KR100890920B1 - Photocurable and alkali-developable copolymer modified with multifunctional polyester oligomer and process for preparing the same - Google Patents

Abstract

The present invention relates to a photocurable alkali-soluble (co) polymer modified with a polyfunctional polyester-based oligomer and a method for preparing the same, more particularly, including an acid functional group; Ethylenically unsaturated bonds; And residues of a multifunctional polyester-based oligomer; and, when applied to photolithographic materials for flat panel displays such as column spacers, color filters, color resists, and photoresists, are not only excellent in developability, but also in other organic binders and pigments. The present invention relates to a photocurable alkali-soluble (co) polymer having excellent miscibility and dispersibility with, improved physical properties such as strength and elasticity, and a method for producing the same.

Polyfunctional, polyester, oligomer, modified, (co) polymer, manufacturing method

Description

Photocurable and alkali-developable (co) polymer modified with multifunctional polyester oligomer and process for preparing the same}

The present invention relates to a photocurable alkali-soluble (co) polymer modified with a polyfunctional polyester-based oligomer and a method for preparing the same, more particularly, including an acid functional group; Ethylenically unsaturated bonds; And residues of a multifunctional polyester-based oligomer; and, when applied to photolithographic materials for flat panel displays such as column spacers, color filters, color resists, and photoresists, are not only excellent in developability, but also in other organic binders and pigments. The present invention relates to a photocurable alkali-soluble (co) polymer having excellent miscibility and dispersibility with, improved physical properties such as strength and elasticity, and a method for producing the same.

Various methods such as dyeing method, electrodeposition method, printing method and pigment dispersion method are known as the manufacturing method of the color filter. However, in consideration of productivity, quality, cost and the like comprehensively, the pigment dispersion method is the best at present, and is currently mainly used. have.

The pigment dispersion method is a method of producing a color filter by forming a fine colored image on a transparent substrate such as glass by photolithography using a color resist which is a photosensitive resin in which an organic pigment is dispersed and colored. The color filter requires a pattern of three primary colors of red, green, and blue, and is formed by repeating photolithography. Since the productivity of the color filter is greatly influenced by the efficiency of photolithography, high sensitivity and development efficiency of the color resist, which is a material, are strongly required. Although it is proposed to use photosensitive resin manufactured according to various principles as a color resist, radical polymerization type photocurable photosensitive resin using the chain reaction from the viewpoint of high sensitivity is mainly used.

In order to realize the photopolymerization of the radical polymerization type, a technique of introducing photosensitive unsaturated bonds into the alkali-soluble polymer side chain structure in the case of a color resist binder is widely known, and the ethylenic properties of polyfunctional acrylates are improved in order to improve sensitivity and curability. Unsaturated compound monomers or oligomers are mainly used.

However, such an ethylenically unsaturated compound is polymerized by a photocuring process, thereby reducing its miscibility with the alkali-soluble polymer binder, making it difficult to obtain a uniform and transparent final cured product, and does not contain alkali-soluble functional groups in the molecular structure. Therefore, there is a problem that developability is inferior.

Accordingly, a method of using a photocurable alkali-soluble polyfunctional oligomer having excellent developability, excellent miscibility and dispersibility, and improved physical properties such as strength and elasticity is mixed with the photosensitive resin composition for photoresist. In the case of low molecular weight and high hydrophilicity of the oligomer, not only the development control is difficult but also it is difficult to induce a uniform curing reaction with the alkali-soluble binder.

The present invention, in order to solve the problems of the prior art as described above, in addition to excellent developability when applied to photolithographic materials for flat panel display such as column spacer, color filter, color resist, photoresist, other organic binders and pigments An object of the present invention is to provide a photocurable alkali-soluble modified (co) polymer having excellent miscibility and dispersibility, and improved physical properties such as strength and elasticity, and a method for producing the same.

In order to achieve the above technical problem, the present invention, an acid functional group (acid functional group); Ethylenically unsaturated bonds; And it provides a photocurable alkali-soluble modified (co) polymer comprising a; a residue of a multifunctional polyester-based oligomer.

According to another aspect of the invention, there is also provided a method comprising the steps of: (1) providing a (co) polymer comprising an acid functional group, and (2) introducing a polyfunctional polyester-based oligomer moiety into the (co) polymer. A method for producing a modified (co) polymer is provided.

In addition, according to another aspect of the invention, (a) polymerizing a hydroxyl group-containing monomer, and a carboxyl group or an acid anhydride group-containing monomer to obtain a first intermediate; (b) adding a glycidyl group-containing monomer to the first intermediate and ring opening to obtain a second intermediate; And (c) polymerizing the second intermediate and the monomer having a hydroxyl group or a carboxyl group together with an unsaturated group to obtain a polyester-based oligomer having a carboxyl group and an unsaturated bond. A method of producing a polyfunctional polyester-based oligomer is provided. .

Furthermore, according to another aspect of the present invention, there is provided a photoresist composition comprising the modified (co) polymer of the present invention.

The photocurable alkali-soluble modified (co) polymer according to the present invention is unique to polyester-based compounds because polyester-based oligomers having functional groups rich in side chains are pendant compared to photocurable acrylic copolymers used in conventional photolithographic processes. In addition to the excellent developability of the compact structure can be realized, it can exhibit excellent developability and excellent cured product properties in photolithographic processes such as color filters, column spaces, etc. which are mainly used for liquid crystal devices of flat panel displays.

In particular, the photoresist composition comprising the photocurable alkali-soluble modified (co) polymer according to the present invention is excellent in adhesiveness, heat resistance, and solvent resistance, which are physical properties required for electronic materials including color filters, and due to carboxyl groups in the oligomer structure. Excellent developability can be obtained, and the structural properties of the monomer having a hydroxyl group per molecule of the monomer having a hydroxyl group and a functional group selected from halogen atoms, hydroxyl groups and carboxyl groups (for example, aliphatic, alicyclic, aromatic functional groups, etc.) ), Etc., it becomes possible to give variously the strength and elasticity of hardened | cured material.

