KR20180044626A - Photosensitive resin composition, cured film prepared therefrom, and electronic device incorporating cured film - Google Patents

Abstract

Provided are a photosensitive resin composition, a cured film manufactured by curing the photosensitive resin composition, and an electronic device including the cured film, which comprises a siloxane copolymer formed by performing hydrolysis condensation reaction with 10-70 mol% of a compound represented by chemical formula 1, (R^1)_aSi(R^2)_4_-a, 5-50 mol% of a compound represented by chemical formula 2, R^3Si(R^4)_3, and 2-40 mol% of a compound represented by chemical formula 3, R^5R^6R^7Si-Y^1-SiR^8R^9R^10, based on total content of 100 mol% consisting of the compound represented by chemical formula 1, the compound represented by chemical formula 2, and the compound represented by chemical formula 3. In chemical formulas 1 to 3, R^1 to R^10, Y^1, and a are as defined in the specification. The present invention is to provide a photosensitive resin composition with excellent surface hardness, resolution, transmittance, and chemical resistance.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a cured film formed therefrom, and an electronic device having the cured film. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a photosensitive resin composition, a cured film obtained from the photosensitive resin composition, and an electronic device including the cured film.

In order to form a column spacer, a barrier rib, an overcoat, and a color resist, as well as a passivation insulating film, a gate insulating film, and a planarizing film for insulating between wirings disposed between the wirings in the TFT type liquid crystal display element or the integrated circuit element A negative photosensitive resin composition is mainly used.

The conventional negative photosensitive resin composition contains components such as a binder, a reactive unsaturated compound, a photopolymerization initiator, and a solvent, and the binder contains an olefinically unsaturated compound to manage the heat resistance of the interlayer insulating film. However, conventional olefinic unsaturated compounds can not be cured at low temperatures and thus can not be applied to a flexible display manufacturing process.

Accordingly, there is a demand for development of a binder and a curing system which can be easily synthesized while having a curing property at a low temperature which is considerably lower than that of a conventional organic film and is easy to supply and supply. However, a low temperature curable photosensitive resin composition The research on this is continuing.

One embodiment is to provide a photosensitive resin composition capable of forming a pattern by light irradiation and having excellent surface hardness, resolution, transmittance, and chemical resistance.

Another embodiment is to provide a cured film produced using the photosensitive resin composition.

Another embodiment is to provide an electronic device comprising the cured film.

One embodiment is a compound represented by the formula (I) in an amount of 10 mol% to 70 mol% based on 100 mol% of the total amount of the compound represented by the formula (1), the compound represented by the formula (2) , 5 to 50 mol% of a compound represented by the general formula (2), and 2 to 40 mol% of a compound represented by the general formula (3) are hydrolyzed and condensed to give a photosensitive resin composition comprising the siloxane copolymer :

[Chemical Formula 1]

(R ¹ ) _a Si (R ² ) _{4 -a}

In Formula 1,

R ¹ is selected from the group consisting of hydrogen, hydroxy, halogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkenyl group, Or an unsubstituted or substituted C2 to C30 alkynyl group, RO-, R (C = O) -, wherein R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, An unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C7 to C30 arylalkyl group), an epoxy group, a glycidoxy group, a C1 to C20 alkyl group substituted with an epoxy group, or a C1 to C20 alkyl group substituted with a glycidoxy group It is a combination thereof,

R ² is a C 1 to C 20 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof,

a is 0? a < 4,

(2)

R ³ Si (R ⁴ ) ₃

In Formula 2,

R ³ is a C1 to C20 alkyl group substituted with a substituted or unsubstituted C2 to C30 alkenyl group, (meth) acrylate group, (meth) acryloyloxy group, (meth) acrylate group, or (meth) acryloyloxy group Lt; RTI ID = 0.0 &gt; Cl-C20 &lt; / RTI &

R ⁴ is a C 1 to C 6 alkoxy group, a hydroxy group, a halogen, a carboxyl group,

(3)

R ⁵ R ⁶ R ⁷ Si-Y ¹ -SiR ⁸ R ⁹ R ¹⁰

In Formula 3,

Y ¹ represents a single bond, oxygen, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 A substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,

R ⁵ to R ¹⁰ are each independently a C 1 to C 6 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof.

