copolymer, the styrene is 1 part by weight or more, 2 parts by weight or more, or 5 parts by weight It may be included in the above amount, and may be included in an amount of 30 parts by weight or less, 25 parts by weight or less, or 20 parts by weight or less.

In one embodiment, when the copolymer further includes (meth)acrylic acid as an additional monomer, based on a total of 100 parts by weight of monomers for forming a copolymer, the (meth)acrylic acid is 1 part by weight or more, 5 parts by weight It may be included in an amount of parts by weight or more or 7 parts by weight or more, and may be included in an amount of 25 parts by weight or less, 20 parts by weight or less, or 15 parts by weight or less.

In one embodiment, the binder resin may be a copolymer represented by the following Formula 1-1:

[Formula 1-1]

In Formula 1-1,

R ₁ to R ₄ , R ₆ to R ₈ , x, y and z are as defined in Formula 1,

R ₅ is independently hydrogen or a methyl group

R ₉ is one or more selected from the group consisting of an aromatic group, a carboxylic acid group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group and an alkoxy group,

t is 0.01 to 0.5.

In Formula 1-1, examples of R ₉ include phenyl, naphthyl, hydroxyphenyl, -COOH, methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, isobutoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, naphthyloxycarbonyl, isobornyloxycarbonyl, 2-oxooxapentyloxycarbonyl, adamantyloxycarbonyl, dicyclopentanyloxycarbonyl, dicyclopentenyloxycarbonyl, dicyclopentanylethyloxycarbonyl, dicyclopentenylethyloxycarbonyl, dimethylamino Ethyloxycarbonyl, methoxy, ethoxy, phenyloxy, and the like, but are not limited thereto.

There is no particular limitation on the synthesis of the copolymer used as the binder resin in the present invention, and known materials and methods may be used.

As a solvent used for the synthesis of the copolymer, alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methylethyl ether; Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, and other propylene glycol alkyl ether acetates selected from one or a combination of two or more, but is not limited thereto. .

The polymerization initiator used in the synthesis of the copolymer is generally a radical polymerization initiator such as 2,2' azobis isobutyronitrile, 2,2' azobis- (2,4-dimethylvaleronitrile), Azo compounds such as 2,2'azobis-(4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, t-butyl peroxy fibarate, and 1,1'bis-(t-butyl peroxy)cyclohexane; And hydrogen peroxide, but are not limited thereto.

In one embodiment, the copolymer used as the binder resin may have a weight average molecular weight of 1,000 to 50,000 and a dispersion degree of 1.0 to 10.0, and more specifically, a weight average molecular weight of 8,000 to 20,000, and a dispersion degree It may be 1.5 to 3.0, but is not limited thereto.

In addition, the copolymer used as the binder resin is not restricted to the order of arrangement of each polymerization unit, and may be a block copolymer or a random copolymer.

The content of the binder resin in the curable resin composition of the present invention is 3 to 40% by weight, based on the total 100% by weight of the composition, more specifically, 5 to 35% by weight, 10 to 30% by weight, or 15 to It may be 30% by weight. If the content of the binder resin in the composition is less than 3% by weight, the adhesive strength and flexibility of the cured film become poor, and the pattern development property and film residual rate are also poor. Conversely, when the content of the binder resin in the composition exceeds 40% by weight, the adhesive strength of the cured film becomes poor, and the pattern development property and the film residual rate are also poor.

(B) hardener

The curing agent contained in the curable resin composition of the present invention is an anhydride of a substituted or unsubstituted alicyclic dicarboxylic acid having 6 to 12 carbon atoms.

