JP5487368B2 - Photoresist composition - Google Patents

Description

  The present invention relates to a photoresist composition, a method for forming a photoresist pattern using the composition, a patterned resin composition, and a method for forming photolithography.

  Photosensitive imageable coatings are currently widely used in various semiconductor and microfabrication applications. By exposing the coating on the substrate to patterned actinic radiation and then treating with an appropriate developer to induce solubility changes in the coating so that exposed or unexposed areas can be selectively removed Optical image formation is achieved.

  The photosensitive imageable coating (photoresist) can be either positive or negative, in which case exposure to actinic radiation increases or decreases solubility in the developer, respectively. One of them.

  Advanced electronic packaging applications requiring high density interconnects at high aspect ratios (defined as the height to width ratio of the imaged features), or applications involving the fabrication of microelectromechanical devices (MEMS) There is often a need for a photosensitive imageable layer capable of producing high aspect ratio images with vertical sidewall profiles in homogeneous spin-coated and thicker coatings. Under such circumstances, many photoresists having photofunctional groups have been developed and marketed.

  The resist composition requires certain rheological properties and must be formulated so that it can be applied, for example, by a coating method such as spin coating.

  In addition, the resist composition must have the property of providing sufficient transmission of the exposure actinic radiation so as to photoactivate the photoinitiator from end to end of the coating thickness. Must have the proper physical and chemical properties to withstand applications such as solder resistance, ink resistance or toughness without loss of adhesion or loss of adhesion. If this photoresist composition is to be used for other purposes such as etch photoresist, further properties may be required.

  Japanese Patent Application Publication No. 2007-522531 describes in detail a thick film photosensitive image-forming composition using bisphenol A-novolak epoxy resin and its use (Patent Document 1). However, since a harmful metal such as antimony or arsenic is used as a metal component in the synthesis of the composition, the composition contains a harmful metal. Furthermore, since it develops with an organic solvent, the environmental load by using this composition is immeasurable.

JP-A-2005-133096 discloses a photoresist composition using a compound having an epoxy group and a chalcone group in the main chain (Patent Document 2). However, the photoresist composition described in Patent Document 2 is developed with an organic solvent or an alkaline developing aqueous solution. As described above, when developing with an organic solvent, for example, when applied to the surface of an ester-based transparent resin, the surface may become turbid due to hydrolysis, and the load on the environment is large. Similarly, when an alkaline aqueous solution is used, there is a problem that the surface may become cloudy due to hydrolysis when applied to the surface of an ester-based transparent resin.
Special table 2007-522531 gazette JP-A-2005-133096

  The main object of the present invention is to provide a photoresist composition, a method of forming a photoresist pattern using the composition, a patterned resin composition, and a method of forming photolithography.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific photoresist composition containing a polymer having a photosensitive image-forming chalcone group in the side chain has a good image resolution, and The resin composition obtained by curing the photoresist composition has thermal stability and chemical resistance, and at the same time has excellent performance in terms of adhesion, delamination, cracking, crazing, stress, and flexibility properties. I found out. In addition, the synthesis of the polymer contained in the photoresist composition of the present invention does not require the use of a metal catalyst, and the polymer and the resin composition obtained by curing the polymer are developed with an aqueous solvent (acidic aqueous solution). And found that peeling can be performed. The present invention has been completed based on such findings and further studies.

  The present invention relates to a photoresist composition, a method for forming a photoresist pattern using the composition, a patterned resin composition obtained by the method, and a photolithography forming method, as described in items 1 to 14 below.

  Item 1. Polymerizable water-soluble compound A having an ethylenically unsaturated double bond, epoxy group-containing unsaturated compound B, and the following general formula (1)

[Wherein, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, an amino group, or a carbon number. 1 to 4 N, N-dialkylamino, azido or nitro groups]
A photoresist composition comprising a polymer obtained by polymerizing compound C represented by formula (1) and a solvent, wherein the proportion of compound A is 0 to 90% by weight and the proportion of compound B is 0 to 0 in the total amount of monomer components. A photoresist composition wherein 50% by weight and the proportion of Compound C is 15 to 100% by weight.
Item 2. Item 2. The photoresist composition according to Item 1, wherein the proportion of Compound A is 10 to 75 wt%, the proportion of Compound B is 0 to 40 wt%, and the proportion of Compound C is 25 to 60 wt% in the total amount of monomer components. object.
Item 3. Item 3. The photoresist composition according to Item 1 or 2, wherein the polymerizable water-soluble compound A having an ethylenically unsaturated double bond is 4′-oxychalcone.
Item 4. Item 4. The photoresist composition according to any one of Items 1 to 3, wherein the epoxy group-containing unsaturated compound B is glycidyl methacrylate.
Item 5. Item ^{5. The} photoresist composition according to any one of Items 1 to 4, wherein the polymer has a weight average molecular weight of 1 × 10 ³ to 4 × 10 ⁵ .
Item 6. Item 6. The photoresist composition according to any one of Items 1 to 5, wherein the solvent is at least one selected from the group consisting of hydrocarbons, halogenated hydrocarbons, nitro compounds, nitriles, ethers, ketones, esters, and carbonates.
Item 7. Item 7. The photoresist composition according to any one of Items 1 to 6, comprising 5 to 9900 parts by weight of a solvent with respect to 100 parts by weight of the polymer.
Item 8. A method for forming a photoresist pattern comprising:
(1) The process of apply | coating the photoresist composition in any one of claim | item 1 -7 on a board | substrate,
(2) heating the substrate coated with the photoresist composition to evaporate most of the solvent to form a polymer film on the substrate;
(3) irradiating the substrate on which the polymer film is formed with active rays through a mask;
(4) A method comprising a step of developing an image with a developer to form a relief image of a mask on a substrate.
Item 9. Item 9. The method according to Item 8, wherein the active ray is visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray.
Item 10. Item 10. The method according to Item 8 or 9, wherein the developer is an acidic aqueous solution.
Item 11. Item 11. The method according to any one of Items 8 to 10, comprising a step of crosslinking the developed relief image by heating after the step (4).
Item 12. 12. A peelable patterned resin composition produced by the method according to any one of Items 8 to 11 having an image aspect ratio of 1 to 100.
Item 13. Item 13. The patterned resin composition according to Item 12, wherein the peelable patterned resin composition is used in the production of MEMS or micromachine parts.
Item 14. Item 12. A method for forming photolithography, comprising a step of peeling a patterned resin composition with an acidic aqueous solution after forming a pattern by the method according to any one of Items 8 to 11.