In Formula 1, a may be 1.

The photosensitive resin composition contains 20 to 60 mol% of the compound represented by the general formula (1) based on 100 mol% of the total amount of the compound represented by the formula (1), the compound represented by the formula (2) %, A compound represented by the formula (2): 10 to 40 mol%, and a compound represented by the formula (3): 5 to 40 mol%.

The weight average molecular weight of the siloxane copolymer in terms of polystyrene may be 4,000 to 200,000.

The photosensitive resin composition may further comprise a photopolymerization initiator and a solvent.

The photopolymerization initiator may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the siloxane copolymer.

The solvent may be included in an amount of 10 parts by weight to 1,000 parts by weight based on 100 parts by weight of the siloxane copolymer.

The photosensitive resin composition may further comprise 1 to 50 parts by weight of a reactive unsaturated compound per 100 parts by weight of the siloxane copolymer.

Another embodiment provides a cured film prepared by curing the photosensitive resin composition.

The cured film exhibits a hole characteristic of less than 12 탆 at a temperature of 100 캜 or less, and a light transmittance at a wavelength of 400 nm can be 95% or more on a 2.0 탆 film thickness basis.

Another embodiment provides an electronic device comprising the cured film.

The photosensitive resin composition according to one embodiment is capable of forming a pattern by light irradiation, securing curing at a low temperature, and is excellent in surface hardness, resolution, transmittance, and chemical resistance.

In addition, the cured film prepared by curing the photosensitive resin composition according to one embodiment is excellent in low temperature curability, resolution, transmittance, and chemical resistance, and is suitable for use as an interlayer insulating film such as a flexible display.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group Quot; means a C3 to C20 heterocycloalkenyl group, "an aryl group" means a C6 to C20 aryl group, an "arylalkyl group" means a C6 to C20 arylalkyl group, Refers to a C 1 to C 20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, "heteroarylene group" refers to a C3 to C20 hetero Quot; means an arylene group, and the "alkoxysilylene group" means a C1 to C20 alkoxysilylene group.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamyl group, A C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S, and P is included in the formula.

&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.

"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.

Unless otherwise defined in the chemical formulas in this specification, when a chemical bond is not connected to a position to which a chemical bond is to be connected, it means that a hydrogen atom is bonded at the above position.

In addition, unless otherwise specified herein, "*" means the same or different atom or moiety connected to the formula.

Hereinafter, the photosensitive resin composition according to one embodiment will be described.

The photosensitive resin composition according to one embodiment contains, relative to 100 mol% of the total amount of the compound represented by the formula (1), the compound represented by the formula (2) and the compound represented by the formula (3), 10 moles of the compound represented by the formula % To 70 mol% of the compound represented by the formula (2), 5 to 50 mol% of the compound represented by the formula (2) and 2 to 40 mol% of the compound represented by the formula (3).

[Chemical Formula 1]

(R ¹ ) _a Si (R ² ) _{4 -a}

In Formula 1,

R ¹ is selected from the group consisting of hydrogen, hydroxy, halogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkenyl group, Or an unsubstituted or substituted C2 to C30 alkynyl group, RO-, R (C = O) -, wherein R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, An unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C7 to C30 arylalkyl group), an epoxy group, a glycidoxy group, a C1 to C20 alkyl group substituted with an epoxy group, or a C1 to C20 alkyl group substituted with a glycidoxy group It is a combination thereof,

R ² is a C 1 to C 20 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof,

a is 0? a < 4,

(2)

R ³ Si (R ⁴ ) ₃

In Formula 2,

R ³ is a C1 to C20 alkyl group substituted with a substituted or unsubstituted C2 to C30 alkenyl group, (meth) acrylate group, (meth) acryloyloxy group, (meth) acrylate group, or (meth) acryloyloxy group Lt; RTI ID = 0.0 &gt; Cl-C20 &lt; / RTI &

R ⁴ is a C 1 to C 6 alkoxy group, a hydroxy group, a halogen, a carboxyl group,

(3)

R ⁵ R ⁶ R ⁷ Si-Y ¹ -SiR ⁸ R ⁹ R ¹⁰

In Formula 3,

Y ¹ represents a single bond, oxygen, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 A substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,

R ⁵ to R ¹⁰ are each independently a C 1 to C 6 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof.

