KR101988931B1 - Photosensitive resin composition and insulating layer prepared from the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition and an insulating film prepared therefrom, and more particularly, by including a non-sulfonamide-based photoacid generator and a sensitizer, a photosensitive resin composition capable of obtaining fast sensitivity and high transmittance and produced therefrom It relates to an insulating film.

Description

Photosensitive resin composition and insulating film manufactured therefrom {PHOTOSENSITIVE RESIN COMPOSITION AND INSULATING LAYER PREPARED FROM THE SAME}

The present invention relates to a photosensitive resin composition capable of obtaining fast sensitivity and high transmittance and an insulating film produced therefrom.

In display devices such as thin film transistor (TFT) type liquid crystal displays, inorganic protective films such as silicon nitride have conventionally been used as protective films for protecting and insulating TFT (Thin Film Transistor) circuits. There is a problem that it is difficult to improve the aperture ratio due to this high, and in order to overcome this, the demand for an organic dielectric film having a low dielectric constant is increasing.

As such an organic insulating film, a photosensitive resin, which is a polymer compound in which the solubility in a specific solvent is changed by chemical reaction by light and electron beams, is generally used, and the microprocessing of the circuit pattern is a polarity of the polymer produced by the photoreaction of the organic insulating film. By change and crosslinking reaction. In particular, the organic insulating film material utilizes a change characteristic of solubility in a solvent such as an aqueous alkali solution after exposure.

The organic insulating film is classified into a positive type and a negative type according to the solubility of the sensitized part. In the positive type photoresist, the exposed portion is dissolved by the developer, and in the negative type photoresist, the exposed portion is not dissolved in the developer and the unexposed portion is dissolved to form a pattern.

Among these, the positive type organic insulating film can eliminate the use of the organic developer used in the negative type organic insulating film by using an aqueous alkali solution, which is advantageous in terms of working environment and theoretically, Since the swelling phenomenon can be prevented, the resolution is improved. In addition, after the organic film is formed, it is easy to remove by the stripping solution, and the substrate recovery and reusability are greatly improved by removing the organic film when a defective panel is generated during the process.

In particular, in forming an insulating film of a liquid crystal display device as such an organic insulating film, the insulating film must not only have excellent insulation property but also have low thermal expansion property to reduce stress at an interface when coated on a substrate, and physically. It must have a strong character.

In addition, the insulating film, the protective film, and the like inevitably form an interface with a metal, a silicon compound, and the like, wherein excellent interface adhesion is a very important factor in terms of reliability of the device. The insulating film is subjected to a fine pattern forming process to provide interconnection passages between the circuits. If the photoresist is provided to the insulating film itself, the process of forming a pattern by applying a separate photoresist on the conventional insulating film can be reduced. It is possible to form a fine pattern.

For this reason, the positive type organic insulating film composition includes a photosensitive compound (PAC) that provides photosensitivity to a binder resin, such as an acrylic photosensitive resin used as a typical binder resin, a noblock resin type, a polyimide, or a siloxane type. Research into applying the added composition has been actively conducted, and recently, the insulating film has been commercialized and various devices using the same have been released.

Sensitivity is mentioned as an important characteristic among the characteristics calculated | required by the said organic insulating film. Since the improvement of the sensitivity enables a significant reduction in the production time in the industrial production of the display apparatus, in the present situation in which the demand for liquid crystal display devices and the like is remarkably increasing, the sensitivity is the most required for this kind of organic insulating film. It is recognized as one of the important characteristics.

However, organic insulating film compositions using acrylic photosensitive resins and PACs, which are conventionally used, are often insufficient in sensitivity, and in particular, they do not have sufficient resolution because the solubility difference between the portion irradiated with ultraviolet rays and the portion not irradiated is not large. .

For example, US Pat. No. 4139391 discloses a photosensitive resin organic insulating film composition prepared by using a copolymer of an acrylic acid compound and an acrylate compound as a binder resin and using an acrylate compound as a multifunctional monomer. However, the difference in solubility between the exposed portion and the non-exposed portion is not large enough, so that the development characteristics are not good, and the binder resin, which should remain during the development process, is partially dissolved in the developing solution to obtain a fine pattern of 15 microns or less.

As described above, the conventional organic insulating film was not able to sufficiently satisfy the problem of sensitivity. Although it is possible to improve the sensitivity by increasing the solubility or development time of the alkaline developer for the polymer used, this method is limited, and also the solubility of the unexposed portion occurs, which lowers the overall residual film rate. In the large display substrate, there existed a fault which causes a film bleeding and a pattern damage.