Hereinafter, the present invention will be described in more detail.

The photocurable alkali-soluble modified (co) polymer (A) according to the present invention is preferably a (co) in which a (co) polymer (C) containing an acid functional group is modified with a polyfunctional polyester oligomer (B). As the polymer, it includes acid functional groups, ethylenically unsaturated bonds, and residues of polyfunctional polyester-based oligomers.

The polyfunctional polyester oligomer (B) is preferably a hydroxyl group-containing monomer (A); Carboxyl group or acid anhydride group-containing monomer (B); Glycidyl group-containing monomer (D); And a monomer (F) having a hydroxyl group or a carboxyl group and an unsaturated group together, and a polyester oligomer having an unsaturated bond and a carboxyl group together.

According to one embodiment of the present invention, the (co) polymer (C) comprising the acid functional group is a monomer (G) alone or the monomer (G) having an acid functional group and an ethylenically unsaturated bond together. ) And a (co) polymer (I) of a monomer (H) having an ethylenically unsaturated bond.

According to another embodiment of the present invention, the (co) polymer (C) comprising the acid functional group further comprises a reactive monomer (J) having an ethylenically unsaturated bond and an addition reactive functional group to the (co) polymer (I). It can also be obtained by reaction.

(One) Multifunctional Polyester Oligomer (I)

In the present invention, the polyfunctional polyester oligomer (B) having an unsaturated bond and a carboxyl group together is preferably a hydroxyl group-containing monomer (A); Carboxyl group or acid anhydride group-containing monomer (B); Glycidyl group-containing monomer (D); And monomer (F) having a hydroxyl group or a carboxyl group and an unsaturated group together.

The monomer (A) having the hydroxyl group has a reactive site that reacts well with the carboxyl group or the acid anhydride group-containing monomer (B). Examples of such a monomer (A) include polyhydric alcohols such as monohydric alcohols, dihydric alcohols, and trihydric alcohols, and more specifically 1,3-butylene glycol, 1,4-butylene glycol, Diethylene glycol, ethylene glycol, 1,6-hexanediol, 2-methyl 1,3-propanediol, neopentyl glycol, propylene glycol, triethylene glycol, trimethylol propane, pentaerythritol, and the like. It does not become, and these can be used individually or in mixture of 2 or more types.

The monomer (A) having the hydroxyl group is 2 to 25% by weight based on the total weight of solids of the monomers (A), (B), (D) and (F) excluding the solvent in the polyfunctional polyester oligomer (B). It is preferable to contain. When the content of the monomer (A) in the oligomer (b) is less than 2% by weight, the cured product may be lost under development conditions by alkaline water, and when it exceeds 25% by weight, the water resistance may be poor, which is not preferable.

The carboxyl group or acid anhydride group-containing monomer (B) plays a role in determining overall physical properties including elasticity and hardness of the final cured product obtained from the photocurable alkali-soluble modified (co) polymer composition. Examples of such a monomer (B) include polyhydric carboxylic acids such as acid anhydride, dihydric carboxylic acid and trivalent carboxylic acid. More specifically, naphthalic anhydride, phosphoric anhydride and 3-fluorophthalic acid. Anhydride, butyric anhydride, hexahydro-4-methylphthalic anhydride, trifluoroacetic anhydride, hexahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, acetic anhydride, trimellitic anhydride, itaconic anhydride, neo Decanoic acid oxiranylmethyl ester, chloric anhydride, succinic anhydride, tetrabromophthalic anhydride, dodecenyl succinic anhydride, nonenylsuccinic anhydride, boric anhydride or methyl-5-norbornene-2,3 -Dicarboxylic acid anhydride, and the like, but is not limited thereto, and these may be used alone or in combination of two or more thereof. And it can be used.

The carboxyl group or acid anhydride group-containing monomer (B) is a polyfunctional polyester oligomer (10 to 60% by weight based on the total weight of the solids of the monomers (A), (B), (D) and (F) excluding the solvent) It is preferable to contain in b). If the content of the monomer (B) in the oligomer (b) is less than 10% by weight, the degree of curing may be lowered. If the content is more than 60% by weight, alkali-soluble resin binders, photosensitive polyfunctional acrylates, and the like are used for preparing photoresists. Miscompatibility with the components may be lowered and a clean cured product may not be obtained.

The monomer having a glycidyl group (D) forms an ester bond through a ring-opening reaction and introduces a secondary alcohol group, and like the carboxyl or acid anhydride group-containing monomer (B), physical properties such as elasticity and hardness of the final cured product It determines the characteristics. Examples of such glycidyl group-containing monomers (D) include glycidyl group-containing ether compounds, glycidyl group-containing ester compounds, glycidyl group-containing unsaturated esters, and the like, and more specifically, butyl glycidyl ether. Resorcinol diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, S-trityl glycidyl ether, glycerol triglycidyl ether, 2,6 -Diglycidylphenyl glycidyl ether, diglycidyl ether of 1,4-cyclohexanedimethanol, R-benzyl glycidyl ether, S-benzyl glycidyl ether, diglycidyl ether of bisphenol A Neopentyl glycol diglycidyl ether, triethylene glycol diglycidyl ether, p-cresyl glycidyl ether, guaiacol glycidyl ether, o-cresyl glycidyl ether ( o-cresyl glycidy l ether), p-chlorophenyl glycidyl ether, ethylene glycol diglycidyl ether, diglycidyl ether, hydroquinone diglycidyl ether, 1,4-butanediol diglycidyl ether, n-butyl glyc Cydyl ether, glycidyl neodecanoate, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, glycerol polyglycidyl ether, cresyl glycidyl ether, arylglycidyl ether, 3, 4-epoxy cyclohexyl methyl methacrylate, glycidyl methacrylate, glycidyl acrylate, and the like, but are not limited thereto, and these may be used alone or in combination of two or more thereof.

