KR101319493B1 - A photosensitive composition And insulation layer prepared by the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition and an insulating film produced therefrom.
The photosensitive resin composition of this invention is a copolymer binder formed including an unsaturated carboxylic acid monomer, an epoxy-group containing unsaturated compound monomer, and an olefinic monomer; Quinone diazide photosensitizers; Mixtures of anhydride curing agents and polyacid curing agents; And organic solvents. The insulating film made of the photosensitive resin composition of the present invention is excellent in transmittance, flatness, pattern properties, heat resistance, adhesion to metals and inorganic materials, UV transmittance, residual film rate, pattern stability, mechanical properties and the like.

Description

A photosensitive composition And insulation layer prepared by the same}

The present invention relates to a photosensitive resin composition and an insulating film produced therefrom. More specifically, the present invention relates to a photosensitive resin composition that can be used to manufacture insulating films used in various display devices.

Recently, as the manufacturing technology of electronic products such as flat panel display devices such as liquid crystal display devices and touch screen devices is developed, miniaturization and thinning of products are required. In order to miniaturize and thin a product, the degree of integration of the internal device of the product is essentially increased, and accordingly, the performance improvement of the interlayer insulating film in the device is required.

Currently, inorganic insulating films and organic insulating films have been introduced as insulating films.

Among these, the inorganic insulating layer uses an inorganic layer formed through a deposition process as an insulating layer. However, the deposition process is an expensive process and causes an increase in manufacturing cost.

As the organic insulating film, a resin layer formed by using the organic photosensitive resin composition is used as the insulating film. The organic photosensitive resin composition can easily form a thin film by a spin coating process, thereby solving the problem of the inorganic insulating film.

However, organic insulating films have a disadvantage in that mechanical properties such as hardness are relatively weaker than inorganic insulating films.

Accordingly, an object of the present invention is to provide a photosensitive resin composition for low temperature curing.

Another object of the present invention is to provide an insulating film made of the photosensitive resin according to the present invention.

In addition, another object of the present invention is to provide an insulating film having excellent mechanical properties according to the present invention.

In order to solve the above problems, the present invention is a copolymer binder formed by including an unsaturated carboxylic acid monomer, an epoxy group-containing unsaturated compound monomer and an olefin monomer; Quinone diazide photosensitizers; Mixtures of anhydride curing agents and polyacid curing agents; And it provides a photosensitive resin composition comprising an organic solvent.

Unsaturated carboxylic acid monomer according to the present invention is acrylic acid; Methacrylic acid; Crotonic acid; Maleic acid; Fumaric acid; Citraconic acid; Mesaconic acid; Itaconic acid; Each anhydride of the fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Succinic mono [2- (meth) acryloyloxyethyl]; Phthalic acid mono [2- (meth) acryloyloxyethyl]; And ω-carboxypolycaprolactone mono (meth) acrylate, or a mixture of two or more thereof.

The epoxy group-containing unsaturated compound monomer according to the present invention is glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, Acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxy Heptyl, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, and p-vinylbenzylglycidylether can be any one selected from the group consisting of or a mixture of two or more thereof.

The olefinic monomers according to the present invention are alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methyl acrylate, Isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyl oxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2 -Methylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentanyloxyethyl acrylate, isobornyl acrylate, phenyl methacrylate, benzyl methacrylate, phenyl acrylate, benzyl acrylate, diethyl maleate, fumaric acid Diethyl, diethyl itaconate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid It may be any one selected from the group consisting of vinyl, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene or a mixture of two or more thereof.

The quinone diazide-based photosensitive agent according to the present invention consists of 1,2-quinone diazide-4-sulfonic acid ester, 1,2-quinone diazide-5-sulfonic acid ester and 1,2-quinone diazide-6-sulfonic acid ester It may be any one selected from the group or a mixture of two or more thereof.

The anhydride curing agent according to the present invention may be any one selected from the group consisting of dodecynyl succinic anhydride, methyltetrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnadic acid anhydride, or a mixture of two or more thereof.

The polyacid curing agent according to the present invention is 1,3-acetone dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, benzyl malonic acid, biphenyl-4,4-dicarboxylic acid , 2,2-bipyridine-4,4-dicarboxylic acid and trimellitic acid may be any one or a mixture of two or more thereof.

The organic solvent according to the present invention is ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, propylene glycol methyl Ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone , Dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme (Diglyme), tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, Ethylene glycol ethyl ether, dipropylene glycol may be one or a mixture of two or more of those selected from ether, toluene, xylene, hexane, the group consisting of heptane and octane.