In addition, the organic insulating film composition has excellent process resistance such as heat resistance, solvent resistance, and long-term high temperature firing resistance, good adhesion with a support layer, and wide process margin for forming a pattern under various process conditions according to the intended use. In addition, various characteristics such as high sensitivity and high permeability, film bleeding after development, and low loss by the developer are required.

Patent Document 1: US Patent Publication No. 4139391

An object of the present invention is to provide a photosensitive resin composition capable of obtaining fast sensitivity and high transmittance.

An object of this invention is to provide the photosensitive resin composition which is excellent in resolution and can adjust the inclination of the formed pattern.

An object of this invention is to provide the resin composition suitable for chemical-resistance and heat resistance which are needed for a post process.

An object of the present invention is to provide an insulating film made of the photosensitive resin composition.

1. Photosensitive resin composition comprising a oxime sulfonate-based photoacid generator represented by Formula 1 or 2 and a sensitizer represented by Formula 3:

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an oxygen atom, a benzyl group, a phenyl group, an alkyl group having 1 to 6 carbon atoms, an acetyl group, a phenylacetyl group, a phenylcarbonyl group or An acetylphenylthio group, the benzyl group, a phenyl group, an alkyl group having 1 to 6 carbon atoms, an acetyl group, a phenylacetyl group and an acetylphenylthio group may be substituted with an acetylphenylthio group; at least one of R ₁ and R ₂ is an oxygen atom R ₁ and R ₂ are connected to each other to form a ring, and when at least one of R ₃ and R ₄ is an oxygen atom, R ₃ and R ₄ are connected to each other to form a ring; X ⁻ is PF _{6 ^{-, AsF 6 -, SbF 6}} -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 ^{_{P -, (C 2 F 5}} SO 2) 2 N -, (CF 3 SO 3) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, CF 3 CF 2 (CF 3) 2 CO - _{, (CF 3 SO 2) 2} CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 COO -, CF 3 SO 3 -, (C 6 F ₅ ) ₄ B ^- and C ₃ F ₇ COO ^- Anion selected from the group consisting of

 [Formula 2]

(Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a benzyl group, a phenyl group, an alkyl group having 1 to 6 carbon atoms, an acetyl group, a phenylacetyl group or an acetylphenylthio group, and the benzyl group , a phenyl group, a group alkyl group, an acetyl group, a phenylacetyl group having 1 to 6 carbon atoms and acetyl phenylthio group may be substituted and a group acetyl-phenylthio; X ^- is ^{_{PF 6 -, AsF 6 -,}} SbF 6 -, (CF 3) 2 ^{_{PF 4 -, (CF 3)}} 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, (C 2 F 5 SO 2) 2 N -, _{(CF 3 SO 3) 2 N} -, (CF 3 SO 2) (CF 3 CO) N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) ^{_{3 C -, (CF 3 SO}} 2) 3 C -, CF 3 COO -, CF 3 SO 3 -, (C 6 F 5) 4 B - , and C ₃ F ₇ COO ^- being an anion, selected from the group consisting of a)

 [Formula 3]

(Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms).

2. according to the above 1, the photosensitive resin composition further comprising a binder resin and a solvent.

3. In the above 2, the photoacid generator comprises a photosensitive resin composition containing 0.1 to 20 parts by weight based on 100 parts by weight of the binder resin.

4. according to the above 2, the sensitizer is contained in 0.1 to 20 parts by weight based on 100 parts by weight of the binder resin.

5. In the above 2, the weight average molecular weight of the binder resin is 5,000 to 30,000 photosensitive resin composition.

6. In the above 2, wherein the binder resin is 5 to 50% by weight based on the total weight of the composition of the photosensitive resin composition.

7. The photosensitive resin composition of claim 2, wherein the solvent is at least one selected from the group consisting of ethers, acetates, esters, ketones, amides, and lactones.

8. according to the above 2, wherein the solvent is a photosensitive resin composition containing 40 to 90% by weight based on the total weight of the composition.

9. The photosensitive resin composition according to the above 2, further comprising at least one selected from the group consisting of a basic compound, a surfactant, an adhesion improving agent, a thermal crosslinking agent, a light stabilizer, a photocuring accelerator, an antihalation agent, and an antifoaming agent.

10. The insulating film cured photosensitive resin composition of any one of the above 1 to 9.

11. Liquid crystal display device having an insulating film of the above 10.

The photosensitive resin composition of this invention can obtain fast sensitivity and high transmittance | permeability.

