KR101030310B1 - Photosensitive resin composition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, in particular a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof; Ii) epoxy group-containing unsaturated compounds; And iii) an acrylic copolymer obtained by copolymerizing an olefinically unsaturated compound; b) 1,2-quinonediazide compounds; And c) a fluorine-based compound.

The photosensitive resin composition according to the present invention not only has excellent performances such as transmittance, insulation, flatness, chemical resistance, and the like, and is particularly suitable for forming an interlayer insulating film in an LCD manufacturing process by remarkably improving high heat resistance.

Interlayer insulating film, photosensitive resin, fluorine compound

Description

Photosensitive Resin Composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition, and more particularly, it has excellent performances such as transmittance, insulation, flatness, chemical resistance, and the like, and in particular, it has a markedly improved high heat resistance and is suitable for forming an interlayer insulating film in an LCD manufacturing process. It relates to a resin composition.

In the TFT type liquid crystal display device or integrated circuit device, an interlayer insulating film is used to insulate the wirings arranged between the layers.

In the case of forming such an interlayer insulating film, a photosensitive material having a small number of steps for obtaining a pattern-shaped interlayer insulating film and excellent flatness is used.

In addition, as the display quality of the liquid crystal display (LCD) is improved, the structure of the TFT type liquid crystal display device is also changed to increase the flatness by increasing the thickness of the interlayer insulating film. In addition, the interlayer insulating film applied to the LCD manufacturing process is required to have excellent high heat resistance.

Conventionally, the interlayer insulating film is composed of a component such as PAC, a binder, a solvent, and the like, and an acrylic resin has been mainly used as the binder. However, in the case of the acrylic resin, it is difficult to exhibit the high heat resistance required for the interlayer insulating film, which causes a problem of reflectivity and adhesion of the insulating film, and causes a problem of damage to photo equipment due to outgassing. .

Therefore, there is a need for further research to improve the high heat resistance of the interlayer insulating film applied to the LCD manufacturing process.

In order to solve the problems of the prior art as described above, the present invention is excellent in a variety of performance, such as transmittance, insulation, flatness, chemical resistance, in particular, it can significantly improve the high heat resistance, interlayer insulating film of the LCD manufacturing process with a thick film thickness It is an object to provide a photosensitive resin composition and a coating solution suitable for use as.

Another object of the present invention is not only to improve the reflectivity and adhesion of the interlayer insulating film applied to the LCD manufacturing process having excellent heat resistance, but also to damage the photo equipment due to outgassing photosensitive resin composition and coating solution To provide.

In order to achieve the above object, the present invention provides a photosensitive resin composition,

a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;

  Ii) epoxy group-containing unsaturated compounds; And

  Iii) olefinically unsaturated compounds                     

  Acrylic copolymer obtained by copolymerizing;

b) 1,2-quinonediazide compounds; And

c) a fluorine compound represented by any one of the following Chemical Formulas 1 to 11

It provides a photosensitive resin composition comprising:

[Formula 1]

In the formula of Formula 1,

n is an integer from 2 to 20,

[Formula 2]

In the formula (2),

n is an integer from 2 to 20,

(3)

In the formula (3),

m is an integer from 0 to 10, n is an integer from 1 to 10,

[Formula 4]

In the formula (4),                     

n is an integer from 1 to 10,

[Chemical Formula 5]

In the formula (5),

n is an integer from 2 to 20,

[Formula 6]

In the formula (6),

n is an integer from 2 to 20,

[Formula 7]

In the formula (7),

m is an integer from 0 to 10, n is an integer from 1 to 10,

[Formula 8]

In the formula (8),

n is an integer from 1 to 10.

[Formula 9]

[Formula 10]

[Formula 11]

Preferably the present invention

a) i) 5 to 40% by weight unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;

  Ii) 10 to 70% by weight of an epoxy group-containing unsaturated compound; And

  V) 10 to 70% by weight of olefinically unsaturated compound

  100 parts by weight of an acrylic copolymer obtained by copolymerizing;

b) 5 to 100 parts by weight of 1,2-quinonediazide compound; And

c) 0.1 to 30 parts by weight of the fluorine compound represented by any one of Formulas 1 to 11

It includes.