The photosensitive resin composition of the present invention may be used to manufacture an insulating film of a display device, the insulating film according to the present invention has a Young's modulus of 5.9 GPa to 7.0 GPa and a hardness of 0.33 GPa to 0.50 GPa desirable.

The insulating film made of the photosensitive resin composition of the present invention not only has excellent transmittance and flatness, but also excellent pattern characteristics and mechanical properties.

Therefore, the insulating film of the present invention can be applied as a photoresist with improved strength and hardness, and can be given a degree of curing so as to secure product properties even at low temperatures (130 to 180 ° C.). The present invention can also be applied to paper and flexible display devices.

In addition, the insulating film of the present invention is also excellent in heat resistance, adhesion to metals and inorganic materials, UV transmittance, residual film rate and pattern stability.

Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

As described above, the present invention is a copolymer binder formed by including an unsaturated carboxylic acid monomer, an epoxy group-containing unsaturated compound monomer and an olefin monomer; Quinone diazide photosensitizers; Mixtures of anhydride curing agents and polyacid curing agents; And it provides a photosensitive resin composition comprising an organic solvent, and when preparing an insulating film with the photosensitive resin composition according to the present invention, the basic characteristics that the insulating film should have transmittance, heat resistance, adhesion to metal and inorganic materials, UV transmittance, residual film rate, In addition to excellent pattern stability and the like, an insulating film excellent in mechanical properties such as strength and hardness, which is a weak point of the conventional organic insulating film, can be obtained.

In the photosensitive resin composition of this invention, the said unsaturated carboxylic acid monomer is monocarboxylic acid, such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Anhydrides of the dicarboxylic acids; Mono [(meth) acryloyloxyalkyl] esters of bivalent or more polyvalent carboxylic acids, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ; Mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate, may be used alone or in combination of two or more thereof. Preferably, acrylic acid, methacrylic acid, maleic anhydride can be used individually or in mixture of 2 or more types, respectively.

The unsaturated carboxylic acid monomer according to the present invention may be used in 5 to 40 parts by weight, more preferably 5 to 25 parts by weight based on 100 parts by weight of the total monomer used in the formation of the copolymer binder. When the content is less than 5 parts by weight, there is a problem that it is difficult to dissolve in the aqueous alkali solution, when it exceeds 40 parts by weight, solubility in the aqueous alkali solution is too large, the development adhesive strength may be lowered.

In the photosensitive resin composition of this invention, the said epoxy-group containing unsaturated compound monomer is glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, alpha-n- Glycidyl butyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, (alpha)-ethylacrylic acid -6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like can be used alone or in combination of two or more thereof. Preferably, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Each can be used individually or in mixture of 2 or more types.

The epoxy group-containing unsaturated compound monomer according to the present invention may be used in 5 to 70 parts by weight, more preferably 5 to 50 parts by weight relative to 100 parts by weight of the total monomer used in the formation of the copolymer binder. If the content is less than 5 parts by weight, there is a problem that the heat resistance of the resulting pattern is lowered. If the content is more than 70 parts by weight, the storage stability of the copolymer is lowered and the pattern taper angle is too high.

In the photosensitive resin composition of the present invention, the olefin monomer is alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, etc. ester; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cyclic alkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate and isoboroyl methacrylate; Acrylic cyclic alkyl esters such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentanyloxyethyl acrylate and isobornyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid; Hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; Styrene; ? -methyl styrene; m-methylstyrene; p-methylstyrene; Vinyl toluene; p-methoxystyrene; Acrylonitrile; Methacrylonitrile; Vinyl chloride; Vinylidene chloride; Acrylamide; Methacrylamide; Vinyl acetate; 1,3-butadiene; Isoprene; 2,3-dimethyl-1,3-butadiene etc. can be used individually or in mixture of 2 or more types, respectively.

The olefin monomer according to the present invention may be used in 30 to 90 parts by weight, more preferably 30 to 60 parts by weight relative to 100 parts by weight of the total monomer used in the formation of the copolymer binder. If the content is less than 30 parts by weight, there is a problem that the degree of photocuring of the copolymer is lowered. If the content is more than 90 parts by weight, the copolymer is difficult to be dissolved in an aqueous alkali solution.

According to the present invention, the copolymer binder formed by using the monomers may use a polystyrene reduced weight average molecular weight (Mw) of 5,000 to 500,000, preferably 8,000 to 20,000. If Mw is less than 5,000, chemical resistance and heat resistance of the formed insulating film are reduced, and if it exceeds 500,000, adhesiveness with the substrate may be lowered.