The photosensitive resin composition of this invention hardens the pattern after image development, and provides post process stability of an organic film.

The photosensitive resin composition of this invention is excellent in resolution, flow property is improved, and processing is easy.

The photosensitive resin composition of this invention has the outstanding electrical property, and is excellent in chemical-resistance and heat resistance.

The present invention relates to a photosensitive resin composition capable of obtaining fast sensitivity and high transmittance by including a nonsulfonamide-based photoacid generator and a sensitizer and an insulating film produced therefrom.

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of the present invention includes a non-sulfonamide-based photoacid generator and a sensitizer, and may further include a binder resin, a solvent, and the like, which are commonly used in the photosensitive resin composition in the art.

Photoacid generators are compounds that generate acids by actinic radiation or radiation.

The nonsulfonamide-based photoacid generator according to the present invention may have a structure represented by the following Chemical Formula 1 or Chemical Formula 2.

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an oxygen atom, a benzyl group, a phenyl group, an alkyl group having 1 to 6 carbon atoms, an acetyl group, a phenylacetyl group, a phenylcarbonyl group or An acetylphenylthio group, the benzyl group, a phenyl group, an alkyl group having 1 to 6 carbon atoms, an acetyl group, a phenylacetyl group and an acetylphenylthio group may be substituted with an acetylphenylthio group; at least one of R ₁ and R ₂ is an oxygen atom R ₁ and R ₂ are connected to each other to form a ring, and when at least one of R ₃ and R ₄ is an oxygen atom, R ₃ and R ₄ are connected to each other to form a ring; X ⁻ is PF _{6 ^{-, AsF 6 -, SbF 6}} -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 ^{_{P -, (C 2 F 5}} SO 2) 2 N -, (CF 3 SO 3) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, CF 3 CF 2 (CF 3) 2 CO - _{, (CF 3 SO 2) 2} CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 COO -, CF 3 SO 3 -, (C 6 F ₅ ) ₄ B ^- and C ₃ F ₇ COO ^- Anion selected from the group consisting of

 [Formula 2]

(Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a benzyl group, a phenyl group, an alkyl group having 1 to 6 carbon atoms, an acetyl group, a phenylacetyl group or an acetylphenylthio group, and the benzyl group , a phenyl group, a group alkyl group, an acetyl group, a phenylacetyl group having 1 to 6 carbon atoms and acetyl phenylthio group may be substituted and a group acetyl-phenylthio; X ^- is ^{_{PF 6 -, AsF 6 -,}} SbF 6 -, (CF 3) 2 ^{_{PF 4 -, (CF 3)}} 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, (C 2 F 5 SO 2) 2 N -, _{(CF 3 SO 3) 2 N} -, (CF 3 SO 2) (CF 3 CO) N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) ^{_{3 C -, (CF 3 SO}} 2) 3 C -, CF 3 COO -, CF 3 SO 3 -, (C 6 F 5) 4 B - , and C ₃ F ₇ COO ^- being an anion, selected from the group consisting of a)

The content of the photoacid generator is not particularly limited within the range capable of performing the function, but may be included in an amount of 0.1 to 20 parts by weight, and preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin. When the content of the photoacid generator is contained in an amount of 0.1 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the binder resin, chemical change due to the catalysis of acid may occur sufficiently, and the coating may be uniformly applied when the composition is applied. have.

A sensitizer is a component which accelerates decomposition of a photoacid generator and improves a sensitivity.

The sensitizer according to the present invention has a structure represented by the following formula (3).

[Formula 3]

(Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms).

The sensitizer represented by the formula (3) may preferably have a structure represented by the formulas (4) to (6).

[Formula 4]

[Formula 5]

[Formula 6]

Conventionally, sulfonamide has been widely used as a photoacid emitter which is highly reactive in complex wavelengths and eyelines. However, the sulfonic acid type acid produced by exposure causes coloring by oxidation upon post-baking. In order to prevent this, it is preferable to use a photoacid generator other than sulfonamide, but there is a problem of low acid generation efficiency in the composite wavelength and the eyeline. However, the photosensitive resin composition of the present invention solves the problem by using the sensitizer for the application of a photoacid generator having an anion other than the sulfonamide type. This ensures fast sensitivity and stable high transmittance even during post-baking or post-treatment heat treatment.