In another aspect, the present invention provides a photosensitive resin composition coating solution comprising the photosensitive resin composition and a solvent.

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of the present invention comprises a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or a mixture thereof, ii) an epoxy group-containing unsaturated compound, and iii) an acrylic copolymer copolymerized with an olefinic unsaturated compound, b) 1, It is characterized in that it comprises a 2-quinone diazide compound, and c) a fluorine-based compound represented by any one of the formulas (1) to (11).

The acrylic copolymer of a) used in the present invention serves to easily form a predetermined pattern in which scum does not occur when developing.

The acrylic copolymer of a) may be a radical in the presence of a solvent and a polymerization initiator, i. Can be prepared by reaction.

A) i) Unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof used in the present invention include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, metaconic acid and itaconic acid; Or anhydrides of these unsaturated dicarboxylic acids, or the like, may be used alone or in combination of two or more thereof. Particularly, acrylic acid, methacrylic acid, or maleic anhydride may be used in terms of copolymerization reactivity and solubility in aqueous alkali solution. Do.

The unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof is preferably included in 5 to 40% by weight, more preferably 10 to 30% by weight based on the total total monomers. If the content is less than 5% by weight, there is a problem that it is difficult to dissolve in the aqueous alkali solution, when the content exceeds 40% by weight there is a problem that the solubility in the aqueous alkali solution is too large.                     

The epoxy group-containing unsaturated compound of a) ii) used in the present invention is glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n- Butyl acrylate glycidyl, acrylic acid-beta -methyl glycidyl, methacrylic acid-beta -methyl glycidyl, acrylic acid-beta -ethyl glycidyl, methacrylic acid-beta -ethyl glycidyl, acrylic acid -3, 4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o- Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like can be used, and the above compounds can be used alone or in combination of two or more thereof.

In particular, the epoxy group-containing unsaturated compounds are methacrylic acid glycidyl, methacrylic acid-β-methylglycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl It is more preferable to use glycidyl ether or p-vinylbenzyl glycidyl ether in improving the copolymerization reactivity and the heat resistance of the obtained pattern.

The epoxy group-containing unsaturated compound is preferably contained in 10 to 70% by weight, more preferably 20 to 60% by weight based on the total total monomers. If the content is less than 10% by weight, there is a problem that the heat resistance of the resulting pattern is lowered, and if it exceeds 70% by weight, there is a problem that the storage stability of the copolymer is lowered.

The olefinically unsaturated compounds of a) iii) used in the present invention are methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate. Isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, Dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl oxyethyl acrylate, isobornyl acrylate, phenyl methacrylate, Phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, α-methyl styrene, m-methyl styrene, p- Methyl styrene, vinyltoluene, p-methoxy styrene, 1,3-butadiene, isoprene, or 2,3-dimethyl 1,3-butadiene may be used, and the compound may be used alone or in combination of two or more thereof. .

In particular, the olefinically unsaturated compound is more preferable in terms of solubility in an aqueous alkali solution which is copolymerization reactivity and developer using styrene, dicyclopentanyl methacrylate, or p-methoxy styrene.

The olefinically unsaturated compound is preferably included in 10 to 70% by weight, more preferably 20 to 50% by weight relative to the total total monomers. If the content is less than 10% by weight, there is a problem that the storage stability of the acrylic copolymer is lowered. If the content exceeds 70% by weight, the acrylic copolymer is difficult to be dissolved in an aqueous alkali solution.

Solvents used to polymerize such monomers into acrylic copolymers include methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol mono. Methyl ether, diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methylethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ethyl propionate, propylene glycol ethyl ether propio Nitrate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate , Butyl acetate, 2-hydroxy ethyl propionate, 2-hydroxy 2-methyl methyl propionate, 2-hydroxy 2-methyl ethyl propionate, hydroxy methyl acetate, hydroxy ethyl acetate, hydroxy butyl acetate, methyl lactate, lactic acid Ethyl, propyl lactate, butyl lactate, methyl 3-hydroxy propionate, ethyl 3-hydroxy propionate, propyl 3-hydroxy propionate, butyl 3-hydroxy propionate, methyl 2-hydroxybutyrate, methoxyacetic acid To methyl, ethyl methoxy acetate, methoxy methoxy acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, propoxy acetate Propyl acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, 2-Methoxy Propionate, 2-Ethoxy Propionate, 2-Ethoxy Propionate, 2-Ethoxy Propionate, 2-Ethoxy Propionate, 2-Butoxy Propionate, 2-Butoxy Propionate Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, Ethers such as methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, or butyl 3-butoxypropionate, etc. may be used, and the compounds may be used alone or in combination of two or more thereof. have.

