KR100537964B1 - Positive Type Photosensitive Resist Composition and Use Thereof - Google Patents

Abstract

The present invention can use an inexpensive photoacid generator, exhibit high resolution with near-ultraviolet exposure and weak alkali development, can cope with a substrate having through holes, and expose with near-ultraviolet light and develop with a weak alkali developer to produce fine pattern processing. Provided is a positive photosensitive resist composition which can be performed with good resolution.

The positive photosensitive resist composition is characterized by containing a compound having at least one dichloroacetyl group as an acid generator.

Description

 Positive Type Photosensitive Resist Composition and Use Thereof {Positive Type Photosensitive Resist Composition and Use Thereof}

The present invention provides a preferable and inexpensive photoacid generator as a positive photosensitive resist material, and a novel acid-sensitive copolymer containing a novel acid-sensitive copolymer and an acid-based generator as an essential component in a positive photosensitive resist material. To provide the material.

Currently, printed wiring boards and the like are manufactured by applying a photoresist to a substrate, attaching a mask, irradiating near ultraviolet light, and etching to draw the wiring on the substrate.

Negative photosensitive resist materials are mainly used as the photoresist materials used in the production of printed boards and the like, and compositions containing polycarboxylic acid resins, ethylenically unsaturated compounds, and photopolymerization initiators are common. Such a composition is applied to a substrate, a mask is attached, irradiated with near-ultraviolet rays (hereinafter referred to as "exposure") to cure the resin, and then immersed in a developing solution such as an aqueous 1% sodium carbonate solution to dissolve the unexposed portion in the developing solution. The photosensitive resist material of the exposed part remains, and a pattern is formed. Moreover, the method of etching the pattern obtained by removing a mask is used.

However, the film becomes thick even if a hole penetrating a substrate such as a through hole or a via hole is formed by this method, so that the uncured portion remains even after exposure, and the uncured portion remains. Since it flows out from the through-hole during development, it may be difficult to use this method as it is. As a method of solving this problem, a method of etching after protecting with a hole-filling ink or the like has been proposed in advance, but the hole-filling ink must be dried by heat, resulting in insufficient productivity. Moreover, in the negative type, since the method of hardening resin of an exposure part is used, it may be difficult to obtain a fine pattern of 50 micrometers or less.

Therefore, a pattern formation method using a positive photosensitive resist material that can be used for a substrate having a through hole and that can be processed finer at the same time has been proposed, and development of a high performance positive photosensitive resist material used therein is required. have. In addition, near-ultraviolet light (300-450 nm) is currently used in the pattern formation method which uses a negative photosensitive resist material in manufacture of a printed board, etc., and can perform a finer process to the board | substrate with a through hole without changing this wavelength. It is important to be able. In the present pattern formation method, a weakly alkaline developer represented by a 1% sodium carbonate aqueous solution is used as the developer, and it is important that the developer can be finely processed without changing the developer. It is also important that the positive photosensitive resist material is inexpensive for printed board applications. In other words, there is a demand for a positive photosensitive resist material that exhibits high resolution due to near-ultraviolet exposure and weak alkali.

As the photoacid generator of the positive photosensitive resist material, for example, NAI-105 and PAI-101 manufactured by Midori Chemical Co., Ltd. are used. The price is about 20,000 yen / g, and the compounding amount of the resist material is also 1 Since it mix | blends with -5 mass parts (100 mass parts of solid content), since it becomes expensive at about 10-500,000 yen / kg only in the photoacid generator component in a resist material, it is difficult to use for a printed circuit board use.

Moreover, as a base polymer of a positive photosensitive resist material, the copolymer represented by the Unexamined-Japanese-Patent No. 8-101507, the copolymer represented by the copolymer of p-isopropenyl phenol and 2-tetrahydropyranyl acrylate, and a radiation radiation A radiation sensitive resin composition comprising an acid generator is described. In addition, Japanese Patent Application Laid-Open No. 12-029215 discloses radiation containing a polymer having an acetal ester or a ketal ester unit which is directly suspended from a phenol unit and a polymer skeleton and reactable upon photoactivation of the photosensitive component. A resin composition is described.

These resin compositions are intended for use in ultra-fine processing of semiconductors and the like, and are coated with a film on a substrate such as silicon, attached with a mask and exposed to ultraviolet rays, or the like with an alkaline developer such as a 2.38% aqueous tetramethylammonium solution. Development to obtain the desired pattern. A very good pattern can be obtained by applying the above resin composition to a silicon substrate, irradiating light at 193 nm, and developing with a 2.38% aqueous tetramethylammonium solution.

However, when these copolymers were used as the base polymer of the near-ultraviolet photosensitive resist material used for manufacturing a printed board, etc., they may not be dissolved even after exposure to a 1% sodium carbonate aqueous solution which is a developing solution. It was found that continuous improvement is necessary for use as the base polymer of the photosensitive resist material.

In view of the above circumstances, an object of the present invention is to provide an inexpensive photoacid generator and an acid sensitive copolymer for a positive photosensitive resist material, and to make the base polymer of an acid sensitive copolymer and an inexpensive photoacid generator as essential components. As a photosensitive resist material, it is providing the positive type photosensitive resist material which shows high resolution by near-ultraviolet exposure and a weak alkali phenomenon. More specifically, it is possible to provide a positive photosensitive resist material that can cope with a substrate having a through hole and that can be exposed to near ultraviolet light and developed with a weak alkali developer to perform fine pattern processing with good resolution.

The present inventors earnestly examined to achieve the above object, and as a result, for example, the price of NAI-105 and PAI-101 manufactured by Midori Chemical Co., Ltd., which are photoacid generators generally used for positive photosensitive resists for acid-sensitive copolymers 4-phenoxy-α, α-dichloroacetophenones (also referred to as α, α-dichloro-4-phenoxyacetophenones) and / or 4,4 ′-(α, It was found that α-dichloroacetyl) diphenyl ethers surprisingly exhibited a remarkable effect as a photoacid generator of the positive photosensitive resist of a printed board, and exhibited high sensitivity as a printed board.

In addition, these photoacid generators are copolymers containing 4- (1-methylethenyl) phenol, (meth) acrylic acid esters, and (meth) acrylic acid alkoxyalkyl esters as a result of various studies, and these structural units are simultaneously When an acid-sensitive copolymer having a specific composition ratio is used as a positive component as a positive photosensitive resist material, it has been found to exhibit more preferably performance, and thus the present invention has been completed.

In other words, according to the present invention,

1. Provided is a positive photosensitive resist composition comprising a compound having at least one dichloroacetyl group as an acid generator.

2. A positive photosensitive resist composition is provided, wherein the compound having at least one dichloroacetyl group is represented by the following general formula (1).

In formula, R <^1> , R <^2> , R <^3> , R <^5> is a C1-C3 linear substituted by a hydrogen atom, a halogen atom, a cyano group, a C1-C3 linear or branched unsubstituted alkyl group, and a hydroxyl group. Or a substituent selected from a branched alkyl group and a phenyl group, R ⁴ represents a hydrogen atom, a halogen atom, a cyano group, a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms, or a C 1 to 3 carbon group substituted with a hydroxy group And a substituent selected from a linear or branched alkyl group, a phenyl group and a dichloroacetyl group, and X represents a divalent linking group selected from O, S, CH ₂ , C (CH ₃ ) ₂ and C═O.

3. An acid-sensitive copolymer comprising the first structural unit represented by the following formula (2), the second structural unit represented by the following formula (3), and the third structural unit represented by the following formula (4), and further comprising the copolymer A positive photosensitive resist composition constituted is provided.

In the formula, R ⁶ represents a hydrogen atom or a methyl group; R ⁷ is a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, a straight or branched alkyl group having 1 to 6 carbon atoms substituted with a hydroxy group, and a straight or branched carbon group having 1 to 6 carbon atoms substituted with a halogen atom C1-C6 linear or branched alkyl group substituted with an alkyl group, a cyano group, or a C1-C6 linear or branched alkyl group substituted with a dialkylamino group is shown.

In the formula, R ⁸ represents a hydrogen atom or a methyl group; R ⁹ represents a hydrogen atom, a halogen atom or a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms; Z represents a hydrogen atom, a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight or branched substituted alkyl group having 1 to 6 carbon atoms; Y represents a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms or a linear or branched substituted alkyl group having 1 to 6 carbon atoms; Y and Z may combine to form a ring structure.

4. R ⁷ of the second structural unit represented by Formula 3 is a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms, a linear or branched alkyl group having 1 to 3 carbon atoms substituted with a hydroxy group, a halogen atom A linear or branched alkyl group having 1 to 3 carbon atoms substituted with a linear or branched alkyl group or a linear or branched alkyl group having 1 to 3 carbon atoms or a dialkylamino group substituted with a cyano group A copolymer characterized by being an alkyl group and a positive photosensitive resist composition comprising the copolymer are provided.

5. In the third structural unit represented by Chemical Formula 4, R ⁹ is a hydrogen atom, fluorine or a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms; Z is a hydrogen atom, a straight or branched unsubstituted alkyl group having 1 to 3 carbon atoms, or a straight or branched substituted alkyl group having 1 to 3 carbon atoms; Y is a straight or branched unsubstituted alkyl group having 1 to 3 carbon atoms or a straight or branched substituted alkyl group having 1 to 3 carbon atoms; Y and Z are bonded to each other to form a ring structure, and the ring structure is an unsubstituted or substituted cyclic ether having 3 to 6 carbon atoms and a positive photosensitive resist composition further comprising the copolymer. Is provided.

6. The composition ratio of the first structural unit represented by Formula 2 is 0.15 to 0.3, the composition ratio of the second structural unit represented by Formula 3 is 0.5 to 0.7, and the composition ratio of the third structural unit represented by Formula 4 Is 0.1 to 0.3, and the sum total of the composition ratios of the three structural units is 1. The copolymer and the positive photosensitive resist composition which further comprise this copolymer are provided.

7. The acid sensitive copolymer is 0.05 to 0.3 mole parts of 4- (1-methylethenyl) phenol and 0.5 to 0.9 mole parts of (meth) acrylic acid esters represented by the following formula (5) and 0.01 to 0.4 mole parts of the following formula (6): A copolymer obtained by heating a copolymer mixture comprising a (meth) acrylic acid alkoxyalkyl ester represented by the formula so that the total of each molar ratio is 1 mol, a radical polymerization initiator and a solvent; The positive photosensitive resist composition which further contains this copolymer is provided.

In the formula, R ⁶ represents a hydrogen atom or a methyl group; R ⁷ is a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, a straight or branched alkyl group having 1 to 6 carbon atoms substituted with a hydroxy group, and a straight or branched carbon group having 1 to 6 carbon atoms substituted with a halogen atom C1-C6 linear or branched alkyl group substituted with an alkyl group, a cyano group, or a C1-C6 linear or branched alkyl group substituted with a dialkylamino group is shown.

In the formula, R ⁸ represents a hydrogen atom or a methyl group; R ⁹ represents a hydrogen atom, a halogen atom or a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms; Z represents a hydrogen atom, a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight or branched substituted alkyl group having 1 to 6 carbon atoms; Y represents a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms or a linear or branched substituted alkyl group having 1 to 6 carbon atoms; Y and Z may combine to form a ring structure.