Photoresist Composition The photoresist composition of the present invention comprises a polymerizable water-soluble compound A having an ethylenically unsaturated double bond (hereinafter sometimes referred to as “compound A”), an epoxy group-containing unsaturated compound B (hereinafter referred to as “compound A”). , Sometimes referred to as “Compound B”) and the following general formula (1)

[Wherein, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, an amino group, or a carbon number. 1 to 4 N, N-dialkylamino, azido or nitro groups]
A compound obtained by polymerizing the compound C (hereinafter sometimes referred to as “compound C”), and a solvent, and the proportion of the compound A is about 0 to 90% by weight in the total amount of the monomer components. The ratio of B is about 0 to 50% by weight and the ratio of compound C is about 15 to 100% by weight.

  In the present invention, the compound A, the compound B and the compound C, and other polymerizable monomers which can be copolymerized with these compounds are generically referred to as a monomer component.

Compound A
Examples of the polymerizable water-soluble compound A having an ethylenically unsaturated double bond used in the present invention include (meth) acrylate derivatives, (meth) acrylamide derivatives, N, N-dialkylaminoalkyl (meth) acrylate derivatives, Nitrogen atom-containing vinyl monomer derivatives, unsaturated carboxylic acids, unsaturated sulfonic acids, (meth) acryloyl polyoxyalkylene (carbon number 1 to 6) sulfates, and the like.

  Examples of the (meth) acrylate derivative include hydroxymethyl (meth) acrylate and diethylene glycol mono (meth) acrylate.

  Examples of the (meth) acrylamide derivative include (meth) acrylamide, N-methyl- (meth) acrylamide, N-isopropyl- (meth) acrylamide, N-methylol- (meth) acrylamide, 3-methacrylamide-N, N-dimethylpropylamine etc. are mentioned.

  Examples of the N, N-dialkylaminoalkyl (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N-diethylaminoethyl (meth). Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dipropylaminopropyl (meth) acrylate, N-methyl, N-ethyl-aminoethyl ( (Meth) acrylate, N-methyl, N-ethyl-aminopropyl (meth) acrylate, N-methyl, N-propyl-aminoethyl (meth) acrylate, N-methyl, N-propyl-aminopropyl (meth) acrylate, N -Ethyl, N-propyl-aminoethyl (meth) acrylate, N-ethyl, N-propyl-aminopropyl (meth) acrylate It is.

  Examples of the nitrogen atom-containing vinyl monomer derivative include acrylonitrile, N-vinyl-2-pyrrolidone, vinylimidazole, N-vinylsuccinimide, p-aminostyrene, N-vinylcarbazole, 2-vinylpyridine, vinylmorpholine, 2- And cyanoethyl- (meth) acrylate.

  Examples of the unsaturated carboxylic acid include (meth) acrylic acid, maleic anhydride, fumaric acid, itaconic acid, vinyl benzoic acid, and the like.

  Examples of the unsaturated sulfonic acid include aliphatic unsaturated sulfonic acids having 2 to 20 carbon atoms, aromatic unsaturated sulfonic acids having 6 to 20 carbon atoms, sulfonic acid group-containing (meth) acrylate, and sulfonic acid group-containing ( Examples include (meth) acrylamide, (meth) allylsulfosuccinic acid ester having an alkyl group having 1 to 20 carbon atoms, and the like.

  Examples of the aliphatic unsaturated sulfonic acid having 2 to 20 carbon atoms include vinyl sulfonic acid.

  Moreover, as said C6-C20 aromatic unsaturated sulfonic acid, a styrenesulfonic acid etc. are mentioned, for example.

  Examples of the sulfonic acid group-containing (meth) acrylate include 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, and 2- (meth) acrylate. ) Acryloyloxybutanesulfonic acid, 4- (meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p- (meth) acryloyloxymethylbenzenesulfonic acid, etc. .

  Examples of the sulfonic acid group-containing (meth) acrylamide include 2- (meth) acryloylaminoethanesulfonic acid, 2- (meth) acryloylaminopropanesulfonic acid, 3- (meth) acryloylaminopropanesulfonic acid, 2- (meth) ) Acryloylaminobutanesulfonic acid, 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, p- (meth) acryloylaminomethylbenzenesulfonic acid, etc. .

  Examples of the (meth) allylsulfosuccinic acid ester having an alkyl group having 1 to 20 carbon atoms include methyl (meth) allylsulfosuccinic acid ester.

  Examples of the (meth) acryloyl polyoxyalkylene (carbon number 1 to 6) sulfate ester include (meth) acryloyl polyoxyethylene (ethylene oxide adduct having 2 to 50 moles) sulfate ester.

