KR20150044629A - Novel compound, photosensitive resin composition and light blocking layer using the same - Google Patents

Abstract

The present invention provides a photosensitive resin composition, a light-shielding layer using the same, and a color filter thereof. The photosensitive resin composition includes (A) a compound represented by chemical formula 1; (B) a pigment; (C) an initiator; (D) a binder resin; and (E) a solvent. (In chemical formula 1, the respective substituents are as defined in the specification.)

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, a photosensitive resin composition, and a light-shielding layer using the same. BACKGROUND OF THE INVENTION [0001]

The present invention relates to a novel compound and a photosensitive resin composition containing the same, a light-shielding layer using the photosensitive resin composition, and a color filter.

The liquid crystal display device includes a lower substrate on which a light-shielding layer, a color filter, and an ITO pixel electrode are formed; An active circuit composed of a liquid crystal layer, a thin film transistor, and a capacitor capacitor layer; And an upper substrate on which ITO pixel electrodes are formed.

The light-shielding layer serves to cut off light which is transmitted through the substrate other than the transparent pixel electrode in order to prevent the contrast caused by the light transmitted through the thin film transistor from deteriorating, and the colored layers of red, green, The main role is to transmit light of a specific wavelength to express color.

In the pigment dispersion method, a photopolymerizable composition containing a colorant is coated on a transparent substrate, a pattern of a pattern to be formed is exposed, and a non-exposed region is removed with a solvent And repeating a series of steps of thermosetting.

However, the photosensitive polyimide or phenol resin used in the pigment dispersion method has a high heat resistance, but has a low sensitivity and develops with an organic solvent. In addition, conventional systems using an azide compound as a photosensitizer have low sensitivity, poor heat resistance, and are subject to the influence of oxygen upon exposure.

On the other hand, conventional acrylic resins are excellent in heat resistance, shrinkage resistance, chemical resistance and the like, but tend to be inferior in sensitivity, developability, resolution, and adhesion. Further, in the case of the light-shielding layer, since the content of the black pigment is increased in order to meet the required optical density, the sensitivity, developability, resolution, and adhesion may be significantly deteriorated.

One embodiment is to provide a novel compound.

Another embodiment is to provide a photosensitive resin composition excellent in resolution and adhesion.

Another embodiment is to provide a light-shielding layer made using the photosensitive resin composition.

Another embodiment is to provide a color filter manufactured using the photosensitive resin composition.

An embodiment provides a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

L ¹ and L ² are each independently a single bond, a C1 to C12 alkylene group or a C1 to C12 arylene group,

R ⁵ is a hydrogen atom, a substituted or unsubstituted C1 to C12 alkyl group or a substituted or unsubstituted C1 to C12 aryl group,

o, p, and q are each independently an integer of 0 to 6,

Y ¹ to Y ³ each independently represent a substituted or unsubstituted C1 to C12 organic group containing an unsaturated bond.

Each of Y ¹ to Y ³ may independently be represented by the following formula (2).

(2)

In Formula 2,

R ⁶ is a hydrogen atom, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C2 to C6 alkenyl group, a substituted or unsubstituted C1 to C6 alkoxy group, or a cyano group.

(A) a compound represented by the above formula (1); (B) a pigment; (C) an initiator; (D) a binder resin; And (E) a solvent.

The photosensitive resin composition may further include a reactive unsaturated compound.

The binder resin may be a cardade resin.

The photosensitive resin composition comprises (A) 0.1 to 30% by weight of a compound represented by the formula (1); (B) 1 to 30% by weight of pigment; (C) 0.01 to 10% by weight of an initiator; (D) 1 to 30% by weight of a binder resin; And (E) solvent balance.

The reactive unsaturated compound may be at least one selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (Meth) may include an acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, or a combination thereof.

The initiator may include a photopolymerization initiator, a radical polymerization initiator, or a combination thereof.

The photosensitive resin composition may further comprise 0.01 to 20 parts by weight of an epoxy compound per 100 parts by weight of the photosensitive resin composition.

Another embodiment provides a light-shielding layer made using the photosensitive resin composition.

Another embodiment provides a color filter manufactured using the photosensitive resin composition.

Other aspects of the present invention are included in the following detailed description.

By including a novel compound, a photosensitive resin composition excellent in resolution and adhesiveness is provided, and thus can be usefully applied to a light shielding layer or the like.

1 is a ¹ H-NMR chart of a compound according to Preparation Example 1. FIG.