8. The copolymer raw material is heated, or after heating, the copolymer raw material is concentrated or diluted as necessary, and the concentration of the unreacted 4- (1-methylethenyl) phenol with respect to the resist raw material is from 50 mass ppb to 0.5 mass%, the concentration of the unreacted (meth) acrylic acid esters with respect to the resist raw material is 5 ppm by mass to 5 mass%, and the concentration of the unreacted (meth) acrylic acid alkoxyalkyl esters with respect to the resist raw material is 200 mass. ppb to 2 mass%, the unreacted 4- (1-methylethenyl) phenol, unreacted (meth) acrylic acid esters, unreacted (meth) acrylic acid alkoxyalkyl esters and the resulting acid sensitive copolymer A resist raw material having a total concentration of 25 to 75% by mass relative to a resist raw material of was prepared, and 4-phenoxy-α, α-dichloroacetophenones and 4,4 '-(α, α-dichloroacetyl were prepared as the resist raw material. Diphenyl ether Obtained by adding one or more of the above-mentioned products, provided that the sum of the added amounts is unreacted 4- (1-methylethenyl) phenol, unreacted (meth) acrylic acid esters, unreacted (meth) acrylic acid alkoxyalkyl esters And 1 to 20 parts by mass based on 100 parts by mass of the total amount of the acid and the resulting acid-sensitive copolymer.

9. The copolymer raw material is 0.15 to 0.3 mole parts of the 4- (1-methylethenyl) phenol and 0.5 to 0.7 mole parts of the (meth) acrylic acid esters and 0.1 to 0.3 mole parts of the (meth) acrylic acid alkoxyalkyl ester. Each of the molar ratios equal to 1, and the total amount of the molar ratios added in the following Chemical Formula 1 is unreacted 4- (1-methylethenyl) phenol, unreacted (meth) acrylic acid esters, A positive photosensitive resist composition is provided, characterized in that 3 to 10 parts by mass relative to 100 parts by mass of the total amount of the reacted (meth) acrylic acid alkoxyalkyl esters and the acid-sensitive copolymer produced above.

<Formula 1>

In formula, R <^1> , R <^2> , R <^3> , R <^5> is a C1-C3 linear substituted by a hydrogen atom, a halogen atom, a cyano group, a C1-C3 linear or branched unsubstituted alkyl group, and a hydroxyl group. Or a substituent selected from a branched alkyl group and a phenyl group, R ⁴ represents a hydrogen atom, a halogen atom, a cyano group, a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms, or a C 1 to 3 carbon group substituted with a hydroxy group And a substituent selected from a linear or branched alkyl group, a phenyl group and a dichloroacetyl group, and X represents a divalent linking group selected from O, S, CH ₂ , C (CH ₃ ) ₂ and C═O.

10. R ⁷ of the (meth) acrylic acid ester represented by Formula 5 is a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms, a linear or branched alkyl group having 1 to 3 carbon atoms substituted with a hydroxy group, Linear or branched alkyl groups having 1 to 3 carbon atoms substituted with halogen, linear or branched carbon groups substituted with linear or branched alkyl groups or dialkylamino groups having 1 to 3 carbon atoms substituted with cyano groups There is provided a positive photosensitive resist composition, which is a ground alkyl group.

11. In the (meth) acrylic acid alkoxyalkyl esters represented by the formula (6), R ⁹ is a hydrogen atom, a fluorine atom or a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms; Z is a hydrogen atom, a straight or branched unsubstituted alkyl group having 1 to 3 carbon atoms, or a straight or branched substituted alkyl group having 1 to 3 carbon atoms; Y is a straight or branched unsubstituted alkyl group having 1 to 3 carbon atoms or a straight or branched substituted alkyl group having 1 to 3 carbon atoms; Y and Z combine to form a ring structure, and the ring structure is an unsubstituted or substituted cyclic ether having 3 to 6 carbon atoms, and a positive photosensitive resist composition comprising the copolymer is provided. .

12. The radical polymerization initiator is azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobisisobutyric acid dimethyl, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, A copolymer characterized in that it is di-tert-butyl peroxide, lauroyl peroxide, diisopropyl dicarbonate or acetyl peroxide, and a positive photosensitive resist composition comprising the copolymer is provided.

13. The above-mentioned solvent is a ketone, an alcohol, a polyhydric alcohol, a derivative of a polyhydric alcohol, a cyclic ether, an ester or an aromatic hydrocarbon, and a copolymer comprising the copolymer and a positive photosensitive resist composition comprising the copolymer are provided.

14. Total concentration of the 4- (1-methylethenyl) phenol, (meth) acrylic acid esters and (meth) acrylic acid alkoxyalkyl esters present in the copolymer raw material from the start of heating to the end of the copolymer raw material. At least one of the above 4- (1-methylethenyl) phenol, (meth) acrylic acid esters and (meth) acrylic acid alkoxyalkyl esters is continuously or intermittently added to the copolymer raw material so that the amount is always 20% by mass or less. Provided is a copolymer characterized in that heating is performed and a positive photosensitive resist composition comprising the copolymer.

15. A copolymer having a heating temperature of 40 to 250 ° C. and a positive photosensitive resist composition comprising the copolymer are provided.

16. Positive Photosensitive Resist Composition Comprising One or More of 4-phenoxy-α, α-dichloroacetophenones and 4,4 '-(α, α-dichloroacetyl) diphenylethers and an acid-sensitive copolymer In the production method of, the acid-sensitive copolymer is 0.05 to 0.3 mole parts of 4- (1-methylethenyl) phenol and 0.5 to 0.9 mole parts of (meth) acrylic acid esters represented by the following formula (5) and 0.01 to 0.4 mole It is obtained by heating the copolymer mixture which consists of a monomer mixture which consists of (meth) acrylic-acid alkoxyalkyl esters of the following general formula (6) so that the sum total of each molar ratio may be 1, and a radical polymerization initiator and a solvent, It is characterized by the above-mentioned. A method for producing a copolymer is provided.

<Formula 5>

In the formula, R ⁶ represents a hydrogen atom or a methyl group; R ⁷ is a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, a straight or branched alkyl group having 1 to 6 carbon atoms substituted with a hydroxy group, and a straight or branched carbon group having 1 to 6 carbon atoms substituted with a halogen atom C1-C6 linear or branched alkyl group substituted with an alkyl group, a cyano group, or a C1-C6 linear or branched alkyl group substituted with a dialkylamino group is shown.

<Formula 6>

In the formula, R ⁸ represents a hydrogen atom or a methyl group; R ⁹ represents a hydrogen atom, a halogen atom or a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms; Z represents a hydrogen atom, a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight or branched substituted alkyl group having 1 to 6 carbon atoms; Y represents a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms or a linear or branched substituted alkyl group having 1 to 6 carbon atoms; Y and Z may combine to form a ring structure.

17. The copolymer raw material is heated or the copolymer raw material is concentrated or diluted as necessary after heating, and the concentration of the unreacted 4- (1-methylethenyl) phenol with respect to the resist raw material is from 50 mass ppb to 0.5 mass%, the concentration of the unreacted (meth) acrylic acid esters with respect to the resist raw material is 5 ppm by mass to 5 mass%, and the concentration of the unreacted (meth) acrylic acid alkoxyalkyl esters with respect to the resist raw material is 200 mass. ppb to 2 mass%, the unreacted 4- (1-methylethenyl) phenol, unreacted (meth) acrylic acid esters, unreacted (meth) acrylic acid alkoxyalkyl esters and the resulting acid sensitive air A method for producing a copolymer comprising the step of preparing a resist raw material having a total concentration of 25 to 75% by mass relative to the resist raw material of the copolymer, and the resist raw material of Formula 1 (However, the sum total of the addition amount is unreacted 4- (1-methylethenyl) phenol, unreacted (meth) acrylic acid esters, unreacted (meth) acrylic acid alkoxyalkyl esters) and the above-mentioned product. Provided is a 1 to 20 parts by mass relative to 100 parts by mass of the total amount of the acid-sensitive copolymer thus prepared).

<Formula 1>

In formula, R <^1> , R <^2> , R <^3> , R <^5> is a C1-C3 linear substituted by a hydrogen atom, a halogen atom, a cyano group, a C1-C3 linear or branched unsubstituted alkyl group, and a hydroxyl group. Or a substituent selected from a branched alkyl group and a phenyl group, R ⁴ represents a hydrogen atom, a halogen atom, a cyano group, a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms, or a C 1 to 3 carbon group substituted with a hydroxy group And a substituent selected from a linear or branched alkyl group, a phenyl group and a dichloroacetyl group, and X represents a substituent selected from O, S, CH ₂ , C (CH ₃ ) ₂ and C═O.

18. In the heating step of the copolymer raw material, the total concentration of the 4- (1-methylethenyl) phenol, (meth) acrylic acid esters and (meth) acrylic acid alkoxyalkyl esters present in the copolymer raw material is Adding at least one of the above 4- (1-methylethenyl) phenol, (meth) acrylic acid esters and (meth) acrylic acid alkoxyalkyl esters to the copolymer raw material continuously or intermittently so that it is always 20% by mass or less; There is provided a method for producing a copolymer, characterized in that the heating.

19. Provided is a method for preparing a copolymer, wherein the heating temperature is 40 to 250 ° C.

20. In the positive photosensitive resist composition having a specific gravity of 0.800 to 0.950, wherein the positive specific photosensitive resist composition further comprises a solvent, a laminate of at least one surface of the metal layer is immersed and dried, thereby photosensitive to the surface of the laminate and the hole inner wall. A resin is uniformly filmed, and then, it exposes and develops, The manufacturing method of the printed wiring board is provided.

21. An electronic component manufactured by the manufacturing method described above is provided.

The positive photosensitive resist composition of this invention contains following formula (1), and is a material which mix | blends an acid sensitive copolymer and a solvent here.

<Formula 1>

In formula, R <^1> , R <^2> , R <^3> , R <^5> is a C1-C3 linear substituted by a hydrogen atom, a halogen atom, a cyano group, a C1-C3 linear or branched unsubstituted alkyl group, and a hydroxyl group. Or a substituent selected from a branched alkyl group and a phenyl group, R ⁴ represents a hydrogen atom, a halogen atom, a cyano group, a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms, or a C 1 to 3 carbon group substituted with a hydroxy group And a substituent selected from a linear or branched alkyl group, a phenyl group and a dichloroacetyl group, and X represents a divalent linking group selected from O, S, CH ₂ , C (CH ₃ ) ₂ and C═O.

It is preferable that it is 1 mass part or more, and, as for the compounding quantity of the acid generator represented with following formula (1) in order to perform pattern formation favorably with respect to a total of 100 mass parts of acid sensitive copolymers, it is more preferable that it is 3 mass parts or more. On the other hand, it is preferable that it is 20 mass parts or less, and it is more preferable that it is 10 mass parts or less from the point which can generate | occur | produce development residue and can form a high performance resist.

<Formula 1>

In formula, R <^1> , R <^2> , R <^3> , R <^5> is a C1-C3 linear substituted by a hydrogen atom, a halogen atom, a cyano group, a C1-C3 linear or branched unsubstituted alkyl group, and a hydroxyl group. Or a substituent selected from a branched alkyl group and a phenyl group, R ⁴ represents a hydrogen atom, a halogen atom, a cyano group, a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms, or a C 1 to 3 carbon group substituted with a hydroxy group And a substituent selected from a linear or branched alkyl group, a phenyl group and a dichloroacetyl group, and X represents a divalent linking group selected from O, S, CH ₂ , C (CH ₃ ) ₂ and C═O.

