KR101751646B1 - Binder resin and photosensitive resin composition containing the same - Google Patents

Abstract

The present invention relates to an organic material for a display such as a TFT-LCD, an OLED and a TSP, which is used for a photoresist composition and a binder resin to be applied to a coating material, and which has high performance and high performance characteristics such as heat resistance, chemical resistance, high permeability, .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a binder resin and a photosensitive resin composition containing the binder resin.

The present invention relates to a binder resin having high performance and high performance properties such as heat resistance, chemical resistance, high permeability and high refractive index, and a photosensitive resin composition containing the binder resin.

A photosensitive resin composition for a display applied to a thin film transistor type liquid crystal display (TFT-LCD), an organic light emitting element (OLED), a touch screen panel (TSP) or the like causes a curing reaction and a photolysis reaction by UV and ultraviolet irradiation to form a pattern A negative photosensitive material and a negative photosensitive material according to a method in which a negative photosensitive material is used. The positive photosensitive material is dissolved in the developing solution in a region irradiated with UV and ultraviolet rays to form a pattern. The negative photosensitive material is photocured at the portion irradiated with UV and ultraviolet rays, and the unexposed portion dissolves in the developing solution This is how the pattern is formed.

In order to increase the light efficiency of a display, a high transmittance and a high refractive index are important in the photosensitive resin composition in recent years. In order to secure the high heat resistance, chemical resistance, high permeability and high refractive index characteristics of the photosensitive resin composition, the structure and properties of the binder among the compositions constituting the photosensitive material are very important. For this reason, studies for imparting photosensitivity to a binder resin such as novolak resin system, polyimide and the like, including acrylic photosensitive resin used as a typical binder resin of a photosensitive resin composition, have been actively studied. However, conventionally used photosensitive resin compositions using acrylic photosensitive resin and novolac resin have poor heat resistance in a high temperature heat treatment process at 300 DEG C or more, so that impurities due to outgassing are generated and the display is seriously contaminated, There is a problem that the transmittance is lowered and the light efficiency characteristic of the display is lowered.

For example, U.S. Patent No. 4,139,391 discloses a photosensitive resin composition prepared by using a copolymer of an acrylate compound and an acrylate compound as a binder resin and an acrylate compound as a polyfunctional monomer. However, the difference in solubility between the exposed portion and the unexposed portion is not sufficiently large, and the developing property is not good, and the binder resin to be left in the developing process is partially dissolved in the developing solution, making it difficult to obtain a fine pattern of 10 탆 or less.

Japanese Patent Application Laid-Open Nos. 52-13315 and 62-135824 disclose photosensitive photoresist compositions containing polyamic acid as a polyimide precursor and a naphthotquinonediazide compound as a dissolution inhibitor to increase thermal stability However, there is a problem that the difference in dissolution rate between the exposed portion and the non-exposed portion is large enough to form a high-resolution pattern.

In addition, since the photosensitive resin composition has good adhesion with the lower layer and the upper layer and has a large process margin capable of forming a fine pattern of high resolution under various process conditions in accordance with the purpose of use, and high sensitivity characteristics are required as the photosensitive material, Research to improve the characteristics is also being actively pursued.

The present invention is directed to a binder resin having excellent heat resistance and high transparency and high refractive index to solve the above-described conventional problems, and an object of the present invention is to provide a photosensitive resin composition using such a high performance and high functionality binder resin.

In order to achieve the above object, the present invention provides a binder resin, which is a polymer represented by the following general formula (I).

(I)

In the formula (I), R ₃ and R ' ₃ each represent an alkyl group with or without a heteroatom of 1 to 20 carbon atoms, an aryl group with or without a heteroatom of 6 to 20 carbon atoms, or RC (= O) R R ₄ is a tetravalent aromatic or cycloaliphatic hydrocarbon radical containing or not containing a heteroatom of 1 to 20 carbon atoms, A is a substituent represented by the following general formulas (I-1) to (I-4) n is an integer of 1 to 6, and p is an integer of 1 to 30. [

(I-1)

[Formula I-2]

[Formula I-3]

[Formula I-4]

R ₂ and R ' ₂ are each independently selected from the group consisting of hydrogen, a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH ₂ ), a nitro group (-NO ₂ ) And X represents O, S, N, Si or Se.

The binder resin may be used, for example, in a photosensitive material for a display.

The binder resin may be a resin terminated with an organic acid, an organic acid anhydride, or an amic acid, for example.

The weight average molecular weight of the binder resin may be, for example, 1,000 to 100,000 g / mol.

The binder resin may have a degree of dispersion of 1.0 to 5.0, for example.

The present invention also provides a negative photosensitive resin composition comprising the binder resin, the photoinitiator, the organic solvent and the additive of the present invention.

The negative photosensitive resin composition may include, for example, 100 parts by weight of a binder resin, 1 to 20 parts by weight of a photoinitiator, 0.01 to 5 parts by weight of a surfactant, and 0 to 10 parts by weight of an adhesion promoter in an organic solvent in an amount of 5 to 80% have.

The present invention also provides a positive photosensitive resin composition comprising the binder resin, the photoactive compound, the organic solvent and the additive of the present invention.

The positive photosensitive resin composition includes, for example, 100 parts by weight of a binder resin, 0.1 to 30 parts by weight of a photoactive compound, 0.01 to 5 parts by weight of a surfactant, and 0 to 10 parts by weight of an adhesion promoter in an organic solvent in an amount of 5 to 80% .

The present invention also provides a substrate comprising a resin curing pattern formed from the photosensitive resin composition.

Since the binder resin of the present invention has excellent heat resistance and transmittance characteristics and optical characteristics of high refractive index, excellent heat resistance, transmittance and refractive index characteristics of the photosensitive resin composition containing the binder resin can be secured. In addition, since the binder resin of the present invention has excellent heat resistance and can minimize the taper angle and outgassing, and has excellent adhesion to the substrate and excellent chemical resistance against strong acids and strong bases, the TFT-LCD, the OLED And TSP display as well as high performance and high performance coating materials.