Quinone diazide-based photosensitizers according to the present invention include 1,2-quinonediazide-4-sulfonic acid esters, 1,2-quinonediazide-5-sulfonic acid esters, 1,2-quinonediazide-6-sulfonic acid esters, and the like. Can be used individually or in mixture of 2 or more types, respectively.

The quinone diazide-based photosensitive agent is preferably included in 5 to 50 parts by weight, more preferably 10 to 35 parts by weight relative to 100 parts by weight of the solid content of the copolymer binder. If the content is less than 5 parts by weight, there is a problem in that the contrast of the pattern is low because the difference in solubility in the alkaline aqueous solution is not large before and after exposure, and if the content is more than 50 parts by weight, the transmittance of the display panel insulating film formed from the photosensitive resin composition is poor. have.

In the photosensitive resin composition of this invention, the hardening | curing agent uses the mixture of anhydride type hardening | curing agent and a polyacid-type hardening | curing agent.

The anhydride-based curing agent according to the present invention may be used alone or in combination of two or more of dodecynyl succinic anhydride, methyltetraphthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, etc., preferably methylna Dixic anhydride can be used.

In addition, the polyacid curing agent according to the present invention is 1,3-acetone dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, benzyl malonic acid, biphenyl-4, 4-dicarboxylic acid, 2,2-bipyridine-4,4-dicarboxylic acid, trimellitic acid, and the like can be used alone or in combination of two or more thereof, preferably trimellitic acid can be used.

The curing agent mixture according to the present invention may be used in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the total photosensitive resin composition. If the content is less than 0.01 parts by weight does not impart a sufficient degree of cure to the thin film, the physical properties are lowered, if more than 10 parts by weight of the thin film is too stiff to reduce the development characteristics, particles may be formed by reducing the solubility.

In addition, preferably, the anhydride curing agent and the polyacid curing agent may be mixed and used in a ratio of 1: 1 to 1:10. By adjusting the mixing ratio, an appropriate taper angle, flow characteristics and mechanical properties can be imparted, and an appropriate taper angle, flow characteristics, and mechanical properties can be obtained in the mixing range.

In addition, when used with PGMEA and MEC, which are general purpose solvents for LCD display compositions, the curing agent according to the present invention preferably has 1 to 6 functional groups so as to have a suitable solubility.

The organic solvent according to the present invention is ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy in consideration of compatibility with binder resins, photosensitizers and curing agents, etc. Propionate (EEP), ethyl lactate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene Glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butylo Lactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, A solvent in which methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, octane, and the like are respectively used alone or in combination of two or more thereof. Can be used.

The solvent may be used in an amount of 20 parts by weight to 120 parts by weight, and more preferably 50 to 90 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin composition. If the content is less than 20 parts by weight, there may be a problem in the storage stability of the photosensitive resin composition, and if it exceeds 120 parts by weight, the viscosity of the resulting photosensitive resin composition is too low. It may be difficult to form a film.

The photosensitive resin composition of this invention can be usefully used for the insulating film for display devices. The insulating film according to the present invention preferably has a Young's modulus of 5.9 GPa to 7.0 GPa and a hardness of 0.33 GPa to 0.50 GPa.

If the modulus of elasticity is less than 5.9 GPa, shrinkage and fracture may occur when external pressure is applied in the process, and if it exceeds 7.0 GPa, cracks may occur on the film due to excessive stiffness. For the same reason, the hardness in the range of 0.33 GPa to 0.50 GPa ensures good mechanical properties of the insulating film.

Especially preferably, the modulus of elasticity is 6.0 GPa to 6.5 GPa and the hardness is 0.33 GPa to 0.40 GPa. The insulating film for a display panel of the present invention is more preferable when the elastic modulus and hardness are within the above range because the desired pattern line size can be secured without too high or low taper angle.

Moreover, it is preferable that the photosensitive resin composition of this invention is 50 to 95% of hardening degree. When the degree of cure is less than 50%, the cure does not occur completely. If the degree of cure exceeds 95%, the taper angle is too large and developability is low.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Synthetic example

2 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 35 parts by weight of glycidyl methacrylate, 54 parts by weight of methyl methacrylate, and methacrylic acid in a flask equipped with a cooling tube and a stirrer. 7 parts by weight and 140 parts by weight of methoxyethylcarbitol were added, followed by nitrogen substitution, followed by slow stirring. The reaction solution was heated to 65 ° C. to prepare a polymer solution containing a binder resin copolymer while maintaining this temperature for 5 hours, and then 2 parts by weight of a polymerization terminator was added to terminate the reaction. The resulting copolymer had a dispersion degree of 2.3, a weight average molecular weight of 11,000 g / mol, and a solid content concentration of 32.5%. Hereinafter, the copolymer prepared above will be referred to as copolymer A.