The glycidyl group-containing monomer (D) is a polyfunctional polyester oligomer (B) at 10 to 45% by weight based on the total weight of solids of the monomers (A), (B), (D) and (F) excluding the solvent. It is preferable to contain in the. If the monomer (D) content of the oligomer (b) is less than 10% by weight, the degree of curing may be lowered. If the content of the monomer (D) is more than 45% by weight, alkali-soluble resin binders, photosensitive polyfunctional acrylates, and other components used for preparing the photoresist may be used. The miscibility with may be reduced and a clean hardened | cured material may not be obtained.

The monomer (F) having a hydroxyl group or a carboxyl group and an unsaturated bond together serves to provide a photocurable functional group in preparing a photoresist. As such a monomer (F), an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid, its anhydride, an unsaturated hydroxyl ester compound, etc. are mentioned, for example. Specifically 2-hydroxy ethyl methacrylate, 2-hydroxy ethyl acrylate, 2-hydroxy propyl acrylate, 2-hydroxy propyl methacrylate, 4-hydroxy butyl acrylate, 4-hydroxy butyl Unsaturated carboxylic ester compounds of hydroxy alkyl esters such as methacrylate and the like; Unsaturated carboxylic esters such as acrylic acid, methacrylic acid and the like; And maleic acid, fumaric acid, maleic anhydride, tetrahydrophthalic anhydride, and the like, and these may be used alone or in combination of two or more thereof.

The monomer (F) having an unsaturated bond together with the hydroxyl group or carboxyl group is 5 to 40% by weight based on the total weight of the solids of the monomers (A), (B), (D) and (F) excluding the solvent, and is a polyfunctional polyester. It is preferable to contain in system type oligomer (b). If the monomer (F) content in the oligomer (b) is less than 5% by weight, the degree of curing may be lowered. If the content of the monomer (F) is more than 40% by weight, alkali-soluble resin binders, photosensitive polyfunctional acrylates, and the like are used for preparing photoresists. Miscompatibility with the components may be lowered and a clean cured product may not be obtained.

The multifunctional polyester oligomer (b) of the present invention is not limited thereto, but the steps of: (a) polymerizing a hydroxyl group-containing monomer and a carboxyl group or an acid anhydride group-containing monomer to obtain a first intermediate; (b) adding a glycidyl group-containing monomer to the first intermediate and ring opening to obtain a second intermediate; And (c) polymerizing the second intermediate and the monomer having a hydroxyl group or a carboxyl group and an unsaturated group together to obtain a polyester-based oligomer having a carboxyl group and an unsaturated bond.

In step (a) of the method for producing a multifunctional polyester oligomer (b), a first intermediate having a hydroxyl group and an ester bond simultaneously by polymerizing a monomer (A) having a hydroxyl group and a monomer (B) containing a carboxyl group or an acid anhydride group (C) is obtained.

In the step (a), the polymerization is preferably carried out at 40 to 200 ℃. If the polymerization temperature is less than 40 ℃ do not proceed enough reaction to lower the conversion rate, if it exceeds 200 ℃ there is a possibility that the side reaction is promoted to cause the gelation of the composite or serious effects on the physical properties. In addition, the polymerization reaction in the step (a) is preferably terminated when the acid value of the first intermediate (C) is 50 to 300 mgKOH / g, which is the application properties of the oligomer is the final product in the above range This is because it exhibits physical properties.

In the step (b) of the method for producing a multifunctional polyester oligomer (b), a glycidyl group-containing monomer (D) is added to the first intermediate (C) and ring-opened to prepare a second intermediate (E).

In the step (b), the glycidyl group-containing monomer (D) is preferably dropped into the first intermediate (C) for 1 to 5 hours, and the second intermediate (E) through a reaction for opening a glycidyl group. ) Is manufactured. The second intermediate (E) has a hydroxyl group or a carboxyl group as a residual functional group. The temperature of the step (b) is preferably from 60 ℃ to 170 ℃, if the temperature is less than 60 ℃ there is a fear that the formation of the desired residual functional group is not enough, if the temperature exceeds 170 ℃ the reaction reacts due to side reaction gelling It is not preferable because it may be. In addition, the reaction of the step (b) is preferably terminated when the acid value of the second intermediate (E) is 0 to 100 mgKOH / g, which is the application properties of the oligomer which is the final product in the lithographic process in the above range This is because it shows the best physical properties at.

In the step (c) of the method for preparing a multifunctional polyester oligomer (b), the second intermediate (E) and a monomer (F) having a hydroxyl group or a carboxyl group and an unsaturated group together are polymerized to have a carboxyl group and an unsaturated bond. The polyfunctional polyester oligomer (B) which is a target object is obtained.

In the step (c), the monomer (F) having a hydroxyl group or a carboxyl group and an unsaturated group together is preferably added dropwise to the second intermediate (E) for 1 to 5 hours, wherein the temperature conditions are 60 ℃ to 200 ℃ desirable. If the temperature of step (c) is less than 60 ℃ it may be difficult to produce the desired carboxyl group, if it exceeds 200 ℃ there is a fear that the appearance and color of the resin and the increase in the molecular weight of the resin due to side reactions and gelation may be caused. . In addition, the reaction of step (c) is preferably terminated when the acid value of the polyfunctional polyester-based oligomer (b) of the reaction product is 40 to 300 mgKOH / g, which is the final step including developability in the lithographic process This is because the application properties of the oligomer exhibit the best properties in the above range.

There is no particular limitation on the solvent that can be used in the multifunctional polyester-based oligomer (b) manufacturing method as described above, and any solvent known in the art may be used without limitation, and may be xylene, toluene, propylene glycol monomethyl ether acetate, ethoxy It is preferable to use, but not limited to, solvents containing no reactive active hydrogen such as ethyl propionate, ethyl cellosolve acetate, diisopropyl ether, propyl acetate, n-butyl propionate and the like. In addition, it is possible to use a catalyst in order to shorten the reaction time and improve the yield in the method of producing the multifunctional polyester oligomer (b), and at this time, a usable catalyst such as zirconium octoate, dibutyl tin dilaurylate, and the like can be used. Metal catalysts, tertiary amines such as triethylamine, ammonium salts and the like can be used, but are not limited thereto. There is no particular limitation on the amount of the catalysts used, and the catalysts may be used in the amount of ordinary catalysts within a range that can exhibit the effect of using the catalyst.