The interlayer insulating film applied to the flexible display is important for low temperature curability, chemical resistance, and etching resistance. In particular, poor cure at low temperatures can cause panel problems due to haze and outgas generation in the CVD (chemical vapor deposition) process of the top film and reduced etching resistance in the post process .

The photosensitive resin composition containing the siloxane copolymer according to one embodiment is capable of securing hardenability and hardness even at a low curing temperature of about 100 ° C or less and has a high hardness of the surface of the cured film and is excellent in transmittance, Chemical properties, outgassing, etc., and at the same time, it has remarkably improved the residual ratio of the sensitivity and thus it is possible to obtain reliability in the use as a flexible interlayer insulating film and to reduce the process cost such as shortening the process time Can be obtained.

In one example, the compound represented by the general formula (1) is used in an amount of 20 to 60 mol%, for example, 30 to 60 mol% based on 100 mol% of the total amount of the compounds represented by the general formulas For example, from 40 mol% to 55 mol%.

In one example, a in the above formula (1) may be 0 or 1, for example, a may be 1.

In one example, R ¹ in the above formula (1) may be a substituted or unsubstituted C1 to C6 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, for example, a substituted or unsubstituted C6 to C18 aryl group. For example, R ¹ may be a methyl group, an ethyl group or a phenyl group.

In one example, R ² in Formula 1 is a C 1 to C 6 alkoxy group, for example, a methoxy group or an ethoxy group.

In one example, the compound represented by Formula 2 is used in an amount of 10 mol% to 40 mol%, for example, 10 mol% to 30 mol% based on 100 mol% of the total amount of the compounds represented by Formulas 1 to 3, For example, from 15 mol% to 30 mol%.

In one embodiment, R ³ in Formula 2 is a (C1-C20) alkyl group substituted with a (meth) acrylate group, a (meth) acryloyloxy group, A C1 to C20 alkyl group, and may be, for example, a C1 to C6 alkyl group substituted with a (meth) acryloyloxy group. For example, R ³ may be a propyl group substituted with a (meth) acryloyloxy group.

In one example, R ⁴ in Formula 2 may be a C1 to C6 alkoxy group, for example, a methoxy group or an ethoxy group.

The acrylic copolymer itself or the acrylic copolymer and the silicone composition are used as the photosensitive resin composition in order to secure the curing at the low temperature and to realize the desired properties, but the acrylic copolymer itself has the desired hardness and chemical resistance It is difficult to ensure the transparency, and when the silicone composition is mixed, the durability is poor, the compatibility of the mixture is low, and it is difficult to ensure transparency.

The photosensitive resin composition according to one embodiment contains a silane compound represented by the above formula (2) having an acrylate group, and thus the siloxane copolymer synthesized through hydrolysis and condensation contains a silicon acrylate group, It is possible to realize a low-temperature organic insulating film material for a flexible display capable of realizing transparency and pattern characteristics while being curable.

In one example, the compound represented by the general formula (3) is used in an amount of 5 mol% to 40 mol%, for example, 10 mol% to 40 mol% based on 100 mol% of the total amount of the compounds represented by the general formulas (1) For example, from 15 mol% to 30 mol%.

In one example, Y ¹ in Formula 3 may be a substituted or unsubstituted C1 to C6 alkylene group, for example, an ethylene group, a propylene group, or a butylene group.

In one example, R ⁵ to R ¹⁰ in Formula 3 may each independently be a C1 to C6 alkoxy group, and may be, for example, a methoxy group or an ethoxy group.

In one example, all of R ⁵ to R ¹⁰ may be the same substituent.

The carbosilane compound represented by Formula 3 according to an embodiment provides cross-linking between siloxane copolymers, and Y ¹ existing between two silicon atoms contains a single bond or a hydrocarbon group having various carbon atom numbers and structures , Flexibility can be imparted in the siloxane copolymer.