Fig. 1 is a graph comparing transmittances of the photosensitive resin compositions of Example 4 and Comparative Example 1. Fig.
Fig. 2 is a graph comparing the heat resistance of the photosensitive resin compositions of Example 4 and Comparative Example 1. Fig.
3 is a pattern SEM photograph of the photosensitive resin composition of Example 4 and Comparative Example 1. Fig.
4 is a photograph showing the refractive index results of Example 4. Fig.

Hereinafter, the present invention will be described in detail.

The present invention relates to a binder resin and a photosensitive resin composition containing the binder resin. The photosensitive resin composition may contain a photoinitiator, a photoactive compound, a solvent, etc. in addition to the binder, and may further include additives such as a heat stabilizer, a thermal crosslinking agent, a photo-curing accelerator, or a surfactant.

First, the binder resin will be described in detail.

1. Binder Resin

The present invention provides a monomer represented by the following general formulas (5) to (8) and a binder resin represented by the following general formula (I) as a polymer having such a monomer as a repeating unit.

In the present invention, the structure of the binder resin is composed of a bisphenylfluorene structure represented by the general formula (1), a bisnaphthylfluorene structure represented by the general formula (2), and a xanthene structure represented by the general formulas (3) Structure.

For example, the binder resin represented by the following formula (I) can be synthesized by synthesizing a monomer having a hydroxy group of the following formulas (5) to (8) from a compound represented by the following formulas (1) to (4) and then reacting it with a carboxylic acid dianhydride.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In the compound structures of the above formulas (1) to (4)

R ₁ and R ₁ each represent a C 1 to C 8 hydrocarbon group containing a heteroatom such as a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH ₂ ), a nitro group (-NO ₂ ) to 20 aliphatic or alicyclic group, or a hetero element represents an aryl group having 6 to 20 carbon atoms containing, R _2, R _'2 are independently a hydrogen or a hydroxyl group (-OH), thiol (-SH), an amino group (- NH ₂ ), a nitro group (-NO ₂ ), or a halogenated group. Wherein X represents O, S, N, Si or Se.

In the present description, " each " means " independently " and includes both cases where the two components are the same or different.

In the compound structures of the formulas (1) to (4), for example, R ₁ and R ' ₁ each include an aliphatic or alicyclic alkyl group having 1 to 10 carbon atoms, 3 to 8 carbon atoms, or 3 to 5 carbon atoms, Or an aryl group having 6 to 15, 6 to 10, or 7 to 10 carbon atoms.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the monomer structures of Formulas 5 to 8,

R ₂ and R ' ₂ each represent hydrogen or a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH ₂ ), a nitro group (-NO ₂ ), or a halogenated group. Wherein X represents O, S, N, Si or Se. R ₃ and R ' ₃ each independently represent an alkyl group with or without a heteroatom of 1 to 20 carbon atoms, an aryl group with or without a heteroatom of 6 to 20 carbon atoms, or an RC (= O) R' substituent And n is an integer of 1 to 6.

R ₃ and R ' ₃ each represent, for example, an alkyl group containing or not containing a heteroatom of 2 to 15 carbon atoms or 2 to 10 carbon atoms, or an alkyl group containing 6 to 15 carbon atoms or 6 to 10 carbon atoms, Lt; / RTI >

The R may be, for example, a bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms.

The R 'may be, for example, an alkyl group or an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.

The n may be, for example, 1 to 3, or 1 to 2.

The hetero element means a monovalent or divalent radical of an element other than carbon and hydrogen, and is, for example, at least one selected from the group consisting of oxygen, nitrogen, sulfur, halogen and silicon, In this case, there is an effect of excellent heat resistance, chemical resistance, high permeability, high refractive index and optical characteristics.

As another example, R ₃ and R ' ₃ may each be R _a SR _b , and R _a may be _a bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms, S may be sulfur, R _b may be an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. In this case, heat resistance, high transmittance and high refractive index are excellent.

(I)

In the formula (I), R ₃ and R ' ₃ each represent an alkyl group with or without a heteroatom of 1 to 20 carbon atoms, an aryl group with or without a heteroatom of 6 to 20 carbon atoms, or RC (= O) R R ₄ is a tetravalent aromatic or cycloaliphatic hydrocarbon radical containing or not containing a heteroatom of 1 to 20 carbon atoms, A is a substituent represented by the following formulas (I-1) to (I-4) n is an integer of 1 to 6, and p is an integer of 1 to 30. [

(I-1)

[Formula I-2]

[Formula I-3]

[Formula I-4]

In the formulas (I-1) to (I-4)

R ₂ and R ₂ each represent hydrogen, a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH ₂ ), a nitro group (-NO ₂ ) , Si or Se.

In the formulas I-1 to I-4, n may be 1 to 3, or 1 to 2, for example. In this case, the heat resistance, high transmittance and high refractive index are excellent.

The binder resin represented by the above formula (I) is, for example, an integer of 1 to 30, or an integer of 1 to 10, and has an excellent heat resistance, high transmittance and high refractive index within the above range.

The method for producing the binder resin of the present invention may include, for example, a step of polymerizing a monomer represented by the above formulas (5) to (8) and a carboxylic acid dianhydride represented by the following formula (9).

[Chemical Formula 9]

Wherein R ₄ is a tetravalent cycloaliphatic hydrocarbon radical having 4 to 20 carbon atoms and containing or not containing a heteroatom or a tetravalent aromatic hydrocarbon radical having 6 to 20 carbon atoms and containing or not containing a heteroatom .

In another embodiment, R ₄ in the general formula (9) is a cycloaliphatic hydrocarbon radical having 4 to 10 carbon atoms, or 4 to 6 carbon atoms, with or without a heteroatom, or a cycloaliphatic hydrocarbon radical having 6 to 15, or 6 to 12 carbon atoms Is a tetravalent aromatic hydrocarbon radical containing or not containing a hetero element, and has an excellent heat resistance, high transmittance and high refractive index in this range.

Specific examples of the carboxylic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride , 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzo Phenanetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3- Bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis {4- (3,4- Naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic acid dianhydride, 3,4,9,10-tetramethyluronium hexafluorophosphate, Perylene tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and the like, and 1,2,4,4-tetracarboxylic acid dianhydride - alicyclic tetracarboxylic acids such as cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride. It may be a mixed acid dianhydride or 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride.