  Among these, the compound A used in the present invention is preferably a (meth) acrylamide derivative, and more preferably 3-methacrylamide-N, N-dimethylpropylamine.

  Compound A may be used alone or in combination of two or more.

  The amount of compound A used is usually about 0 to 90% by weight, preferably about 10 to 75% by weight, and more preferably about 20 to 70% by weight in the total amount of monomer components.

Compound B
Examples of the epoxy group-containing unsaturated compound B used in the present invention include glycidyl acrylate, glycidyl α-ethyl acrylate, glycidyl α-N-propyl acrylate, glycidyl α-N-butyl acrylate, acrylate-β -Epoxy group-containing acrylic acid such as methyl glycidyl, acrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl glycidyl methacrylate; methacrylic acid- Epoxy group-containing methacrylic acid such as β-methylglycidyl, methacrylic acid-3,4-epoxybutyl, methacrylic acid-6,7-epoxyheptyl; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and epoxy group-containing vinylbenzyl compounds such as p-vinylbenzylglycidyl ether.

  Among these, the compound B used in the present invention is preferably an epoxy group-containing methacrylic acid, and particularly preferably glycidyl methacrylate.

  Compound B may be used alone or in combination of two or more.

  The amount of compound B used is usually about 0 to 50% by weight, preferably about 0 to 40% by weight, and more preferably about 0 to 30% by weight in the total amount of monomer components.

Compound C
Compound C used in the present invention has the following general formula (1):

[Wherein, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, an amino group, It is a C 1-4 N, N-dialkylamino group, azide group or nitro group]
It is a compound shown by these.

In the compound represented by the general formula (1), R is preferably a methyl group. R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and particularly preferably a hydrogen atom.

  Preferred specific compounds of Compound C include, for example, 4′-acryloxy chalcone, 4′-methacryloxy chalcone, 4 ′-(α-ethyl) -acryloxy chalcone, 4 ′-(α-propyl) -acrylic. Roxychalcone, 4 ′-(α-butyl) -acryloxychalcone, 4′-acryloxy-4-methoxychalcone, 4′-acryloxy-4-ethoxychalcone, 4′-methacryloxy-4-methoxychalcone, 4′-methacryloxy -4-ethoxychalcone, 4'-acryloxy-4-butoxychalcone, 4'-methacryloxy-4-butoxychalcone, 4 '-(α-ethyl) acryloxy-4-methoxychalcone, 4'-(α-butyl) acryloxy -4-methoxychalcone, 4 '-(α-butyl) acryloxy-4-ethoxychalcone, 4'-acryloxy-4-methylchalcone, 4'-acryloxy-4-ethylchalcone, 4'-acryloxy-4-butylchalcone , 4'-acrylo Cy-4-aminochalcone, 4'-acryloxy-4- (N, N-dimethyl) aminochalcone, 4'-acryloxy-4- (N, N-diethyl) aminochalcone, 4'-methacryloxy-4-aminochalcone 4'-methacryloxy-4- (N, N-dimethyl) aminochalcone, 4'-methacryloxy-4- (N, N-diethyl) aminochalcone, 4'-acryloxy-4-nitrochalcone, 4'-methacryloxy- Examples include 4-nitrochalcone, 4′-acryloxy-4-chlorochalcone, 4′-methacryloxy-4-chlorochalcone, 4′-methacryloxy-4-azidochalcone, and the like.

  Among these, the compound C used in the present invention is particularly preferably 4′-methacryloxychalcone. Compound C may be used alone or in combination of two or more.

  The amount of compound C used is usually about 15 to 100% by weight, preferably about 25 to 60% by weight, and more preferably about 30 to 50% by weight in the total amount of monomer components. The polymer contained in the photoresist composition of the present invention is obtained by polymerizing Compound C as an essential component as a monomer.

Other Polysynthetic Monomers In addition to Compound A, Compound B, and Compound C, the polymer contained in the photoresist composition of the present invention is obtained by polymerizing other polymerizable monomers copolymerizable with these compounds. It may be obtained.

  Examples of such other polymerizable monomers include radical polymerizable unsaturated compounds such as methacrylic acid.

  Another polymerizable monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  The usage-amount of another polymerizable monomer is about 0-50 weight% normally in the total amount of a monomer component, Preferably it is about 0-10 weight%, More preferably, it is about 0-5 weight%.

Production method of polymer The method of producing a polymer obtained by polymerizing the compound A, the compound B, the compound C and, if necessary, another polymerizable monomer may be a conventionally known method, and is not particularly limited. For example, the solution polymerization method etc. are mentioned.

  When a polymer is produced by a solution polymerization method, a conventional operation method or the like generally performed by a solution polymerization method can be used, and the monomer component having the above ratio may be mixed with a solvent and polymerized.

  Examples of the solvent used in the solution polymerization method include ethers such as tetrahydrofuran and 1,4-dioxane; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene such as methyl cellosolve acetate and ethyl cellosolve acetate. Glycol alkyl ether acetates; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether; propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether Propylene glycol monoalkyl ethers such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate propylene glycol alkyl ether acetates such as propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl Propylene glycol alkyl ether acetates such as ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; and acetic acid Methyl, ethyl acetate, propyl acetate, vinegar Butyl, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, lactic acid Propyl, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, butoxyacetate , Ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -Ethyl ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxy Butyl propionate, 3-propyl Methyl lopoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, 3- Examples thereof include esters such as butyl butoxypropionate. Among these, 1,4-dioxane is preferable. The solvent used for the solution polymerization method may be used alone or in combination of two or more depending on the type and mixing ratio of the monomers.