The molecular weight of the siloxane copolymer formed by the hydrolysis condensation polymerization is preferably from 4,000 to 200,000, for example, from 4,000 to 200,000, in terms of a polystyrene standard sample measured by Gel Permeation Chromatography (GPC) For example from 4,000 to 15,000, such as from 4,000 to 10,000, such as from 4,000 to 8,000, for example, from 4,000 to 30,000, for example from 4,000 to 20,000, For example, from 5,000 to 8,000, for example from 6,000 to 8,000.

When the weight average molecular weight of the siloxane copolymer is within the above range, cracks do not occur on the surface during curing, and a preferable thickness of the cured film can be realized, and the surface planarization property can be improved while maintaining the viscosity required for coating.

The photosensitive resin composition according to one embodiment may further include a photopolymerization initiator. For example, the photopolymerization initiator is an initiator generally used in a photosensitive resin composition, for example, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, a oxime compound, or the like .

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -Bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like. .

Examples of the oxime compounds include O-acyloxime compounds, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-a-oxyamino-1-phenylpropan- Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione -1-one oxime-O-acetate and 1- (4-phenylsulfanylphenyl) -butan-1-one oxime- O-acetate and the like can be used.

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .

The photopolymerization initiator may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the siloxane copolymer. For example, the photopolymerization initiator may be included in an amount of 0.2 to 15 parts by weight, for example, 0.3 to 10 parts by weight, for example, 0.5 to 5 parts by weight, based on 100 parts by weight of the siloxane copolymer. When the content of the photopolymerization initiator is less than 0.1 part by weight, the effect of addition of the photopolymerization initiator is insignificant. When the content of the photopolymerization initiator is more than 20 parts by weight, the colorant concentration of the photosensitive resin composition may be increased or precipitated.

The photosensitive resin composition according to one embodiment may further include a solvent. The solvent has compatibility with the siloxane copolymer, the reactive unsaturated compound, and the photopolymerization initiator, and materials that do not react with these components can be used.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, 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- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among them, glycol ethers such as ethylene glycol monoethyl ether and diethylene glycol dimethyl ether are preferable in view of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be used in an amount of from 10 parts by weight to 1,000 parts by weight, for example, from 50 parts by weight to 800 parts by weight, for example, from 100 parts by weight to 500 parts by weight, for example, from 150 parts by weight To 400 parts by weight, and 200 parts by weight to 300 parts by weight. By including the solvent within the above range, uniform coating properties can be achieved by controlling the concentration of the photosensitive resin composition.

The photosensitive resin composition according to one embodiment may further contain a reactive unsaturated compound in addition to the photopolymerization initiator and the solvent. For example, the reactive unsaturated compound may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond as a monomer or oligomer generally used in a photosensitive resin composition.

Examples of commercially available monofunctional (meth) acrylates include Aronix M-101, M-111, M-114 (manufactured by Toagosei Chemical Industry Co., Ltd.), AKAYARAD TC-110S, (Manufactured by Nihon Kayaku Co., Ltd.), V-158 and V-2311 (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.). As the bifunctional (meth) acrylate, commercially available products such as Aronix M-210, Dong M-240, Dong M-6200 (manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD HDDA, Dong HX- R-604 (manufactured by Nihon Kayaku Co., Ltd.), V260, V312, and V335 HP (manufactured by Osaka Yukigagaku Kogyo Co., Ltd.). Examples of the (meth) acrylate having three or more functional groups include trimethylol propane triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, And M-8060, M-8060, M-8060, M-8030, M-8060, (Manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD TMPTA, copper DPCA-20, copper-30, copper-60, copper-120 (manufactured by Nihon Kayaku Co., Ltd.) -360, copper-GPT, copper-3PA, and copper-400 (manufactured by Osaka Yukigaya Chemical Co., Ltd.). These compounds may be used singly or in combination of two or more.

The content of the reactive unsaturated compound may be 1 to 50 parts by weight based on 100 parts by weight of the siloxane copolymer. For example, from 5 to 50 parts by weight, for example, from 10 to 40 parts by weight, for example, from 10 to 30 parts by weight, based on 100 parts by weight of the siloxane copolymer. When the reactive unsaturated compound is contained in an amount of less than 1 part by weight based on 100 parts by weight of the siloxane copolymer, the addition of the reactive unsaturated compound is insignificant and the reactive unsaturated compound is contained in an amount of more than 50 parts by weight based on 100 parts by weight of the siloxane copolymer The compatibility with the siloxane copolymer tends to be lowered, and the surface of the coating film may be roughened after the formation of the coating film.