The polymerization initiator used to polymerize such monomers into an acrylic copolymer may use a radical polymerization initiator, specifically 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethyl Valeronitrile), 2,2-azobis (4-methoxy 2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), or dimethyl 2,2-azobis Isobutylate and the like can be used.

The acrylic copolymer of a) prepared by radical reaction of such a monomer in the presence of a solvent and a polymerization initiator has a polystyrene reduced weight average molecular weight (Mw) of 5,000 to 30,000, more preferably 5,000 to 20,000. In the case of the interlayer insulating film having a polystyrene reduced weight average molecular weight of less than 5,000, there is a problem in that developability, residual film ratio, etc. are inferior, or pattern shape and heat resistance are poor. There is a problem that the phenomenon is inferior.                     

The 1,2-quinonediazide compound of b) used in the present invention is used as a photosensitive compound.

As the 1,2-quinonediazide compound, 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, or 1,2-quinonediazide 6-sulfonic acid ester may be used. have.

The quinonediazide compound as described above may be prepared by reacting a naphthoquinonediazide sulfonic acid halogen compound and a phenol compound under a weak base.

Examples of the phenolic compounds include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2'-tetrahydroxybenzophenone, and 4,4'-tetrahydroxybenzophenone. , 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy 4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy 3'-methoxybenzophenone, 2,3,4,2'-pentahydroxybenzophenone, 2,3,4,6'-pentahydroxybenzophenone, 2,4,6,3'-hexahydroxybenzophenone, 2,4,6,4'-hexahydroxybenzophenone, 2,4,6,5'-hexahydroxybenzophenone, 3,4,5 , 3'-hexahydroxybenzophenone, 3,4,5,4'-hexahydroxy benzophenone, 3,4,5,5'-hexahydroxy hydroxybenzophenone, bis (2,4-dihydroxyphenyl ) Methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxy Phenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-di Methyl 4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, or bis ( 2,5-dimethyl 4-hydroxyphenyl) -2-hydroxyphenylmethane etc. can be used, The said compound can be used individually or in mixture of 2 or more types.                     

When the quinone diazide compound is synthesized with the phenol compound and the naphthoquinone diazide sulfonic acid halogen compound as described above, the esterification degree is preferably 50 to 85%. When the esterification degree is less than 50%, the residual film rate may be worse, and when the esterification degree is more than 85%, there is a problem that the storage stability is lowered.

The 1,2-quinonediazide compound is preferably included in an amount of 5 to 100 parts by weight, and more preferably 10 to 50 parts by weight, based on 100 parts by weight of the acrylic copolymer of a). If the content is less than 5 parts by weight, the difference in solubility between the exposed and non-exposed parts becomes small, and if it exceeds 100 parts by weight, a large amount of unreacted 1,2-quinonediazide compound is produced when irradiated with light for a short time. There is a problem that the development is difficult because the solubility in the alkali aqueous solution remaining as a developer is too low.

The fluorine-based compound represented by any one of Chemical Formulas 1 to 11 of c) used in the present invention functions to improve heat resistance, transparency, chemical resistance and the like of the pattern obtained from the photosensitive resin composition.

Of course, the fluorine-based compound represented by any one of Formulas 1 to 11 may be used alone or in mixture of two or more thereof, and the content thereof may be included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer of a). Preferably, it is more preferably included in 0.1 to 10 parts by weight. If the content is less than 0.1 parts by weight, there is a problem that the heat resistance is lowered. If the content is more than 30 parts by weight, there is a problem that the development is difficult because the decrease in sensitivity and the solubility in the aqueous alkali solution is too low.

The photosensitive resin composition of this invention which consists of such a component as needed may further contain d) epoxy resin, e) adhesive agent, f) acrylic compound, and g) surfactant as needed.

The epoxy resin of said d) functions to improve heat resistance, sensitivity, etc. of the pattern obtained from the photosensitive resin composition.