The polyfunctional polyester oligomer (B) of the present invention prepared by the above production method has an acid value of 40 to 300 mg KOH / g, a hydroxyl value of 0 to 100, and a nonvolatile content of the solvent. It is 60% by weight or more based on the total amount of oligomer including, the viscosity is 100 to 20,000 centipoise, the number average molecular weight is 400 to 4,000, the weight average molecular weight is 600 to 5,000, and has a molecular weight distribution of 2 or less In addition, it is preferable in view of obtaining excellent physical properties in a photolithographic process including developability desired in the present invention.

In addition, the multifunctional polyester-based oligomer (b) of the present invention is preferably used in a pendant form in the side chain of the binder resin skeleton through addition, polymerization or condensation reaction with the binder resin in order to obtain a more uniform curable composition. However, as needed, it can also be used individually or in the form of mixing with another monomer, oligomer, and / or binder resin.

(2) (co) polymers containing acid functional groups (C)

Hereinafter, in the preparation of the photocurable alkali-soluble modified (co) polymer (A) according to the present invention, the (co) polymer (C) containing an acid functional group to which the polyfunctional polyester oligomer (B) is introduced is introduced. The manufacture will be described.

According to one embodiment of the invention, the (co) polymer (C) comprising the acid functional group is homopolymerization of the ethylenically unsaturated compound monomer (G) containing the acid functional group, or the monomer (G) and ethylenic It is prepared through copolymerization of an unsaturated compound monomer (H) [(co) polymer (I)].

According to another embodiment of the present invention, the (co) polymer (C) comprising the acid functional group further adds a reactive monomer (J) having an ethylenically unsaturated bond to the (co) polymer (I) as described above. And polymerization or condensation reaction.

Examples of the ethylenically unsaturated compound monomer (G) containing the acid functional group include (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid and maleic acid alkyl esters, and the like. Furnaces include monomethyl maleic acid, ethyl maleic acid, n-propyl maleic acid, isopropyl maleic acid, n-butyl maleic acid, n-hexyl maleic acid, n-octyl maleic acid, 2-ethyl Hexyl maleic acid, n-nonyl maleic acid, n-dodecyl maleic acid, and the like.

Examples of the ethylenically unsaturated compound monomer (H) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, and the like. (Meth) acrylic acid ester, styrene, styrene derivative, etc. are mentioned, Specifically, benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylamino Ethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- Phenoxyethyl (meth) acrylate, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypro (Meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol ( Meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, meth Oxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, glycidyl (Meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) a Relate, tribromophenyl (meth) acrylate, methylα-hydroxy methylacrylate, ethylα-hydroxy methylacrylate, propylα-hydroxy methylacrylate, butylα-hydroxymethyl acrylate, dish Unsaturated carboxylic esters such as clofentanil (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl oxyethyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate; Aromatic vinyls such as styrene, α-methylstyrene, vinyl toluene, methoxy styrene, and chloro styrene; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; N-vinyl tertiary amines such as N-vinyl pyrrolidone, N-vinyl carbazole and N-vinyl morpholine; Unsaturated imides such as N-phenyl maleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide; Maleic anhydrides such as maleic anhydride and methyl maleic anhydride; Unsaturated glycidyl compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and mixtures thereof.

The (co) polymer (I) prepared by homopolymerization of the monomer (G) or copolymerization of the monomer (G) and (H) may be used as an alkali-soluble (co) polymer (C) by itself, but ethylene It is preferable to make and use the alkali-soluble copolymer which contains 1 or more photopolymerizable unsaturated bonds in a molecule | numerator further by reacting with the reactive monomer (J) which has a sex unsaturated bond.

Examples of the reactive monomer (J) having an ethylenically unsaturated bond include oxirane ring groups and ethylenic compounds such as glycidyl (meth) acrylate, arylglycidyl ether, α-methyl glycidyl acrylate, and the like. Compounds having an unsaturated bond together; Compounds having a hydroxyl group and an ethylenically unsaturated bond together, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like; Maleic anhydrides such as maleic anhydride and methyl maleic anhydride; (Meth) acryloyl oxy alkyl isocyanate, specifically, the compound which has an isocyanate group and ethylenically unsaturated double bond, such as 2-acryloyl oxy ethyl isocyanate and 2-methacryloyl oxy ethyl isocyanate, is mentioned. .

In the above, the compound having an oxirane group and an ethylenically unsaturated bond reacts with the (co) polymer (I) having a high acid value, and the compound having a hydroxyl group and an ethylenically unsaturated bond has a copolymer (I) having an anhydrous group. Half-Esterification ring-opening reaction with maleic anhydride compound undergoes esterification ring-opening reaction with copolymer (I) having hydroxyl group, isocyanate group and ethylenically unsaturated double bond The compound having an addition reaction with the copolymer (I) having a hydroxyl group produces an alkali-soluble (co) polymer (C) containing at least one photopolymerizable unsaturated bond in the molecule.

The (co) polymer (I) is, for example, radical polymerization while removing monomers by mixing a monomer selected from the groups (G) and (I) exemplified above with a polymerization solvent, heating to an appropriate temperature and removing oxygen through a nitrogen purging or refluxing process. It can be prepared by adding an initiator and maintaining the polymerization temperature. In addition, if necessary, a chain transfer agent may be used in combination to control the molecular weight of the (co) polymer.

As the radical polymerization initiator, those known in the art may be used, and general examples thereof include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis- (2,4-dimethyl valero Nitrile), 2,2'azobis- (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butylperoxyvalate, t-butylperoxybenzoate and t-butylperoxy octoate.

As a solvent which can be used, the organic solvent conventionally used in the art is suitable, and there is no restriction | limiting in particular.

In the polymerization, the polymerization temperature and the polymerization time may be determined in consideration of the half-life according to the temperature of the polymerization initiator to be used.