The photosensitive resin composition according to one embodiment includes malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; Or a combination thereof.

For example, the photosensitive resin composition may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group or an epoxy group in order to improve adhesion with a substrate or the like.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanate propyltriethoxysilane,? -Glycine (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These may be used singly or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, the adhesion and storage stability are excellent.

The above-mentioned photosensitive resin composition may further contain a surfactant such as a fluorine-based surfactant for the purpose of improving coatability and preventing defect formation, if necessary.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; Mechacup F 142D ^® , copper F 172 ^® , copper F 173 ^® , copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray Silicone ^® (Note)社SH-28PA, the same -190 ^®, may be used a fluorine-containing surfactants commercially available under the name such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is contained within the above range, uniformity of coating is ensured, no staining occurs, and wetting of the glass substrate is excellent.

In addition, a certain amount of other additives such as antioxidants and stabilizers may be added to the photosensitive resin composition within a range that does not impair the physical properties.

The photosensitive resin composition may be a negative type photosensitive resin composition.

The photosensitive resin composition can be cured at a low temperature of 100 占 폚 or lower, for example, 90 占 폚 or lower, for example, 80 占 폚 to 85 占 폚.

Another embodiment provides a cured film produced using the above-described photosensitive resin composition. For example, the cured film may be an insulating film.

The cured film obtained by curing the siloxane copolymer formed by hydrolyzing and condensing the compound represented by the general formulas (1) to (3) according to one embodiment exhibits hole characteristics of less than 12 μm at a low temperature of 100 ° C. or lower, The light transmittance at a wavelength of 400 nm is 95% or more based on a thickness of 2.0 mu m.

When the hole characteristic is 12 占 퐉, it can be considered that the cured film obtained from the above-described composition has sufficiently high resolution.

The method of manufacturing the insulating film is as follows.

(1) Coating and Film Formation Step

The above-mentioned photosensitive resin composition is coated on a predetermined pretreated substrate by a method such as spin or slit coat method, roll coating method, screen printing method or applicator method to a desired thickness, for example, 1.2 to 3.0 탆 After coating, the coating is formed by removing the solvent by heating at a temperature of 70 ° C to 90 ° C for 1 minute to 10 minutes.

(2) Exposure step

After forming a mask of a predetermined type in order to form a pattern necessary for the obtained coating film, an active line of 200 nm to 500 nm is irradiated. As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used.

The exposure intensity may be, for example, 10 mW / cm ³ to 50 mW / cm ³ (depending on the 365 nm sensor), and the irradiation time may be 5 Second to one minute, but is not limited thereto.

(3) Development step

Following the above exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developing solution, so that only the exposed portion is left to form an image pattern.

(4) Post-treatment step

The image pattern obtained by the above-described development can be cured by heating again or by active ray irradiation or the like in order to obtain a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability.

By using the above-described photosensitive resin composition, excellent heat resistance and chemical resistance can be obtained even in a low temperature process.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

Example

Synthetic example  One: Siloxane  Copolymer production

A 500-ml three-necked flask was charged with 53.38 g (0.27 mol) of phenyltrimethoxysilane, 50.14 g (0.20 mol) of 3-methacryloxypropyltrimethoxysilane and 71.59 g (0.20 mol) of 1,2-bistriethoxysilylethane ) And 87.56 g of PGMEA. While stirring at room temperature, an aqueous hydrochloric acid solution in which 0.016 mol of 1 molar hydrochloric acid was dissolved in 36.38 g of water was added dropwise over 15 minutes. Thereafter, the flask was immersed in an oil bath at 70 DEG C and stirred for 250 minutes. Then, the temperature of the oil bath was cooled to 60 DEG C, and 50 parts by weight of PGMEA was further added based on 100 parts by weight of the reaction product. Thereafter, the reaction by-products such as methanol, ethanol, and water were evaporated using a vacuum pump and Deanstock to obtain a siloxane copolymer having a controlled molecular weight over time.