The sensitizer is not particularly limited in the content within the range that can function, but may be included in 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin. When the content of the sensitizer is included in an amount of 0.1 to 20 parts by weight or less based on 100 parts by weight of the binder resin, there is an advantage of maximizing the effect of improving the sensitivity or improving the transmittance by spectral sensitization.

The binder resin may be a polymer of monomers commonly used in the art or a copolymer of two or more monomers. The polymerization order and arrangement of the monomers are not particularly limited.

The kind of monomer is not specifically limited, For example, the monomer represented by following formula (7) and formula (8) is mentioned.

[Formula 7]

Wherein R ₁ is a hydrogen atom or a methyl group;

R ₂ is a hydrogen atom; Or an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxirane group, an oxetane group and a bicycloalkyl group having 4 to 12 carbon atoms Or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a tetrahydrofuranyl group, a tetrahydropyranyl group, or an oxirane. Group, an oxetane group, a bicycloalkyl group having 4 to 12 carbon atoms or a tricycloalkyl group having 6 to 18 carbon atoms;

[Formula 8]

Wherein R is a hydrogen atom; or an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxirane group, an oxetane group A C1-C6 alkoxy group, a C1-C6 alkyl group, a C4-C8 cycloalkyl group, tetrahydrofura unsubstituted or substituted with a C4-C12 bicycloalkyl group or a C6-C18 tricycloalkyl group A silyl group, a tetrahydropyranyl group, an oxirane group, an oxetane group, a bicycloalkyl group having 4 to 12 carbon atoms or a tricycloalkyl group having 6 to 18 carbon atoms;

The binder resin may be polymerized by further including an acrylate monomer commonly known in the art and commonly used in addition to the monomer.

The acrylate monomers are, for example, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, methyl (Meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butyl cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-jade (Meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth ) Acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol Monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, cyclopentanyl (meth) acrylate,Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) Acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

The weight average molecular weight of the binder resin according to the present invention is preferably 5,000 to 30,000 in terms of maintaining excellent resolution, pattern straightness, and the like during pattern formation.

The binder resin is not particularly limited in its content within the range capable of its function, but may be included in the range of 5 to 50% by weight, preferably 10 to 40% by weight based on the total weight of the composition. When the content of the binder resin is included in more than 5% by weight, 50% by weight or less based on the total weight of the composition has the advantage that the effect of improving the sensitivity and resolution with an appropriate viscosity can be maximized.

The kind of solvent is not particularly limited, and any solvent may be used as long as it can dissolve the above-mentioned components, has a suitable drying speed, and can form a uniform and smooth coating film after evaporation of the solvent.

Specific examples include ethers, acetates, esters, ketones, amides and lactones. These can be used individually or in mixture of 2 or more types.

Specific examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether; Dipropylene glycol dialkyl ether, such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether, etc. are mentioned.

Specific examples of the acetates include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate; Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate; Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate.

Specific examples of the esters include methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate, n-butyl acetate, isobutyl acetate, and acetic acid. n-amyl, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, N-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, Ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxypart Tilacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetic acid, ethyl acetoacetate, methyl pirbate, ethyl pirbate, diethylene glycol methylethyl ester, etc. Can be mentioned.

Specific examples of the ketones include methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone and the like.

Specific examples of the amides include N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

Specific examples of the lactones include γ-butyrolactone.

Preferably, propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ester, or a mixture thereof is used in view of coating properties and uniformity of the film thickness of the insulating film.

The content of the solvent is not particularly limited within the range capable of functioning thereof, but may be included in an amount of 40 to 90% by weight, and preferably 50 to 80% by weight, based on the total weight of the composition. If the content of the solvent is included in more than 40% by weight, 90% by weight or less relative to the total weight of the composition can maintain the solid content and viscosity at an appropriate level has the advantage of increasing the coating properties.

The photosensitive resin composition of the present invention is an additive such as a basic compound, a surfactant, an adhesion improving agent, a thermal crosslinking agent, a light stabilizer, a photocuring accelerator, an antihalation agent (leveling agent), an antifoaming agent, and the like, which are generally used. It may further include within the scope does not deviate.

The kind of basic compound is not specifically limited, It can select arbitrarily and can use from what is used by chemically amplified resist. Specific examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. These can be used individually or in mixture of 2 or more types.

Specific examples of aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanol Amine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

Specific examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine, and the like.

Specific examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4- Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline , Pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1, 8-diazabicyclo [5.3.0] -7-undecene, etc. are mentioned.

Specific examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexyl ammonium hydroxide, and the like.

Specific examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.