The polymerization may be carried out, for example, at from 100 to 130 ° C, or from 110 to 120 ° C for from 2 hours to 24 hours, or from 4 hours to 12 hours.

The carboxylic acid dianhydride may be added in an amount of 5 to 40 parts by weight, 10 to 30 parts by weight, or 10 to 20 parts by weight based on 100 parts by weight of the monomer represented by the above formulas 5 to 8.

The binder resin of the present invention can be prepared by, for example, introducing an end-capping agent after the initiation of the polymerization reaction.

The end capping reaction may be carried out at from 100 to 130 ° C, or from 110 to 120 ° C for 30 minutes to 4 hours, or 1 hour to 3 hours, for example.

The end capping agent may be added in an amount of 2 to 10 parts by weight, 2 to 5 parts by weight, or 3 to 5 parts by weight based on 100 parts by weight of the monomer represented by the above formulas 5 to 8.

As the end capping agent, for example, an aromatic carboxylic acid anhydride is preferable, and a specific example thereof is phthalic anhydride and the like. In this case, the end capping agent is excellent in heat resistance, high transmittance and high refractive index.

The binder resin may have a weight average molecular weight of 1,000 to 100,000 g / mol, preferably 2,000 to 50,000 g / mol, more preferably 3,000 to 10,000 g / mol, The development speed of the ash and the development by the developing solution are appropriate, and the pattern formation is good and the residual film ratio is high.

The weight average molecular weight of the present invention can be measured by a gel permeation chromatography (GPC) method.

The degree of dispersion of the binder resin may be in the range of 1.0 to 5.0, preferably in the range of 1.5 to 4.0. Within this range, the heat resistance is excellent and the developing rate of the photosensitive material and development by the developer are appropriate, The membrane ratio is highly effective.

The dispersion degree of the present invention can be measured by a GPC measurement method.

2. Negative-type photosensitive resin composition

The negative photosensitive resin composition of the present invention is characterized by comprising the binder resin, photoinitiator, organic solvent and additives of the present invention.

As another example, the negative-working photosensitive resin composition of the present invention is characterized in that the binder resin of the present invention contains a photoinitiator, a crosslinkable compound having an ethylenically unsaturated bond, an additive, and an organic solvent.

(B) a crosslinkable compound having an ethylenically unsaturated bond, (C) at least one photoinitiator, (D) a solvent, and (E) at least one photoinitiator. ) ≪ / RTI > additive.

In the negative photosensitive resin composition of the present invention, the photoinitiator refers to a component that generates active species capable of initiating polymerization of the above-mentioned binder resin by visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-

Examples of the photoinitiator include oxime ester compounds, imidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, alpha-diketone compounds, polynuclear quinone compounds, phosphine compounds, Compounds and the like. Of these, acetophenone compounds or oxime ester compounds are preferable.

The oxime ester compound is excellent in pattern stability after the development process with a very high exposure sensitivity, and can form a stable development pattern even at a low exposure dose, and is excellent in adhesion to a substrate, light diffusing property and insulation property, Has the advantage of forming an excellent resin.

Examples of the oxime ester compound include 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime), 1,3- 1 [(4-phenylthio) phenyl] 2-benzoyl-oxime and the like.

Examples of the acetophenone-based compound include an alpha-hydroxy ketone compound, an alpha-amino ketone compound, and other compounds.

Specific examples of the alpha-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and the like, and the above-mentioned alpha-amino ketone compound 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- -Butanone-1, and specific examples of the other compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and the like . These acetophenone compounds may be used singly or in combination of two or more. By using these acetophenone compounds, the strength of the thin film can be further improved.

Specific examples of the nonimidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2 -Imidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl- , 2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis -Tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, and the like.

Among the imidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis , 4,4'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like are particularly preferable, and 2,2'-bis (2,4-dichlorophenyl) -4,4' , 5'-tetraphenyl-1,2'-biimidazole.

The content of the photoinitiator is 1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight based on 100 parts by weight of the binder resin.

The crosslinkable compound having an ethylenically unsaturated bond is generally a crosslinkable unit having at least two ethylenic double bonds, and examples thereof include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, tri Ethylene glycol diacrylate, ethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, Trimethylolpropane triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacryl 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexa methacrylate, , Polyfunctional (meth) acrylic monomers and oligomers such as 6-hexanediol dimethacrylate, cardo-epoxy diacrylate and poly- compounds thereof (polyethylene glycol diacrylate); (Meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid, a polyester (meth) acrylate obtained by reacting a polyol group with a compound having two isocyanate groups, (Meth) acrylate obtained by reacting polyurethane (meth) acrylate; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, And an epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as a cyydecyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, or a dihydroxybenzene type epoxy resin with (meth) acrylic acid. Also, It may be advantageous to use a multifunctional (meth) acrylic monomer in consideration of exposure sensitivity and the like.

The crosslinkable compound having an ethylenically unsaturated bond is preferably contained in an amount of 10 to 200 parts by weight, more preferably 30 to 150 parts by weight, based on 100 parts by weight of the binder resin. Within this range, The pattern is well-formed and the hardness and resolution of the formed pattern are excellent.

As the organic solvent for preparing the negative photosensitive resin composition of the present invention, the polymer may be dissolved in an organic solvent such as acetate, ether, glycol, ketone, alcohol, or carbonate used in a general photopolymerizable composition It is not particularly limited. Examples of the solvent include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, cyclohexanone, cyclopentanone, 3-ethoxypropionic acid, N , N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, and the like.

The content of the solvent may be 20 to 95 parts by weight, preferably 30 to 90 parts by weight, more preferably 50 to 80 parts by weight based on 100 parts by weight of the entire photosensitive resin composition. Within this range, It is easy to form a thin film and a thin film having a desired thickness after coating can be easily obtained.

In the present invention, additives may be used if necessary. Examples of such additives include heat stabilizers, heat crosslinking agents, photocuring accelerators, surfactants, base quenchers, antioxidants, adhesion promoters, light stabilizers and antifoaming agents, and may be used alone or in combination as required.