The polystyrene reduced weight average molecular weight (Mw) of the obtained siloxane copolymer was 7,600.

Synthetic example  2: Siloxane  Copolymer production

(0.40 mol) of phenyltrimethoxysilane, 50.14 g (0.20 mol) of 3-methacryloxypropyltrimethoxysilane, and 35.80 g (0.10 mol) of 1,2-bistriethoxysilylethane and 87.60 g of PGMEA A siloxane copolymer was obtained in the same manner as in Synthesis Example 1, except that the siloxane copolymer was added.

The polystyrene reduced weight average molecular weight (Mw) of the obtained siloxane copolymer was 4,000.

Synthetic example  3: Siloxane  Copolymer production

(0.32 mol) of phenyltrimethoxysilane, 37.61 g (0.15 mol) of 3-methacryloxypropyltrimethoxysilane, and 71.59 g (0.20 mol) of 1,2-bistriethoxysilylethane and 85.03 g of PGMEA The siloxane copolymer was prepared in the same manner as in Synthesis Example 1, except that it was added.

The polystyrene reduced weight average molecular weight (Mw) of the obtained siloxane copolymer was 6,800.

Synthetic example  4: Siloxane  Copolymer production

Into a 500 ml three-necked flask, 98.69 g (0.50 mol) of phenyltrimethoxysilane, 55.13 g (0.22 mol) of 3-methacryloxypropyltrimethoxysilane and 87.60 g of PGMEA were added and stirred at room temperature to 40.00 g An aqueous hydrochloric acid solution in which 0.018 mol of 1 molar hydrochloric acid was dissolved was added dropwise over 15 minutes. Thereafter, the flask was immersed in an oil bath at 70 DEG C and stirred for 250 minutes. Then, the temperature of the oil bath was cooled to 60 DEG C, and 50 parts by weight of PGMEA was further added based on 100 parts by weight of the reaction product. Then, the reaction by-products such as methanol, ethanol and water were evaporated using a vacuum pump and Deanstock to obtain a siloxane copolymer.

The polystyrene reduced weight average molecular weight (Mw) of the obtained siloxane copolymer was 1,300.

Synthetic example  5: Siloxane  Copolymer production

91.25 g (0.67 mol) of methyltrimethoxysilane, 71.30 g (0.29 mol) of 3-methacryloxypropyltrimethoxysilane and 81.28 g of PGMEA were added to a 500-ml three-necked flask, and while stirring at room temperature, 51.74 g An aqueous hydrochloric acid solution in which 0.019 mol of 1 molar hydrochloric acid was dissolved was added dropwise over 15 minutes. Thereafter, the flask was immersed in an oil bath at 70 DEG C and stirred for 250 minutes. Then, the temperature of the oil bath was cooled to 60 DEG C, and 50 parts by weight of PGMEA was further added based on 100 parts by weight of the reaction product. Then, the reaction by-products such as methanol, ethanol and water were evaporated using a vacuum pump and Deanstock to obtain a siloxane copolymer.

The weight average molecular weight (Mw) of the obtained siloxane copolymer in terms of polystyrene was 120,000.

The compositions and molecular weights of the siloxane copolymer solutions prepared in Synthesis Examples 1 to 5 were summarized in Table 1 below.

Phenyl
Trimethoxysilane
(mole%) methyl
Trimethoxysilane
(mole%) 3-methacryloxy
profile
Trimethoxysilane
(mole%) 1,2-bis
Triethoxysilylethane
(mole%) Molecular Weight
(g / mol) Synthesis Example 1 40 - 30 30 7,600 Synthesis Example 2 55 - 30 15 4,000 Synthesis Example 3 48 - 22 30 6,800 Synthesis Example 4 70 - 30 0 1,300 Synthesis Example 5 - 70 30 0 12,000

Example  1 to Example  3 and Comparative Example  1 to Comparative Example  3: Preparation of Photosensitive Resin Composition

The siloxane copolymer prepared in Synthesis Examples 1 to 5 and the components described below were respectively mixed in the compositions shown in Table 2 and dissolved in diethylene glycol dimethyl ether to have a solid concentration of 30% Mu] m of Millipore filter to prepare the photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 4.