The basic compound is not particularly limited in the range within which it can function, but may be included 0.001 to 1 parts by weight, preferably 0.005 to 0.5 parts by weight based on 100 parts by weight of the binder resin. When the content of the basic compound is included in an amount of 0.001 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the binder resin, there is an advantage in that an interlayer insulating film having good heat resistance and solvent resistance can be formed.

Surfactant is a component which improves the adhesiveness of a board | substrate and the photosensitive resin composition.

The kind of surfactant is not specifically limited, Various surfactants, such as a fluorine-containing surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant, can be used. These can be used individually or in mixture of 2 or more types.

Specific examples of fluorine-containing surfactants include MAGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 and F781 (trade name, manufactured by DIC Corporation), FLUORAD FC430, FC431 and FC171 (trade name, product of Sumitomo 3M Limited), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH- 40 (brand name, the product made by Asahi Glass Co., Ltd.), SOLSPERSE 20000 (brand name, the product made by Lubrizol Japan Limited), etc. are mentioned.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane and trimethylol ethane, and their ethoxylates or propoxylates (eg, glycerol propoxylate or glycerine ethoxylate); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, such as PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2, and TETRONIC 304, 701, 704, 901, 904 and 150R1 (trade name, manufactured by BASF) Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester and the like.

Specific examples of cationic surfactants include phthalocyanine-modified compounds such as EFKA-745 (trade name, manufactured by Morishita & Co., Ltd.), and organo such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Siloxane polymers; (Meth) acrylic acid-based (co) polymers such as POLYFLOW No. 75, No. 90, No. 95 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), W001 (trade name, manufactured by Yusho Co., Ltd.), and the like. Can be mentioned.

Specific examples of the anionic surfactant include W004, W005, and W017 (trade name, manufactured by Yusho Co., Ltd.).

Specific examples of silicone surfactants include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA and SH8400 (trade name, manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, 4300, 4445, 4460 and 4452 ( Trade names, manufactured by Momentive Performance Materials Inc.), KP341, KF6001 and KF6002 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, 323, and 330 (trade name, manufactured by BYK Chemie).

The amount of the surfactant is not particularly limited within the range capable of functioning thereof, but may be included in an amount of 0.01 to 5 parts by weight, and preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the binder resin. When the amount of the surfactant is contained in an amount of 0.01 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the binder resin, there is an advantage of maximizing the effect of improving the adhesion between the substrate and the resin composition.

An adhesive improving agent improves the adhesiveness between the inorganic material used as a base material, for example, silicon compounds, such as silicon, silicon oxide, and silicon nitride, metals, such as gold, copper, and aluminum, and an insulating film, and is useful also in adjusting the taper angle with a board | substrate. Do.

The kind of adhesive improving agent is not specifically limited, As a specific example, a silane coupling agent or a thiol type compound is mentioned, Preferably it is a silane coupling agent.

The kind of the silane coupling agent is not particularly limited, and specific examples thereof include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, and γ-glycidoxypropylalkyldi. Alkoxysilane, (gamma) -methacryloxypropyltrialkoxysilane, (gamma) -methacryloxypropylalkyl dialkoxysilane, (gamma)-chloropropyltrialkoxysilane, (gamma)-mercaptopropyltrialkoxysilane, (beta)-(3, 4- epoxycyclo Hexyl) ethyl trialkoxysilane, vinyl trialkoxysilane, etc. are mentioned, Preferably it is (gamma)-glycidoxy propyl trialkoxysilane or (gamma)-methacryloxypropyl trialkoxysilane, More preferably, (gamma)-glycidoxy Propyltrialkoxysilane. These can be used individually or in mixture of 2 or more types.

Although the content of the adhesion improving agent is not particularly limited within the range capable of its function, it may be included in an amount of 0.1 to 20 parts by weight, and preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin. When the content of the adhesion improving agent is included in an amount of 0.1 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the binder resin, there is an advantage in that the adhesion with the insulating film and the adjustment of the taper angle with the substrate can be maximized.

The thermal crosslinking agent is a component for smoothly generating a crosslinking reaction through UV irradiation and heat treatment when forming an insulating film as a composition, and improving heat resistance.

The type of thermal crosslinking agent is not particularly limited, and specific examples thereof include polyacrylate resins, epoxy resins, phenol resins, melamine resins, organic acids, amine compounds, anhydride compounds, and the like. These can be used individually or in mixture of 2 or more types.