Among the additives that are typically included among the above additives, the adhesion aid is a component having an action to improve adhesion with the substrate, and includes, for example, reactive functional groups such as carboxyl group, methacryloyl group, vinyl group, isocyanate group, epoxy group, Is preferred. Specific examples include trimethoxysilylbenzoic acid,? -Methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyl Trimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

The content of the adhesive aid is preferably 0 to 10 parts by weight, 0.01 to 10 parts by weight, 0.02 to 1 part by weight, or 0.05 to 0.1 part by weight based on 100 parts by weight of the binder resin, The adhesive strength of the adhesive layer is excellent.

The surfactant is a component having an effect of improving coatability, coatability, uniformity and stain removal on a substrate, and may contain one or more selected from the group consisting of a fluorinated surfactant, a silicone surfactant and a nonionic surfactant And may be used in combination. Preferably, the surfactant is a silicone surfactant. Examples of the surfactant include polysiloxane modified with polyisocyanate. More specific examples thereof include polyether-modified polydimethylsiloxane.

The amount of the surfactant is, for example, 0.01 to 5 parts by weight, 0.02 to 1 part by weight, or 0.05 to 0.1 parts by weight based on 100 parts by weight of the binder resin.

The adhesion aid is not particularly limited in the case of an adhesion aid which can be generally used in a photosensitive resin composition, but it is preferable that at least one member selected from the group consisting of an isocyanate compound, an epoxy compound, an acrylate compound, a vinyl compound and a mercapto- More preferred is an epoxy compound, for example, an organosilane compound having an epoxy group, and more specifically, there is a methoxysilane having an epoxy group.

The stabilizer may be, for example, a heat stabilizer, a light stabilizer, or a mixture thereof.

The heat stabilizer is not particularly limited in the case of a heat stabilizer that can be generally used in a photosensitive resin composition. For example, the heat stabilizer is a heat stabilizer capable of suppressing lowering of the transmittance during the post-heat treatment process of the organic film formed to increase the permeability of the residual organic film, May be at least one member selected from the group consisting of a phenolic heat stabilizer, a phosphite-based heat stabilizer and a lactone-based heat stabilizer, more preferably at least one member selected from the group consisting of heat It is a stabilizer.

[Chemical formula 10]

(11)

[Chemical Formula 12]

The light stabilizer is not particularly limited when it is a light stabilizer that can be generally used in a photosensitive resin composition. For example, the light stabilizer may be a light stabilizer capable of maximizing the light resistance of the organic insulating film composition. Preferably, the light stabilizer is a benzotriazole light stabilizer, Based light stabilizer, a benzophenone light stabilizer, a hindered aminoether light stabilizer, and a hindered amine light stabilizer.

The present invention also provides an element comprising a photosensitive curing pattern formed from the photosensitive resin composition. The photosensitive binder composition may be applied to a semiconductor device, an LCD device, an OLED device, a solar cell device, a flexible display device, a touch screen device, or a nanoimprint lithography device.

For example, the photosensitive resin composition of the present invention may have a sensitivity of 140 mJ / cm ² or less, 100 to 20 mJ / cm ² , or 60 to 30 mJ / cm ² , and the effect of excellent photosensitivity have.

For example, the photosensitive resin composition of the present invention may have a residual film ratio of 91% or more, 95% or more, or 96 to 98% after development, and the optical characteristics of the photosensitive material are excellent within this range.

For example, the photosensitive resin composition of the present invention may have a residual film ratio after curing of 89% or more, 93% or 94-97%, and the optical characteristics of the photosensitive material are excellent within this range.

For example, the photosensitive resin composition of the present invention may have a tephar angle of not less than 41 degrees, not less than 45 degrees, or not more than 50 degrees and not more than 65 degrees, and has an excellent heat resistance within this range.

The photosensitive resin composition of the present invention may have a refractive index of 1.51 or more, 1.60 or 1.62 to 1.66 as an example, and the optical characteristics of the photosensitive material are excellent within this range.

For example, the photosensitive resin composition of the present invention may have a transmittance of 94% or more, 95% or more, or 96 to 99% after curing, and the optical characteristics of the photosensitive material are excellent within this range.

3. Positive type photosensitive resin composition

The present invention provides a positive photosensitive resin composition comprising the binder resin. The photosensitive resin composition of the present invention is characterized in that the binder resin contains a photoactive compound, an additive and an organic solvent.

In the present invention, the photoactive compound is not particularly limited as long as it is a photoactive compound (PAC) that can be used in a photoresist, but may be a photo-acid generator, for example.

As another example, the positive photosensitive resin composition of the present invention may contain (A) the binder resin of the present invention, (F) the photoactive compound, (G) the base resin, (D) have.

The photoacid generator is a compound that generates an acid when irradiated with an actinic ray or radiation. Any material can be used as long as it does not adversely affect the film formation because the photoacid generator has a suitable light absorption at a wavelength of 250 nm to 450 nm.

Examples of the photoacid generator include a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, a disulfone, ortho-nitrobenzylsulfonate Based compounds and triazine-based compounds.

The content of the photoacid generator, which is a photoactive compound, is 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the binder resin. In this range, The solubility of the composition in the solvent is not lowered, and the solubility of the composition in the composition is not compromised and the solid particles are not likely to be precipitated.

The base quencer may be at least one selected from the group consisting of primary amines, secondary amines, tertiary amines and amide compounds, although it is not particularly limited.

In order to prepare the positive type photosensitive resin composition according to the present invention, an organic solvent and an additive may be included. The kind and content of the organic solvent and the additive are the same as those for producing a negative photosensitive resin composition.

For example, the photosensitive resin composition of the present invention may have a sensitivity of 140 mJ / cm ² or less, 100 to 20 mJ / cm ² , or 70 to 50 mJ / cm ² , and an effect of excellent photosensitivity have.

For example, the photosensitive resin composition of the present invention may have a residual film ratio of 91% or more, 95% or more, or 96 to 99% after development, and the optical characteristics of the photosensitive material are excellent within this range.

For example, the photosensitive resin composition of the present invention may have a residual film ratio after curing of 89% or more, 93% or 94-97%, and the optical characteristics of the photosensitive material are excellent within this range.

The photosensitive resin composition of the present invention may have a teepahr angle of 41 degrees or more, 45 degrees or 50 to 65 degrees, for example, and has an excellent heat resistance within this range.