As the acid generator of the present invention, any compound having at least one dichloroacetyl group can be used without particular limitation, but the compound represented by the formula (1) is preferable. As the compound represented by the formula (1), for example, α, α-dichloro-4-phenoxyacetophenone, α, α-dichloro-2-methyl-4-phenoxyacetophenone, α, α-dichloro-2,6 -Dimethyl-4-phenoxycetophenone, α, α-dichloro-2-methyl-4- (3-methylphenoxy) acetophenone, α, α-dichloro-2-methyl-4- (3,5-dimethyl Phenoxy) acetophenone, α, α-dichloro-2,6-dimethyl-4- (3,5-dimethylphenoxy) acetophenone, α, α-dichloro-2-ethyl-4-phenoxyacetophenone, α , α-dichloro-2,6-diethyl-4-phenoxyacetophenone, α, α-dichloro-2-ethyl-4- (3-ethylphenoxy) acetophenone, α, α-dichloro-2-ethyl 4- (3,5-diethylphenoxy) acetophenone, α, α-dichloro-2,6-diethyl-4- (3,5-diethylphenoxy) acetophenone, α, α-dichloro- 2-propyl-4-phenoxycetophenone, α, α-dichloro-2,6-dipropyl-4-phenoxycetophenone, α, α-dichloro-2-propyl-4- (3-propylphenoxy) Acetophenone, α, α-dichloro-2-propyl-4- (3 , 5-dipropylphenoxy) acetophenone, α, α-dichloro-2,6-dipropyl-4- (3,5-dipropylphenoxy) acetophenone, α, α-dichloro-2-chloro-4 Phenoxycetophenone, α, α-dichloro-2,6-dichloro-4-phenoxyacetophenone, α, α-dichloro-2-chloro-4- (3-chlorophenoxy) acetophenone, α, α -Dichloro-2-chloro-4- (3,5-dichlorophenoxy) acetophenone, α, α-dichloro-2,6-dichloro-4- (3,5-dichlorophenoxy) acetophenone, α, α -Dichloro-2-methyl-4-phenoxycetophenone, α, α-dichloro-2,6-dicyano-4-phenoxycetophenone, α, α-dichloro-2-cyano-4- (3- Cyanophenoxy) acetophenone, α, α-dichloro-2-cyano-4- (3,5-dicyanophenoxy) acetophenone, α, α-dichloro-2,6-dicyano-4- ( 3,5-dicyanophenoxy) acetophenone, α, α-dichloro-2-bromo-4-phenoxycetophenone, α, α-dichloro-2,6-dibromo-4-phenoxyacetophenone , α, α-dichloro-2-bromo-4- (3-bromo Acytophenone, α, α-dichloro-2-bromo-4- (3,5-dibromophenoxy) acetophenone, α, α-dichloro-2,6-dibromo-4- (3 , 5-dibromophenoxy) acetophenone, α, α-dichloro-2-hydroxy-4-phenoxycetophenone, α, α-dichloro-2,6-dihydroxy-4-phenoxycetophenone , α, α-dichloro-2-hydroxy-4- (3-hydroxyphenoxy) acetophenone, α, α-dichloro-2-hydroxy-4- (3,5-dihydroxyphenoxy) aceto Phenone, α, α-dichloro-2,6-dihydroxy-4- (3,5-dihydroxyphenoxy) acetophenone, α, α-dichloro-2-phenyl-4-phenoxyacetophenone, α , α-dichloro-2,6-diphenyl-4-phenoxyacetophenone, α, α-dichloro-2-phenyl-4- (3-phenylphenoxy) acetophenone, α, α-dichloro-2-phenyl 4- (3,5-diphenylphenoxy) acetophenone, α, α-dichloro-2,6-diphenyl-4- (3,5-diphenylphenoxy) acetophenone, 3,5-dialkyl 4-α, α-dichloroacetylphenylphenylthioether 2,6-alkyl-4- (3,5-alkylbenzyl) α, α -Dichloroacetophenone, 3,5-dialkyl-4-α, α -dichloroacetylphenyl-3 ', 5'-dialkylphenylbenzophenone, 2,6-alkyl-4- (3,5-alkylphenylpropyl Lidene) α, α-dichloroacetophenone and 4,4 '-(α, α-dichloroacetyl) -3,5-dialkylphenyl-3', 5'-dialkylphenylether, 4,4 '-(α , α-dichloroacetyl) -3,5-dialkylphenyl-3 ', 5'-dialkylphenylthioether, 4,4'-(α, α-dichloroacetyl) -3,5-dialkylphenyl-3 ', 5'-dialkylphenylketone, 4,4'-(α, α-dichloroacetyl) -3,5-dialkylphenyl-3 ', 5'-dialkylmethylene, 4,4'-(α, α-dichloroacetyl) -3,5-dialkylphenyl-3 ', 5'-dialkylphenylpropylene and the like. These may be used alone or in combination.

As said alkyl, a C1-C3 linear or branched unsubstituted alkyl group and a C1-C3 linear or branched alkyl group substituted by the hydroxyl group are mentioned.

The positive photosensitive resist composition of the present invention exhibits high resolution by near-ultraviolet exposure and weak alkali development, can cope with substrates having through holes, and is exposed to near-ultraviolet light and developed with a weak alkali developer to provide fine resolution for fine pattern processing. It can be done by sex.

As the acid-sensitive copolymer of the positive photosensitive resist material of the present invention, a copolymer having a structural unit represented by the following formulas (2), (3) and (4) is particularly preferably used.

<Formula 2>

<Formula 3>

In the formula, R ⁶ represents a hydrogen atom or a methyl group; R ⁷ is a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, a straight or branched alkyl group having 1 to 6 carbon atoms substituted with a hydroxy group, and a straight or branched carbon group having 1 to 6 carbon atoms substituted with a halogen atom C1-C6 linear or branched alkyl group substituted with an alkyl group, a cyano group, or a C1-C6 linear or branched alkyl group substituted with a dialkylamino group is shown.

<Formula 4>

In the formula, R ⁸ represents a hydrogen atom or a methyl group; R ⁹ represents a hydrogen atom, a halogen atom or a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms; Z represents a hydrogen atom, a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight or branched substituted alkyl group having 1 to 6 carbon atoms; Y represents a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms or a linear or branched substituted alkyl group having 1 to 6 carbon atoms; Y and Z may combine to form a ring structure, and a, b, and c represent molar composition ratios, and the sum is one.

R ⁶ in Formula 3 is a hydrogen atom or a methyl group. In addition, R ⁷ of Formula 3 is a linear or branched unsubstituted, hydroxy substituted, halogen substituted, cyano substituted or dialkylamino substituted alkyl group having 1 to 6 carbon atoms, and specifically, for example, methyl group, ethyl group, unsubstituted alkyl groups such as n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclohexyl group or cyclopentyl group, hydroxymethyl group, 1-hydroxyethyl group , 2-hydroxyethyl group, 1-hydroxy n-propyl group, 2-hydroxy n-propyl group, 3-hydroxy n-propyl group, 1-hydroxyisopropyl group, 2,3-dihydroxy- Hydroxy substituted alkyl groups, such as n-propyl, 1-hydroxy n-butyl group, 2-hydroxy n-butyl group, 3-hydroxy n-butyl group, or 4-hydroxy n-butyl group, and a trifluoromethyl group , 2,2,2-trifluoroethyl group, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl group, 2,2,3,4,4,4-hexafluorobutyl Group, 2-chloroethyl group, Halogen-substituted alkyl groups such as chloroethyl group, 3-bromoethyl group or heptafluoroisopropyl group, cyano-substituted alkyl groups such as 2-cyanoethyl group, or 2- (dimethylamino) ethyl group, 3- (dimethylamino) propyl group Or dialkylamino substituted alkyl groups such as 3-dimethylamino neopentyl group.

Preferably it is a C1-C4 linear or branched unsubstituted, hydroxy substituted, halogen substituted, cyano substituted or dialkylamino substituted alkyl group, Specifically, methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-hydroxyethyl group, trifluoromethyl group or 2,2,2-trifluoroethyl group.

More preferably, they are a C1-C3 linear or branched unsubstituted, hydroxy substituted, halogen substituted, cyano substituted or dialkylamino substituted alkyl group, specifically, methyl group, ethyl group, n-propyl group, isopropyl A group, a trifluoromethyl group, 2-hydroxyethyl group, a trifluoromethyl group, or a 2,2,2- trifluoroethyl group etc. are mentioned.

R ⁸ in Formula 4 is a hydrogen atom or a methyl group. In addition, R ⁹ of Formula 4 is a hydrogen atom, a halogen atom or a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, and Z is a hydrogen atom or a straight or branched unsubstituted or substituted group having 1 to 6 carbon atoms. It is an alkyl group, Y is a C1-C6 linear or branched unsubstituted or substituted alkyl group, Y and Z may combine and have ring structure.

R ⁹ is specifically a straight or branched phase such as a hydrogen atom, a fluorine atom or a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group or tert-butyl group Is an unsubstituted alkyl group, Y is a straight or branched unsubstituted group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group or tert-butyl group, Hydroxy substituted, halogen substituted, cyano substituted or dialkylamino substituted alkyl group and the like, Z is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group or tert-butyl Linear or branched unsubstituted, hydroxy substituted, halogen substituted, cyano substituted or dialkylamino substituted alkyl groups such as groups.

More specifically, the parts of the alkoxyalkyl ester group represented by the formula (4), R ⁹ , C, O, Y and Z are collectively described as methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n -Butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, tert-butoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1- n-butoxyethyl group, 1-isobutoxyethyl group, 1-sec-butoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2 -Isobutoxyethyl group, 2-sec-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-n-propoxypropyl group, 1-isopropoxypropyl group, 1-n-butoxy Propyl group, 1-isobutoxypropyl group, 1-sec-butoxypropyl group, 1-tert-butoxypropyl group, 2-methoxypropyl group, 2-ethoxypropyl group, 2-n-propoxypropyl group , 2-isopropoxypro Group, 2-n-butoxypropyl group, 2-isobutoxypropyl group, 2-sec-butoxypropyl group, 2-tert-butoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3-n-butoxypropyl group, 3-isobutoxypropyl group, 3-sec-butoxypropyl group, 3-tert-butoxypropyl group Hydroxy substituted alkoxy groups, such as an unsubstituted alkyl group, 1-methoxy-1-hydroxymethyl group, 1- (1-hydroxy) methoxymethyl group, and 1- (1-hydroxy) methoxyethyl group, such as these, and trifluoro Halogen-substituted alkoxy groups, such as methoxymethyl group, 1-methoxy-2,2,2-trifluoroethyl group, and 1-trifluoromethoxy-2,2,2-trifluoroethyl group, 1-methoxy-1 Dialkylamino such as cyano-substituted alkoxy groups such as -cyanomethyl group, 1- (1-cyano) methoxymethyl group, 1- (1-cyano) methoxyethyl group, and 1,1-dimethylaminomethoxymethyl group Substituted alkoxy group, tetrahydrofuran-2-yloxy group, te Unsubstituted cyclic ethers such as hydropyran-2-yloxy group, alkyl-substituted cyclic ethers such as 2-methyltetrahydrofuran-2-yloxy group, 2-methyltetrahydropyran-2-yloxy group, or 2-fluorotetra Halogen substituted cyclic ethers such as hydrofuran-2-yloxy group and 2-fluorotetrahydrofuran-2-yloxy group.

In addition, preferably, R ⁹ of Formula 4 is a hydrogen atom, a fluorine atom or a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms, and Z is a hydrogen atom or a straight or branched non-substituted carbon atom having 1 to 3 carbon atoms A ring or substituted alkyl group, Y is a linear or branched unsubstituted or substituted alkyl group having 1 to 3 carbon atoms, and a ring structure formed by combining Y and Z is an unsubstituted or substituted cyclic ether having 3 to 6 carbon atoms, and In general, if R ⁹ , C, O, X and Z of the general formula (4) are collectively described, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group , 1-n-propoxyethyl group, 1-isopropoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group , 1-methoxy-1-hydroxymethyl group, 1- (1-hydroxy) methoxymethyl group, 1- (1-hydroxy Roxy) methoxyethyl group, trifluoromethoxymethyl group, 1-methoxy-2,2,2-trifluoroethyl group, 1-trifluoromethoxy-2,2,2-trifluoroethyl group, tetrahydrofuran- 2-yloxy group, tetrahydropyran-2-yloxy group, 2-methyltetrahydrofuran-2-yloxy group, 2-methyltetrahydropyran-2-yloxy group or 2-fluorotetrahydrofuran-2-yloxy group And so on.