The thermal crosslinking agent is not particularly limited in its content within the range capable of its function, but may be included 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight based on 100 parts by weight of the binder resin. When the content of the thermal crosslinking agent is included in an amount of 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the binder resin, there is an advantage in that the effect of improving heat resistance is maximized.

The light stabilizer is a component that improves light resistance of the insulating film composition.

The kind of the light stabilizer is not particularly limited, and specific examples thereof include benzotriazole type, triazine type, benzophenone type, hindered aminoether type, hindered amine compound and the like. These can be used individually or in mixture of 2 or more types.

The light stabilizer is not particularly limited in its content within the range capable of its function, but may be included 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight based on 100 parts by weight of the binder resin. When the content of the light stabilizer is contained in an amount of 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the binder resin, there is an advantage in that the light resistance improvement effect is maximized.

The resin composition of this invention comprised as mentioned above is excellent in a sensitivity and a resolution, and can adjust the inclination of the formed pattern.

The present invention provides an insulating film made of the composition.

The method for forming an insulating film according to the present invention comprises the steps of applying the photosensitive resin composition of the present invention on a substrate or a source / drain or silicon nitride layer formed on the substrate of the display device; Pre-bake the photosensitive resin composition; Selectively exposing and developing the photosensitive resin composition to form a pattern; It may include the step of forming an insulating protective film by exposing the entire surface and heat treatment of the photosensitive resin composition.

As the substrate, glass or transparent plastic resins commonly used in liquid crystal displays, organic ELs, and the like are mainly used, but are not particularly limited depending on the characteristics of the display apparatus used. For example, a metal film constituting a gate electrode is formed on an insulating substrate such as a glass substrate, and the metal film is used as a surface layer.

The method of applying the photosensitive resin composition to the upper part of the substrate is not particularly limited, and for example, a rotary coating such as a coating method using a slit nozzle such as a spray coating method, a roll coating method, a discharge nozzle type coating method, or a central dropping spin method. Method, extrusion coating method, bar coating method and the like, can be coated by combining two or more coating methods.

The applied film thickness varies depending on the application method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness becomes 0.5 to 100 m after drying.

After the grilling step is performed, the solvent is volatilized by applying vacuum, infrared rays, or heat to obtain a non-flowable coating film after forming the coating film. Heating conditions vary depending on the type and composition of each component, but may be performed at 60 to 130 ° C. for 5 to 500 seconds in case of heating a hot plate, and 60 to 140 when using a heat oven. It may be carried out at 20 ° C for 20 to 1,000 seconds.

Next, the selective exposure process may be excimer laser, far ultraviolet, ultraviolet light, visible light, electron beam, X-ray or g-ray (wavelength 436nm), i-ray (wavelength 365nm), h-ray (wavelength 405nm) or mixed rays thereof. Is carried out while examining. The exposure may be performed by contact, porximity, projection exposure, or the like.

In the present invention, after performing the alkali development, the step of performing the entire surface exposure and heat treatment (high temperature firing) of the photosensitive resin composition. The thermal crosslinking agent is applied to the composition of the photosensitive resin composition for the high temperature baking. The heat treatment step may be performed for 30 minutes to 3 hours under a temperature of 150 to 350 ℃ using a heating apparatus such as a hot plate or oven. After the heat treatment, a completely cross-cured pattern is obtained.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Example  1-5 and Comparative example  1-6

To the photosensitive resin composition was prepared with the components and compositions (% by weight) described in Table 1 below.

division bookbinder
(A) Photoacid generator
(B) /
Sensitizer (C) menstruum
(D) Basic compound
(E) Surfactants
(F) Adhesion improver
(G) Kinds Parts by weight Kinds Extension Kinds Parts by weight Kinds Extension Kinds Extension Kinds Extension Example 1 A1 100 B1 / C 6.0 / 3.0 D1 / D2 120/80 E 0.01 F1 / F2 0.1 / 0.1 G 5 Example 2 A1 100 B2 / C 4.0 / 1.5 D1 / D2 120/80 E 0.01 F1 / F2 0.1 / 0.1 G 5 Example 3 A2 100 B2 / C 4.0 / 1.5 D1 / D2 120/80 E 0.01 F1 / F2 0.1 / 0.1 G 5 Example 4 A3 100 B2 / C 3.0 / 1.0 D1 / D2 120/80 E 0.01 F1 / F2 0.1 / 0.1 G 5 Example 5 A3 100 B3 / C 4.0 / 2.0 D1 / D2 120/80 E 0.01 F1 / F2 0.1 / 0.1 G 5 Comparative Example 1 A1 100 B4 / C 3.0 / 1.5 D1 / D2 120/80 E 0.01 F1 / F2 0.1 / 0.1 G 5 Comparative Example 2 A3 100 B4 / C 2.0 / 1.0 D1 / D2 120/80 E 0.01 F1 / F2 0.1 / 0.1 G 5 Comparative Example 3 A3 100 B5 / C 2.0 / 1.0 D1 / D2 120/80 E 0.01 F1 / F2 0.1 / 0.1 G 5 Comparative Example 4 A1 100 B1 8.0 D1 / D2 120/80 E 0.01 F1 / F2 0.1 / 0.1 G 5 Comparative Example 5 A1 100 B2 6.0 D1 / D2 120/80 E 0.01 F1 / F2 0.1 / 0.1 G 5 Comparative Example 6 A3 100 B3 6.0 D1 / D2 120/80 E 0.01 F1 / F2 0.1 / 0.1 G 5