In one embodiment, the curing agent is unsubstituted or substituted with an alkyl group or an alkoxy group (eg, an alkyl group or alkoxy group having 1 to 6 or 1 to 4 carbon atoms), 6 to 12, 6 to 10 or 6 to 8 carbon atoms It may be an anhydride of an alicyclic dicarboxylic acid of, and more specifically, an anhydride of hexahydrophthalic acid unsubstituted or substituted with an alkyl group or an alkoxy group (eg, an alkyl group or alkoxy group having 1 to 6 or 1 to 4 carbon atoms) Can be

In one embodiment, the curing agent may be an acid anhydride represented by the following formula (2), an acid anhydride represented by the following formula (3), or a mixture thereof:

[Formula 2]

[Formula 3]

The content of the curing agent in the curable resin composition of the present invention is 0.1 to 11.5% by weight, and more specifically, 0.5 to 10% by weight, 1 to 10% by weight, or 1 to 5, based on 100% by weight of the total composition. It may be weight percent. When the content of the curing agent in the composition is less than 0.1% by weight, the degree of curing of the cured film is lowered. Conversely, when the content of the curing agent in the composition exceeds 11.5% by weight, the residual film ratio of the cured film becomes poor.

(C) polyfunctional monomer

As the polyfunctional monomer contained in the curable resin composition of the present invention, a bifunctional or trifunctional or higher (meth)acrylate can be used.

In one embodiment, as the polyfunctional monomer, for example, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene oxide groups, trimethylol propane di (meth) acrylate , Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, di Pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tri(meth)acrylate, obtained by esterifying polyhydric alcohol and acrylic acid or methacrylic acid, selected from the group consisting of compound; Compounds obtained by adding (meth)acrylic acid to a glycidyl group-containing compound such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; Addition of a compound having a hydroxyl group and an acrylic group, such as a phthalic acid diester of β hydroxyethyl (meth) acrylate and a toluene diisocyanate adduct of β hydroxyethyl (meth) acrylate, and an ester compound of a polyvalent carboxylic acid or polyisocyanate water; And the like, but are not limited thereto.

The content of the polyfunctional monomer in the curable resin composition of the present invention may be appropriately adjusted as necessary. In one embodiment, for example, based on 100% by weight of the total composition, the polyfunctional monomer may be included in an amount of 1% by weight or more, 2% by weight or more, 3% by weight or more, or 5% by weight or more, and, It may be included in an amount of 30% by weight or less, 25% by weight or less, 20% by weight or less, or 15% by weight or less, but is not limited thereto.

(D) organic solvent

As the organic solvent contained in the curable resin composition of the present invention, an appropriate one may be used in consideration of compatibility with the binder resin, the curing agent, the polyfunctional monomer, and other additives described below, for example, methanol and ethanol. Alcohols such as; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; Lactate esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl methoxy acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxypropionic acid alkyl esters such as 3-oxy methyl propionate and 3-oxy ethyl propionate; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionic acid alkyl esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate, and 2-oxy propionate propyl; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-methylpropionic acid esters such as 2-oxy-2-methyl methyl propionate and 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methyl propionate such as ethyl methyl propionate; Esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, and 2-hydroxy-3-methyl methyl butanoate; Ketone acid esters such as ethyl pyruvate, etc., and further, N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate , Diethyl oxalate, diethyl maleate, γ butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like, alone or a mixture of two or more solvents may be used.

The content of the organic solvent in the curable resin composition of the present invention can be appropriately adjusted as necessary. In one embodiment, for example, based on 100% by weight of the total composition, the organic solvent may be included in an amount of 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more, , In addition, it may be included in an amount of 95.9% by weight or less, 94% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less, but is not limited thereto.

(E) Photoinitiator

The curable resin composition of the present invention may be used as a negative resist composition, and in this case, may further include a photoinitiator.