The photosensitive resin composition of the present invention may have a refractive index of 1.51 or more, 1.60 or more, 1.60 to 1.70 or 1.63 to 1.68 as an example, and the optical property of the photosensitive material is excellent within this range.

For example, the photosensitive resin composition of the present invention may have a transmittance of 94% or more, 95% or more, or 96 to 98% after curing, and the optical characteristics of the photosensitive material are excellent within this range.

The method of applying the photosensitive resin composition containing the binder resin of the present invention as a thin film to a display device such as a TFT-LCD, an OLED and a touch screen panel is not particularly limited, and a method known in the art can be used . For example, the coating solution may be applied by spin coating, dip coating, roll coating, screen coating, spray coating, flow coating, screen printing, printing, ink jet, drop casting, and the like can be applied.

The applied film thickness may vary depending on the application method, the solid content concentration of the composition, the viscosity, and the like, and is usually applied so that the film thickness after drying is 0.5 to 100 m, but is not limited thereto. Then, in the pre-baking step, the solvent is volatilized by applying vacuum, infrared rays or heat. Next, the selective exposure process may be performed using an excimer laser, a deep ultraviolet ray, an ultraviolet ray, a visible ray, an electron ray, an X-ray or a g- ray (wavelength 436 nm), an i- ray (wavelength 365 nm), an h- Investigate using light rays. The exposure may be performed by a contact method, a proximity method, or a projection method.

The photosensitive resin composition of the present invention can use an aqueous alkali solution as a developer, which is eco-friendly and economical than an organic solvent. Examples of the alkali developing solution include aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and amine-based aqueous solutions such as ammonia, ethylamine, diethylamine and triethylamine. Among them, an aqueous solution of tetramethylammonium hydroxide (TMAH) is most commonly used.

The present invention also provides an element comprising a photosensitive curing pattern formed from the binder. The photosensitive binder resin composition can be applied to a semiconductor device, an LCD device, an OLED device, a solar cell device, a flexible display device, a touch screen manufacturing device, or a nanoimprint lithography device.

The present invention will be described in more detail through the following specific Synthesis Examples and Examples. The following examples serve to illustrate the present invention and do not limit the scope of the present invention.

Synthetic example

Monomer synthesis

Bis (methylene)) bis (oxirane) Synthesis (Synthesis of Compound (1)) [0154] Step 1: Synthesis of 2,2'-bis (4-phenylene) Yes)

Step A: After setting the reflux condenser and thermometer on the 3-neck flask, 42.5 g of 9,9-bisphenolfluorene was added and 220 mL of 2- (chloromethyl) oxirane was injected and injected. After adding 100 mg of tetrabutylammonium bromide, the temperature was raised to 90 캜 while stirring was started. After confirming that the unreacted content was less than 0.3%, it was distilled under reduced pressure.

Step B: After lowering the temperature to 30 ° C, dichloromethane was injected and NaOH was slowly added. The product was confirmed to be 96% or more by a high performance liquid chromatography (HPLC) method, and 5% HCl was added dropwise to terminate the reaction. The reaction product was extracted and layered, and the organic layer was washed with water and neutralized. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure using a rotary evaporator. Dichloromethane was added to the concentrated product, and methanol was added to the solution while the temperature was raised to 40 ° C. The solution temperature was lowered and stirred. The resulting solid was filtered and vacuum-dried at room temperature to obtain 52.7 g (yield 94%) of a white solid powder, which was confirmed by 1H NMR.

2H NMR (CDCl3): 7.75 (2H), 7.36-7.25 (6H), 7.09 (4H) ).

Monomers having the structures of formulas (2) to (4) can be conventionally prepared by the method disclosed in the one-step synthesis method.

Bis (1- (phenylthio) propan-2-ol) (BTCP (2-ethylhexyl) ) Synthesis (Example of Chemical Formula 5)

A reflux condenser and a thermometer were set in a 3-neck flask, and then a first-stage reaction product (1000 g), 524 g of thiophenol and 617 g of ethanol were added and stirred. 328 g of triethylamine was slowly added dropwise to the reaction solution. After confirming that the starting material disappeared by high performance liquid chromatography (HPLC) method, the reaction was terminated. After completion of the reaction, the ethanol was distilled off under reduced pressure. The organics were dissolved in dichloromethane, washed with water and then dichloromethane was removed by distillation under reduced pressure. The concentrated organic material was dissolved in ethyl acetate, ether solvent was added dropwise, and the mixture was stirred for 30 minutes. The compound was distilled under reduced pressure to obtain 945 g (yield: 64%) of pale yellow oil. Its structure was confirmed by 1H NMR.

2H NMR (CDCl3): 7.82 (2H), 7.38-6.72 (2H), 6.51 (2H), 4.00 (2H), 3.97 ).

Monomers having the groups of formulas (6) to (8) can be conventionally prepared by the method disclosed in the two-step synthesis method.

Binder manufacturing

Preparation Example 1: Preparation of BTCP / BPDA binder

After setting the reflux condenser and thermometer on the 3-neck flask, 200 g of the BTCP monomer synthesized in Step 2, which was dissolved in 50% PGMEA solvent, was added and the temperature was raised to 115 캜. 31.1 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (compound of the formula (9-1)) was added dropwise at 115 DEG C, and the mixture was stirred at 115 DEG C for 6 hours. Phthalic anhydride (7.35 g) was added thereto, followed by further stirring for 2 hours, and the reaction was terminated. After cooling, a binder solution having a weight average molecular weight of 3,500 g / mol was obtained.

Production Example 2: Preparation of BTCP / BTDA binder

After setting the reflux condenser and thermometer on the 3-neck flask, 200 g of the BTCP monomer synthesized in Step 2, which was dissolved in 50% PGMEA solvent, was added and the temperature was raised to 115 캜. 28.4 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (compound of formula (9-2)) was added dropwise at 115 ° C, and the mixture was stirred at 115 ° C for 6 hours. Phthalic anhydride (7.35 g) was added thereto, followed by further stirring for 2 hours, and the reaction was terminated. After cooling, a binder solution having a weight average molecular weight of 5,000 g / mol was obtained.