The reaction between the (co) polymer (I) and the reactive monomer (J) having an ethylenically unsaturated bond can be carried out, for example, at a temperature of 20 to 150 ° C., and an appropriate catalyst can be added to promote the reaction if necessary. have.

The type of catalyst may include catalysts commonly known in the art, including tertiary amines, and the type of catalyst is not particularly limited.

In addition, in the preparation of an alkali-soluble (co) polymer (C) containing at least one photopolymerizable unsaturated bond in a molecule by reacting the (co) polymer (I) with a reactive monomer (J) having an ethylenically unsaturated bond, In order to prevent consumption of unsaturated bonds due to polymerization reaction between the photopolymerizable unsaturated bonds, unreasonable viscosity increase due to molecular weight increase or copolymerization of gels, an appropriate polymerization inhibitor may be added during the reaction. Representative polymerization inhibitors include 4-methoxyphenol (MeHQ).

The acid value of the alkali-soluble (co) polymer (C) containing at least one photopolymerizable unsaturated bond in the molecule prepared according to the above method is preferably in the range of 30 to 300 KOH mg / g based on solid content, and 80 to 150 mg. It is more preferable that it is the range of KOH / g. If the acid value of the (co) polymer (C) is less than 30, the developability with respect to alkaline water may be lowered and residues may remain on the substrate. If the acid value is more than 300, the possibility of desorption of the pattern may increase.

In addition, the weight average molecular weight of the alkali-soluble (co) polymer (C) containing at least one photopolymerizable unsaturated bond in the molecule is preferably in the range of 1,000 to 200,000, and more preferably in the range of 3,000 to 50,000. If the weight average molecular weight of the (co) polymer (C) is less than 1,000, the binding function between the components required as the binder polymer may be weakened, and the pattern may be lost because it cannot withstand the physical external force during development, and may have heat resistance and solvent resistance. May not satisfy the property of. On the contrary, if the weight average molecular weight exceeds 200,000, the developability of the alkaline developer is excessively reduced, so that the development process characteristics are deteriorated, so that the development may not be possible, and the flowability may be deteriorated, thereby controlling the coating film thickness or securing uniformity. It can be difficult.

(3) Photocurable alkali-soluble modified (co) polymers

The photocurable alkali-soluble modified (co) polymer (A) according to the present invention can be obtained by modifying the (co) polymer (C) containing the acid functional group with the polyfunctional polyester-based oligomer (B).

The modified (co) polymer (A) may be prepared by direct addition of a polymer-based oligomer (B) and the functional period included in the (co) polymer (C), polymerization or condensation reaction, It may be prepared by combining the oligomer (I) and the (co) polymer (C) at a temperature of 130 ° C or less using a compound having a reactor as a medium. In view of preventing reactivity deterioration due to steric hindrance and preventing viscosity increase and gelation by reaction between unsaturated bonds, a method using a compound having two or more reactors in a molecule as a medium may be preferably recommended.

As a compound which has two or more reactors in a molecule | numerator which can be used as a mediator in the manufacturing process of a modified (co) polymer (a), A compound containing hydroxyl groups, such as ethylene glycol and diethylene glycol; Oxirane group-containing compounds such as bisphenol-A epoxy compounds; Isocyanate group-containing compounds such as hexamethylene diisocyanate; Acid anhydride group containing compounds, such as tetracarboxylic dianhydride, etc. are mentioned.

Examples of the mechanism using a compound having two or more reactors in a molecule as a medium in the process of producing the modified (co) polymer (A) include hydroxyl groups and oligomers (b) and (co) in compounds such as ethylene glycol and diethylene glycol. Half-Esterification reaction by ring-opening reaction of the polymer (C) with an anhydrous group; Esterification reaction with epoxy groups in compounds such as bisphenol-A epoxy compounds and carboxylic acid groups of (B) and (C); Urethane bond reaction of isocyanate groups in a compound such as hexamethylene diisocyanate with hydroxyl groups of (b) and (c); And a half-esterification reaction according to the ring-opening reaction of an anhydride group in a compound such as tetracarboxylic dianhydride and the hydroxyl group of (B) and (C).

The weight average molecular weight of the photocurable alkali-soluble modified (co) polymer (a) according to the present invention is preferably in the range of 1,000 to 200,000, and more preferably in the range of 5,000 to 100,000. If the weight average molecular weight of the (co) polymer (a) is less than 5,000, the binding function between the components required as the binder polymer is weakened, so that it may not be able to withstand the physical external force at the time of development, resulting in the loss of the pattern. Properties may be vulnerable. On the contrary, when the weight average molecular weight exceeds 200,000, the developability of the alkaline developer to the alkaline developer is excessively reduced, so that the development process characteristics are deteriorated, so that the development may not be possible, and the flowability may be deteriorated, resulting in poor coating thickness control or uniformity ( Uniformity can be difficult to secure.

In addition, the acid value of the (co) polymer (a) is preferably in the range of 30 to 300 KOH mg / g on a solids basis. If the acid value is less than 30, developability with respect to alkaline water may be lowered, and residues may remain on the substrate. If the acid value exceeds 300, the possibility of desorption of the pattern may increase.

The photocurable alkali-soluble modified (co) polymer (A) according to the present invention can impart excellent development characteristics, especially when used in negative photosensitive resin compositions, and photocurable resists and colors for liquid crystal devices used in photolithographic processes Excellent compatibility with other organic materials used in organic materials such as filters and column spaces, and when applied to photolithographic materials, photocurability for liquid crystal devices that shows excellent developability, optical properties, elastic properties and excellent residual reduction A resist can be obtained.

The present invention will be described in more detail with reference to the following Examples, but the present invention is in no way limited by these Examples.

[ Example ]

Synthesis Example  1-1

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel.

The A and B monomers were added to the reaction vessel in the presence of a solvent and a catalyst according to Table 1, and then heated to 150 ° C. while stirring, and then the reaction was performed to determine the acid value of the product when the acid value was 250 mg KOH / g. Caught up as the ending point.