As the photoinitiator that can be used in the present invention, compounds such as triazine-based, benzoin, acetophenone-based, imidazole-based, toxanthone or oxime ester-based compounds that are generally used may be mentioned. For example, triphenylphosphine oxide , Benzophenone, phenylbiphenylketone, 1-hydroxy-1-benzoylcyclohexane, benzyldimethylketal, 1-benzyl-1-dimethylamino-1-(4-morpholino-benzoyl)propane, 2-morpholyl -2-(4-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propyl thioxanthone, isopropyl thioxanthone, diethyl thioxanthone, ethylanthraquinone, 4-benzoyl -4-methyldiphenylsulfide, benzoinbutyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4-isopropyl)benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxy Cybenzoyldichloromethane, methyl benzoylformate, 1,7-bis(9-acridinyl)heptane, 9-n-butyl-3,6-bis(2-morpholino-isobutyloyl)carbazole, 2 -Methyl-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis( Trichloromethyl)-s-triazine, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[(4-methylthio)phenyl] -2-morpholinopropan-1-one, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 4 ,4'-bis(diethylamino)benzophenone, 2-mercaptobenzothiazole, Ciba Special Chemical's Irgacure 369, Irgacure 379 Irgacur 651, Irgacure 907, Darocur TPO, Irgacure 819, OXE-01, OXE-02, Adeca's N-1919 and NCI-831 compounds may be used alone or in combination of two or more.

In one embodiment, when the photoinitiator is included in the curable resin composition of the present invention, the content is 0.01 to 10% by weight, 0.1 to 7% by weight, 0.5 to 5% by weight, or 1 To 5% by weight. If the amount of photoinitiator used is too small, the residual film rate is deteriorated due to low sensitivity, and there may be difficulties in pattern formation, whereas if the amount of the photoinitiator is too large, the problem of lowering the transmittance may occur, and foreign substances are generated on the surface of the film due to the decrease in the solubility of the photoinitiator. I can make it.

(F) other additives

In addition to the above-described components (A) to (E), the curable resin composition of the present invention may optionally further contain one or more other additives within a range capable of achieving the object of the present invention.

As such other additives, one or more additives commonly included in the curable resin composition (eg, adhesion aids, surfactants, photosensitizers, thermal polymerization inhibitors, antifoaming agents, leveling agents, etc.) may be used without particular limitation. .

For example, the adhesion aid may be used for the purpose of improving the adhesion between the ITO electrode and the negative resist composition, and increasing heat resistance after curing. As such an adhesion aid, a silicone-based compound having an epoxy group or an amine group may be used. For example, (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxy) Doxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4 -Epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrie Each of oxysilane and aminopropyltrimethoxysilane may be used alone or in combination, and the amount thereof may be 0.0001 to 3% by weight based on 100% by weight of the total composition, but is not limited thereto.

In addition, for example, a surfactant may be used for the purpose of improving coating properties by controlling the surface energy of the cured film. As such a surfactant, a fluorine-based surfactant or a silicone surfactant may be used. For example, as a commercial product of a fluorine-based surfactant, BM-1000, BM-1100 (BM Chemie), Prolide FC-135/FC-170C/FC- 430 (Sumitomo 3M Co., Ltd.), SH-28PA/-190/SZ-6032 (Toray Silicon Co., Ltd.), etc., as commercial products of silicone surfactants, BYK's BYK-307, BYK-310, BYK-313, BYK-320, BYK -333 and the like may be used, and the amount thereof may be 0.01 to 5% by weight, based on 100% by weight of the total composition, but is not limited thereto.

According to another aspect of the present invention, an electronic device (eg, a flexible organic electroluminescent device or a flexible touch panel) including a cured layer (eg, an organic insulating layer or an overcoat layer) formed from the curable resin composition of the present invention ) Is provided.

In one embodiment, by using the curable resin composition of the present invention, for example, an organic insulating film of a flexible organic light emitting device or an overcoat of a flexible touch panel may be formed by the following method. After coating the resin composition on the substrate, removing the solvent to uniformly form a coating film, (optionally, exposure to ultraviolet rays transmitted through the mask and developing the non-exposed part using an aqueous alkali solution) heat treatment to form an organic insulating film or an overcoat. Can be obtained.

As the substrate, for example, a flexible material may be used, and glass, quartz, silicon, ITO, or the like may be used.