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.

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

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

Unless otherwise specified herein, an unsaturated bond includes not only multiple bonds between carbon-carbon atoms but also other molecules such as carbonyl bonds, azo bonds, and the like.

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

The compound according to one embodiment is represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

L ¹ and L ² are each independently a single bond, a C1 to C12 alkylene group or a C1 to C12 arylene group,

R ⁵ is a hydrogen atom, a substituted or unsubstituted C1 to C12 alkyl group or a substituted or unsubstituted C1 to C12 aryl group,

o, p, and q are each independently an integer of 0 to 6,

Y ¹ to Y ³ each independently represent a substituted or unsubstituted C1 to C12 organic group containing an unsaturated bond.

For example, R < ⁵ > may be a substituted or unsubstituted C1 to C10 alkyl group.

For example, each of Y ¹ to Y ³ may independently be represented by the following formula (2).

(2)

In Formula 2,

R ⁶ is a hydrogen atom, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C2 to C6 alkenyl group, a substituted or unsubstituted C1 to C6 alkoxy group, or a cyano group.

The photosensitive resin composition according to another embodiment includes (A) a compound represented by the above formula (1); (B) a pigment; (C) an initiator; (D) a binder resin; And (E) a solvent.

The compound represented by the above formula (1) not only improves adhesion to a substrate such as glass including a siloxane but also improves the bonding force with other organic compounds including unsaturated bonds, Can be implemented.

Each component will be described in detail below.

(A) a compound represented by the formula (1)

The photosensitive resin composition according to another embodiment includes the compound represented by the above formula (1).

Due to the compound represented by the formula (1), the adhesion between the photosensitive resin composition containing the compound and the substrate such as glass can be improved and the resolution can be improved.

Each of Y ¹ to Y ³ may independently be represented by the formula (2).

Y ¹ to Y ³ may be represented by the general formula (2). For example, the compound represented by Formula 1 may be an acrylic monomer.

The compound represented by Formula 1 may be contained in an amount of 0.1 to 30% by weight, for example, 0.5 to 20% by weight based on the total amount of the photosensitive resin composition. When the compound is contained within the above range, excellent sensitivity, developability, and adhesion can be obtained.

(B) Pigment

The above-mentioned pigments can be used both as organic pigments and as inorganic pigments.

The pigment may be a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, or the like.

Examples of the red pigment include C.I. Red pigment 254, C.I. Red pigment 255, C.I. Red pigment 264, C.I. Red pigment 270, C.I. Red pigment 272, C.I. Red pigment 177, C.I. Red pigment 89 and the like. Examples of the green pigment include C.I. Green pigment 36, C.I. Halogen-substituted copper phthalocyanine pigments such as green pigment 7 and the like. Examples of the blue pigments include C.I. Blue pigment 15: 6, C.I. Blue pigment 15, C.I. Blue pigment 15: 1, C.I. Blue pigment 15: 2, C.I. Blue pigment 15: 3, C.I. Blue pigment 15: 4, C.I. Blue pigment 15: 5, C.I. Blue pigment 16, and the like. Examples of the yellow pigments include C.I. Yellow pigments 139 and the like, C.I. Quinophthalone-based pigments such as yellow pigment 138 and the like, C.I. And yellow complex pigments such as yellow pigment 150 and the like. Examples of the black pigment include aniline black, perylene black, titanium black, and carbon black. These pigments can be used singly or in combination of two or more thereof, but are not limited to these examples.

Among them, the above-mentioned black pigment may be used in order to effectively cut off the light blocking layer. When the black pigment is used, it may be used in combination with a color correcting agent such as an anthraquinone pigment, a perylene pigment, a phthalocyanine pigment or an azo pigment.

A dispersant may be used together with the photosensitive resin composition to disperse the pigment. Specifically, the pigment may be surface-treated beforehand with a dispersant, or a dispersant may be added together with the pigment when the photosensitive resin composition is prepared.

As the dispersing agent, a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent and the like can be used. Specific examples of the dispersing agent include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid Salts, alkylamide alkylene oxide adducts, and alkylamines. These may be used singly or in combination of two or more.

DISPERBYK-161, DISPERBYK-160, DISPERBYK-161, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160 and DISPERBYK-160 of BYK Co., -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711 and PB821.

The dispersant may be contained in an amount of 0.1 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is contained within the above range, the dispersibility of the photosensitive resin composition is excellent, and therefore, the stability, developability and patternability of the light-shielding layer are excellent.