  When a polymer is produced by a solution polymerization method, the amount of the solvent used is usually about 0 to 50000 parts by weight, preferably about 1000 to 10000 parts by weight with respect to 100 parts by weight of the monomer components.

  When a polymer is produced by a solution polymerization method, a polymerization initiator may be used. In the present invention, as the polymerization initiator, those generally known as radical polymerization initiators can be used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile) Azo compounds such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, organic peroxides such as 1,1′-bis- (t-butylperoxy) cyclohexane, and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

  The usage-amount of a polymerization initiator is about 0.1-20 weight part normally with respect to 100 weight part of monomer components, Preferably it is about 1-5 weight part.

  In the solution polymerization method, the mixing order of each component is not particularly limited. However, when a polymerization initiator is used, it is preferable to gradually drop the polymerization initiator into a mixed solution of the monomer component and the solvent (so-called dropping weight). legal).

  In the solution polymerization method, the polymerization temperature is usually about 20 to 100 ° C., preferably about 60 to 80 ° C., and the polymerization time is usually about 2 to 24 hours, preferably about 8 to 12 hours.

  When a polymer is produced by a solution polymerization method, the polymer is obtained by removing the solvent by reducing the pressure. The polymer residue obtained by decompression or the like may be used as it is for the preparation of a photoresist composition, and after the polymer residue is purified by a method such as precipitation or reprecipitation, the polymer obtained by sufficiently drying is used as a resin for photoresist. You may use for preparation of a composition.

  Since the polymer contained in the photoresist composition of the present invention can be produced without using a metal catalyst, the photoresist composition does not contain any harmful metals, and a resin obtained by curing the composition. A composition can be obtained.

The weight average molecular weight (Mw) of the polymer contained in the photoresist composition of the present invention is usually about 1 × 10 ³ to 4 × 10 ⁵ , preferably about 1 × 10 ³ to 1 × 10 ⁴ . The degree of dispersion (Mw / Mn) of the polymer is usually about 1.00 to 3.00, preferably about 1.10 to 1.50. The measuring method of the weight average molecular weight and dispersion degree of the polymer in this invention is the value measured by the method as described in an Example.

Solvent for Photoresist Composition The photoresist composition of the present invention is obtained by mixing the polymer obtained as described above and a solvent for a photoresist composition (hereinafter sometimes referred to as “resist solvent”). can get.

  As the resist solvent, a solvent that uniformly dissolves the polymer and does not react with each component such as a polymer and a substrate is used.

  Specific examples of the resist solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol such as methyl cellosolve acetate and ethyl cellosolve acetate. Alkyl ether acetates; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; propylene glycol Propylene glycol alkyl ether acetates such as methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate propylene glycol butyl ether acetate, etc .; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether pro Propylene glycol alkyl ether acetates such as pionate and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; and Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypro Ethyl onate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, Methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, protyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, Butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, Propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3 -Ethyl methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3- Propoxypropionic acid meth , Ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc. Of these esters. Among these, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycols are preferably used from the viewpoint of solubility and ease of forming a coating film. The solvent for resist may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Further, the resist solvent may be a high-boiling solvent used in combination with the solvent. Examples of high-boiling solvents that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl. Ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, Examples include propylene carbonate and phenyl cellosolve acetate. These high boiling point solvents may be used alone or in combination of two or more.

  The amount of the resist solvent used is usually about 5 to 9900 parts by weight, preferably about 5 to 900 parts by weight, and more preferably about 11 to 566 parts by weight with respect to 100 parts by weight of the polymer.

  The exact amount of resist solvent used depends on the desired film thickness. Compositions containing lower amounts of solvent result in higher solids concentrations and are useful for preparing thick films. On the other hand, compositions containing higher amounts of solvent reduce the solids content and such compositions are useful for preparing thin films.

Method for forming a photoresist pattern The method for forming a photoresist pattern of the present invention comprises:
(1) A step of applying the photoresist composition to a substrate,
(2) heating the substrate coated with the photoresist composition to evaporate most of the resist solvent to form a polymer film on the substrate;
(3) irradiating the substrate on which the polymer film is formed with active rays through a mask;
(4) The method includes developing the image with a developer to form a relief image of the mask on the substrate. Hereinafter, steps (1) to (4) will be described in detail.

  Step (1) is a step of applying the photoresist composition to the surface of the base substrate. As a method for applying the photoresist composition, various known methods such as a spray method, a roll coating method, and a spin coating method can be employed.

  The coating amount of the photoresist composition is usually about 0.1 to 10 ml, preferably about 2 to 5 ml, although it varies depending on the kind of each component in the photoresist composition, the mixing ratio, the thickness of the target resist phase, and the like. .

  As substrates, organic films (plastic) such as polycarbonate and polyester, silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, steel, copper -Including but not limited to silicon substrates, indium-tin oxide coated glass, metals, semiconductors, and any substrate containing a patterned region of insulating material. If necessary, a baking step may be performed on the substrate to remove moisture absorbed by the substrate before applying the photoresist composition.

  Step (2) is a step of heating the substrate coated with the photoresist composition in step (1) to evaporate most of the resist solvent to form a polymer film on the substrate. The solvent can be removed by prepreg or the like. The pre-bake conditions vary depending on the type of each component in the photoresist composition, the blending ratio, and the like, but are usually 90 to 150 ° C. for about 1 to 180 minutes.

  The thickness of the polymer film formed in the step (2) is usually about 1 μm to 2000 μm, preferably about 50 μm to 100 μm.

  Step (3) is a step of irradiating the substrate on which the polymer film is formed with active rays through a predetermined pattern mask. Active rays include visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like, and among these, ultraviolet rays are preferable.