Acrylic copolymer

RY-35-1 (SHOWA DENCO; methacrylic acid / benzyl methacrylate / methylbenzyl acrylate copolymer, weight average molecular weight 15,800)

The reactive unsaturated compound

Dipentaerythritol hexaacrylate (Nippon Kayaku)

Light curing Initiator

IGACURE OXE01 (BASF)

menstruum

Diethylene glycol dimethyl ether

Siloxane copolymer Acrylic copolymer The reactive unsaturated compound Light curing
Initiator menstruum Kinds content Example 1 Synthesis Example 1 24.5 - 5.0 0.5 70 Example 2 Synthesis Example 2 24.5 - 5.0 0.5 70 Example 3 Synthesis Example 3 24.5 - 5.0 0.5 70 Comparative Example 1 Synthesis Example 4 23.7 - 6.8 0.5 70 Comparative Example 2 Synthesis Example 5 20.5 - 9.0 0.5 70 Comparative Example 3 - 24.5 5.0 0.5 70

(In Table 2, the units are all% by weight.)

Cured film  Manufacturing and Evaluation

(1) Evaluation of pencil hardness

The resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 3 were coated on a glass substrate using a spin coater and then pre-coated on a hot plate at 85 占 폚 for 2 minutes and 30 seconds. -bake to form a film. The obtained film was irradiated with ultraviolet rays using a predetermined pattern mask, developed with an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide at 25 DEG C for 65 seconds, washed with ultrapure water for 60 seconds, and then blown dry with compressed air. The film thus formed was cured in an oven at 85 캜 for 60 minutes to obtain a photoresist film. The pencil hardness of the formed photoresist film was measured at room temperature using a pencil hardness tester KP-M5000M (Maker: Kipae E & T) based on ASTM D3363 test standard, and the results are shown in Table 3 below.

(2) Sensitivity evaluation

The photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were coated on a glass substrate using a spin coater and then hot-plate coated at 85 DEG C for 2 minutes and 30 seconds To form a film. The obtained film was irradiated with ultraviolet rays using a predetermined pattern mask, developed with an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide at 25 DEG C for 65 seconds, washed with ultrapure water for 60 seconds, and then blown dry with compressed air. At this time, the hole pattern of 10 mu m was formed to have a width of 1: 1, and the exposure amount (mW / cm3, hereinafter referred to as the optimum exposure amount) at 365 nm realized at 10 mu m was calculated with sensitivity sensitivity, (Exposure apparatus: Proximity exposure system, UX-1200SM-AKS02 (USHIO Inc.)).

(3) Evaluation of resolution

The minimum hole pattern dimension at the optimum exposure dose was evaluated by resolution and is shown in Table 3 below.

(4) Chemical resistance evaluation

After the initial thickness of the formed photoresist film was measured, it was allowed to stand at 60 DEG C for 3 minutes in NMP solvent, followed by cleaning with ultrapure water for 30 seconds, followed by blowing with compressed air to dryness. After that, the thickness was re-measured (Alpha-step, Surface profiler, KLA Tencor), and the chemical resistance was confirmed through the thickness change ratio. The results are shown in Table 3 below.

(5) Light transmittance  evaluation

First, using MultiSpec-1500 (SHIMADZU Corporation), the light transmittance of only the glass substrate was measured, and this ultraviolet visible absorption spectrum was taken as a reference. Subsequently, a 2.0 μm-thick cured film of the composition was formed on a glass substrate. The sample was measured with a single beam to determine a light transmittance of 400 nm per 1 μm and a light transmittance of the cured film, The results are shown in Table 3 below.