In addition, Formula 3 or 4 may have not only 1 type of structural unit but 2 or more types of structural units. That is, a copolymer having four or more structural units, such as a copolymer having a structural unit represented by the formula (2), two or more formulas (3) and two or more formulas (4), is also included in the copolymer of the present invention.

In the copolymer of the present invention, the composition ratio of the structural units represented by the formulas (2), (3) and (4) is very important, and when the total of the three structural units is 1, the composition ratio of the formula (2) is 0.05 or more. It is preferable that it is 0.15 or more, It is more preferable that it is 0.2 or more, On the other hand, 0.3 or less are preferable. Moreover, it is preferable that the composition ratio of General formula (3) is 0.5 or more, On the other hand, it is preferable that it is 0.9 or less, and it is more preferable that it is 0.7 or less. Moreover, it is preferable that the composition ratio of Formula (4) is 0.01 or more, It is more preferable that it is 0.1 or more, On the other hand, It is preferable that it is 0.4 or less, It is more preferable that it is 0.3 or less. In addition, when the structural unit represented by General formula (3) or (4) is 2 or more types, the composition ratio at this time is the sum total of the composition ratio of each structural unit. In addition, the composition ratio of three structural units can be measured by <^1> H-NMR, <^13> C-NMR, etc., for example.

In addition, the acid-sensitive copolymer used in the present invention is one in which the structural units represented by the formulas (2), (3) and (4) are randomly copolymerized, or three structural units are alternately copolymerized. It may be block copolymerized.

Although the weight average molecular weight (Mw) of the acid sensitive copolymer used for this invention differs according to the purpose of use of the said copolymer, and is not uniform, For example, normally 3,000 or more are preferable, 4,000 or more are more preferable, on the other hand, 80,000 or less are preferable and 60,000 or less are more preferable. Moreover, molecular weight dispersion degree (Mw / Mn, Mn is number average molecular weight) is 1.0 or more normally, On the other hand, 5.0 or less are preferable, 4.0 or less are more preferable, 3.0 or less are more preferable. In addition, a weight average molecular weight and molecular weight dispersion degree can be measured by polystyrene conversion using gel permeation chromatography (GPC) etc., for example.

The copolymer used in the present invention is a monomer mixture comprising 4- (1-methylethenyl) phenol, (meth) acrylic acid esters represented by the formula (4), and (meth) acrylic acid alkoxyalkyl esters represented by the formula (5). And a radical polymerization initiator and a solvent can be obtained by mixing and heating the monomer molar ratio in the monomer mixture to a predetermined value.

As the (meth) acrylic acid esters represented by the general formula (5) which is a raw material monomer of the acid-sensitive copolymer used in the present invention, R ^{6 in the} chemical formula is a hydrogen atom or a methyl group, and R ⁷ is a linear or branched carbon having 1 to 6 carbon atoms. As an unsubstituted, hydroxy substituted, halogen substituted, cyano substituted or dialkylamino substituted alkyl group of, specifically, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isoacrylate Acrylic acid unsubstituted alkyl esters such as butyl, sec-butyl acrylate, tert-butyl acrylate, cyclohexyl acrylate or cyclopentyl acrylate, hydroxymethyl acrylate, 1-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 1-hydroxy acrylate Hydroxy n-propyl, acrylic acid 2-hydroxy n-propyl, acrylic acid 3-hydroxy n-propyl, acrylic acid 1-hydroxy Acrylic acid such as propyl, 2,3-dihydroxypropyl acrylic acid, 1-hydroxy n-butyl acrylate, 2-hydroxy n-butyl acrylate, 3-hydroxy n-butyl acrylate or 4-hydroxy n-butyl acrylate Hydroxy substituted alkyl esters, trifluoromethyl acrylate, 2,2,2-trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl, acrylic acid Acrylic acid halogen-substituted alkyl esters such as 2-chloroethyl, trichloroethyl acrylate, 3-bromoethyl acrylate or heptafluoro-2-propyl acrylate, cyano-substituted alkyl esters such as 2-cyanoethyl acrylate, acrylic acid 2 Acrylic acid dialkylamino substituted alkyl esters such as (dimethylamino) ethyl, 3- (dimethylamino) propyl acrylate or 3-dimethylaminonepentyl acrylate, methyl methacrylate and methacrylic acid Methyl, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate or methacrylic Methacrylic acid unsubstituted alkyl esters such as cyclopentyl acid, methacrylic acid hydroxymethyl, methacrylic acid 1-hydroxyethyl, methacrylic acid 2-hydroxyethyl, methacrylic acid 1-hydroxy n-propyl, meta Methacrylic acid 2-hydroxy n-propyl, methacrylic acid 3-hydroxy n-propyl, methacrylic acid 1-hydroxyisopropyl, methacrylic acid 2,3-dihydroxypropyl, methacrylic acid 1-hydroxy Methacrylic acid hydroxy substituted alkyl esters, methacrylic acid, such as n-butyl, methacrylic acid 2-hydroxy n-butyl, methacrylic acid 3-hydroxy n-butyl, or methacrylic acid 4-hydroxy n-butyl Trifluoromethyl, methacrylic acid 2,2,2-trifluoroethyl, methacrylic acid hexafluoro Sopropyl, 2,2,3,4,4,4-hexafluorobutyl, methacrylic acid 2-chloroethyl, methacrylic acid trichloroethyl, methacrylic acid 3-bromoethyl or methacrylic acid Methacrylic acid halogen substituted alkyl esters, such as heptafluoro 2-propyl, methacrylic acid cyano substituted alkyl esters, such as 2-cyanoethyl methacrylate, 2- (dimethylamino) ethyl methacrylic acid, and methacrylic acid 3 Methacrylic acid dialkylamino substituted alkyl ester, such as-(dimethylamino) propyl or methacrylic acid 3-dimethylamino neopentyl, etc. are mentioned.

Preferably, R ⁷ in formula (5) is a straight or branched unsubstituted, hydroxy substituted, halogen substituted, cyano substituted or dialkylamino substituted alkyl group having 1 to 4 carbon atoms, and is preferably a specific (meth) acrylic acid ester. Examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, hydroxymethyl acrylate, 1 acrylic acid Hydroxyethyl, 2-hydroxyethyl acrylate, trifluoromethyl acrylate, 2,2,2-trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,4,4,4- acrylic acid Hexafluorobutyl, 2-cyanoethyl acrylate, 2- (dimethylamino) ethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacrylic acid Sopropyl, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, hydroxymethyl methacrylate, meta 1-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, trifluoromethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, hexafluoroisopropyl methacrylic acid, methacrylic acid Acids 2,2,3,4,4,4-hexafluorobutyl, 2-cyanoethyl methacrylate or 2- (dimethylamino) ethyl methacrylate.

More preferably, R ⁷ of Formula 5 is a linear or branched unsubstituted, hydroxy substituted, halogen substituted, cyano substituted or dialkylamino substituted alkyl group having 1 to 3 carbon atoms, and more preferred (meth) acrylic acid esters. Specific examples of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, hydroxymethyl acrylate, 1-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 1-hydroxy-n-propyl acrylate, and 1- acrylic acid Hydroxyisopropyl, 2,3-dihydroxypropyl acrylate, trifluoromethyl acrylate, 2,2,2-trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2-chloroethyl acrylate, trichloroethyl acrylate , 3-bromoethyl acrylate, heptafluoro-2-propyl acrylate, 2-cyanoethyl acrylate, 2- (dimethylamino) ethyl acrylate, 3- (di Methylamino) propyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, hydroxymethyl methacrylate, 1-hydroxyethyl methacrylate, 2-hydroxy methacrylate Hydroxyethyl, methacrylic acid 1-hydroxy-n-propyl, methacrylic acid 2-hydroxy n-propyl, methacrylic acid 3-hydroxy-n-propyl, methacrylic acid 1-hydroxyisopropyl, methacrylic Acid 2,3-dihydroxypropyl, methacrylic acid trifluoromethyl, methacrylic acid 2,2,2-trifluoroethyl, methacrylic acid hexafluoroisopropyl, methacrylic acid 2-chloroethyl, meta Trichloroethyl methacrylate, 3-bromoethyl methacrylate, heptafluoro-isopropyl methacrylate, 2-cyanoethyl methacrylate or 2- (dimethylamino) ethyl methacrylate.

In addition, the above-mentioned (meth) acrylic acid esters may be used alone or in combination of two or more thereof, and in this case, a copolymer having a structure in which two or more structural units represented by the formula (3) are randomly copolymerized. You can get it. At this time, the composition ratio of the formula (3) is the sum of the composition ratios of the structural units represented by two or more kinds of formula (3).

As (meth) acrylic acid alkoxyalkyl esters represented by the general formula (6) which is another raw material of the acid-sensitive copolymer used in the present invention, R ^{8 in the} formula is a hydrogen atom or a methyl group, and R ⁹ is a hydrogen atom, a halogen atom or A straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, Z is hydrogen or a straight or branched unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, and Y is a straight or branched carbon group having 1 to 6 carbon atoms As an unsubstituted or substituted alkyl group, Y and Z may combine to form a ring structure.