For example, when ultraviolet rays (high pressure mercury lamp, light intensity 30 mW / cm ² ) are used, irradiation is usually performed for 10 minutes or more, preferably about 30 to 60 minutes.

  Step (4) is a step of developing the image with a developer to form a relief image of the mask on the substrate. By irradiation with actinic radiation in the step (3), the polymer film is cured and a resin composition is obtained. The portion other than the cured portion (unnecessary portion covered with the mask) is dissolved in the developer in the step (4), and only the resin composition remains, and a relief image (predetermined pattern) of the mask is formed.

  The developing method may be any of a liquid piling method, a dipping method, a shower method and the like, and the developing time is usually about 180 to 600 seconds.

  An acidic aqueous solution is used as the developer. There is no restriction | limiting in particular in the kind of acid and acid salt used for preparation of acidic aqueous solution, Any of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt can be used.

  Examples of inorganic acids and inorganic acid salts include hydrofluoric acid, hydrofluoric acid salt, hydrochloric acid, hydrochloride, hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate, Hydroiodic acid, hydroiodide, hypoiodic acid, hypoiodite, iodic acid, iodate, periodic acid, periodate, hydrobromic acid, hydrobromide, next Bromite, hypobromite, bromate, bromate, perbromate, perbromate, sulfuric acid, sulfate, sulfite, sulfite, persulfate, persulfate, nitric acid, nitrate, nitrous acid, Examples thereof include nitrite, phosphoric acid, phosphate, phosphorous acid, phosphite, hypophosphorous acid, hypophosphite, carbonic acid, and carbonate.

  Examples of organic acids and organic acid salts include carboxylic acids such as formic acid, acetic acid, propionic acid, and trichloroacetic acid, oxalic acid, citric acid, malonic acid, malic acid, glycolic acid, maleic acid, phthalic acid, and fumaric acid. And polycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and glutamic acid, phenols such as phenol and salicylic acid, sulfonic acids such as methanesulfonic acid and toluenesulfonic acid, and salts of these acids.

  These inorganic acids, inorganic acid salts, organic acids, and organic acid salts may be used singly or in combination of two or more.

  Among the inorganic acids, inorganic acid salts, organic acids, and organic acid salts used in the developer, phosphoric acid and acetic acid are preferable, and phosphoric acid is particularly preferable.

  The proportion of water contained in the developer (acidic aqueous solution) is about 70 to 99% by volume, preferably about 80 to 99% by volume, more preferably 90 to 99% by volume of the total volume of water, acid and / or acid salt. Degree. The ratio of the acid and / or acid salt contained in the developer is about 1 to 30% by volume, preferably about 1 to 20% by volume, more preferably 1 to 10% by volume of the total volume of water, acid and / or acid salt. %.

  Further, an acidic aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, or tetrahydrofuran and / or a surfactant to the acidic aqueous solution can also be used as a developer.

  When adding a water-soluble organic solvent and / or surfactant, the proportion of water is about 70 to 99% by volume of the total volume of water, acid and / or acid salt and water-soluble organic solvent and / or surfactant, Preferably it is about 80-99 volume%, More preferably, it is about 90-99 volume%. The ratio of acid and / or acid salt is about 0.1 to 15% by volume, preferably 0.5 to 10% by volume of the total volume of water, acid and / or acid salt and water-soluble organic solvent and / or surfactant. %, More preferably about 0.9 to 5% by volume. The ratio of the water-soluble organic solvent and / or surfactant is about 0.01 to 10% by volume, preferably 0.8%, of the total volume of water, acid and / or acid salt and water-soluble organic solvent and / or surfactant. It is about 05-5 volume%, More preferably, it is about 0.1-2 volume%.

  As the developer, a mixed solvent of water, phosphoric acid and tetrahydrofuran is particularly preferable. The ratio of water in the mixed solvent is usually about 70 to 99% by volume, preferably about 80 to 99% by volume, more preferably about 90 to 99% by volume of the total volume of water, phosphoric acid and tetrahydrofuran. The proportion of phosphoric acid is about 0.1 to 15% by volume of the total volume of water, phosphoric acid and tetrahydrofuran, preferably about 0.5 to 10% by volume, more preferably about 0.9 to 5% by volume. The ratio of tetrahydrofuran is about 0.01 to 10% by volume of the total volume of water, phosphoric acid and tetrahydrofuran, preferably about 0.05 to 5% by volume, more preferably about 0.1 to 2% by volume.

  Since the resin composition obtained by curing the photoresist composition (polymer) of the present invention can be developed with the acidic aqueous solution as described above, it can be applied to a substrate soluble in an organic solvent such as an organic film (plastic). Can do.

  After forming a photoresist pattern by the development process of step (4), washing with running water is performed for 30 to 90 seconds, and further air-dried with compressed air or compressed nitrogen to form a peelable patterned resin composition.

  The image aspect ratio (resist pattern height to width ratio) of the patterned resin composition obtained by development is usually about 1 to 100, preferably about 1 to 5.

  After the pattern formation, after processing the part (substrate) not covered with the patterned resin composition, the pattern (exposed part) of the resin composition remaining on the substrate can be peeled off to form photolithography.

  As a process to the board | substrate before peeling a patterned resin composition, a metal plating process, an etching process, etc. are mentioned, for example.

  As the metal plating treatment, for example, either an electroless plating method or an electrolytic plating method can be employed. The metal film deposited by plating is not particularly limited, and examples thereof include a copper film, a nickel film, a palladium film, a tin film, a tungsten film, a cobalt film, and an alloy film thereof. Among these, a nickel film Is preferred.