The coating method of the composition solution is not particularly limited, and for example, spin coating, slot die coating, spray, roll coating, and the like may be used.

It is preferable that the removal of the solvent is carried out by depressurization and heat treatment through a vacuum device. These conditions for decompression and heat treatment are different depending on the type and ratio of the organic solvent component used in the composition, but it is preferable to heat-treat for about 80 to 200 seconds at 80 to 120°C under reduced pressure at 0.5 to 2.0 torr.

The UV exposure process uses a GHI mixed wavelength and can be performed at an exposure amount of 10 to 300 mJ/cm ² .

The curing through the heat treatment may be performed for 15 to 120 minutes at a temperature of 120 to 180°C.

The thickness of the cured film formed as described above may be 0.1 to 6 μm, and when there are irregularities on the substrate, the value is understood as a value at the top of the irregularities.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited to these.

[ Example ]

Manufacturing example : Preparation of copolymer

In a 500 mL polymerization vessel equipped with a reflux condenser and a stirrer, 5 parts by weight of 2,2′ azobis-2,4-dimethylvaleronitrile as a polymerization initiator based on 100% by weight of the total monomers according to the components and compositions shown in Table 1 below. And 200 parts by weight of diethylene glycol methyl ethyl ether were added as a solvent. Subsequently, monomers according to the components and compositions shown in Table 1 were added, and the copolymer was polymerized by stirring at a polymerization temperature of 65° C. for 7 hours in a nitrogen atmosphere. The solid content of the monomer was added at 30% by weight.

[Table 1]

Examples 1 to 19 and Comparative Examples 1 to 9: Preparation of curable resin composition

Each of the copolymers obtained in Preparation Example was used as a binder resin to prepare curable resin compositions of Examples 1 to 19 and Comparative Examples 1 to 9.

By mixing the components shown in Table 2 below in the corresponding content, a curable resin composition solution having a solid content concentration of 20% by weight was prepared. The balance shown in Table 2 below is based on 100% by weight of the total composition, excluding a binder resin, a curing agent, a polyfunctional monomer, a photoinitiator, and a surfactant, and the solvent (3-methoxy methyl propionate (MMP) and diethylene. It means adding a 6:4 weight ratio mixture of glycol methylethyl ether (MEDG)). That is, in the case of Example 1, it means that the solvent was added in an amount of 53.99% by weight excluding 30% by weight of a binder resin, 3% by weight of a curing agent, 10% by weight of a polyfunctional monomer, 3% by weight of a photoinitiator, and 0.01% by weight of a surfactant.

[Table 2]

Acid anhydride 1: 4-methylhexahydrophthalic anhydride

Acid anhydride 2: hexahydrophthalic anhydride

Acid anhydride 3: maleic anhydride

Acid anhydride 4: succinic anhydride

Acid anhydride 5: phenylsuccinic anhydride

On a glass substrate or an ITO substrate, apply each of the prepared curable resin composition solutions to a thickness of 1.5 μm on the substrate, and at a low pressure of 0.5 to 2.0 torr, then on a hot plate at 80 to 120° C. for about 80 to 200 seconds. To remove the solvent to prepare a thin film. After UV irradiation (GHI mixed wavelength, exposure amount of 10 to 300 mJ/cm ² ) on the prepared thin film, the pattern formed by developing with an alkaline aqueous solution (sodium hydroxide) was heat-treated (120 to 180°C, 15 to 120 minutes) in an oven. The final cured film was obtained.

For each of the prepared compositions and cured films of Examples and Comparative Examples, the following evaluation was performed, and the results are shown in Tables 3 to 7.