Specific examples of the (meth) acrylic acid alkoxyalkyl esters are methoxymethyl acrylate, ethoxymethyl acrylate, n-propoxymethyl acrylate, isopropoxymethyl acrylate, n-butoxymethyl acrylate, isobutoxymethyl acrylate and sec- acrylic acid. Butoxymethyl, tert-butoxymethyl acrylate, 1-methoxyethyl acrylate, 1-ethoxyethyl acrylate, 1-n-propoxyethyl acrylate, 1-isopropoxyethyl acrylate, 1-n-butoxyethyl acrylate 1-isobutoxyethyl acrylate, 1-sec-butoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-n-propoxyethyl acrylate, 2-isopropoxyethyl acrylate, 2-n-butoxyethyl acrylate, 2-isobutoxyethyl acrylate, 2-sec-butoxyethyl acrylate, 1-methoxypropyl acrylate, 1-ethoxypropyl acrylate, 1-n-propoxypropyl acrylate, 1-isopropoxypropyl acrylate, 1- acrylic acid n-butoxypro Pill, 1-isobutoxypropyl acrylate, 1-sec-butoxypropyl acrylate, 1-tert-butoxypropyl acrylate, 2-methoxypropyl acrylate, 2-ethoxypropyl acrylate, 2-n-propoxypropyl acrylate, 2-isopropoxypropyl acrylate, 2-n-butoxypropyl acrylate, 2-isobutoxypropyl acrylate, 2-sec-butoxypropyl acrylate, 2-tert-butoxypropyl acrylate, 3-methoxypropyl acrylate, acrylic acid 3-ethoxypropyl, acrylic acid 3-n-propoxypropyl, acrylic acid 3-isopropoxypropyl, acrylic acid 3-n-butoxypropyl, acrylic acid 3-isobutoxypropyl, acrylic acid 3-sec-butoxypropyl or acrylic acid 3 acrylic acid unsubstituted alkyl alkoxylates such as -tert-butoxypropyl, acrylic acid 1-methoxy-1-hydroxymethyl, acrylic acid 1- (1-hydroxy) methoxymethyl or acrylic acid 1- (1-hydroxy) Acrylic acid hydroxy substituted eggs, such as methoxy ethyl Halogen substitution of acrylic acid, such as a silicate, trifluoromethoxymethyl acrylate, 1-methoxy-2,2,2-trifluoroethyl acrylate, or 1-trifluoromethoxy-2,2,2-trifluoroethyl acrylate Cyanoacrylate acrylates such as alkoxylates, 1-methoxy-1-cyanomethyl acrylate, 1- (1-cyano) methoxymethyl acrylate or 1- (1-cyano) methoxyethyl acrylate Acrylic acid unsubstituted cyclic oxalate or acrylic acid such as dialkylamino substituted alkoxylate such as acrylic acid 1,1-dimethylaminomethoxymethyl, tetrahydro-2-yloxy acrylate or tetrahydropyran-2-yloxy acrylate. Acrylic acid halides, such as alkyl-substituted cyclic oxalates such as 2-methyltetrahydrofuran-2-yloxy or acrylic acid 2-methyltetrahydropyran-2-yloxy, and acrylic acid 2-fluorotetrahydrofuran-2-yloxy Chloro substituted cyclic oxalate, methoxymethyl methacrylate, ethoxymethyl methacrylate, n-propoxymethyl methacrylate, isopropoxymethyl methacrylate, n-butoxymethyl methacrylate, isomethacrylate Methoxymethyl, methacrylic acid sec-butoxymethyl, methacrylic acid tert-butoxymethyl, methacrylic acid 1-methoxyethyl, methacrylic acid 1-ethoxyethyl, methacrylic acid 1-n-propoxyethyl, Methacrylic acid 1-isopropoxyethyl, methacrylic acid 1-n-butoxyethyl, methacrylic acid 1-isobutoxyethyl, methacrylic acid 1-sec-butoxyethyl, methacrylic acid 2-ethoxyethyl, 2-n-propoxyethyl methacrylate, 2-isopropoxyethyl methacrylate, 2-n-butoxyethyl methacrylate, 2-isobutoxyethyl methacrylate, 2-sec-butoxy methacrylate Ethyl, methacrylic acid 1-methoxypropyl, methacrylic acid 1-ethoxypropyl, methacrylic acid 1-n-propoxypropyl, methacrylic acid 1-isopropoxy Phil, methacrylic acid 1-n-butoxypropyl, methacrylic acid 1-isobutoxypropyl, methacrylic acid 1-sec-butoxypropyl, methacrylic acid 1-tert-butoxypropyl, methacrylic acid 2-methic acid Methoxypropyl, methacrylic acid 2-ethoxypropyl, methacrylic acid 2-n-propoxypropyl, methacrylic acid 2-isopropoxypropyl, methacrylic acid 2-n-butoxypropyl, methacrylic acid 2-isopart Methoxypropyl, methacrylic acid 2-sec-butoxypropyl, methacrylic acid 2-tert-butoxypropyl, methacrylic acid 3-methoxypropyl, methacrylic acid 3-ethoxypropyl, methacrylic acid 3-n- Propoxypropyl, methacrylic acid 3-isopropoxypropyl, methacrylic acid 3-n-butoxypropyl, methacrylic acid 3-isobutoxypropyl, methacrylic acid 3-sec-butoxypropyl or methacrylic acid 3- Methacrylic acid unsubstituted alkyl alkoxylates such as tert-butoxypropyl, methacrylic acid 1-methoxy-1-hydroxymethyl, methacrylic acid 1- (1-hydroxy) methoxy Methacrylic acid hydroxy substituted alkoxylates such as methyl or methacrylic acid 1- (1-hydroxy) methoxyethyl, methacrylic acid trifluoromethoxymethyl, methacrylic acid 1-methoxy-2,2,2 Methacrylic acid halogen-substituted alkoxylates, such as trifluoroethyl or methacrylic acid 1-trifluoromethoxy-2,2,2-trifluoroethyl, and methacrylic acid 1-methoxy-1-cyanomethyl Methacrylic acid cyano substituted alkoxylates, such as 1- (1-cyano) methoxymethyl methacrylate or 1- (1-cyano) methoxyethyl methacrylate, 1,1-dimethyl methacrylate Methacrylic acid unsubstituted cyclic oxalate, such as methacrylic acid dialkylamino substituted alkoxylate, such as aminomethoxymethyl, tetrahydrofuran-2-yloxy methacrylate, or tetrahydropyran-2-yloxy methacrylate Methacrylic acid 2-methyltetrahydrofuran-2-yloxy or methacrylic acid 2-methyltetrahydropyran Methacrylic acid alkyl substituted cyclic oxalate, such as 2-yloxy, Methacrylic acid fluorine substituted cyclic oxalate, such as methacrylic acid 2-fluorotetrahydrofuran-2-yloxy, etc. are mentioned.

Preferably in the (meth) acrylic acid alkoxyalkyl esters represented by the formula (6), R ⁹ in the formula is a hydrogen atom, a fluorine atom or a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms, Z is a hydrogen atom or A straight or branched unsubstituted or substituted alkyl group having 1 to 3 carbon atoms, Y is a straight or branched unsubstituted or substituted alkyl group having 1 to 3 carbon atoms, and a ring structure formed by combining Y and Z is carbon As an unsubstituted or substituted cyclic ether of 3 to 6, specific examples of preferable (meth) acrylic acid alkoxyalkyl esters are methoxymethyl acrylate, ethoxymethyl acrylate, n-propoxymethyl acrylate, isopropoxymethyl acrylate, and acrylic acid 1-. Methoxyethyl, 1-ethoxyethyl acrylate, 1-n-propoxyethyl acrylate, 1-isopropoxyethyl acrylate, 2-ethoxyethyl acrylate, acrylic Acid 2-n-propoxyethyl, 2-isopropoxyethyl acrylate, 1-methoxypropyl acrylate, 1-ethoxypropyl acrylate, 1-methoxy-1-hydroxymethyl acrylate, 1- (1-hydric acid) Hydroxy) methoxymethyl, acrylic acid 1- (1-hydroxy) methoxyethyl, acrylic acid trifluoromethoxymethyl, acrylic acid 1-methoxy-2,2,2-trifluoroethyl, acrylic acid 1-trifluoromethoxy -2,2,2-trifluoroethyl, tetrahydrofuran-2-yloxy acrylate, tetrahydropyran-2-yloxy acrylate, 2-methyltetrahydrofuran-2-yloxalate acrylate, 2-methyl acrylate Tetrahydropyran-2-yloxy, 2-fluorotetrahydrofuran-2-yloxy acrylate, methoxymethyl methacrylate, ethoxymethyl methacrylate, n-propoxymethyl methacrylate, iso methacrylate Propoxymethyl, methacrylic acid 1-methoxyethyl, methacrylic acid 1-ethoxyethyl, methacrylic acid 1-n-prop Cethyl, Methacrylic Acid 1-isopropoxyethyl, Methacrylic Acid 2-ethoxyethyl, Methacrylic Acid 2-n-propoxyethyl, Methacrylic Acid 2-isopropoxyethyl, Methacrylic Acid 1-methoxy Propyl, methacrylic acid 1-ethoxypropyl, methacrylic acid 1-methoxy-1-hydroxymethyl, methacrylic acid 1- (1-hydroxy) methoxymethyl, methacrylic acid 1- (1-hydroxy Methoxyethyl, methacrylic acid trifluoromethoxymethyl, methacrylic acid 1-methoxy-2,2,2-trifluoroethyl, methacrylic acid 1-trifluoromethoxy-2,2,2-tri Fluoroethyl, methacrylic acid tetrahydrofuran-2-yloxy, methacrylic acid tetrahydropyran-2-yloxy, methacrylic acid 2-methyltetrahydrofuran-2-yloxy, methacrylic acid 2-methyltetra Hydropyran-2-yloxy, methacrylic acid 2-fluorotetrahydrofuran-2-yloxy, methacrylic acid 2-fluorotetrahydropyran-2-yloxy, etc. are mentioned.

In addition, the above-mentioned (meth) acrylic-acid alkoxyalkyl esters can be used 1 type, or 2 or more types simultaneously or in mixture, In this case, the air of the structure by which the 2 or more types of structural unit represented by Formula 4 was copolymerized randomly. Coalescing can be obtained. The composition ratio at this time is the sum of the composition ratios of the structural units represented by the two or more formulas (4).

In addition, 4- (1-methylethenyl) phenol, (meth) acrylic acid esters and (meth) acrylic acid alkoxyalkyl esters may contain alkaline compounds such as potassium hydroxide, polymerization inhibitors, etc. as stabilizers. Although these are preferably used after carrying out normal purification operations such as recrystallization and distillation to remove the stabilizer, commercially available products may be used as they are without performing purification operations in particular.

It is preferable that the usage-amount of these 4- (1-methylethenyl) phenols, (meth) acrylic acid ester, and (meth) acrylic-acid alkoxyalkyl ester suits the composition ratio of the target copolymer, and it is 4 with respect to 1 mol part of these monomer total amounts. It is preferable that-(1-methylethenyl) phenol is 0.05 mol part or more, It is more preferable that it is 0.15 mol part or more, It is further more preferable that it is 0.2 mol part or more, It is preferable that it is 0.3 mol part or less. Moreover, it is preferable that (meth) acrylic acid ester is 0.5 mol part or more, On the other hand, it is preferable that it is 0.9 mol part or less, and it is more preferable that it is 0.7 mol part or less. Moreover, it is preferable that (meth) acrylic-acid alkoxy alkyl ester is 0.01 mol part or more, It is more preferable that it is 0.1 mol part or more, On the other hand, It is preferable that it is 0.4 mol part or less, It is more preferable that it is 0.3 mol part or less.

Moreover, when (meth) acrylic acid ester is 2 or more types, it is preferable that the total mole number exists in the said range, and even when (meth) acrylic acid alkoxyalkyl esters are 2 or more types, it is preferable that the total mole number is in the said range. .

As the radical polymerization initiator in the method of the present invention, for example, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis-2-amidinopropane hydrochloride, Azo initiators such as dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride or 4,4'-azobis-4-cyanovaleric acid, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tert- Butyl, lauroyl peroxide, acetyl peroxide, diisopropyldicarbonate, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, p-mentane hydroperoxide, evacuation hydroperoxide, methyl ethyl ketone Peroxide, cyclohexanoneperoxide, diisopropylperoxydicarbonate, tert-butylperoxylaurate, di-tert-butylperoxyphthalate, dibenzyloxide or 2,5-dimethylhexane-2,5 Dehydroper Peroxide initiators, such as an oxide, or redox initiators, such as benzoyl peroxide-N, N- dimethylaniline or peroxodisulfate- sodium hydrogensulfite, etc. are mentioned.

Of these, azo initiators or peroxide initiators are preferable, and azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobisisobutyric acid dimethyl, benzoyl peroxide, 2, More preferred are 4-dichlorobenzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, diisopropyldicarbonate or acetyl peroxide.

Such radical polymerization initiators may be used alone or in combination of two or more thereof. These usage amounts are 4- (1-methylethenyl) phenol, (meth) acrylic acid esters represented by the formula (5), and (meth) acrylic acid alkoxyalkyl esters represented by the formula (6) at the start of heating of the copolymer raw material. It is preferable that it is 0.0001 mol times or more with respect to the total usage amount of, It is more preferable that it is 0.001 mol times or more, It is more preferable that it is 0.005 mol times or more, On the other hand, It is preferable that it is 0.1 mol times or less, It is more preferable that it is 0.05 mol times or less. As long as the total amount of radical polymerization initiator is the said amount, whole quantity may be thrown in at the time of a heating start, or whole quantity or a part may be further used after a heating start.

As the solvent in the method of the present invention, any solvent can be used as long as it does not inhibit the reaction. Specifically, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone or γ-buty Ketones such as rolactone, alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, n-octanol, 2-ethylhexanol or n-dodecyl alcohol, ethylene glycol, propylene glycol Or ethers such as glycols such as diethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, tetrahydrofuran or dioxane Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether or Alcohol ethers such as diethylene glycol monomethyl ether, n-propyl formate, isopropyl formate, n-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, Esters such as n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate or methyl butyrate, methyl 2-oxypropionate, ethyl 2-oxypropionate, n-propyl 2-oxypropionate, isopropyl 2-oxypropionate, Monooxycarboxylic acid esters such as ethyl 2-oxy-2-methylpropionate or methyl 2-oxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxy Alkoxycarboxylic acid esters such as ethyl propionate or methyl 3-ethoxypropionate, cellosolve acetate, methyl cellosolve acetate, Cellosolve esters such as cellosolve acetate or butyl cellosolve acetate, aromatic hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as trichloroethylene, chlorobenzene or dichlorobenzene or dimethylacetamide, dimethylformamide, Amides, such as N-methylacetamide, N-methylpyrrolidone, or N, N'- dimethyl imidazolidinone, etc. are mentioned.