A1: (a)/(b)/(c)/(d)/(e)/(f) = 35/0/15/10/25/15
A2: (a)/(b)/(c)/(d)/(e)/(f) = 20/20/15/10/20/15
A3: (a)/(b)/(c)/(d)/(e)/(f) = 0/40/15/10/25/10

2. 산발생제 (B)
B1 : Irgacure PAG290 (BASF 사)

B2 :

B3 :

B4 :

B5 : CGI-1397 ( Ciba 사)


3. 증감제 (C)

3. 용매 (D)
D1 : 프로필렌글리콜메틸에틸아세테이트, D2 : 디에틸렌글리콜메틸에틸에스테르

4. 염기성 화합물 (E):디시클로헥실메틸아민

5. 계면활성제 (F)
F1 : SH-8400 , F2 : F-475

6. 밀착성 개량제 (G): KBM-403(γ-글리시독시프로필트리알콕시실란)1. Binder (A)

A1: (a) / (b) / (c) / (d) / (e) / (f) = 35/0/15/10/25/15
A2: (a) / (b) / (c) / (d) / (e) / (f) = 20/20/15/10/20/15
A3: (a) / (b) / (c) / (d) / (e) / (f) = 0/40/15/10/25/10

2. Acid Generator (B)
B1: Irgacure PAG290 (BASF Corporation)

B2:

B3:

B4:

B5: CGI-1397 (Ciba Corporation)


3. Sensitizer (C)

3. Solvent (D)
D1: propylene glycol methyl ethyl acetate, D2: diethylene glycol methyl ethyl ester

4. Basic compound (E): dicyclohexylmethylamine

5. Surfactant (F)
F1: SH-8400, F2: F-475

6. Adhesive improver (G): KBM-403 (γ-glycidoxypropyltrialkoxysilane)

Test Example

Evaluation was carried out as follows for the resin composition prepared according to Examples and Comparative Examples, the results are shown in Table 2 below.

(1) sensitivity

On a 0.7 mm-thick glass substrate (Corning 1735, Corning), the photosensitive resin compositions of Examples and Comparative Examples were respectively applied with a spinner, heated for 125 seconds on a 100 ° C hotplate to volatilize the solvent, and the photoresist was 4.0 µm thick. The resin composition layer was formed.

Thereafter, in order to obtain a contact hole pattern having a diameter of 10 m, the exposure part was exposed with an i-line stepper (NSR-205i11D, Nikon Corporation) using a mask having a rectangular pattern opening having a side of 10 m.

The board | substrate after exposure was puddle-developed for 40 second at 23 degreeC with the 2.38% tetramethylammonium hydroxide aqueous solution, and it heated for 30 minutes in 230 degreeC oven, and obtained the hardened film.

Subsequently, the substrate was cut vertically and the exposure amount which becomes a 10 micrometer contact hole in each composition was selected as a sensitivity.

(2) transmittance

The transmittance at 400 nm was measured using a spectrophotometer.