Preparation Example 3: Preparation of BTCP / PMDA binder

After setting the reflux condenser and thermometer on the 3-neck flask, 200 g of the BTCP monomer synthesized in Step 2, which was dissolved in 50% PGMEA solvent, was added and the temperature was raised to 115 캜. 21.1 g of Pyromellitic dianhydride (compound of Formula 9-3) was added dropwise at 115 캜 and stirred at 115 캜 for 6 hours. Phthalic anhydride (7.35 g) was added thereto, and the reaction was terminated after stirring for an additional 2 hours. After cooling, a binder solution having a weight average molecular weight of 4,500 g / mol was obtained.

Preparation Example 4: Preparation of BTCP / CHDA binder

After setting the reflux condenser and thermometer on the 3-neck flask, 200 g of the BTCP monomer synthesized in Step 2, which was dissolved in 50% PGMEA solvent, was added and the temperature was raised to 115 캜. 21.7 g of cyclohexyl dianhydride (compound of formula (9-4)) was added dropwise at 115 DEG C, followed by stirring at 115 DEG C for 6 hours. Phthalic anhydride (7.35 g) was added thereto, and the reaction was terminated after stirring for an additional 2 hours. After cooling, a binder solution having a weight average molecular weight of 4,200 g / mol was obtained.

(A polymer having a unit of the formula (1-5), a polymer having the unit of the formula (1-6), a polymer having the unit of the formula (1-7), a polymer having the unit of the formula (1-8) , A photoactive compound (PAC), a photoinitiator, an organic solvent and other additives at room temperature for 3 hours, and then a positive photosensitive resin composition and a negative photosensitive resin composition were prepared and evaluated.

Production Example 5: Preparation of BTCP / CBDA binder

After setting the reflux condenser and thermometer on the 3-neck flask, 200 g of the BTCP monomer synthesized in Step 2, which was dissolved in 50% PGMEA solvent, was added and the temperature was raised to 115 캜. 18.7 g of cyclobutyl dianhydride (compound of the formula 9-5) was added dropwise at 115 ° C, and the mixture was stirred at 115 ° C for 6 hours. Phthalic anhydride (7.35 g) was added thereto, and the reaction was terminated after stirring for an additional 2 hours. After cooling, a binder solution having a weight average molecular weight of 4,200 g / mol was obtained.

The binder resin (polymer having a unit of Formula 1-9), photoactive compound (PAC), photoinitiator, organic solvent and other additives prepared using the monomer synthesis method and the binder polymerization method were stirred at room temperature for 3 hours A post-positive photosensitive resin composition and a negative photosensitive resin composition were prepared and evaluated.

[Example 1]

The insert the binder prepared in Example 1 the BTCP / BPDA binder 35g and Tris-P PAC ^® 3g prepared by dissolving in an organic solvent, PGMEA (propylene glycol methyl ether acetate) of these solids content so that 35% by weight, to the solution 60g 0.03 g of a silicone surfactant (BYK333, BYK) and 0.02 g of an epoxy adhesive agent (KBM403, Shinetsu) were added and mixed to prepare a positive type organic insulating film composition.

[Example 2]

A positive type organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the BTCP / BTDA binder resin produced by the binder preparation example 2 was used.

[Example 3]

A positive type organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the BTCP / PMDA binder resin produced by the binder preparation example 3 was used.

[Example 4]

A positive type organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the BTCP / CHDA binder resin produced by the binder preparation example 4 was used.

[Example 5]

A positive type organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the BTCP / CBDA binder resin produced by the binder production example 5 was used.

[Example 6]

Is manufactured by the above-mentioned Production Example 1 Binder BTCP / BPDA binder 35g and oxime ester-based photoinitiator 1.0g (TPM-P07 ^®) was dissolved to 35 weight part with respect to the organic solvent PGMEA, surfactant (BYK333) 0.03g to this solution And 0.02 g of an adhesive preparation (KBM403) were added and mixed to prepare a negative photosensitive resin composition.

[Example 7]

A negative photosensitive resin composition was prepared in the same manner as in Example 5 except that 35 g of the BTCP / BTDA binder resin produced by the binder preparation example 2 was used.

[Example 8]

A negative type photosensitive resin composition was prepared in the same manner as in Example 5 except that 35 g of the BTCP / PMDA binder resin prepared in the binder preparation example 3 was used.

[Example 9]

A negative photosensitive resin composition was prepared in the same manner as in Example 5 except that 35 g of the BTCP / CHDA binder resin prepared in the binder preparation example 4 was used.

[Example 10]

A negative photosensitive resin composition was prepared in the same manner as in Example 5 except that 35 g of the BTCP / CBDA binder resin prepared in the above-mentioned binder preparation example 5 was used.

[Comparative Example 1]

In Example 1, 30 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, 10 parts by weight of methacrylic acid, and 10 parts by weight of styrene monomer were polymerized in a PGMEA solvent at 40% solids content instead of the BTCP / BPDA binder A positive type organic insulating film composition was prepared in the same manner as in Example 1, except that 30 g of an acrylic polymer having an average molecular weight of 15,000 g / mol was used.

[Comparative Example 2]

In Example 1, 30 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, 10 parts by weight of methacrylic acid, and 10 parts by weight of styrene monomer were polymerized in a PGMEA solvent at 40% solids content instead of the BTCP / BPDA binder average molecular weight 15,000 g / mol of an acrylic polymer and a photoinitiator 30g 1.0g (OXE01 ^®) a surfactant (BYK333) 0.03g, adhesive preparation (KBM403) was dissolved at a concentration 0.02 to 35% by weight relative to the organic solvent PGMEA, the solution g were added and mixed to prepare a negative photosensitive resin composition.

[Comparative Example 3]

After setting the reflux condenser and thermometer on the 3-neck flask, remind Bis (4, 1-phenylene)) bis (oxy)) bis (methylene)) bis (oxirane ), 46 g of acrylic acid and 1.5 g of TBAB were charged and 200 g of PGMEA was added thereto so as to have a concentration of 50% by weight. The temperature was raised to 115 캜 and the reactivity was checked by HPLC to synthesize an acrylate group-substituted monomer.

After confirming that the content of the oxirane compound was 0.5%, 56 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added dropwise thereto, and the mixture was stirred at 115 ° C for 6 hours. Then, 14 g of phthalic anhydride was added and stirring was continued for 2 hours. The reaction was terminated. After cooling, a binder solution substituted with an acrylate group having a weight average molecular weight of 4,000 g / mol was obtained.