The epoxy resin is bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, cycloaliphatic epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, heterocyclic epoxy resin, Or a resin obtained by co-polymerizing glycidyl methacrylate different from the acrylic copolymer of a), and in particular, bisphenol A type epoxy resin, cresol novolac type epoxy resin, or glycidyl ester type Preference is given to using epoxy resins.

The epoxy resin is preferably contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer of a). If the content is outside the above range, compatibility with the acrylic copolymer may be insufficient to obtain sufficient coating performance. There is a problem that can not be.

The adhesive of e) serves to improve the adhesion to the substrate, it is preferably included in 0.1 to 20 parts by weight based on 100 parts by weight of the acrylic copolymer of a).

As the adhesive, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group, or an epoxy group can be used. Specifically, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or β- (3 , 4-epoxy cyclohexyl) ethyltrimethoxysilane and the like can be used.

The acrylic compound of the said f) functions to improve the transmittance | permeability, heat resistance, a sensitivity, etc. of the pattern obtained from the photosensitive resin composition.

Preferably, a representative example of the acrylic compound is represented by the following formula (12).

[Chemical Formula 12]

In the formula (12),

R is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, or an alkanoyl group of 1 to 5 carbon atoms,

1 <a <6 and a + b = 6.

The acrylic compound is preferably included in an amount of 0.1 to 30 parts by weight, more preferably 0.1 to 15 parts by weight based on 100 parts by weight of the acrylic copolymer. When the content is in the above range, it is better in improving the transmittance, heat resistance, sensitivity, and the like of the pattern.                     

The surfactant of g) serves to improve the applicability and developability of the photosensitive composition.

The surfactant may be polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172, F173 (trade name: Japan Nippon Ink Company), FC430, FC431 (trade name: Sumitomo Triem, Inc.), or KP341 (trade name: Shinwol) Chemical industry) and the like.

The surfactant is preferably included in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the acrylic polymer of a). If the content is in the above range, the surfactant is more preferable in coating properties and developability of the photosensitive composition.

The present invention also includes a) an acrylic copolymer, b) a 1,2-quinonediazide compound, and c) a fluorine compound represented by any one of Formulas 1 to 11, and d) an epoxy resin, e) Provided is a photosensitive resin composition coating solution prepared by adding a solvent to the photosensitive resin composition further comprising an adhesive, f) an acrylic compound, or g) a surfactant, the solid content concentration of the photosensitive resin composition coating solution is 10 to 50 It is preferable that it is weight%, and the coating solution which has solid content of the said range is good to use, after filtering with a 0.1-0.2 micrometer pre-pore filter.

Solvents commonly used in the photosensitive resin composition coating solution include alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy 4-methyl 2-pentanone, or methyl acetate, ethyl acetate, propyl acetate, butyl acetate and 2-hydroxy propionic acid Ethyl, 2-hydroxy methyl 2-methylpropionate, ethyl 2-hydroxy 2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3 Methyl hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy 3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxy Propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate propyl, ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, butoxy Methyl acetate, part Ethyl acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 Ethoxy ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxy ethyl propionate, 2-butoxypropionate propyl, 2-butoxy propionate , 3-Methoxypropionate Methyl 3-methoxypropionate, 3-methoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, butyl 3-ethoxypropionate, 3 Methyl propoxypropionate, 3-propoxy propionate, 3-propoxypropionate, propyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionate, 3- Butoxypro The esters, such as butyl acid can be used. In particular, it is preferable to select and use 1 or more types from the group which consists of solubility, reactivity with each component, and easy to form a coating film, glycol ether, ethylene alkyl ether acetate, and diethylene glycol.

The photosensitive resin composition coating solution of the present invention containing the above components is applied to the surface of the substrate by a spray method, a roll coater method, a rotary coating method, or the like, and the solvent is removed by prebaking to form a coating film. At this time, it is preferable to perform the said prebaking for 1 to 15 minutes at the temperature of 70-100 degreeC.

Then, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like are irradiated on the formed coating film, and developed with a developer to remove unnecessary portions to form a predetermined pattern.