After completion of the first reaction, the D monomer of Table 1 was added dropwise to the reaction vessel at a uniform rate over 3 hours, and after completion of dropping, the reaction temperature was 160 ° C., and the acid value of the product was confirmed by stirring. The secondary reaction was carried out by setting the time of 3.91 mg KOH / g to the end of the secondary reaction.

After completion of the second reaction, maleic anhydride (F) shown in Table 1 below at 120 ° C. was added dropwise to the reaction vessel at a uniform rate for 2 hours to carry out a tertiary reaction to finally terminate the acid value of 115 mg KOH / g. Photocurable alkali-soluble polyfunctional polyester-type oligomer which was used was manufactured.

It was confirmed that the polyester oligomer prepared above had characteristic values of an acid value of 115 mg KOH / g, a nonvolatile content of 75 wt%, a viscosity of 1500 cps, a number average molecular weight of 820, a weight average molecular weight of 1100, and a molecular weight distribution of 1.34.

Synthesis Example  1-2

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel.

After adding A and B monomers to the reaction vessel in the presence of the solvent shown in Table 2 below, the temperature was raised to 140 ° C. while stirring, and then the acid value of the product was checked to determine the acid value of 250 mg KOH / g. It was made.

After the completion of the first reaction, the D monomer of Table 2 was added dropwise to the reaction vessel at a uniform rate over 2 hours, and after completion of dropping, the acid temperature of the product was confirmed by stirring the reaction temperature to 120 ° C. and stirring the acid value to 3.67. When the mg KOH / g was the end of the secondary reaction was terminated the secondary reaction.

After completion of the secondary reaction, the F monomer was added dropwise to the reaction vessel at 170 ° C. at a uniform rate for 2 hours to carry out the tertiary reaction. Finally, the photocurable alkali-soluble polyfunctional end point having an acid value of 88 mg KOH / g Polyester-based oligomer was prepared.

The prepared polyester oligomer was confirmed to have a characteristic value of the acid value 90mg KOH / g, non-volatile content 83% by weight, viscosity 1,700cps, number average molecular weight 1216, weight average molecular weight 1520, molecular weight distribution 1.25.

Synthesis Example  1-3

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel.

The A and B monomers were added to the reaction vessel in the presence of the solvent and catalyst shown in Table 3, the temperature was raised to 130 ° C. while stirring, and then the acid value of the product was checked to determine the acid value of 250 mg KOH / g. The end point was set.

After completion of the first reaction, the D monomer of Table 3 was added dropwise to the reaction vessel at a uniform rate over 2 hours, and after completion of dropping, the reaction temperature was 110 ° C. and stirred, and the acid value of the product was confirmed to be 1.9. When the mg KOH / g was the end of the secondary reaction was terminated the secondary reaction.

After completion of the secondary reaction, the E monomer was added dropwise to the reaction vessel at 170 ° C. at a uniform rate for 2 hours to carry out the tertiary reaction. Finally, the photocurable alkali-soluble polyfunctional end point having an acid value of 88 mg KOH / g Polyester-based oligomer was prepared.

The prepared polyester oligomer was confirmed to have a characteristic value of the acid value of 87mg KOH / g, nonvolatile content of 80% by weight, viscosity 800cps, number average molecular weight 2116, weight average molecular weight 2730, molecular weight distribution 1.29.

Synthesis Example  2-1

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel.

The solvent described in Table 4 was added to the flask and heated to 120 ° C. under a nitrogen atmosphere to uniformly add the monomer A and the thermal initiator mixture for 3 hours, and then maintained for 2 hours, and the polymerization initiator was maintained at 120 ° C. And catalyst were added to the flask, and then B monomer was uniformly added for 1 hour while supplying oxygen instead of nitrogen. Thereafter, the acid value of the reactants was checked while maintaining a reaction temperature of 120 ° C. under an oxygen atmosphere to prepare a photocurable alkali-soluble acrylic copolymer having an end point when the acid value was 70 to 75 mg KOH / g based on the resin solid content.

It was confirmed that the photocurable alkali-soluble acrylic copolymer resin prepared had an acid value of 73 mg KOH / g, a nonvolatile content of 40% by weight, a viscosity of 900 cps, and a weight average molecular weight of 24,000.

Synthesis Example  2-2

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel.

The solvent described in Table 5 below was added to the flask and heated to 120 ° C. under a nitrogen atmosphere to uniformly add the monomer A and the thermal initiator mixture for 3 hours, and then maintained for 2 hours, and the polymerization initiator was maintained at 120 ° C. And catalyst were added to the flask, and then B monomer was uniformly added for 1 hour while supplying oxygen instead of nitrogen. Thereafter, the acid value of the reactants was confirmed while maintaining a reaction temperature of 120 ° C. under an oxygen atmosphere to prepare a photocurable alkali-soluble acrylic copolymer having an end point when the acid value was 82-89 mg KOH / g based on the resin solid content.

It was confirmed that the photocurable alkali-soluble acrylic copolymer resin prepared had an acid value of 88 mg KOH / g, a nonvolatile content of 40 wt%, a viscosity of 600 cps, and a weight average molecular weight of 38,000.

Example  One

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel.

13 g of the polyfunctional polyester oligomer prepared in Synthesis Example 1-1 and 250 g of the photocurable alkali-soluble acrylic copolymer resin prepared in Synthesis Example 2-1 were added to the flask, followed by addition of 2.2 g of tetracarboxylic dianhydride. The photocurable alkali-soluble modified copolymer which prepared as a reaction termination point when the acid value was 82-89 mg KOH / g on the basis of resin solid content was maintained at 2 degreeC.

The prepared modified copolymer was confirmed to have an acid value of 85 mg KOH / g, non-volatile content of 42% by weight, viscosity 2,500cps, weight average molecular weight 55,000.

Example  2

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel.