(3) heat resistance stability evaluation

After leaving the substrate prepared in Test Example (1) in an oven at 230 ° C. for 2 hours, the transmittance at 400 nm was measured, and thermal stability was evaluated based on the transmittance difference before and after standing.

division Sensitivity (mJ / cm ² ) Transmittance (%) Heat stability
(Transmittance difference) Example 1 33 96 -0.5 Example 2 32 94 0.0 Example 3 27 90 -0.5 Example 4 20 92 -2.2 Example 5 21 91 -0.8 Comparative Example 1 25 73 -20.4 Comparative Example 2 21 83 -26.3 Comparative Example 3 19 78 -32.0 Comparative Example 4 280 87 -1.2 Comparative Example 5 No pattern formation 83 -1.0 Comparative Example 6 460 84 -0.8

Referring to Table 2, it can be seen that the insulating film formed of the photosensitive resin compositions of Examples 1 to 5 has good sensitivity and excellent transmittance. And the difference in transmittance before and after heat treatment was only a maximum of -2.2, it was confirmed that the excellent heat stability.

However, although the insulating film formed from the composition of Comparative Examples 1-3 was excellent in sensitivity, it was confirmed that the transmittance | permeability is inferior to heat resistance stability.

Although the insulating film formed from the composition of Comparative Examples 4-6 was excellent in heat resistance stability, the transmittance | permeability and the sensitivity were very inferior, and Comparative Example 5 confirmed that pattern formation itself was impossible.

Claims (11)

Binder resins;
A non-oxime sulfonate-based photoacid generator represented by the formula (1) or (2) to increase the solubility of the binder resin in the developer in the exposed portion;
Sensitizers represented by Formula 3; And
Photosensitive resin composition comprising a solvent:
[Formula 1]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an oxygen atom, a benzyl group, a phenyl group, an alkyl group having 1 to 6 carbon atoms, an acetyl group, a phenylacetyl group, a phenylcarbonyl group or An acetylphenylthio group, wherein the benzyl group, phenyl group, alkyl group having 1 to 6 carbon atoms, acetyl group, phenylacetyl group and acetylphenylthio group may be substituted with acetylphenylthio group, provided that at least one of R ₁ and R ₂ is If the oxygen atom R ₁ and R ₂ are connected to each other when forming a ring, and at least one of R ₃ and R ₄ is an oxygen atom R ₃ and R ₄ are connected to each other to form a ring, and; X ^- is ^{_{PF 6 -, AsF 6 -,}} SbF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3 ^{_{) 6 P -, (C 2}} F 5 SO 2) 2 N -, (CF 3 SO 3) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, CF 3 CF 2 (CF 3) 2 ^{_{CO -, (CF 3 SO 2}} ) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 COO -, CF 3 SO 3 -, (C ₆ F ₅ ) ₄ B ^- and C ₃ F ₇ COO ^-which is an anion selected from the group consisting of
[Formula 2]

(Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a benzyl group, a phenyl group, an alkyl group having 1 to 6 carbon atoms, an acetyl group, a phenylacetyl group or an acetylphenylthio group, and the benzyl group , a phenyl group, a group alkyl group, an acetyl group, a phenylacetyl group having 1 to 6 carbon atoms and acetyl phenylthio group may be substituted and a group acetyl-phenylthio; X ^- is ^{_{PF 6 -, AsF 6 -,}} SbF 6 -, (CF 3) 2 ^{_{PF 4 -, (CF 3)}} 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, (C 2 F 5 SO 2) 2 N -, _{(CF 3 SO 3) 2 N} -, (CF 3 SO 2) (CF 3 CO) N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) ^{_{3 C -, (CF 3 SO}} 2) 3 C -, CF 3 COO -, CF 3 SO 3 -, (C 6 F 5) 4 B - , and C ₃ F ₇ COO ^- being an anion, selected from the group consisting of a)
[Formula 3]

(Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms).
delete The photosensitive resin composition of claim 1, wherein the photoacid generator is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the binder resin.
The photosensitive resin composition of claim 1, wherein the sensitizer is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the binder resin.
The photosensitive resin composition of claim 1, wherein the binder resin has a weight average molecular weight of 5,000 to 30,000.
The photosensitive resin composition of claim 1, wherein the binder resin is included in an amount of 5 to 50% by weight based on the total weight of the composition.
The photosensitive resin composition of claim 1, wherein the solvent is at least one selected from the group consisting of ethers, acetates, esters, ketones, amides, and lactones.
The photosensitive resin composition of claim 1, wherein the solvent is included in an amount of 40 to 90% by weight based on the total weight of the composition.
The photosensitive resin composition of claim 1, further comprising at least one selected from the group consisting of a basic compound, a surfactant, an adhesion improving agent, a thermal crosslinking agent, a light stabilizer, a photocuring accelerator, an antihalation agent, and an antifoaming agent.
The insulating film which hardened the photosensitive resin composition of any one of Claims 1 and 3-9.
A liquid crystal display device comprising the insulating film of claim 10.