Example 1

The copolymer A, 18 parts by weight of 1,2-naphthoquinone diazide as the photosensitizer to 100 parts by weight of the solid content of the copolymer A, 1 part by weight of trimellitic acid as the curing agent to 100 parts by weight of the solid content of the copolymer A and methyl Nadic acid anhydride was mixed with 1 part by weight based on 100 parts by weight of solids of Copolymer A. Thereafter, the above components were dissolved in methoxyethylcarbitol such that the solid content concentration of the photosensitive composition solution was 29% by weight, and filtered through a Millipore filter having a pore size of 0.45 um to prepare a photosensitive resin composition .

Example  2

A composition was prepared in the same manner as in Example 1, except that 3 parts by weight of trimellitic acid was used.

Example 3

Except that 5 parts by weight of trimellitic acid was used to prepare a composition in the same manner as in Example 1.

Comparative Example 1

The composition was prepared in the same manner as in Example 1 except that no curing agent was used.

Comparative Example 2

A composition was prepared in the same manner as in Example 1, except that trimellitic acid was not used.

Comparative Example 3

The composition was prepared in the same manner as in Example 1 except that methylnadic acid anhydride was not used.

Comparative Example 4

The composition was prepared in the same manner as in Example 1, except that trimellitic acid and methylnadic acid anhydride were not used, and 2 parts by weight of diethyl triamine, an amine curing agent, was used.

Test Example

The photosensitive resin compositions prepared in Examples and Comparative Examples were spin coated on a substrate, and then prebaked at 90 ° C. for 150 seconds to form a film. Thereafter, the coating film was exposed to ultraviolet light having an intensity of 15 W / m ² for 13 seconds at a wavelength of 365 nm through a mask having a predetermined pattern in air, followed by 80 ° C. at 23 ° C. with an aqueous 0.4 wt% tetramethyl ammonium hydroxide solution. After developing for a second, it was washed with ultrapure water for 1 minute. The resultant was cured by heating at 130 ° C. for 1 hour in an oven to obtain a cured film pattern having a height of 3.5 μm (micrometer).

The following tests were performed on the prepared insulating film, and the results are shown in Table 1 below.

(1) degree of curing

Infrared spectral peaks of the insulating film patterns obtained in Examples and Comparative Examples were obtained through IR measurement. After normalizing the raw data on the carbonyl peak basis, the degree of curing of the insulating film pattern was obtained by integrating the area of the epoxy groups remaining without reacting even after the thermal curing step.

(2) Measurement of elastic modulus and hardness of thin film

The mechanical properties of the insulating film patterns obtained in Examples and Comparative Examples were evaluated by a nanoindenter (MTS) at a measurement temperature of 25 ° C. Using a diamond indenter with a Berkovich tip, the specimen surface was press-fitted to a constant load. The indentation depth versus indentation area obtained at this time was modeled by Oliver-Pharr's equation to obtain the strength and hardness of the insulating film pattern.

  The prepared organic thin film includes a polymer binder, thereby having inherent viscoelastic properties. Therefore, the modeling should be considered in consideration of the ratio of transverse strain / longitudinal strain occurring within the elastic limit of the sample, that is, Poisson's ratio. Based on the inventors' experience, the appropriate Poisson's ratio was determined to be 0.1 to 0.5. More preferably, 0.22 was used.

 Substrate effect occurs in the indentation experiment. Especially, in the case of thin film within a few um (micrometer), it is measured as the property value increases by the action of the support as the indentation depth increases. Therefore, 5-30% of the total thickness of the thin film was defined as the crystal range, and more preferably 10% of the film thickness was determined as the crystal range. If the thickness is within 5%, measurement errors may occur due to the surface tension of the substrate and the vibration of the tip module. In the thickness of 30% or more, inaccurate data is generated by the substrate effect.

(3) Residual film ratio  Measure:

The thickness ratio (%) of the film formed after spin coating the photosensitive resin composition obtained in Examples and Comparative Examples on the substrate, removing the solvent by pre-baking and removing the solvent by post-baking Measured.