The binder 35g Tris-P PAC ^® 3g into their solid content is dissolved in an organic solvent, PGMEA (propylene glycol methyl ether acetate) so that 35% by weight of a silicone surfactant to the binder solution, 60g (BYK333, BYK) 0.03g And 0.02 g of an epoxy-based adhesive preparation (KBM403, Shin-Etsu) were added and mixed to prepare a positive-type organic insulating film composition.

[Comparative Example 4]

Comparative Example 3 The solid content of the binder and a photoinitiator 35g 1.0g (OXE01 ^®) of this was dissolved in organic solvent PGMEA such that 35% by weight, surfactant (BYK333) to this solution 0.03g, adhesive preparation (KBM403) 0.02g Were added and mixed to prepare a negative photosensitive resin composition.

[Property evaluation]

Each of the photosensitive resin compositions obtained through Examples 1 to 10 and Comparative Examples 1 to 4 was applied to a spin coater at 800 to 900 rpm for 15 seconds and then dried on a hot plate at 90 DEG C for 100 seconds. After exposure using an ultrahigh pressure mercury lamp as a light source using a predetermined mask, it was spin-developed at 25 DEG C for 60 seconds in a water-soluble alkali developing solution and then washed with water. After washing with water and drying, it was baked at 230 ° C for 40 minutes to obtain a pattern. The following evaluation was made on the obtained pattern.

(1) Sensitivity evaluation

Each of the thus-formed photosensitive resin compositions was applied to a glass substrate (Eagle 2000, manufactured by Samsung Corning Incorporated) with a spin coater and dried at 90 캜 for 1 minute with a hot plate. After drying, the photosensitive thin film was obtained by measuring with a contact-type film thickness meter (? -Step 500, manufactured by KLA-Tencor Co., Ltd.). After exposure with an ultra-high pressure mercury lamp using a photomask having a pattern, the resist was spray-developed with a water-soluble alkali developer to obtain a photoresist pattern. (MJ / cm < ² >) capable of forming the same dimensions as the mask pattern of 20 microns. That is, a resist having a small exposure dose shows high sensitivity because a pattern can be formed even with a small light energy.

(2) Residual film ratio after development

In the sensitivity evaluation process, the evaluation of the residual film ratio can be performed by measuring the pattern thickness after development.

(3) Transmittance

The composition was spin-coated on a glass substrate to form the same thickness of 3 microns and then subjected to a 400 mJ / cm ² front exposure and post-baking at 240 ° C for 40 minutes. Using a UV-spectrometer, Was measured.

(4) taper angle

In the above evaluation, after development, the pattern substrate on which sensitivity of the same dimension as the 20-micron mask pattern was formed was subjected to post-baking at 240 ° C for 40 minutes, and then the patter angle of the pattern was measured using SEM.

(5) Adhesion

According to the test method of JIS D 0202, a crosscut was formed in a lattice pattern on a coated film heated at 240 캜 for 40 minutes after exposure and development, and then subjected to a peeling test with a cellophane tape to observe and evaluate the lattice peeling state . &Amp; cir & ≤ & cir &

The results of the results of sensitivity, residual film ratio and adhesion are shown in Table 1 below.

Example bookbinder Sensitivity
(mJ / cm ² ) Remaining film ratio after development (%) Film retention after curing (%) Adhesiveness One Production Example 1 60 98 94 ○ 2 Production Example 2 40 99 95 ○ 3 Production Example 3 40 99 97 ○ 4 Production Example 4 35 98 95 ○ 5 Production Example 5 35 97 94 ○ 6 Production Example 1 45 98 97 ○ 7 Production Example 2 30 97 96 ○ 8 Production Example 3 35 97 96 ○ 9 Production Example 4 25 96 95 ○ 10 Production Example 5 25 95 94 ○ Comparative Example 1 Comparative Example 1 200 90 85 x Comparative Example 2 Comparative Example 1 150 89 88 x Comparative Example 3 Comparative Example 3 180 89 88 ○ Comparative Example 4 Comparative Example 3 150 92 90 ○

Table 2 shows the results of measurement of the toughness angle to confirm the heat resistance to be confirmed in the present invention and the measurement results of the refractive index and the cured permeability of the thin film prepared from the compositions shown in the respective Examples.

Example bookbinder Taegeukgak
(Degree) Refractive index Transmittance after curing
(%) One Production Example 1 52 1.65 96 2 Production Example 2 50 1.66 97 3 Production Example 3 55 1.68 97 4 Production Example 4 50 1.68 98 5 Production Example 5 50 1.64 98 6 Production Example 1 55 1.64 98 7 Production Example 2 60 1.64 98 8 Production Example 3 65 1.65 98 9 Production Example 4 60 1.65 99 10 Production Example 5 58 1.63 99 Comparative Example 1 Comparative Example 1 32 1.46 91 Comparative Example 2 Comparative Example 1 33 1.45 93 Comparative Example 3 Comparative Example 3 35 1.49 88 Comparative Example 4 Comparative Example 3 38 1.47 90

Table 1 and Table 2 show the characteristics of the organic film composition using the positive type high sensitivity organic film composition and the negative type organic film composition according to the present invention and the acrylic binder prepared according to Comparative Examples 1 to 4. Among the photosensitive materials applied to the TFT-LCD process, the OLED process and the TSP process, the characteristics of the organic film photosensitive material are very important for the characteristics of the display. In particular, optical properties such as sensitivity, heat resistance, transmittance and refractive index are very important characteristics of the organic photoresist. The sensitivity characteristic is a very important characteristic for shortening the TACT time. The high sensitivity characteristics can improve the productivity by shortening the processing time. It can be seen that the organic film compositions according to the examples shown in Table 1 exhibit excellent high sensitivity characteristics as compared with the compositions of Comparative Examples 1 to 4. These characteristics indicate that the binder structure according to the present invention is excellent in the interaction property with the photoactive material (PAC) or the photoinitiator that affects the sensitivity characteristics, thereby maximizing the dissolution rate difference between the exposed region and the non- . It can be confirmed that the residual film ratio and the adhesion property after development due to the interaction property between the binder of the present invention and the photoactive material are superior to the photosensitive resin composition of the comparative example using the acrylic binder.