11 g of the polyfunctional polyester oligomer prepared in Synthesis Example 1-2 and 250 g of the photocurable alkali-soluble acrylic copolymer resin prepared in Synthesis Example 2-1 were added to the flask, followed by addition of 1.6 g of tetracarboxylic dianhydride. The photocurable alkali-soluble modified copolymer which prepared as the end point of reaction when hold | maintaining at 2 degreeC at the acid value of 76-84 mgKOH / g based on resin solid content was prepared.

The prepared modified copolymer was confirmed to have an acid value of 80 mg KOH / g, non-volatile content of 42% by weight, viscosity 2,000cps, weight average molecular weight 40,000.

Example  3

A four-necked flask equipped with a thermometer, condenser, dropping funnel and stirrer was used as the reaction vessel.

12 g of the polyfunctional polyester oligomer prepared in Synthesis Example 1-3 and 250 g of the photocurable alkali-soluble acrylic copolymer resin prepared in Synthesis Example 2-2 were added to the flask, followed by addition of 1.6 g of tetracarboxylic dianhydride. The photocurable alkali-soluble modified copolymer which prepared as a reaction termination point when the acid value was 90-97 mgKOH / g on the basis of resin solid content was maintained at 2 degreeC.

The prepared modified copolymer was confirmed to have an acid value of 93 mg KOH / g, nonvolatile content 42% by weight, viscosity 6,000cps, weight average molecular weight 76,000.

Example  4-6 and Comparative example

The photoresist compositions of Examples 4 to 6 were prepared using the photocurable alkali-soluble modified copolymers prepared in Examples 1 to 3 as the binder resins respectively. [Composition of photoresist composition: 20 wt% of binder resin, c. 4% by weight of functional monomer (TMPTA-trimetholpropanetriacrylate), 3% by weight of photoinitiator (Irgacura 907), 73% by weight of solvent (PGMEA-propylene glycol monomethyl ether acetate)).

On the other hand, using a general photocurable alkali-soluble acrylic copolymer having a structure of the general formula (1) as a comparative example was used as a binder resin to prepare a photoresist composition in the same manner and composition.

The resist properties of the prepared photoresist compositions were evaluated and shown in Table 6 below.

[Formula 1]

In Formula 1, p is 0.15, q is 0.2, r is 0.5 and S is 0.15.

(Heat resistance evaluation)

Pyrolysis temperature was measured by a thermogravimetric analysis (TGA) using a heating loss method, and compared to the initial weight of the sample reduced by 5%.

(Evaluation evaluation)

On a glass substrate, 1.5 micrometers was apply | coated with a spin coater (1H-DX2 by MIKASA), baked at 100 degreeC for 3 minutes, the photomask was arrange | positioned so that a predetermined exposure pattern may be formed, and an ultraviolet-ray may be 100 mJ / cm <2>. When spray-developing the investigated board | substrate using 0.05 weight% KOH aqueous solution, the time required for image development was measured.

(Adhesive evaluation)

After developing according to the developability evaluation method, the presence or absence of residues or cross-section residues was compared to evaluate the relative adhesion.

(Contents Rating)

3 wt% of a red colorant (KCC SY903-SR2) was added to the photoresist compositions prepared in Examples 4-6 and Comparative Examples, and then uniformly mixed using Dispermat to prepare respective coloring compositions.

Apply 1.5 micrometers of said coloring composition with a spin coater (1H-DX2 by MIKASA) on a glass substrate, bake for 3 minutes at 100 degreeC, and arrange | position a photomask so that a predetermined exposure pattern may be formed, and ultraviolet-ray 100mJ The substrate irradiated at / cm 2 was immersed in NMP (N-METHYL PYRROLIDONE) at 25 ° C. for 60 minutes and then evaluated by visually determining the etching state of the substrate.

Claims (18)