Preferably methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isopropyl alcohol, n-butyl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, propylene Glycol monomethyl ether, ethyl acetate, propylene glycol monomethyl ether monoacetate, cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate or toluene.

These solvents may be used alone or in combination of two or more thereof. Moreover, although it is preferable that a reaction liquid becomes a homogeneous phase by use of these solvent, it may become a some non-uniform phase. The amount of the solvent used varies depending on the type and amount of the raw material and the radical polymerization initiator used, the molecular weight of the desired copolymer, and the like, but is not uniform, but is preferably 5 parts by mass or more, based on 100 parts by mass of the total amount of the monomer mixture, It is more preferable that it is more than a part, It is further more preferable that it is 50 mass parts or more, On the other hand, It is preferable that it is 10,000 mass parts or less, It is more preferable that it is 5,000 mass parts or less, It is further more preferable that it is 1,000 mass parts or less.

Most preferably, the concentration of the copolymer produced after the polymerization reaction is 25 to 75% by mass even when no concentration is adjusted, that is, in the range of 33 to 400 parts by mass with respect to 100 parts by mass of the monomer mixture.

The manner of carrying out the polymerization reaction of the acid-sensitive copolymer used in the present invention is not particularly limited, and is represented by 4- (1-methylethenyl) phenol, (meth) acrylic acid esters represented by the formula (5), and the formula (6). Any method may be used as long as the (meth) acrylic acid alkoxyalkyl esters, radical polymerization initiators, and solvents are effectively mixed and contacted, and may be any of batch, semi-batch, or continuous flow type. For example, a method of incorporating these compounds into a reaction vessel to start heating and a method of inserting monomers, radical polymerization initiators, and solvents into a reactor in which at least some solvents are inserted continuously or intermittently is commonly used.

Among these methods, in the method of the present invention, the total concentration of 4- (1-methylethenyl) phenol, (meth) acrylic acid esters and (meth) acrylic acid alkoxyalkyl esters present in the reaction system from the start of heating to the end of the heating is always It is preferable to perform reaction, adjusting so that it may become 20 mass% or less.

Specifically, 4- (1-methylethenyl) phenol, (meth) acrylic acid esters and (meth) acrylic acid alkoxyalkyl esters are consumed in the polymerization reaction, so that monomers, polymerization initiators, solvents, and the like are newly added in accordance with the amount. It is the method to introduce into a reaction system continuously or intermittently.

More specifically, for example, a method in which only a solvent is added to a reactor, and then these monomers and a radical polymerization initiator are continuously or intermittently introduced into the reaction system, and a monomer is continuously or intermittently added after a solvent and a radical polymerization initiator are added to the reactor. Method of adding into the reaction system, some solvent and radical polymerization initiator into the reactor and then adding the monomer and the remaining solvent and radical polymerization initiator into the reaction system continuously or intermittently, or adding some monomer, radical polymerization initiator and solvent into the reactor And a method of adding the remaining monomer, the radical polymerization initiator and the solvent into the reaction system continuously or intermittently.

In the manufacturing method of the acid sensitive copolymer used for this invention, a polymerization reaction is advanced by heating. The heating temperature may be any temperature as long as the polymerization reaction proceeds. The heating temperature is not uniform depending on the degree of polymerization, composition and molar ratio of the desired polymer, radical polymerization initiator and solvent used, but is preferably 40 ° C. or higher. It is more preferable that it is 45 degreeC or more, It is more preferable that it is 50 degreeC or more, It is most preferable that it is 60 degreeC or more, On the other hand, It is preferable that it is 250 degrees C or less, It is more preferable that it is 180 degrees C or less, It is further more preferable that it is 160 degrees C or less, 150 Most preferably, it is below C.

The polymerization reaction time is also not uniform depending on the degree of polymerization, composition and molar ratio of the desired polymer, the type and amount of the radical polymerization initiator and the solvent used. However, it is preferable that it is 0.01 hours or more, On the other hand, it is preferable that it is 40 hours or less, and it is more preferable that it is 20 hours or less.

In addition, if necessary, the reaction can be carried out under reflux, under reduced pressure, atmospheric pressure or under pressure. Particularly, the reaction is preferably performed under reflux because the heat of reaction is efficiently removed. Moreover, although it is preferable to carry out in inert gas atmosphere, such as nitrogen and argon, it can carry out also in presence of molecular oxygen, such as air.

Moreover, in the manufacturing method of the acid sensitive copolymer used by this invention, additives, such as a phenol compound, can also be used for the purpose of improving the yield of a copolymer, the purpose of changing the arrangement of the structural unit of a copolymer, and the like.

As a solution (resist raw material) containing the above copolymer, 0.05-0.3 mol part 4- (1-methylethenyl) phenol, 0.5-0.9 mol part (meth) acrylic acid ester, 0.01-0.4 mol part (meth) Unreacted 4- (1-methylethenyl) by heating a copolymer raw material containing alkoxyalkyl esters of acrylic acid so that the total mole number is 1 mole part, or by heating or heating the copolymer raw material as necessary. The concentration of the phenol to the resist raw material is 50 mass ppb to 0.5 mass%, the concentration of the unreacted (meth) acrylic acid esters to the resist raw material is 5 mass ppm to 5 mass%, and the unreacted (meth The density | concentration with respect to the resist raw material of acrylic acid alkoxy alkyl esters is 200 mass ppb-2 mass%, and also about the resist raw material of these unreacted monomers and the produced acid sensitive copolymer. To a concentration of 25 to 75% by weight it is preferred in view of the solution coating properties of the resist material, such as a film controllability.

After completion of the polymerization reaction, the copolymer produced by a conventional method such as solvent extraction, fractional precipitation or thin film evaporation can be isolated from the reaction mixture. Moreover, the solution containing the produced copolymer can also be used as a resist raw material, without isolating the copolymer which is a target object as needed.

In addition, when used for the positive type photosensitive resist of this invention, the dissolution rate of a copolymer is 1.5 micrometer / min or less, Preferably it is 1.2 micrometer / min or less before exposure, and 2.5 micrometer / min or more is preferable after exposure. Preferably it is greatly changed to 3 µm / minute or more.

In the present invention, the measurement of the dissolution rate is carried out using a spin coating machine or bar on a substrate such as a laminated plate coated with a mixed solution of 30% by weight of the copolymer and 1% by weight of a photoacid generator such as naphthalimidyltrifluorosulfonate. It measures about the coating film apply | coated so that the film thickness at the time of heating and removing a solvent using a coater etc. may be set to 5 micrometers. The dissolution rate before exposure is determined by measuring the time until the coating film on a board | substrate melt | dissolves all in the 1% sodium carbonate aqueous solution which is a developing solution. The dissolution rate after exposure is measured by measuring the time until the coating film which irradiated 200 mJ / cm <2> of light of wavelength 365nm, after apply | coating a film | membrane on a board | substrate similarly melt | dissolves in the 1% sodium carbonate aqueous solution which is a developing solution.

A positive photosensitive resist composition can be adjusted by adding at least one of α, α-dichloro-4-phenoxyacetophenones and 4,4 ′-(α, α-dichloroacetyl) diphenyl ethers to such a resist raw material. .

It is preferable that the sum total of addition amount is 1 mass part or more with respect to 100 mass parts of total amounts of the unreacted monomers and the produced acid sensitive copolymer, It is more preferable that it is 3 mass parts or more, On the other hand, it is preferable that it is 20 mass parts or less, 10 It is more preferable that it is below a mass part. If the addition amount is within this range, it is preferable because the pattern formation at the time of development can be performed satisfactorily.

In addition, the sum total of addition amount is the addition amount of (alpha), (alpha)-dichloro-4- phenoxy cetophenones when adding only (alpha), (alpha)-dichloro-4- phenoxy cetophenones; When only 4,4 '-((alpha), (alpha)-dichloroacetyl) diphenyl ether is added, it is the addition amount of 4,4'-((alpha,)-dichloroacetyl) diphenyl ether, and when adding these two It is the sum of the two addition amounts.

Moreover, when the density | concentration of the copolymer after heating is less than 25 mass%, it concentrates, and when it exceeds 75 mass%, it dilutes and adjusts concentration. The concentration of the copolymer in the resist raw material can be measured by, for example, placing the resist raw material in a tin dish, placing the tin dish in a hot air dryer, and again refining the dish from which the solvent is removed to remove the solvent.

A solvent can also be added to the positive photosensitive resist composition of this invention for the reason of improvement of coating film property.

Specific examples of such a solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone or methyl-2-n-amyl ketone, ethanol, n-propanol Alcohols such as isopropanol, 1-butanol, 2-butanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol or 1-ethoxy-2-propanol, and ethylene glycol , Polyhydric alcohols such as propylene glycol or dipropylene glycol, ethylene glycol ethylene, propylene glycol, glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl Polyhydric alcohol derivatives such as ether, monobutyl ether, monophenyl ether, dimethyl ether or diethyl ether, and cyclic ethers such as tetrahydrofuran or dioxane Esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, tert-butyl acetate or tert-butyl propionate And aromatic hydrocarbons such as benzene, toluene or xylene, or halogenated aromatic hydrocarbons such as chlorobenzene and orthodichlorobenzene.

Of these, ketones, alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, cyclic ethers, esters or aromatic hydrocarbons are preferable, and acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, isopropanol and ethylene glycol dimethyl More preferred are ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, ethyl acetate, ethyl lactate or toluene. These solvents may be used alone or in combination of two or more thereof.

Furthermore, in order to improve developability, storage stability, heat resistance, etc. as needed, the positive photosensitive resist composition of this invention is a copolymer of styrene and acrylic acid, methacrylic acid, or maleic anhydride, an alkene, and a maleic acid, for example. The copolymer with an acid anhydride, a vinyl alcohol copolymer, a vinylpyrrolidone polymer, etc. can be added. The addition amount of these arbitrary components is 30 mass parts or less normally with respect to 100 mass parts of acid sensitive copolymers, Preferably it is 15 mass parts or less.

Furthermore, in order to improve developability, storage stability, heat resistance, etc. as needed, the positive photosensitive resist composition of this invention is a copolymer of styrene and acrylic acid, methacrylic acid, or maleic anhydride, an alkene and a maleic acid, for example. A copolymer with an anhydride, a vinyl alcohol copolymer, a vinylpyrrolidone copolymer, etc. can be added. The addition amount of these arbitrary components is 30 mass parts or less normally with respect to 100 mass parts of acid sensitive copolymers, Preferably it is 15 mass parts or less.

The positive photosensitive resist material obtained above is applied and heated to dry on a copper-clad laminated substrate for a motherboard, a package substrate, and a flexible printed substrate using a dip coating machine to form a positive photosensitive film layer. A mask having a predetermined pattern is closely adhered on the film, exposed to near ultraviolet light (300-400 nm) through the mask, and then developed with an alkaline developer such as an aqueous 1% sodium carbonate solution to form a desired pattern on the printed board. Can be.

At this time, the liquid specific gravity of the positive photosensitive resist composition of the present invention is preferably 0.800 or more, more preferably 0.850 or more, and more preferably 0.850 or more because of using a solvent having a small specific gravity to increase the drying speed. It is preferable that it is 0.950 or less, and, as for there is no residual tuck, it is more preferable that it is 0.900 or less.

By using a dip coating machine, even a very thin substrate (100 μm or less) can be coped with and can be coated up to the end face without being influenced by the surface shape. Therefore, there is an advantage that the processing efficiency is good, and the tack time per sheet can be significantly shortened.

The positive photosensitive resist composition of this invention can be used suitably for manufacture of electronic components, such as a printed wiring board, a landless printed wiring board, a flexible printed wiring board, and a printed wiring board for packages.