Hardness (%) Modulus of elasticity (GPa) Hardness (GPa) Remaining film ratio (%) Example 1 68 6.34 0.34 92 Example 2 72 6.39 0.33 92 Example 3 76 6.40 0.34 93 Comparative Example 1 67 5.83 0.31 92 Comparative Example 2 Not measurable Not measurable Not measurable Not measurable Comparative Example 3 68 5.85 0.31 91 Comparative Example 4 Not measurable Not measurable Not measurable Not measurable

In the case of Comparative Example 2, after the development step, fine white particles were generated on the surface, and the strength and hardness did not improve evenly, and showed regional differences. Therefore, it was impossible to perform the test due to the solubility problem between the photosensitive composition components.

In addition, in the case of Comparative Example 4, the viscosity of the photosensitive composition liquid increased with time, which means that the storage stability is inferior. Therefore, it was confirmed that the amine curing agent was too reactive with the composition and could not be used for photoresist.

In addition, as shown in Table 1, it can be seen that the insulating films made of the compositions of Comparative Examples 1 and 3 do not satisfy the elastic modulus and hardness of the insulating film of the present invention. Specifically, since the insulating films made of the compositions of Comparative Examples 1 and 3 have an elastic modulus of less than 5.9 GPa (5.83 GPa, 5.85 GPa), shrinkage and breakage may occur when external pressure is applied in the process, and hardness is also seen. It turns out that it is less than 0.33 GPa which is the minimum value which the insulating film of this invention requires.

Therefore, it can be seen that the insulating film of the present invention is superior to the insulating film of Comparative Example 1 and Comparative Example 3.

Claims (9)

A copolymer binder formed of an unsaturated carboxylic acid monomer, an epoxy group-containing unsaturated compound monomer and an olefinic monomer;
Quinone diazide photosensitizers;
Mixtures of anhydride curing agents and polyacid curing agents; And
Organic solvent
As a photosensitive resin composition containing,
The mixture of the anhydride-based curing agent and the polyacid-based curing agent is contained in 0.01 to 10 parts by weight based on 100 parts by weight of the total photosensitive resin composition, the anhydride-based curing agent and the polyacid-based curing agent is mixed in a ratio of 1: 1 to 1:10 Composition. The method of claim 1,
The unsaturated carboxylic acid monomer is acrylic acid; Methacrylic acid; Crotonic acid; Maleic acid; Fumaric acid; Citraconic acid; Mesaconic acid; Itaconic acid; Each anhydride of the fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Succinic mono [2- (meth) acryloyloxyethyl]; Phthalic acid mono [2- (meth) acryloyloxyethyl]; And ω-carboxypolycaprolactone mono (meth) acrylate, or a mixture of two or more thereof selected from the group consisting of photosensitive resin compositions. The method of claim 1,
The epoxy group-containing unsaturated compound monomers are glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, acrylic acid-3 , 4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o A photosensitive resin composition, which is any one selected from the group consisting of -vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether, or a mixture of two or more thereof. The method of claim 1,
The olefin monomer is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate , 2-methylcyclohexyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl Acrylate, dicyclopentanyloxyethyl acrylate, isobornyl acrylate, phenyl methacrylate, benzyl methacrylate, phenyl acrylate, benzyl acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate, 2- Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, styrene, α-methylstyrene, m-methylstyrene, p-meth Styrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3- Photosensitive resin composition, characterized in that any one or a mixture of two or more selected from the group consisting of dimethyl-1,3-butadiene. The method of claim 1,
The quinone diazide-based photosensitizer is selected from the group consisting of 1,2-quinone diazide-4-sulfonic acid ester, 1,2-quinone diazide-5-sulfonic acid ester and 1,2-quinone diazide-6-sulfonic acid ester Photosensitive resin composition, characterized in that any one or a mixture of two or more thereof. The method of claim 1,
The anhydride-based curing agent is any one selected from the group consisting of dodecynyl succinic anhydride, methyltetraphthalic anhydride, methylhexahydrophthalic anhydride, and methylnadic acid anhydride, or a mixture of two or more thereof. . The method of claim 1,
The polyacid curing agent is 1,3-acetone dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, benzyl malonic acid, biphenyl-4,4-dicarboxylic acid, 2, Photosensitive resin composition, characterized in that any one selected from the group consisting of 2-bipyridine-4,4-dicarboxylic acid and trimellitic acid or a mixture of two or more thereof. An insulating film made of the photosensitive resin composition of any one of claims 1 to 7, wherein the Young's modulus is 5.9 GPa to 7.0 GPa and the hardness is 0.33 GPa to 0.50 GPa. A display device comprising the insulating film of claim 8.