  In the case of performing electroless plating treatment, as the electroless plating solution, a conventionally known autocatalytic electroless plating solution may be used. For example, electroless nickel using sodium hypophosphite or the like as a reducing agent Phosphorus plating solution, electroless nickel-boron plating solution using dimethylamine borane as reducing agent, electroless copper plating solution using ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, formalin, etc. as reducing agent Electroless palladium plating solution, electroless palladium-phosphorous plating solution with sodium hypophosphite as reducing agent, electroless gold plating solution, electroless silver plating solution, electroless nickel with sodium hypophosphite as reducing agent An electroless plating solution such as a cobalt-phosphorous plating solution can be used.

  The thickness (total thickness) of the metal film layer varies depending on the thickness of the patterned resin composition, and is usually about 0.05 μm to 5 μm, preferably about 0.05 μm to 3 μm, more preferably about 0.1 μm to 1 μm. .

  Also, for example, when a resist pattern is formed on a substrate having a metal film, unnecessary metal film is removed by etching the metal film using openings, and then the resist film is removed. By doing so, a desired metal pattern can also be formed.

  The etching process may be either a wet etching process or a dry etching process.

  In the formation of the metal pattern by the wet etching process, an unnecessary nickel film can be removed by immersing in a heated nitric acid / ferric chloride mixed aqueous solution. The nitric acid concentration in the nitric acid / ferric chloride mixed aqueous solution is usually about 5 to 30%, preferably about 10 to 20%, and the ferric chloride concentration is usually about 1 to 20%, preferably 3 About 10%.

  When the metal pattern is formed by wet etching, the immersion temperature is usually about 40 to 80 ° C., preferably about 50 to 70 ° C., and the immersion time is usually about 10 seconds to 5 minutes, preferably 30 seconds to 2 It is preferable to set it to about a minute.

  When the metal pattern is formed by dry etching, unnecessary metal film may be removed by applying argon plasma to the metal film from the opening.

  Examples of the method for peeling the pattern of the resin composition remaining on the substrate include a method of immersing the substrate in a peeling solution being stirred at room temperature to 50 ° C. for 1 to 120 minutes.

  As the stripping solution, an acidic aqueous solution is used, but the acid and / or acid salt is not particularly limited, and any of inorganic acid, inorganic acid salt, organic acid, and organic acid salt can be used.

  Examples of inorganic acids and inorganic acid salts include hydrofluoric acid, hydrofluoric acid salt, hydrochloric acid, hydrochloride, hypochlorous acid, hypochlorite, chloric acid, chlorate, perchloric acid, perchlorate, Hydroiodic acid, hydroiodide, hypoiodic acid, hypoiodite, iodic acid, iodate, periodic acid, periodate, hydrobromic acid, hydrobromide, next Bromite, hypobromite, bromate, bromate, perbromate, perbromate, sulfuric acid, sulfate, sulfite, sulfite, persulfate, persulfate, nitric acid, nitrate, nitrous acid, Examples thereof include nitrite, phosphoric acid, phosphate, phosphorous acid, phosphite, hypophosphorous acid, hypophosphite, carbonic acid, and carbonate.

  Examples of organic acids and organic acid salts include carboxylic acids such as formic acid, acetic acid, propionic acid, and trichloroacetic acid, oxalic acid, citric acid, malonic acid, malic acid, glycolic acid, maleic acid, phthalic acid, and fumaric acid. And polycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and glutamic acid, phenols such as phenol and salicylic acid, sulfonic acids such as methanesulfonic acid, sulfamic acid and toluenesulfonic acid, and salts of these acids.

  Among these inorganic acids, inorganic acid salts, organic acids, and organic acid salts used in the stripper, acetic acid and phosphoric acid are preferable, and acetic acid is particularly preferable.

  The ratio of water contained in the stripping solution (acidic aqueous solution) is about 1 to 99% by volume, preferably about 80 to 95% by volume, more preferably 90 to 95% by volume of the total volume of water, acid and / or acid salt. Degree. The ratio of acid and / or acid salt contained in the stripper is about 1 to 99% by volume, preferably about 5 to 20% by volume, more preferably 5 to 10% by volume of the total volume of water, acid and / or acid salt. %.

  The stripping solution may be used alone or as a mixture of two or more.

  In the present invention, since an acidic aqueous solution can be used for both the developer and the stripper, it is suitable for forming a photoresist pattern on a substrate soluble in an organic solvent such as an organic film (plastic). In addition, since the development and peeling process can be performed with an acidic aqueous solution, the surface of the ester-based transparent resin is not hydrolyzed, and a transparent photoresist pattern formed product in which the substrate and the resin composition are not turbid is obtained. Can do.

  If necessary, after the step (4), (5) a step of crosslinking the developed relief image by heating may be included. By heating, the developed relief image may be further crosslinked, and the patterned resin composition may be cured more completely. Specifically, post-baking is performed on the relief image to advance the crosslinking reaction to a higher degree of conversion. The crosslinking reaction can be easily performed by using a heating facility such as a hot plate or a convection oven.

  By the above method, a patterned resin composition is obtained, and a photoresist pattern can be formed on the substrate.

  The patterned resin composition of the present invention can be used as a resist mold in manufactured articles including MEMS (Micro Electro Mechanical Systems) and micromachine parts. For example, it is a micromachine component as disclosed in Japanese Patent Laid-Open No. 2000-343463; an office component for an inkjet head as disclosed in Japanese Patent Laid-Open No. 2001-10068; Magnetic actuator (MEMS) component as disclosed in Japanese Patent No. 71299; Microchip for capillary gel electrophoresis (μ-TAS) as disclosed in Japanese Patent Application Laid-Open No. 2001-157855; and biological It can be used to manufacture microfluidic channels and cell growth platforms for MEM devices, microreactor components, dielectric layers, insulating layers, and resin substrates.