The pigment may be used by pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used in the pretreatment, the primary particle size of the pigment can be reduced.

The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be carried out at a temperature of 40 to 100 DEG C, and the filtration and washing may be performed by washing the inorganic salt with water, etc., followed by filtration.

Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. The wetting agent acts as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed to easily pulverize the pigment. Examples of the wetting agent include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and the like Alkylene glycol monoalkyl ethers; And alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol and the like. These may be used singly or in combination of two or more thereof.

The pigment after the kneading step may have an average particle diameter of 30 nm to 100 nm. When the average particle diameter of the pigment is within the above range, it is possible to effectively form a fine pattern with excellent heat resistance and light resistance.

The pigment dispersion may be contained in an amount of 1 to 30% by weight, for example, 2 to 20% by weight based on the total amount of the photosensitive resin composition. When the pigment is included in the above range, the color reproducibility is excellent and the pattern is excellent in hardenability and adhesion.

(C) Initiator

The initiator may be a photopolymerization initiator, a radical polymerization initiator, or a combination thereof.

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, Can be used.

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) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Piperonyl) -6-triazine, and 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine.

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- Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- (4-phenylsulfanylphenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- -Oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate and 1- (4-phenylsulfanylphenyl) 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 radical polymerization initiator may be a peroxide compound, an azobis compound, or the like.

Examples of the peroxide compound include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, and acetylacetone peroxide; Diacyl peroxides such as isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, and bis-3,5,5-trimethylhexanoyl peroxide; Hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide; Dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butyloxyisopropyl) Dialkyl peroxides such as esters; Alkyl peresters such as 2,4,4-trimethylpentyl peroxyphenoxyacetate,? -Cumyl peroxyneodecanoate, t-butyl peroxybenzoate and di-t-butyl peroxytrimethyl adipate; Di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis-4-t-butylcyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, acetylcyclohexylsulfonyl peroxide, t And percarbonates such as butyl peroxyaryl carbonate.

Examples of the azobis compound include 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis Azoisobutyrate), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), α, α'-azobis (isobutylnitrile) and 4,4'-azobis - cyanobalenoic acid), and the like.

The initiator may be used in combination with a photosensitizer that causes a chemical reaction by absorbing light to become excited 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 initiator may be included in an amount of 0.01 to 10% by weight, for example, 0.1 to 5% by weight based on the total amount of the photosensitive resin composition. When the initiator is contained within the above-described range, the pattern can be sufficiently cured during exposure in order to obtain excellent reliability, excellent in heat resistance, light resistance and chemical resistance, excellent in resolution and adhesion, It is possible to prevent the transmittance from being lowered.

(D) binder resin

The binder resin may be a cardade resin. When the binder resin is a cadmium-based resin, the photosensitive resin composition containing the binder resin is excellent in developability, has good sensitivity in photo-curing, and is excellent in fine pattern formation.

The binder resin may be represented by the following formula (3).

(3)

In Formula 3,

R ¹ And R ² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ⁷ R ⁸ , SiR ⁹ R ¹⁰ (wherein R ⁷ to R ¹⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) Or a linking group represented by the following formulas (3-1) to (3-11)

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

(In the above Formula 3-5,

R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH = CH ₂ , or a phenyl group.

[Chemical Formula 3-6]

[Chemical Formula 3-7]

[Chemical Formula 3-8]

[Chemical Formula 3-9]

[Chemical Formula 3-10]

[Formula 3-11]

Z ² is an acid anhydride residue or an acid anhydride residue,

m1 and m2 are each independently an integer of 0 to 4,

n is an integer of 1 to 30;

The weight average molecular weight of the binder resin may be 500 to 50,000 g / mol, such as 1,000 to 30,000 g / mol. When the weight average molecular weight of the binder resin is within the above range, pattern formation is good without residue during the production of the light-shielding layer, no loss of film thickness during development, and good patterns can be obtained.

The binder resin may include a functional group represented by the following formula (4) in at least one of the two terminals.

[Chemical Formula 4]

In Formula 4,

Z ³ may be represented by the following general formulas (4-1) to (4-7).

[Formula 4-1]

(Wherein R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group).

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

Wherein R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 allylamine group.

[Formula 4-6]

[Formula 4-7]

Examples of the binder resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, Anhydride compounds such as lyrenetetracarboxylic acid dianhydride, tetrahydrofuran tetracarboxylic acid dianhydride, and tetrahydrophthalic anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Propylene glycol methyl ethyl acetate, and N-methyl pyrrolidone; Phosphorus compounds such as triphenylphosphine; And an amine or an ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, or the like.