The developer is preferably an aqueous alkali solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; primary amines such as n-propylamine; Secondary amines such as diethylamine and ethylamine n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyl diethanolamine and triethanolamine; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. In this case, the developer is used by dissolving the alkaline compound at a concentration of 0.1 to 10% by weight, and may be added an appropriate amount of a water-soluble organic solvent and a surfactant such as methanol, ethanol and the like.

In addition, after developing with the developer as described above, it is washed with ultrapure water for 30 to 90 seconds to remove unnecessary parts and dried to form a pattern. After irradiating the formed pattern with light such as ultraviolet rays, the pattern is applied to a heating apparatus such as an oven. By heating at a temperature of 150 to 250 ° C. for 30 to 90 minutes to obtain a final pattern.

The photosensitive resin composition according to the present invention as described above is excellent in a variety of performance, such as transmittance, insulation, flatness, chemical resistance, in particular, can be significantly improved high heat resistance to use as an interlayer insulating film of the LCD manufacturing process with a thick film thickness Not only is it suitable, the reflection of the interlayer insulating film applied to the LCD manufacturing process, the adhesion can be improved, there is an advantage that does not damage the photo equipment due to outgassing.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

Example 1

(Acrylic copolymer production)                     

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 20 parts by weight of methacrylic acid, and methacrylic acid in a flask equipped with a cooling tube and a stirrer 25 parts by weight of cydyl, 40 parts by weight of styrene, 5 parts by weight of 2-hydroxyethyl acrylate, and 10 parts by weight of isobornyl acrylate were added, and nitrogen-substituted, followed by gentle stirring. The reaction solution was heated to 62 ° C. to prepare a polymer solution containing an acrylic copolymer while maintaining this temperature for 5 hours.

Solid content concentration of the polymer solution containing the said acrylic copolymer was 45 weight%, and the weight average molecular weight of the polymer was 10,000. At this time, the weight average molecular weight is the polystyrene reduced average molecular weight measured using GPC.

(1,2-quinonediazide compound preparation)

1 mole of 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid [ Chloride] condensation reaction of 2 moles to give 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide -5-sulfonic acid ester was prepared.

(Photosensitive resin composition production)

100 parts by weight of the polymer solution containing the acrylic copolymer prepared above, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] 25 parts by weight of bisphenol 1,2-naphthoquinone diazide-5-sulfonic acid ester and 4 parts by weight of a fluorine compound represented by Formula 1a were mixed. Diethylene glycol dimethyl ether was added and dissolved so that the solid content concentration of the mixture was 35% by weight, and then filtered through a 0.2 μm millipore filter to prepare a photosensitive resin composition coating solution.

[Formula 1a]

Example 2

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the fluorine-based compound of Formula 2a was used instead of the fluorine-based compound of Formula 1a in the preparation of the photosensitive resin composition of Example 1.

(2a)

Example 3

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the fluorine-based compound of Formula 3a was used instead of the fluorine-based compound of Formula 1a in the preparation of the photosensitive resin composition of Example 1.

[Chemical Formula 3]

Example 4

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the fluorine-based compound of Formula 4a was used instead of the fluorine-based compound of Formula 1a in the preparation of the photosensitive resin composition of Example 1.                     

[Chemical Formula 4a]

Example 5

Except for using the fluorine-based compound of Formula 5a in place of the fluorine-based compound of Formula 1a in the preparation of the photosensitive resin composition of Example 1 in the preparation of the photosensitive resin composition of Example 1 To prepare a photosensitive resin composition coating solution.

[Formula 5a]

Example 6

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the fluorine-based compound of Formula 6a was used instead of the fluorine-based compound of Formula 1a in the preparation of the photosensitive resin composition of Example 1.

[Formula 6a]

Example 7

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the fluorine-based compound of Formula 7a was used instead of the fluorine-based compound of Formula 1a in the preparation of the photosensitive resin composition of Example 1.                     

[Formula 7a]

Example 8

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the fluorine-based compound of Formula 8a was used instead of the fluorine-based compound of Formula 1a in the preparation of the photosensitive resin composition of Example 1.

[Formula 8a]

Example 9

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1 except that the fluorine-based compound of Formula 9a was used instead of the fluorine-based compound of Formula 1a in the preparation of the photosensitive resin composition of Example 1.