  The patterned resin composition obtained by applying, imaging and developing the photoresist composition of the present invention has a high density for biological ink printing as disclosed in US 2003/0059344. Fabrication of area array printing plates, fabrication of cell transfection plates and transfection devices as disclosed in US Pat. Nos. 6,652,878 and 6,670,129, can be used to form reactive ion etch masks.

  The composition according to the invention is used for biological applications to fabricate a plurality of microfluidic channels in a biomolecular activity parallel in vivo screening device as taught in US Pat. Nos. 6,576,478 and 6,682,942. it can.

  In the field of MEMS, the patterned resin composition of the present invention is a micropower switching device as taught in US Pat. No. 6,506,689; a microrelay device as taught in US Pat. No. 6,624,730; US Pat. No. 6,663,615 Can be used in the manufacture of pharmaceutical delivery devices and sensors as taught in US Pat. No. 6,582,890; multilayer relief structures as described in US Pat. No. 6,582,890; and electromagnetic actuators as described in US Pat. No. 6,674,350.

  Further, in the sensor domain, the photoresist compositions of the present invention are useful in the fabrication of microfiber optic pressure transducers, for example, as taught in US Pat. No. 6,506,313, and as taught in US Pat. No. 6,219,140. It can be used to fabricate cantilever tips for use in atomic force microscopy (AFM).

  The patterned resin composition of the present invention can be used in electronic packaging applications related to the formation of protective coatings on semiconductor wafers and specific devices as taught in US Pat. No. 6,544,902.

  Further, for example, U.S. Pat. Nos. 5,859,655, 6,193,359, 5,969,736, 6,606,681, 6,6419,346, 6,447,102, 6,305,790, and 6,375,313 include print head components of inkjet printer cartridges. The usefulness of epoxy resin-containing photoresists in fabrication is disclosed, and the photoresist composition of the present invention can be suitably used for these applications.

  The photoresist composition of the present invention can also be used as a substrate bonding adhesive. That is, an adhesive for contacting the substrate coated with the photoresist composition of the present invention with the second substrate so that an adhesive bond is formed between the two substrates under appropriate conditions of heat and pressure. Can be used. Depending on the heat and pressure conditions used, this adhesive bond may be either temporary or permanent. In this use, a temporary adhesive bond is an adhesive bond that can be broken by treating the bonded substrates with a solvent, whereas a permanent bond is an adhesive bond that is not weakened by solvent treatment. is there.

  The photoresist composition of the present invention has excellent imaging properties, good image resolution, thermal stability, chemical resistance, and at the same time adhesion, delamination, cracking, crazing, stress, and flexibility. Excellent performance regarding sexual characteristics. Moreover, it is not necessary to use a metal catalyst for the synthesis of the photoresist composition of the present invention, and the polymer and the resin composition obtained by curing the polymer are developed and peeled with an aqueous solvent (acidic aqueous solution). Therefore, the present invention can also be applied to those in which the substrate is dissolved in an organic solvent such as an organic film (plastic). Furthermore, since the development and peeling process can be performed with an acidic aqueous solution, the transparent transparent resin pattern surface is obtained without the ester-based transparent resin surface being hydrolyzed and the substrate and the resin composition being both turbid. Can do. The resin composition has excellent chemical resistance against alkalis and acids, and has good thermal stability properties.

[Example]
Hereinafter, the present invention will be further clarified by giving polymer synthesis examples, photoresist composition production examples, and test examples, but the present invention is not limited thereto.

Polymer synthesis examples 1-7
Under a nitrogen stream, 3-methacrylamide-N, N-dimethylpropylamine (component A in Table 1 below), glycidyl methacrylate (component B in Table 1 below), 2-methyl-acrylic acid-4- (3-phenyl) An amount of acryloyl) -phenyl ester (component C in Table 1 below) shown in Table 1 and 200 ml of 1,4-dioxane were placed in a four-necked flask and heated to 70 ° C. To this, 20 mmol of a polymerization initiator 2,2′-azobis- (2,4-dimethylvaleronitrile) was gradually added dropwise. After completion of the dropwise addition, the mixture was further reacted at 70 ° C. for 8 hours to obtain a copolymer reaction liquid of components A, B, and C. The reaction formulas of components A, B and C in Table 1 are shown below.

[Wherein, a, b and c represent the proportions of components C, B and A in Table 1, respectively, and each repeating unit is not limited to this order, and may be a block or random. ]
The resulting reaction solution was developed into 1000 ml of methanol, and 1,4-dioxane and methanol were removed by concentration under reduced pressure to obtain a yellow polymer. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the polymer obtained by standard polystyrene conversion from GPC measurement were calculated. The results are shown in Table 1.

Polymer synthesis examples 8 to 16
Under nitrogen flow, 2-hydroxyethyl methacrylate (component A in Table 2), glycidyl methacrylate (component B in Table 2), 2-methyl-acrylic acid-4- (3-phenylacryloyl) -phenyl ester (table Component C) 2 was charged in the amount shown in Table 2, 200 ml of 1,4-dioxane was placed in a four-necked flask and heated to 70 ° C. To this, 20 mmol of a polymerization initiator 2,2′-azobis- (2,4-dimethylvaleronitrile) was gradually added dropwise. After completion of the dropwise addition, the mixture was further reacted at 70 ° C. for 8 hours to obtain a copolymer reaction liquid of components A, B, and C. The reaction formulas of components A, B and C in Table 2 are shown below.