In addition, the binder of the present invention has excellent heat resistance and can control the taper angle and the outgassing characteristics. In particular, since the TFT process is performed at a high-temperature heat treatment process of 300 ° C or more, the heat resistance of the binder is an important property for securing the heat resistance of the organic photosensitive film. An organic photoresist using an acrylic binder having a low heat resistance property is decomposed in a high temperature heat treatment process and is found as an impurity or a foreign substance in the process, which causes deterioration of display characteristics. It is difficult to control the shape and taper angle of the pattern, so it is difficult to realize the high resolution characteristics of the photosensitive material. The binder structure of the present invention is capable of securing the heat resistance property of 300 占 폚 or more, thereby solving the problem of property deterioration due to impurities due to the high-temperature heat treatment step and realizing a pattern having high-resolution characteristics.

 The binder structure according to the present invention exhibits high refractive index and transmittance characteristics. Since the binder structure of the present invention contains a specific monomer structure and a specific element, it can exhibit a high refractive index characteristic compared to a binder having a general acrylic structure. The high refractive index of the light-sensitive material can minimize the deterioration of the optical characteristics of the display due to light, thereby improving the transmittance characteristic of light and the sharpness characteristic of the display. In particular, the thin film produced from the photosensitive resin composition using the binder according to the present invention exhibited a very high transmittance of 97% or more even after heat curing at a temperature of 200 ° C or higher. Since the transparency characteristic of the photosensitive material can realize a clear display characteristic and can realize a wide aperture ratio of the TFT layer, it is possible to realize a display having a high contrast ratio and to reduce power consumption for driving.

As a result, it was confirmed that the use of the binder resin according to the present invention makes it possible to produce photosensitive resin compositions having excellent properties such as sensitivity, heat resistance, transmittance and refractive index.

Claims (13)

A binder resin characterized by being a polymer represented by the following formula (I)
(I)

R ₃ and R ' ₃ in the formula (I) are each R _a SR _b substituent, R _a is bonding, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms, , R _b is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms and R ₄ is a quaternary cycloaliphatic hydrocarbon radical containing or not containing a heteroatom having 4 to 20 carbon atoms, A is a substituent represented by any one of the following formulas (I-1) to (I-4), n is an integer of 1 to 6, and p is an integer of 1 to 30.
(I-1)

[Formula I-2]

[Formula I-3]

[Formula I-4]

R ₂ and R ' ₂ are each independently selected from the group consisting of hydrogen, a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH ₂ ), a nitro group (-NO ₂ ) And X represents O, S, N, Si or Se. The method according to claim 1,
Wherein R ₄ in the above formula (I) is a substituent group introduced from at least one compound selected from the following formulas (9-4) to (9-5):
[Formula 9-4]

[Formula 9-5]

The method according to claim 1,
The binder resin is used as a binder in a photosensitive material for a display, and is a polymer comprising at least one structure selected from the following Formulas 1-8 to 1-9 as a unit.

[Chemical Formula 1-8]

[Chemical Formula 1-9]

The method according to claim 1,
Wherein the binder resin is a resin terminated with an organic acid, an organic acid anhydride or an amic acid.
The method according to claim 1,
Wherein the binder resin has a weight average molecular weight of 1,000 to 100,000 g / mol.
The method according to claim 1,
Wherein the binder resin has a degree of dispersion of 1.0 to 5.0.
A negative photosensitive resin composition comprising the binder resin according to any one of claims 1 to 6, a photoinitiator, an organic solvent and a surfactant.
8. The method of claim 7,
Wherein the negative photosensitive resin composition comprises 100 parts by weight of a binder resin, 1 to 20 parts by weight of a photoinitiator, 0.01 to 5 parts by weight of a surfactant, and 0 to 10 parts by weight of an adhesion promoter in an organic solvent in an amount of 5 to 80% Negative type photosensitive resin composition.
A positive photosensitive resin composition comprising the binder resin according to any one of claims 1 to 6, a photoactive compound, an organic solvent and a surfactant.
10. The method of claim 9,
Wherein the positive photosensitive resin composition comprises 100 parts by weight of a binder resin, 0.1 to 30 parts by weight of a photoactive compound, 0.01 to 5 parts by weight of a surfactant, and 0 to 10 parts by weight of an adhesion promoter in an organic solvent in an amount of 5 to 80% Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.
A substrate comprising a resin curing pattern formed from the photosensitive resin composition of claim 7.
A substrate comprising a resin curing pattern formed from the photosensitive resin composition of claim 9.
And polymerizing the monomer represented by the following formulas (5) to (8) and the carboxylic acid dianhydride represented by the following formula (9) to prepare a polymer represented by the following formula
Method of producing binder resin:
[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(In the monomer structures of the above formulas 5 to 8,
R ₂ and R ₂ each represent a substituent including a hydrogen or a heteroatom such as a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH ₂ ), a nitro group (-NO ₂ ) Wherein X represents O, S, N, Si or Se. R ₃ and R ' ₃ each independently represent an alkyl group with or without a heteroatom of 1 to 20 carbon atoms, an aryl group with or without a heteroatom of 6 to 20 carbon atoms, or an RC (= O) R' substituent And n is an integer of 1 to 6.)
[Chemical Formula 9]

(In the above formula (9)
R ₄ is a quadrivalent cycloaliphatic hydrocarbon radical having 4 to 20 carbon atoms and containing or not containing a heteroatom.
(I)

R ₃ and R ' ₃ in the formula (I) are each R _a SR _b substituent, R _a is bonding, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms, , R _b is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms and R ₄ is a quaternary cycloaliphatic hydrocarbon radical containing or not containing a heteroatom having 4 to 20 carbon atoms, A is a substituent represented by any one of formulas (I-1) to (I-4), n is an integer of 1 to 6, and p is an integer of 1 to 30.
(I-1)

[Formula I-2]

[Formula I-3]

[Formula I-4]

R ₂ and R ' ₂ are each independently selected from the group consisting of hydrogen, a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH ₂ ), a nitro group (-NO ₂ ) And X represents O, S, N, Si or Se.

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