The binder resin may be contained in an amount of 1 to 30% by weight, for example, 3 to 20% by weight based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, excellent sensitivity, developability and adhesiveness can be obtained.

(E) Solvent

The solvent may be a binder resin, a reactive unsaturated compound to be described later, a material which is compatible with the pigment and the initiator but does not react with the initiator.

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 and ethylene glycol monoethyl 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 Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, And high boiling solvents such as ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among them, glycol ethers such as ethylene glycol monoethyl ether and the like are preferably used in consideration 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 methyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be included as a residual amount relative to the total amount of the photosensitive resin composition, specifically, 40 to 90% by weight. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability in the production of the light-shielding layer is excellent.

(F) Reactive unsaturated compound

The photosensitive resin composition may further include a reactive unsaturated compound.

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.

By having the ethylenically unsaturated double bond, the reactive unsaturated compound can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern formation step.

The reactive unsaturated compound may be, for example, at least one selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol moiety It may be a methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, or a combination thereof.

Examples of commercially available products of the above reactive unsaturated compounds are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The reactive unsaturated compound may be treated with an acid anhydride so as to give better developing properties.

The reactive unsaturated compound may be contained in an amount of 1 to 40% by weight, for example, 1 to 20% by weight based on the total amount of the photosensitive resin composition. When the reactive unsaturated compound is contained within the above range, the pattern formation process sufficiently cures upon exposure to light, thereby providing excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, and excellent resolution and adhesion.

(G) Other additives

The photosensitive resin composition may further include an epoxy compound to improve adhesion with the substrate.

Examples of the epoxy compound include a phenol novolak epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The epoxy compound may be included in an amount of 0.01 to 20 parts by weight, for example, 0.1 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is contained within the above range, the adhesiveness and storage stability are excellent.

The photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group in order to improve adhesion with a substrate.

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

The silane-based 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 for improving coatability and preventing defect formation if necessary.

Examples of the surfactants include, BM Chemie Corporation ^{BM-1000 ®, BM-1100} ® , and the like; Mecha Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; M. Sumitomo Co., Inc. Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Inc. Saffron S-112 ^®, the same S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; ^® Toray Silicone Co., Ltd.'s SH-28PA, copper -190 ^®, may be used copper ^® -193, fluorine-based surfactants and commercially available under the name, such as ^{SZ-6032 ®, SF-8428} ®.

The surfactant may be used in an amount of 0.001 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, coating uniformity is ensured, no staining occurs, and wetting of the glass substrate is excellent.

The photosensitive resin composition may contain a certain amount of other additives such as an antioxidant and a stabilizer within a range that does not impair the physical properties.

Another embodiment provides a light-shielding layer made using the above-described photosensitive resin composition. The method of manufacturing the light-shielding layer is as follows.

(1) Coating and Film Formation Step

The above-mentioned photosensitive resin composition is coated on a predetermined pretreated substrate to a desired thickness, for example, a thickness of 0.5 탆 to 25 탆 by a method such as spin, slit coat, roll coating, screen printing, or applicator After coating, the solvent is removed by heating at a temperature of 70 to 110 DEG C for 1 to 10 minutes to form a coating film.

(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 190 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, and the like can be used.

The exposure dose varies depending on the kind of each component of the above-mentioned black photosensitive resin composition, the blending amount, and the dried film thickness. For example, when a high-pressure mercury lamp is used, the exposure dose is 500 mJ / cm ² (By a 365 nm sensor).

(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, high insulation and optical density required for the light-shielding layer can be obtained.

Another embodiment provides a color filter manufactured using the above-described photosensitive resin composition.

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 )

(Preparation of new compound)

Manufacturing example  1: Preparation of new compounds

63 g of pentaerythritol triacrylate (Aldrich), 50 g of KBE-9007 (Showa Denko) and 0.1 g of dibutyl tin dilaurate (Aldrich) were added to the reactor, and the temperature was raised to 40 캜 and maintained for 16 hours. 5 was synthesized.

[Chemical Formula 5]

(Preparation of Pigment Dispersion)

Manufacturing example  2: Preparation of Red Pigment Dispersion

The reactor was charged with C.I. 4 g of DISPERBYK-163 (BYK), 3 g of acrylic acid / benzyl methacrylate copolymer (Miwon Supporter, NPR8000) and 78 g of propylene glycol methyl ethyl acetate were mixed, and the paint shaker and dispersed for 12 hours using a paint-shaker (Asada) to prepare a red pigment dispersion.