[Wherein, d, e, and f represent the proportions of components C, B, and A in Table 2, respectively, and each repeating unit is not limited to this order, and may be a block or random. ]
The resulting reaction solution was developed into 1000 ml of methanol, and 1,4-dioxane and methanol were removed by concentration under reduced pressure to obtain a yellow polymer. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the polymer obtained by standard polystyrene conversion from GPC measurement were calculated. Table 2 shows the examples and results. Moreover, the GPC measurement result of the obtained polymer (polymer 12) is shown in FIG. 1, the infrared absorption spectrum is shown in FIG. 2, the NMR chart is shown in FIGS. 3 and 4, and the sensitivity curve is shown in FIG.

Comparative Examples 1-17 and Examples 1-11 (Preparation of Photoresist Composition and Development Evaluation)
The polymers 1 to 16 were dissolved in ethyl lactate to prepare a 40% by mass solid content solution, which was filtered through a 0.2 μm polyethylene filter to prepare a negative photoresist composition.

  Each negative resist solution was applied by a bar coater (# 40) on a polycarbonate substrate subjected to electroless Ni plating treatment, and dried at 100 ° C. for 2 hours to form a 30 μm resist film.

This resist film is exposed for 30 minutes with a double-sided mask aligner (PEM-800 manufactured by Union Optics Co., Ltd.) through a mask pattern having a diameter of 1 mm (all wavelengths with a high-pressure mercury lamp; output is light intensity 30 mW / cm ² ). Thereafter, development was performed at 20 ° C. using the developer shown in Table 3, rinsed with pure water for 30 seconds, and then dried at 20 ° C. to obtain a resist pattern. The results are shown in Table 3.

Examples 12 to 21 (Examples of resist peeling evaluation test)
Using the polymer 12 that was particularly good in patterning, ten resist patterns were prepared by the method of the above example, and each resist pattern was immersed in a stripping solution described in Table 4 below at room temperature. Examined. The results are shown in Table 4.

  As is apparent from the evaluation test results, the photoresist composition of the present invention has excellent patterning performance on an organic film (plastic) substrate. In addition, both the developing solution and the stripping solution are aqueous solvents and have excellent performance not found in conventional photoresists. Furthermore, since the development and peeling process can be performed with an acidic aqueous solution, the transparent transparent resin pattern surface is obtained without the ester-based transparent resin surface being hydrolyzed and the substrate and the resin composition being both turbid. Can do. Therefore, it can be used for structural materials for MEMS and micromachines produced using electroforming technology, thick film photoresists for microreactors and μ-TAS, and inkjet printer heads. Although the present invention has been described above with reference to specific embodiments thereof, many changes, modifications and variations can be made without departing from the inventive concepts disclosed herein.

GPC measurement result of polymer 12 obtained in Synthesis Example 12 Infrared absorption spectrum of polymer 12 obtained in Synthesis Example 12 NMR chart of polymer 12 obtained in Synthesis Example 12 (low magnetic field side) NMR chart of polymer 12 obtained in Synthesis Example 12 (high magnetic field side) Sensitivity curve of polymer 12 obtained in Synthesis Example 12.

Claims (12)

Polymerizable water-soluble compound A having an ethylenically unsaturated double bond (excluding unsaturated carboxylic acid and its anhydride) , epoxy group-containing unsaturated compound B and the following general formula (1)

[Wherein, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, an amino group, or a carbon number. 1 to 4 N, N-dialkylamino, azido or nitro groups]
In polymer obtained by polymerizing a compound C represented, and a photoresist composition containing a solvent, in the total amount of monomer components, a compound ratio of A 10 to 75 wt%, compound rate of B is 5 0 A photoresist composition having a weight percent or less (excluding 0 wt%) and the proportion of Compound C of 15 to 60 wt%. The photoresist composition according to claim 1, wherein the epoxy group-containing unsaturated compound B is glycidyl methacrylate. The photoresist composition according to claim 1 or 2 weight-average molecular weight of the polymer is ^{1 × 10 3 ~4 × 10 5} . The photoresist composition according to any one of claims 1 to 3 , wherein the solvent is at least one selected from the group consisting of hydrocarbons, halogenated hydrocarbons, nitro compounds, nitriles, ethers, ketones, esters, and carbonates. . The photoresist composition according to any one of claims 1 to 4 containing solvent 5-9900 parts by weight per 100 parts by weight of the polymer. A method for forming a photoresist pattern comprising:
(1) The process of apply | coating the photoresist composition as described in any one of Claims 1-5 to a board | substrate,
(2) heating the substrate coated with the photoresist composition to evaporate most of the solvent to form a polymer film on the substrate;
(3) irradiating the substrate on which the polymer film is formed with active rays through a mask;
(4) A method comprising a step of developing an image with a developer to form a relief image of a mask on a substrate. The method according to claim 6 , wherein the actinic ray is visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. The method according to claim 6 or 7 , wherein the developer is an acidic aqueous solution. The method according to any one of claims 6 to 8 , further comprising the step of (5) crosslinking the developed relief image by heating after the step (4). The peelable patterned resin composition produced by the method according to any one of claims 6 to 9 , wherein the image aspect ratio is 1 to 100. The patterned resin composition according to claim 10 , wherein the peelable patterned resin composition is used in the production of MEMS or micromachine parts. After forming a pattern by a method according to any one of claims 6-9, the method of forming the photolithography comprising the step of separating the patterned resin composition with an acidic aqueous solution.

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