When forming the fine pattern in the board | substrate with a through hole using the positive photosensitive resist material of this invention, it can be set as landless. In the case of the negative type, since the inside of the through hole is not hardened, the etching liquid penetrates into the inside of the through hole when the etching liquid is immersed, and the internal plating is corroded and disconnected. In addition, in the dry film system, if there is no adhesiveness around the through-holes, the etching solution penetrates into the inside, and the plating is corroded and disconnected. Therefore, this material is the only material which can realize landlessness.

<Example>

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not restrict | limited by these Examples. In addition, unless otherwise indicated, reagents etc. used the favorable commercially available product.

Examples of the acid-sensitive copolymer used in the present invention will first be described.

<Example 1>

200 mL of tetrahydrofuran was charged into a 1,000 mL four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a 500 mL dropping funnel, and heated to 80 ° C by reflux while stirring. Separately, 100 g (0.75 mol) of 4- (1-methylethenyl) phenol (hereinafter abbreviated as "PIPE") purified by crystallization from 2-ethylhexanol solution in a 1,000 ml Erlenmeyer flask, and distilled and purified acrylic acid 193.7 g (2.25 mol) of methyl and 108 g (0.75 mol) of 1-ethoxyethyl acrylate, 16.4 g (0.10 mol) of azobisisobutyronitrile as a radical polymerization initiator, and 200 ml of tetrahydrofuran were added as a solvent.

After stirring and dissolving this solution, the whole quantity was divided into 2 times and it was transferred to the dropping funnel, and it was dripped at the speed | rate to the reflux state to the said four-necked flask. Internal temperature of the reaction initial stage was 72 degreeC, but internal temperature rose during superposition | polymerization, and it was 80 degreeC after 8 hours. The water bath was removed with continued stirring, cooled to room temperature (25 ° C.) for 2 hours, and then the polymerization reaction solution was poured into 2 L of n-hexane in a 5 L beaker to precipitate the resulting polymer. The precipitated polymer was filtered and separated, and then dissolved in 400 ml of tetrahydrofuran, and poured into 2 l of n-hexane to precipitate a solid. This filtration, separation and precipitation were repeated twice. After the last filtration and separation, the product was dried under reduced pressure at 100 mmHg and 100 DEG C for 2 hours to obtain 320.4 g of a white polymer.

The obtained white polymer was found to be the target copolymer from the results of ¹ H-NMR analysis, ¹³ C-NMR analysis and elemental analysis. ¹ H-NMR in d6-dimethylsulfoxide is shown in FIG. 1 and ¹³ C-NMR is shown in FIG. 2. The molar ratios of the structural unit represented by General formula (1) in the polymer obtained from such NMR result were a = 0.24, b = 0.58, and c = 0.18, and were the molar ratio substantially the same as the input ratio of raw material. Moreover, as a result of GPC analysis which uses polystyrene as a standard, the weight average molecular weight (Mw) was 10,000 and molecular weight dispersion degree (Mw / Mn) was 1.94. GPC analysis is shown in FIG. 3.

When the obtained copolymer was dissolved in each solvent of methyl ethyl ketone and cyclohexanone, this copolymer was dissolved in 50 wt% or more in any solvent.

After dissolving the obtained copolymer in cyclohexanone, it coated on the board | substrate with copper so that dry film thickness might be set to 5 micrometers using the bar coater, and it heated at 80 degreeC for 30 minutes, and formed the film. When this was immersed in 1.0 weight% sodium carbonate aqueous solution (alkali developing solution), the film on the board | substrate coated with copper did not melt | dissolve within 3 minutes. That is, the dissolution rate of the obtained copolymer became 1.5 micrometer / min or less.

In addition, the obtained copolymer was dissolved in cyclohexanone, and a solution in which 1 wt% of naphrimidyltrifluorosulfonate (Midori Kagaku NAI-105) was added thereto was dried on a laminate coated with copper so as to have a thickness of 5 μm. It was applied with a bar coater and heated at 80 ° C. for 30 minutes to form a film. After irradiating 365 nm of light at 200 mJ / cm <2>, it was immersed in 1.0 weight% sodium carbonate aqueous solution, and all the coating films melt | dissolved within 2 minutes. That is, the dissolution rate of the obtained copolymer became 2.5 micrometer / min or more.

After dissolving the obtained copolymer in methyl ethyl ketone, the coated film was coated on a quartz plate using a spin coater so as to have a dry film thickness of 1 μm, and heated at 120 ° C. for 10 minutes to form a film. When the transmittance at 365 nm was measured by an ultraviolet visible spectrophotometer, the transmittance was 98% or more. Ultraviolet visible light intensity analysis is shown in FIG. 4.

Moreover, it was 70 degreeC when the glass transition point was measured with the differential scanning calorimeter.

Moreover, when the thermal stability was measured by the differential thermograph, it was stable to 200 degreeC or more. Thermogravimetric analysis is shown in FIG. 5.

<Examples 2 to 4>

The methyl acrylate used in Example 1 was changed as shown in Table 1, and all other conditions were the same as Example 1, and reaction and post-treatment were performed. In the same manner as in Example 1, the molar ratio, yield, weight average molecular weight, and molecular weight dispersion degree of the obtained copolymer were measured. Moreover, solvent solubility, the dissolution rate, transparency, and thermal stability with respect to the alkaline developing solution were evaluated similarly to Example 1. These analysis results and the evaluation result are shown in Table 1 with the result of Example 1.

Comparative Example 1

The amount of PIPE used in Example 1 was changed to 251.9 g (1.88 mol), the amount of methyl acrylate was changed to 161.8 g (1.88 mol), and all were the same as in Example 1 except that 1-ethoxyethyl acrylate was not used. The reaction, post-treatment, analysis and evaluation were carried out. The injection molar ratio and the analysis and evaluation results of the obtained copolymer are shown in Table 1 together with the results of Examples 1 to 4.

Comparative Example 2

The amount of PIPE used in Example 1 was changed to 251.9 g (1.88 mol), the amount of 1-ethoxyethyl acrylate was changed to 270.7 g (1.88 mol), and all were the same as in Example 1 except that methyl acrylate was not used. The reaction, post-treatment, analysis and evaluation were carried out. The injection molar ratio and the analysis and evaluation results of the obtained copolymer are shown in Table 1 together with the results of Examples 1 to 4 and Comparative Example 1.

<Examples 5 to 6>

The reaction, post-treatment, analysis and evaluation were carried out in the same manner as in Example 1 except that the acrylate alkoxyalkyl esters shown in Table 2 were used in the molar ratios shown in Table 2 instead of the 1-ethoxyethyl acrylate used in Example 1. It was done. The analysis result and evaluation result of the obtained copolymer are shown in Table 2 with the result of Example 1.

<Examples 7 to 8>

The molar ratios of PIPE, methyl acrylate, and 1-ethoxyethyl acrylate used in Example 1 were changed as shown in Table 3, except that the total molar amount of the monomers was 3.75 mol in the same manner as in Example 1. In the same manner as in the reaction, post-treatment, analysis and evaluation were performed. The analysis results and the evaluation results of the obtained copolymer are shown in Table 3 together with the results of Example 1.

<Examples 9 to 12>

The solvent shown in Table 4 was used in the amount shown in Table 4 instead of the tetrahydrofuran used in Example 1, and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature and the reaction time were changed as shown in Table 4. , Post-treatment, analysis and evaluation were performed. The molar ratio, quantity, weight average molecular weight, and molecular weight dispersion degree of the obtained copolymer are shown in Table 4 with the result of Example 1. Moreover, solvent solubility, the dissolution rate with respect to alkaline developing solution, transparency, and thermal stability were all favorable similarly to Example 1.

<Examples 13 to 17>

Example 1 was used in place of the azobisisobutyronitrile used in Example 1, except that the radical polymerization initiator shown in Table 5 was used in the amount shown in Table 5, and the reaction temperature and reaction time were changed as shown in Table 5. In the same manner as in the reaction, post-treatment, analysis and evaluation were performed. The molar ratio, quantity, weight average molecular weight, and molecular weight dispersion degree of the obtained copolymer are shown in Table 5 with the result of Example 1. Moreover, solvent solubility, the dissolution rate with respect to alkaline developing solution, transparency, and thermal stability were all favorable similarly to Example 1.

Example 18

230 mL of methyl ethyl ketone was charged into a 1,000 mL four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a 500 mL dropping funnel, and heated to reflux at 80 ° C. by a water bath while stirring. Separately, 100 g (0.75 mol, 0.2 mol part) of 4- (1-methylethenyl) phenol purified by crystallization from 2-ethylhexanol solution in a 1,000 ml Erlenmeyer flask and 225 g (2.25 methyl dimethacrylate) purified by distillation Mole, 0.6 mole parts), 107.7 g (0.75 mole, 0.2 mole parts) of 1-ethoxyethyl acrylate, 6.09 g (0.037 mole) of azobisisobutyronitrile as a radical polymerization initiator, and 229 mL of methyl ethyl ketone were added as a solvent.

After stirring and dissolving this solution, the whole quantity was divided into 2 times, it was transferred to the dropping funnel, and it was dripped at the rate which the reflux state continued to the said sand dune flask. At this time, the dropping rate was adjusted so that the total concentration of PIPE, methyl methacrylate and 1-ethoxyethyl acrylate became 20% by mass or less.

Internal temperature of the reaction initial stage was 72 degreeC, but internal temperature rose during superposition | polymerization, and it was 80 degreeC after 8 hours. Thereafter, the water bath was removed while stirring was continued, and the mixture was cooled to room temperature (25 ° C) for 2 hours to obtain a resist raw material 1 including an acid-sensitive copolymer 1.

At this point, unreacted PIPE was 0.02 mass% of the resist raw material, unreacted methyl methacrylate was 1.0 mass% of the resist raw material, and unreacted 1-ethoxyethyl acrylic acid was 0.5 mass% of the resist raw material.

In addition, the total amount of unreacted PIPE, unreacted methyl methacrylate, unreacted acrylic acid 1-ethoxyethyl and the obtained copolymer was 49 mass% of the resist raw material.

Moreover, the GPC analysis which makes polystyrene the standard with respect to the obtained copolymer showed that the weight average molecular weight (Mw) was 24,000, and molecular weight dispersion degree (Mw / Mn) was 2.6.

Example 19

The methyl methacrylate used in Example 18 was replaced with methyl acrylate to use 223.9 g (2.60 mol, 0.69 mol part), and 14.0 acrylate (1-n-butoxyethyl methacrylate) was replaced with 64.0 g (0.40 mol). , 0.11 mole parts) and a resist raw material 2 containing an acid-sensitive copolymer 2 were obtained in the same manner as in Example 18 except that 6.11 g (0.037 mole) of azobisisobutyronitrile was used.

Also, by controlling the amount of methyl ethyl ketone, unreacted PIPE is 0.02 mass% of the resist raw material, unreacted methyl acrylate is 1.5 mass% of the resist raw material, and unreacted methacrylic acid 1-n-butoxyethyl is resist It was 0.3 mass% of raw materials.

In addition, the total amount of unreacted PIPE, unreacted methyl acrylate, unreacted methacrylic acid 1-n-butoxyethyl and the obtained copolymer was 50 mass% of the resist raw material.

Moreover, the GPC analysis which makes polystyrene the standard about the obtained copolymer showed that the weight average molecular weight was 22,000, and molecular weight dispersion degree was 2.3.

Example 20

In the same manner as in Example 19, except that 162.7 g (1.89 mol, 0.5 mol part) of methyl acrylate used in Example 19 was used and 179.2 g (1.12 mol, 0.3 mol part) of 1-n-butoxyethyl methacrylic acid was used. The resist raw material 3 containing the acid sensitive copolymer 3 was obtained.

In addition, the total amount of unreacted PIPE, unreacted methyl acrylate, unreacted methacrylic acid 1-n-butoxyethyl and the obtained copolymer was 50 mass% of the resist raw material.