[Formula 9a]

Example 10

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the fluorine-based compound of Formula 10a was used instead of the fluorine-based compound of Formula 1a in the preparation of the photosensitive resin composition of Example 1.                     

[Formula 10a]

Example 11

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the fluorine-based compound of Formula 11a was used instead of the fluorine-based compound of Formula 1a in the preparation of the photosensitive resin composition of Example 1.

[Formula 11a]

Comparative Example 1

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1 except that the fluorine-based compound of Formula 1a was not used in the preparation of the photosensitive resin composition of Example 1.

After evaluating the physical properties by the following method using the photosensitive resin composition coating solution prepared in Examples 1 to 11 and Comparative Example 1, the results are shown in Table 1 below.

A) Sensitivity-After coating the photosensitive resin composition solution prepared in Examples 1 to 11 and Comparative Example 1 using a spin coater on a glass substrate, and prebaked on a hot plate for 2 minutes at 90 ℃ Formed.

The film | membrane obtained above was irradiated with the ultraviolet-ray whose intensity | strength at 365 nm is 15 mW / cm <2> for 15 second using the predetermined pattern mask. Thereafter, the solution was developed at 25 DEG C for 2 minutes in an aqueous solution of 0.38 wt% of tetramethyl ammonium hydroxide, and then washed with ultrapure water for 1 minute.

Subsequently, the developed pattern was irradiated with ultraviolet rays having a intensity of 15 mA / cm 2 at 365 nm for 34 seconds, midbaked at 120 ° C. for 3 minutes, and then cured by heating at 220 ° C. for 60 minutes in an oven. A membrane was obtained.

B) Resolution-Measured with the minimum size of the patterned film formed during the sensitivity measurement of a).

C) Heat resistance-The widths of the top, bottom, left and right of the pattern film formed when the sensitivity of the a) was measured. In this case, the case where the change rate of each angle was 0 to 20% before the mid-baking, and the case where 20 to 40% exceeded △ and 40% were indicated by x.

D) transparency—evaluation of transparency The transmittance of 400 nm of the patterned film was measured using a spectrophotometer.

ㅁ) Heat dissipation resistance-Evaluation of heat dissipation resistance The measurement substrate was heated in an oven at 220 ℃ for 1 hour, and the heat dissipation resistance was evaluated according to the change of transmittance of the pattern film before and after heating. In this case, the case where the change rate was less than 5% was represented by ○, and the case where the change rate was 5% by 10% was indicated by Δ and the case where the change rate was greater than 10%.

division Sensitivity (mJ / ㎠) Resolution (μm) Heat resistance Transparency Heat discoloration resistance Example 1 270 3 ○ 90 ○ Example 2 290 3 ○ 90 ○ Example 3 280 3 ○ 90 ○ Example 4 300 3 ○ 90 ○ Example 5 260 3 ○ 89 ○ Example 6 270 3 ○ 89 ○ Example 7 260 3 ○ 89 ○ Example 8 270 3 ○ 89 ○ Example 9 260 3 ○ 90 ○ Example 10 270 3 ○ 90 ○ Example 11 270 3 ○ 89 ○ Comparative Example 1 240 5 × 90 ○

Through Table 1, Examples 1 to 11 including the fluorine-based compound represented by any one of Formulas 1 to 11 in accordance with the present invention was excellent in resolution and heat resistance, from which a thick interlayer insulating film for high heat resistance It can be seen that it is applicable to. On the other hand, Comparative Example 1 was somewhat poor in resolution, it was difficult to apply as a thick interlayer insulating film due to poor heat resistance.

The photosensitive resin composition according to the present invention is excellent in various performances such as transmittance, insulation, flatness, chemical resistance, etc., and in particular, it is possible to significantly improve high heat resistance, so that it may be suitable for use as an interlayer insulating film in LCD manufacturing process with a thick film thickness. In addition, the reflection of the interlayer insulating film applied to the LCD manufacturing process may improve the adhesion, and may not damage the photo equipment due to the outgassing.