(1) Hardness

After the composition was applied to the KBR disk, the solvent was removed by heat treatment near 100°C. The spectrum of the coating film formed on the KBR disk was obtained through Fourier transform infrared spectroscopy. At this time, the area of the 910cm ^-1 peak, which is an epoxy characteristic peak, is referred to as A0. Thereafter, the coating film formed on the KBR disk was cured by exposure and heat treatment (130° C./60 min), and a spectrum was obtained again through Fourier transform infrared spectroscopy. At this time, the area of the epoxy characteristic peak is called Ac. And the curing degree of the cured film was calculated using Equation 1 below, and the results are shown in Table 3 below. In addition, the Fourier transform infrared spectroscopy spectrum of the composition prepared in Example 1 before/after thermosetting is shown in FIG. 1.

[Equation 1]

(2) adhesion

The cured film prepared on the substrate was allowed to stand for 24 hours under a high temperature (121°C), high pressure (2 atm), and high humidity (100% humidity) condition, and then the adhesion was evaluated using a checkered tape method. In the checkered tape method, using a cutter knife on the cured film, cut 11 rows of 1 mm spacing to the depth of the top surface of the substrate, and then in the vertical direction, cut 11 rows of 1 mm spacing to the depth of the top surface of the substrate to create 100 checkers. After formation, an adhesive tape (3M company, 310-M) was applied to the checkerboard pattern and then peeled off. The number of peeled checkerboard patterns was measured, and the adhesion of the cured film was evaluated according to the following criteria. It is shown in Table 3 below.

○: 5 or less of the number of peeled checkers

△: 6 to 49 number of peeled checkers

Χ: 50 or more of the number of peeled checkers

(3) Resolution

Using each composition, after forming a pattern having a mask size of 30x30㎛ on the substrate, the length of the bottom surface of the square hole was measured through a scanning electron microscope, and the results are shown in Table 3 below.

(4) flexibility

After each composition was applied to a thickness of 1.5 μm on a cycloolefin polymer film, the solvent was removed through reduced pressure and heat treatment, and exposure, development, and heat treatment (130° C./60 min) were performed to prepare a patterned cured film. Subsequently, the cured film prepared on the film was bent 100,000 times using a YUASA film folding machine with a bending radius of 5 mm in each of the front and back sides. After the bending repetition was completed, the fine pattern was checked with a microscope, and if there was no breakage or dropout, it was judged as “good”, and if breakage or dropout occurred, it was judged as “bad”, and the results are shown in Table 3 below.

(5) Film remaining rate

Exposure was performed without interposing a mask, and the ratio (%) of the film thickness after heat curing compared to the film thickness before exposure (100%) was calculated. If the film thickness ratio after curing was 60% or more, it was judged as “excellent”, and if it was less than 60%, it was judged as “poor”, and the results are shown in Table 3 below.

(6) Acid resistance

The cured films prepared from the compositions of Examples 1, 4 and 5 and Comparative Examples 1 and 4 were immersed in 7N aqua regia aqueous solution at 40°C for 180 seconds, washed with ultrapure water for 60 seconds, and dried. Thereafter, the rate of change in thickness and adhesion are evaluated, and when the rate of thickness change is 0~3% based on the thickness after heat curing, it is “excellent”, when it is more than 3 to 5%, it is “good”, and when it exceeds 5%, it is “defective”. And the adhesion was determined using the above (2) adhesion evaluation method, and the results are shown in Table 4 below.

(7) Stripper tolerance

The cured films prepared from the compositions of Examples 1, 4 and 5 and Comparative Examples 1 and 4 were immersed in a stripper at 60° C. for 180 seconds, washed with ultrapure water for 60 seconds, and dried. Thereafter, the rate of change in thickness and adhesion are evaluated, and when the rate of thickness change is 0~3% based on the thickness after heat curing, it is “excellent”, when it is more than 3 to 5%, it is “good”, and when it exceeds 5%, it is “defective”. And the adhesion was determined using the above (2) adhesion evaluation method, and the results are shown in Table 4 below.