Example
One Example
2 Example
3 Comparative Example
One Comparative Example
2 Comparative Example
3 Pencil hardness
(H) 4 2 2 2 5 One Sensitivity (mJ) 35 30 35 15 30 35 resolution
(탆) 8 7 9 12 18 8 Chemical Resistance (%) 101 99 99 98 99 64 Permeability (%) 98 99 98 94 92 98

Referring to Table 3, according to one embodiment, a siloxane copolymer prepared by hydrolysis and condensation polymerization of a compound represented by the formula (1), a compound represented by the formula (2) and a compound represented by the formula (3) It can be seen that a cured film having a high surface hardness and resolution and excellent in transmittance and chemical resistance can be obtained even when the photosensitive resin composition is cured at 85 캜.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention. It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (12)

(1) to 70% by mole of a compound represented by the formula (1), (2) a compound represented by the formula (2), and a compound represented by the formula A siloxane copolymer formed by hydrolysis and condensation of 5 to 50 mol% of a compound to be displayed, and 2 to 40 mol% of a compound of formula (3)
[Chemical Formula 1]
(R ¹ ) _a Si (R ² ) _{4 -a}
In Formula 1,
R ¹ is selected from the group consisting of hydrogen, hydroxy, halogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkenyl group, Or an unsubstituted or substituted C2 to C30 alkynyl group, RO-, R (C = O) -, wherein R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, An unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C7 to C30 arylalkyl group), an epoxy group, a glycidoxy group, a C1 to C20 alkyl group substituted with an epoxy group, or a C1 to C20 alkyl group substituted with a glycidoxy group It is a combination thereof,
R ² is a C 1 to C 20 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof,
a is 0? a < 4,
(2)
R ³ Si (R ⁴ ) ₃
In Formula 2,
R ³ is a C1 to C20 alkyl group substituted with a substituted or unsubstituted C2 to C30 alkenyl group, (meth) acrylate group, (meth) acryloyloxy group, (meth) acrylate group, or (meth) acryloyloxy group Lt; RTI ID = 0.0 &gt; Cl-C20 &lt; / RTI &
R ⁴ is a C 1 to C 6 alkoxy group, a hydroxy group, a halogen, a carboxyl group,
(3)
R ⁵ R ⁶ R ⁷ Si-Y ¹ -SiR ⁸ R ⁹ R ¹⁰
In Formula 3,
Y ¹ represents a single bond, oxygen, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 A substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,
R ⁵ to R ¹⁰ are each independently a C 1 to C 6 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof. The method of claim 1,
, 20 to 60 mol% of a compound represented by the general formula (1), 2 to 60 mol% of a compound represented by the general formula (1), and the compound represented by the general formula A siloxane copolymer formed by hydrolysis and condensation of 10 to 40 mol% of a compound to be displayed, and 5 to 40 mol% of a compound of formula (3). The method of claim 1,
Wherein R ¹ is a substituted or unsubstituted C 1 to C 6 alkyl group or a substituted or unsubstituted C 6 to C 30 aryl group, and R ² is a C 1 to C 6 alkoxy group. The method of claim 1,
R ³ in Formula 2 is a C1 to C20 alkyl group substituted with a (meth) acrylate group, a (meth) acryloyloxy group, a (meth) acrylate group, or a C1 to C20 alkyl group substituted with a (meth) acryloyloxy group And R &lt; ⁴ &gt; is a C1 to C6 alkoxy group. The method of claim 1,
Y ¹ in Formula 3 is a substituted or unsubstituted C1 to C6 alkylene group and R ⁵ to R ¹⁰ are a C1 to C6 alkoxy group. The method of claim 1,
Wherein the siloxane copolymer has a polystyrene reduced weight average molecular weight of 4,000 to 200,000. The method of claim 1,
Wherein the photosensitive resin composition further comprises a photopolymerization initiator and a solvent. 8. The method of claim 7,
Wherein the photosensitive resin composition comprises 0.1 to 20 parts by weight of the photopolymerization initiator and 10 to 1,000 parts by weight of the solvent based on 100 parts by weight of the siloxane copolymer. 8. The method of claim 7,
Wherein the photosensitive resin composition further comprises 1 to 50 parts by weight of a reactive unsaturated compound per 100 parts by weight of the siloxane copolymer. A cured film produced by curing the photosensitive resin composition of any one of claims 1 to 9. 11. The method of claim 10,
Wherein the cured film exhibits hole characteristics less than 12 占 퐉 at a temperature of 100 占 폚 or less and has a light transmittance of 95% or more at a wavelength of 400 nm based on a 2.0 占 퐉 film thickness. An electronic device comprising a cured film according to claim 10.