Claims (11)

In the photosensitive resin composition, a) i) unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;   Ii) epoxy group-containing unsaturated compounds; And   Iii) olefinically unsaturated compounds   Acrylic copolymer obtained by copolymerizing; b) 1,2-quinonediazide compounds; And c) a fluorine compound represented by any one of the following Chemical Formulas 1 to 11 Photosensitive resin composition comprising: [Formula 1]

In the formula of Formula 1, n is an integer from 2 to 20, [Formula 2]

In the formula (2), n is an integer from 2 to 20, (3)

In the formula (3), m is an integer from 0 to 10, n is an integer from 1 to 10, [Formula 4]

In the formula (4), n is an integer from 1 to 10, [Chemical Formula 5]

In the formula (5), n is an integer from 2 to 20, [Formula 6]

In the formula (6), n is an integer from 2 to 20, [Formula 7]

In the formula (7), m is an integer from 0 to 10, n is an integer from 1 to 10, [Formula 8]

In the formula (8), n is an integer from 1 to 10. [Formula 9]

[Formula 10]

[Formula 11]

The method of claim 1, a) i) 5 to 40% by weight unsaturated carboxylic acid, unsaturated carboxylic anhydride, or mixtures thereof;   Ii) 10 to 70% by weight of an epoxy group-containing unsaturated compound; And   V) 10 to 70% by weight of olefinically unsaturated compound   100 parts by weight of an acrylic copolymer obtained by copolymerizing; b) 5 to 100 parts by weight of 1,2-quinonediazide compound; And c) 0.1 to 30 parts by weight of the fluorine compound represented by any one of Formulas 1 to 11 Photosensitive resin composition comprising a. The method of claim 1, The unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof of a) iii) is composed of anhydride of acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, and unsaturated dicarboxylic acid thereof 1 or more types are selected from the group. Photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The epoxy group-containing unsaturated compound of a) ii) is glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl , Acrylic acid-beta -methyl glycidyl, methacrylic acid-beta -methyl glycidyl, acrylic acid-beta -ethyl glycidyl, methacrylic acid-beta -ethyl glycidyl, acrylic acid -3,4-epoxybutyl , Methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethyl acrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glyci A photosensitive resin composition, characterized in that at least one selected from the group consisting of dill ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. The method of claim 1, The olefinically unsaturated compound of a) iii) is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate , Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl meth Acrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, isoboroyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acryl Latex, 2-hydroxyethyl methacrylate, styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyltol Yen, p- methoxystyrene, 1,3-butadiene, isoprene, and 2,3-dimethyl-1, a photosensitive resin composition characterized in that the species or more selected from the group consisting of 1,3-butadiene. The method of claim 1, The polystyrene reduced weight average molecular weight (Mw) of the acryl-type copolymer of said a) is 5,000-30,000, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The 1,2-quinonediazide compound of b) is used as 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, and 1,2-quinonediazide 6-sulfonic acid ester 1 or more types are chosen from the group which consists of a photosensitive resin composition characterized by the above-mentioned. The method of claim 1, D) 0.1 to 30 parts by weight of epoxy resin, e) 0.1 to 20 parts by weight of adhesive, f) 0.1 to 30 parts by weight of acrylic compound, and g) interface with respect to 100 parts by weight of the acrylic copolymer of a). The photosensitive resin composition characterized by further including the additive selected from the group which consists of 0.0001-2 weight part of active agents. The photosensitive resin composition coating solution containing the photosensitive resin composition and solvent of any one of Claims 1-8. 10. The method of claim 9, Solid content concentration of the photosensitive resin composition coating solution is 10 to 50% by weight of the photosensitive resin composition coating solution. 10. The method of claim 9, The solvent is methanol, ethanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol dimethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate Propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone, Chlohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxy propionate, methyl 2-hydroxy 2-methylpropionate, 2-hydroxy 2 Ethyl methyl propionate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate, methyl 3-hydroxypropionate, 3-hydroxy Propyl propionate, butyl 3-hydroxypropionate, methyl 2-hydroxy 3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxymethyl acetate, ethyl ethoxyacetate , Ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate Methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate , Methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate 3-ethylpropionate, 3-methoxypropionic acid Propyl, 3-Ethoxy Propionate, 3-Ethoxy Propionate, 3-Ethoxy Propionate, 3-Ethoxy Propionate, 3-Propoxy Propionate, 3-Ethyl Propoxypropionate, 3-Propoxy Propionate Photosensitive water selected from the group consisting of butyl 3-propoxy propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate Composition of coating solution.