Carboxyl group or carboxylic anhydride group; Ethylenically unsaturated bonds; And residues of a multifunctional polyester-based oligomer; The polyfunctional polyester oligomer may include a hydroxyl group-containing monomer (A); Carboxyl group or acid anhydride group-containing monomer (B); Glycidyl group-containing monomer (D); And a monomer (F) having a hydroxyl group or a carboxyl group and an unsaturated group together is sequentially polymerized, From here The monomer (A) is 1,3-butylene glycol, 1,4-butylene glycol, diethylene glycol, ethylene glycol, 1,6-hexanediol, 2-methyl 1,3-propanediol, neopentyl glycol, propylene At least one selected from the group consisting of glycol, triethylene glycol, trimethylol propane and pentaerythritol, Monomer (B) is naphthalic anhydride, phosphoric anhydride, 3-fluorophthalic anhydride, butyric anhydride, hexahydro-4-methylphthalic anhydride, trifluoroacetic anhydride, hexahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetra Hydrophthalic anhydride, acetic anhydride, trimellitic anhydride, itaconic anhydride, neodecanoic acid oxyranylmethyl ester, chloric acid anhydride, succinic anhydride, tetrabromophthalic anhydride, dodecenyl succinic anhydride, nonenyl succinic anhydride, boric anhydride And methyl-5-norbornene-2,3-dicarboxylic acid anhydride, Monomer (D) is butyl glycidyl ether, resorcinol diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, S-trityl glycidyl ether, glycerol triglycidyl ether, 2,6 -Diglycidylphenyl glycidyl ether, diglycidyl ether of 1,4-cyclohexanedimethanol, R-benzyl glycidyl ether, S-benzyl glycidyl ether, diglycidyl ether of bisphenol A , Neopentyl glycol diglycidyl ether, triethylene glycol diglycidyl ether, p-cresyl glycidyl ether, guiacol glycidyl ether, o-cresyl glycidyl ether, p-chlorophenyl glyc Cydyl ether, ethylene glycol diglycidyl ether, diglycidyl ether, hydroquinone diglycidyl ether, 1,4-butanediol diglycidyl ether, n-butyl glycidyl ether, glycidyl neode Decanoate, 2-ethylhexyl glycidyl ether, lauryl Group consisting of cydyl ether, glycerol polyglycidyl ether, cresyl glycidyl ether, arylglycidyl ether, 3,4-epoxy cyclohexyl methyl methacrylate, glycidyl methacrylate and glycidyl acrylate At least one selected from Monomer (F) is 2-hydroxy ethyl methacrylate, 2-hydroxy ethyl acrylate, 2-hydroxy propyl acrylate, 2-hydroxy propyl methacrylate, 4-hydroxy butyl acrylate, 4-hydroxy At least one selected from the group consisting of oxybutyl methacrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride and tetrahydrophthalic anhydride, Photocurable alkali-soluble modified (co) polymers having a weight average molecular weight of 1,000 to 200,000. delete delete delete delete delete (1) providing a (co) polymer comprising a carboxyl group or a carboxylic anhydride group, and (2) introducing a polyfunctional polyester-based oligomer moiety into the (co) polymer, The (co) polymer containing the said carboxyl group or carboxylic anhydride group, Homopolymerization of at least one monomer (G) selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid and maleic acid alkyl esters; or The monomer (G) and an unsaturated carboxylic acid ester; Aromatic vinyl compounds; Unsaturated ethers; N-vinyl tertiary amines; Unsaturated imides; Maleic anhydride compounds; And copolymerization of at least one monomer (H) selected from the group consisting of unsaturated glycidyl compounds; or The monomer (G) and an unsaturated carboxylic acid ester; Aromatic vinyl compounds; Unsaturated ethers; N-vinyl tertiary amines; Unsaturated imides; Maleic anhydride compounds; And (co) polymers prepared through copolymerization of at least one monomer (H) selected from the group consisting of unsaturated glycidyl compounds, compounds having an oxirane ring group and an ethylenically unsaturated bond; Compounds having a hydroxyl group and an ethylenically unsaturated bond together; Maleic anhydride compounds; And an addition, polymerization or condensation reaction of at least one reactive monomer (J) selected from the group consisting of compounds having an isocyanate group and an ethylenically unsaturated bond together, The polyfunctional polyester oligomer may include a hydroxyl group-containing monomer (A); Carboxyl group or acid anhydride group-containing monomer (B); Glycidyl group-containing monomer (D); And a monomer (F) having a hydroxyl group or a carboxyl group and an unsaturated group together is sequentially polymerized, From here The monomer (A) is 1,3-butylene glycol, 1,4-butylene glycol, diethylene glycol, ethylene glycol, 1,6-hexanediol, 2-methyl 1,3-propanediol, neopentyl glycol, propylene At least one selected from the group consisting of glycol, triethylene glycol, trimethylol propane and pentaerythritol, Monomer (B) is naphthalic anhydride, phosphoric anhydride, 3-fluorophthalic anhydride, butyric anhydride, hexahydro-4-methylphthalic anhydride, trifluoroacetic anhydride, hexahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetra Hydrophthalic anhydride, acetic anhydride, trimellitic anhydride, itaconic anhydride, neodecanoic acid oxyranylmethyl ester, chloric acid anhydride, succinic anhydride, tetrabromophthalic anhydride, dodecenyl succinic anhydride, nonenyl succinic anhydride, boric anhydride And methyl-5-norbornene-2,3-dicarboxylic acid anhydride, Monomer (D) is butyl glycidyl ether, resorcinol diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, S-trityl glycidyl ether, glycerol triglycidyl ether, 2,6 -Diglycidylphenyl glycidyl ether, diglycidyl ether of 1,4-cyclohexanedimethanol, R-benzyl glycidyl ether, S-benzyl glycidyl ether, diglycidyl ether of bisphenol A , Neopentyl glycol diglycidyl ether, triethylene glycol diglycidyl ether, p-cresyl glycidyl ether, guiacol glycidyl ether, o-cresyl glycidyl ether, p-chlorophenyl glyc Cydyl ether, ethylene glycol diglycidyl ether, diglycidyl ether, hydroquinone diglycidyl ether, 1,4-butanediol diglycidyl ether, n-butyl glycidyl ether, glycidyl neode Decanoate, 2-ethylhexyl glycidyl ether, lauryl Group consisting of cydyl ether, glycerol polyglycidyl ether, cresyl glycidyl ether, arylglycidyl ether, 3,4-epoxy cyclohexyl methyl methacrylate, glycidyl methacrylate and glycidyl acrylate At least one selected from Monomer (F) is 2-hydroxy ethyl methacrylate, 2-hydroxy ethyl acrylate, 2-hydroxy propyl acrylate, 2-hydroxy propyl methacrylate, 4-hydroxy butyl acrylate, 4-hydroxy At least one selected from the group consisting of oxybutyl methacrylate, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride and tetrahydrophthalic anhydride, A method of producing a modified (co) polymer having a weight average molecular weight of 1,000 to 200,000 and an acid value of 30 to 300 KOH mg / g based on solid content. 8. The polyfunctional polyester oligomer according to claim 7, wherein the polyfunctional polyester oligomer has a weight average molecular weight of 600 to 5,000, an acid value of 40 to 300 mg KOH / g, a hydroxyl value of 0 to 100, A method of producing a modified (co) polymer, characterized in that the weight average molecular weight of the (co) polymer containing a carboxyl group or a carboxylic anhydride group is 1,000 to 200,000 and the acid value is 30 to 300 KOH mg / g based on solid content. delete delete delete delete 8. The method of claim 7, wherein the introduction of the polyfunctional polyester oligomer moiety is by direct addition, polymerization or condensation reaction of the polyfunctional polyester oligomer with a (co) polymer comprising a carboxyl group or a carboxylic anhydride group. A method for producing a modified (co) polymer. 8. The compound according to claim 7, wherein the introduction of the multifunctional polyester oligomer moiety comprises a hydroxyl group-containing compound having two or more reactors; Oxirane group-containing compounds having two or more reactors; Isocyanate group containing compound which has two or more reactors; And at least one member selected from the group consisting of carboxylic acid anhydride group-containing compounds having two or more reactors as a medium. delete delete delete A photoresist composition comprising the modified (co) polymer of claim 1.