Manufacturing example  3: Preparation of black pigment dispersion

15 g of carbon black (VULCAN? XC72R, Cabot), 4 g of DISPERBYK-163 (BYK), 3 g of acrylic acid / benzyl methacrylate copolymer (Miwon Company, NPR8000) and 78 g of propylene glycol methyl ethyl acetate were mixed in a reactor, And dispersed using a paint-shaker (Asada) for 12 hours to prepare a black pigment dispersion.

(Preparation of photosensitive resin composition)

Example  1 to 4, Comparative Example  1 to Comparative Example  6

The photosensitive resin composition according to each of Examples 1 to 4 and Comparative Examples 1 to 6 was prepared with the compositions shown in the following Table 1 by using the following components.

Specifically, the initiator was dissolved in a solvent and stirred at room temperature for 2 hours. Then, the novel compound prepared in Preparation Example 1 and a binder resin (or a binder resin and a reactive unsaturated compound) were added thereto and stirred for 2 hours at room temperature Respectively. Then, the red pigment dispersion prepared in Production Example 2, the black pigment dispersion prepared in Production Example 3, and the silane coupling agent were added to the obtained reaction product and stirred at room temperature for 1 hour. Subsequently, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(A) A novel compound

As the acrylic monomer, the compound represented by the formula (5) prepared in Preparation Example 1 was used.

(B) Pigment dispersion

(B-1) The red pigment dispersion prepared in Preparation Example 2 was used. At this time, the solid content of the pigment is 15% by weight based on the total amount of the red pigment dispersion.

(B-2) The black pigment dispersion prepared in Preparation Example 3 was used. At this time, the pigment solid content is 15% by weight based on the total amount of the black pigment dispersion.

(C) Initiator

IRGACURE OXE02 from BASF was used.

(D) Binder resin

V259ME from NSCC was used.

(E) Solvent

Propylene glycol methyl ether acetate was used.

(F) Reactive unsaturated compound

(F-1) dipentaerythritol hexaacrylate manufactured by Nippon Catalyst Co., Ltd. was used.

(F-2) pentaerythritol tetraacrylate manufactured by Nippon Catalyst Co., Ltd. was used.

(G) Additive

As the silane coupling agent,? -Glycidoxypropyltrimethoxysilane (S-510 from Chisso) was used.

(Unit: wt%) Example Comparative Example One 2 3 4 One 2 3 4 5 6 (A) A novel compound 1.5 1.5 0.75 0.75 - - - - - - (B) Pigment dispersion (B-1) 40
(6 *) - 40
(6 *) - 40
(6 *) - 40
(6 *) - 40
(6 *) - (B-2) - 40
(6 *) - 40
(6 *) - 40
(6 *) - 40
(6 *) - 40
(6 *) (C) Initiator 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 (D) binder resin
(Solid content 50%) 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 (E) Solvent 50.8 50.8 50.8 50.8 50.8 50.8 50.8 50.8 50.8 50.8 (F) Reactive unsaturated compound (F-1) - - 0.75 0.75 1.5 1.5 0.75 0.75 - - (F-2) - - - - - - 0.75 0.75 1.5 1.5 (G) Additive 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

(* Represents the solid content of the pigment with respect to the total amount of (C-1) red pigment dispersion or (C-2) black pigment dispersion).

Evaluation 1: Evaluation of resolution

The photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 6 were coated on a glass plate having a size of 10 cm x 10 cm with a spin coater (Mikasa, Opticoat MS-A150) to a thickness of 1.3 탆, hot- baked at 80 ° C for 150 seconds and exposed at 50 mJ using a photomask with an exposure machine (HB-50110AA, Ushio). Subsequently, the resultant was developed with a 0.2 wt% aqueous solution of potassium hydroxide (KOH) using a developing machine (SVS, SSP-200) and hard-baked at 230 ° C for 30 minutes in an oven, Psalms were obtained. The patterns of the obtained glass specimens were observed with a CD (Critical Dimension) of a pattern having a thickness of 1.3 μm or more by an optical microscope, and samples having the finest linewidths were observed. The results are shown in Table 2 below.