(8) heat resistance

For the cured film prepared from the compositions of Examples 1, 4, 5 and Comparative Example 5, the weight change was measured while increasing the temperature from room temperature to 600°C at a rate of 10°C per minute through a thermogravimetric analyzer, If the temperature corresponding to 5% was 300°C or higher, it was determined as “excellent”, and if it was 300°C or less, it was determined as “defective”, and the results are shown in Table 5 below. In addition, the result of measuring the weight change by temperature using a thermogravimetric analyzer for the cured film of the composition of Example 1 is shown in FIG. 2.

(9) Outgassing

For the cured film prepared from the compositions of Examples 1, 4, 5 and Comparative Example 5, gas generated under the condition of 230°C 10min was collected and quantitatively analyzed through ATD GC-MS to take a graph and calculate the area of all peaks The total amount of outgassing was calculated. At this time, the total amount of outgassing of Comparative Example 5 was compared with the amount of outgassing of Examples 1, 4, and 5 based on 100%, and the results are shown in Table 5 and FIG. 3 below.

(10) Vickers Hardness

For the cured films prepared from the compositions of Examples 1, 6, 7 and Comparative Example 4, Vickers hardness was measured by pressing a Vickers indenter on the sample with a force of 10 mN for 5 seconds using a nanoindenter, and the results are as follows. It is shown in Table 6 and Figure 4.

[Table 3]

[Table 4]

[Table 5]

[Table 6]

From Tables 3 to 6, when forming an organic insulating film or an overcoat on a substrate, when the curable resin composition of the present invention is used, the degree of curing, adhesion, resolution, flexibility and film residual rate (Table 3), acid resistance and stripper resistance It can be seen that (Table 4), heat resistance and outgassing properties (Table 5), and Vickers hardness (Table 6) are all superior to those of Comparative Examples.

Claims (10)

(A) a copolymer represented by the following formula (1), a copolymer represented by the following formula (1-1), or a binder resin which is a combination thereof;
(B) a curing agent which is an anhydride of a substituted or unsubstituted alicyclic dicarboxylic acid having 6 to 12 carbon atoms;
(C) polyfunctional monomer; And
(D) an organic solvent; and,
Based on the total 100% by weight of the composition, the content of the binder resin is 5 to 35% by weight, the content of the curing agent is 1 to 5% by weight,
Curable resin composition:
[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or a methyl group; R ₆ is an alkylene group, a cycloalkylene group or an arylene group; R ₇ is hydrogen; R ₈ is an alkyl group, a cycloalkyl group or an aryl group including an epoxy group; x, y and z are the molar ratios of each polymerized unit, where x is 0.01 to 0.5, y is 0.01 to 0.4, and z is 0.01 to 0.8;
[Formula 1-1]

In Formula 1-1, R ₁ , R ₂ , R ₃ , R ₄ , R ₆ , R ₇ , R ₈ , x, y and z are as defined in Formula 1; R ₅ is hydrogen or a methyl group; R ₉ is one or more selected from the group consisting of an aromatic group, a carboxylic acid group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group and an alkoxy group; t is the molar ratio of the polymerization unit, and is 0.01 to 0.5. The curable resin composition according to claim 1, wherein the binder resin is a copolymer represented by Chemical Formula 1. The curable resin composition according to claim 1, wherein the binder resin is a copolymer represented by Formula 1-1. The curable resin composition of claim 1, wherein the curing agent is an acid anhydride represented by the following formula (2), an acid anhydride represented by the following formula (3), or a mixture thereof:
[Formula 2]

[Formula 3]

The curable resin composition according to claim 1, wherein the polyfunctional monomer is a bifunctional or trifunctional or higher (meth)acrylate. The curable resin composition according to claim 1, further comprising a photoinitiator. An electronic device comprising a cured layer formed from the curable resin composition according to any one of claims 1 to 6. The electronic device according to claim 7, wherein the cured layer is an organic insulating film layer or an overcoat layer. The electronic device according to claim 7, wherein the electronic device is a flexible organic light emitting device or a flexible touch panel. delete

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