Evaluation 2: Adhesion evaluation

The photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 6 were coated on a glass plate having a size of 10 cm x 10 cm with a spin coater (Mikasa, Opticoat MS-A150) to a thickness of 1.3 탆, hot- baked at 80 ° C for 150 seconds and exposed at 50 mJ using a photomask with an exposure machine (HB-50110AA, Ushio). Subsequently, the resultant was developed with a 0.2 wt% aqueous solution of potassium hydroxide (KOH) using a developing machine (SVS, SSP-200) and hard-baked at 230 ° C for 30 minutes in an oven, Psalms were obtained. The glass specimens thus prepared were cut into 2 cm * 2 cm, and the stud pins were fixed with a mount crip on the cut specimens. The specimens were heated at 150 ° C. for 30 minutes using an oven, Secure the stud pin and remove the mount crip. UTM (Hegewald & Peschke, Inspekt 10-1) was used to confirm the substrate adhesion. The results are shown in Table 2 below.

Minimum pattern size (resolution)
(탆) Substrate adhesion
(N) Example 1 5.6 241 Example 2 6.9 234 Example 3 4.3 256 Example 4 5.9 239 Comparative Example 1 7.3 205 Comparative Example 2 8.7 184 Comparative Example 3 7.7 196 Comparative Example 4 8.4 174 Comparative Example 5 8.0 181 Comparative Example 6 8.5 172

Through the above Table 2, it can be seen that the photosensitive resin compositions of Examples 1 to 4 prepared using the novel compounds represented by Chemical Formula 5 can realize a fine line width as compared with the photosensitive resin compositions of Comparative Examples 1 to 6, Also, it can be confirmed that it is high.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (12)

A compound represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
L ¹ and L ² are each independently a single bond, a C1 to C12 alkylene group or a C1 to C12 arylene group,
R ⁵ is a hydrogen atom, a substituted or unsubstituted C1 to C12 alkyl group or a substituted or unsubstituted C1 to C12 aryl group,
o, p, and q are each independently an integer of 0 to 6,
Y ¹ to Y ³ each independently represent a substituted or unsubstituted C1 to C12 organic group containing an unsaturated bond.
The method according to claim 1,
Y ¹ to Y ³ each independently represent a compound represented by the following formula (2):
(2)

In Formula 2,
R ⁶ is a hydrogen atom, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C2 to C6 alkenyl group, a substituted or unsubstituted C1 to C6 alkoxy group, or a cyano group.
(A) a compound represented by the following formula (1);
(B) a pigment;
(C) an initiator;
(D) a binder resin; And
(E) Solvent
: ≪ EMI ID =
[Chemical Formula 1]

In Formula 1,
L ¹ and L ² are each independently a single bond, a C1 to C12 alkylene group or a C1 to C12 arylene group,
R ⁵ is a hydrogen atom, a substituted or unsubstituted C1 to C12 alkyl group, a substituted or unsubstituted C1 to C12 aryl group,
o, p, and q are each independently an integer of 0 to 6,
Y ¹ to Y ³ each independently represent a substituted or unsubstituted C1 to C12 organic group containing an unsaturated bond.
The method of claim 3,
Y ¹ to Y ³ each independently represent a photosensitive resin composition represented by the following formula (2):
(2)

In Formula 2,
R ⁶ is a hydrogen atom, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C2 to C6 alkenyl group, a substituted or unsubstituted C1 to C6 alkoxy group, or a cyano group.
The method of claim 3,
Wherein the photosensitive resin composition further comprises a reactive unsaturated compound.
The method of claim 3,
Wherein the binder resin is a carded resin.
The method of claim 3,
The photosensitive resin composition
(A) 0.1 to 30% by weight of a compound represented by the formula (1);
(B) 1 to 30% by weight of pigment;
(C) 0.01 to 10% by weight of an initiator;
(D) 1 to 30% by weight of a binder resin; And
(E) Residue of solvent
Wherein the photosensitive resin composition is a photosensitive resin composition.
6. The method of claim 5,
The reactive unsaturated compound may be at least one selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, or a combination thereof.
The method of claim 3,
Wherein the initiator comprises a photopolymerization initiator, a radical polymerization initiator, or a combination thereof.
The method of claim 3,
Wherein the photosensitive resin composition further comprises 0.01 to 20 parts by weight of an epoxy compound per 100 parts by weight of the photosensitive resin composition.
A light-shielding layer produced by using the photosensitive resin composition of any one of claims 3 to 10.
A color filter produced by using the photosensitive resin composition of any one of claims 3 to 10.

Images