Moreover, the GPC analysis which makes polystyrene the standard with respect to the obtained copolymer showed that the weight average molecular weight was 20,300 and molecular weight dispersion degree was 2.6.

Comparative Example 3

Example 18 except that the amount of PIPE used in Example 18 was changed to 251.9 g (1.88 mol), the amount of methyl methacrylate was changed to 188 g (1.88 mol), and no 1-ethoxyethyl acrylate was used. Reaction and post-treatment were performed similarly to the following. The weight average molecular weight of the obtained copolymer was 19,000, and molecular weight dispersion degree was 2.1.

<Comparative Example 4>

Example 18 except that the amount of PIPE used in Example 18 was changed to 251.9 g (1.88 mol) and the amount of 1-ethoxyethyl acrylate was changed to 270.7 g (1.88 mol), and methyl methacrylate was not used. Reaction and post-treatment were performed similarly to the following. The weight average molecular weight of the obtained copolymer was 19,500, and molecular weight dispersion degree was 2.1.

Hereinafter, the Example of the positive photosensitive resist composition of this invention is described.

<Examples 21 to 23>

100 parts by mass of an unreacted monomer and an acid sensitive copolymer of α, α-dichloro-4-phenoxyacetophenone in the resist raw materials 1 to 3 including the acid sensitive copolymers 1 to 3 prepared in Examples 18 to 20, respectively 6 parts by mass was added to dissolve the solution, and a predetermined amount of methyl ethyl ketone was further added to prepare a dip type positive photosensitive resist composition with a concentration of 35% of the components other than the solvent.

In addition, a hole of 0.2 mmφ was drilled separately in a 0.5 mm thick FR-4 substrate having a copper foil thickness of 9 μm, and 9 μm copper plating was performed by a known method. The positive photosensitive resist composition obtained on both sides of this substrate with through holes was applied by a dip coater to 4 占 퐉 after drying, and dried for 30 minutes in a 80 DEG C dryer until there was no turk. The inner surface of the through hole of 0.2 mmφ was covered with a resist material. Thereafter, a patterned film having a model pattern of line / space = 45/35 μm and a land of 0.35 mmφ was brought into close contact with the coating surface and irradiated with light of 365 nm at 200 mJ / cm 2 with a high pressure mercury lamp, followed by 1.0 mass% sodium carbonate. The aqueous solution was sprayed, then washed with water and developed.

When the ejection condition was observed at this stage, the resist pattern of the predetermined line / space was confirmed. Subsequently, the etching process was performed with the ferric chloride type well-known copper etching line, the aqueous solution of 3.0 mass% caustic soda was sprayed, the resist material was peeled off, the washing process was performed with water, and the circuit formation state was observed after drying. The copper circuit / space was 40/40 micrometers, and the through hole maintained the state after copper plating.

<Examples 24 to 26>

In each of Examples 18 to 20, except that α, α-dichloro-4-phenoxyacetophenone was changed to 4,4 '-(α, α-dichloroacetyl) diphenyl ether so that the compounding amount was 4 parts by mass. In the same manner as in Example 21, the state after developing with an aqueous solution of sodium carbonate and the state of the circuit after etching with a ferric chloride copper etching line were observed. It was good like 21-23.

Example 27

In Example 21, 3 parts by mass of α, α-dichloro-4-phenoxyacetophenone and 4,4 ′-(α, α-dichloro instead of 6 parts by mass of α, α-dichloro-4-phenoxycetophenone Except having used 2 mass parts of acetyl) diphenyl ether, it carried out similarly to Example 21, and observed the resist pattern state, the circuit formation state, and the through hole state similarly to Example 21, and were favorable.

Comparative Example 5

Example 1 WHEREIN: Example 1 except having used 3 mass parts of (alpha), (alpha), (alpha)-tribromomethylphenyl sulfone as a main component as a photo-acid generator instead of (alpha), (alpha)-dichloro-4- phenoxy acetophenone. In the same manner as in the above, the resist pattern state, the circuit formation state, and the state in the through hole were observed. As a result, the resist pattern state, the circuit formation state, and the through hole state were inferior in comparison with Example 21.

<Reference Examples 2 and 3>

In the copolymer solutions prepared in Comparative Examples 3 and 4, 6 parts by mass of α, α-dichloro-4-phenoxyacetophenone were added to 100 parts by mass of the unreacted monomer and the acid sensitive copolymer, respectively, and dissolved in methylethyl. A predetermined amount of ketone was further added to make the concentration of components other than the solvent 35% to prepare a dip type resin coating material.

In addition, a hole of 0.2 mmφ was drilled separately in a 0.5 mm thick FR-4 substrate having a copper foil thickness of 9 μm, and 9 μm copper plating was performed by a known method. The resin coating material was applied to both surfaces of the substrate with the through-holes by a dip coater so as to be 4 占 퐉 after drying, and dried for 30 minutes in a 80 DEG C dryer until there was no turk. The inner surface of the through hole of 0.2 mmφ was covered with a resist material. Thereafter, after exposure and development were carried out in the same manner as in Example 21, when the developed state was observed, the dissolution of the resin film in the predetermined space portion was insufficient and the resist pattern could not be confirmed.

According to the present invention, the photoacid generator used for the positive photosensitive resist material can be provided at low cost, and the positive photosensitive resist material can be used in the field of printed substrate processing. In particular, by combining inexpensive photoacid generators with novel acid sensitive copolymers comprising industrially available 4- (1-methylethenyl) phenols, (meth) acrylic acid esters and (meth) acrylic acid alkoxyalkyl esters It is possible to provide inexpensively the positive photosensitive resist material which is required in the field of printed circuit board processing, in which low price is important.

1 shows the ¹ H-NMR spectrum in d6-dimethylsulfoxide of a copolymer comprising 4- (1-methylethenyl) phenol, methyl acrylate, and 1-ethoxyethyl acrylate synthesized in Example 1. FIG.

FIG. 2 shows the ¹³ C-NMR spectrum in d6-dimethylsulfoxide of a copolymer comprising 4- (1-methylethenyl) phenol, methyl acrylate, and 1-ethoxyethyl acrylate synthesized in Example 1. FIG.

3 shows a GPC elution curve of a copolymer comprising 4- (1-methylethenyl) phenol, methyl acrylate, and 1-ethoxyethyl acrylate synthesized in Example 1. FIG.

4 is an ultraviolet visible light analysis diagram of a copolymer including 4- (1-methylethenyl) phenol, methyl acrylate, and 1-ethoxyethyl acrylate synthesized in Example 1. FIG.

FIG. 5 is a thermogravimetric analysis of a copolymer including 4- (1-methylethenyl) phenol, methyl acrylate, and 1-ethoxyethyl acrylate synthesized in Example 1. FIG.

Claims (9)

delete delete A compound having at least one dichloroacetyl group represented by Formula 1, and An acid sensitive copolymer comprising a first structural unit represented by the following formula (2), a second structural unit represented by the following formula (3), and a third structural unit represented by the following formula (4). The composition ratio a of the first structural unit represented by Formula 2 is 0.05 to 0.3, the composition ratio b of the second structural unit represented by Formula 3 is 0.5 to 0.9, and the composition ratio of the third structural unit represented by Formula 4 c is 0.01-0.4, and the sum total of three structural units is 1, The positive type photosensitive resist composition characterized by the above-mentioned. <Formula 1> In formula, R <^1> , R <^2> , R <^3> , R <^5> is a C1-C3 linear substituted by a hydrogen atom, a halogen atom, a cyano group, a C1-C3 linear or branched unsubstituted alkyl group, and a hydroxyl group. Or a substituent selected from a branched alkyl group and a phenyl group, R ⁴ represents a hydrogen atom, a halogen atom, a cyano group, a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms, or a C 1 to 3 carbon group substituted with a hydroxy group And a substituent selected from a linear or branched alkyl group, a phenyl group and a dichloroacetyl group, and X represents a divalent linking group selected from O, S, CH ₂ , C (CH ₃ ) ₂ and C═O. <Formula 2> <Formula 3> In the formula, R ⁶ represents a hydrogen atom or a methyl group; R ⁷ is a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, a straight or branched alkyl group having 1 to 6 carbon atoms substituted with a hydroxy group, and a straight or branched carbon group having 1 to 6 carbon atoms substituted with a halogen atom C1-C6 linear or branched alkyl group substituted with an alkyl group, a cyano group, or a C1-C6 linear or branched alkyl group substituted with a dialkylamino group is shown. <Formula 4> In the formula, R ⁸ represents a hydrogen atom or a methyl group; R ⁹ represents a hydrogen atom, a halogen atom or a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms; Z represents a hydrogen atom, a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight or branched substituted alkyl group having 1 to 6 carbon atoms; Y represents a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms or a linear or branched substituted alkyl group having 1 to 6 carbon atoms; Y and Z may combine to form a ring structure, and a, b, and c represent molar composition ratios, and the sum is one. delete According to claim 3, wherein the acid-sensitive copolymer is 0.05 to 0.3 mole parts of 4- (1-methylethenyl) phenol and 0.5 to 0.9 mole parts of (meth) acrylic acid esters represented by the formula (5) and 0.01 to 0.4 mole It is a copolymer obtained by heating the copolymer mixture which consists of a monomer mixture which consists of (meth) acrylic-acid alkoxyalkyl esters represented by following General formula (6) so that the sum total of each molar ratio may be 1, and a radical polymerization initiator and a solvent. A positive type photosensitive resist composition characterized by the above-mentioned. <Formula 5> In the formula, R ⁶ represents a hydrogen atom or a methyl group; R ⁷ is a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, a straight or branched alkyl group having 1 to 6 carbon atoms substituted with a hydroxy group, and a straight or branched carbon group having 1 to 6 carbon atoms substituted with a halogen atom C1-C6 linear or branched alkyl group substituted with an alkyl group, a cyano group, or a C1-C6 linear or branched alkyl group substituted with a dialkylamino group is shown. <Formula 6> In the formula, R ⁸ represents a hydrogen atom or a methyl group; R ⁹ represents a hydrogen atom, a halogen atom or a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms; Z represents a hydrogen atom, a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight or branched substituted alkyl group having 1 to 6 carbon atoms; Y represents a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms or a linear or branched substituted alkyl group having 1 to 6 carbon atoms; Y and Z may combine to form a ring structure. 6. The copolymer raw material according to claim 5, wherein the copolymer raw material is 0.15 to 0.3 mole parts of the 4- (1-methylethenyl) phenol and 0.5 to 0.7 mole parts of the (meth) acrylic acid esters and 0.1 to 0.3 mole parts of the (meth). The acrylic acid alkoxyalkyl esters are included so that the sum of the molar ratios is 1, and the total amount of the addition of the alkoxyalkyl esters in the following Chemical Formula 1 is the unreacted 4- (1-methylethenyl) phenol and the unreacted (meth) A positive photosensitive resist composition, characterized in that 3 to 10 parts by mass based on 100 parts by mass of the total amount of acrylic acid esters, the unreacted (meth) acrylic acid alkoxyalkyl esters and the produced acid-sensitive copolymer. <Formula 1> In formula, R <^1> , R <^2> , R <^3> , R <^5> is a C1-C3 linear substituted by a hydrogen atom, a halogen atom, a cyano group, a C1-C3 linear or branched unsubstituted alkyl group, and a hydroxyl group. Or a substituent selected from a branched alkyl group and a phenyl group, R ⁴ represents a hydrogen atom, a halogen atom, a cyano group, a linear or branched unsubstituted alkyl group having 1 to 3 carbon atoms, or a C 1 to 3 carbon group substituted with a hydroxy group And a substituent selected from a linear or branched alkyl group, a phenyl group and a dichloroacetyl group, and X represents a divalent linking group selected from O, S, CH ₂ , C (CH ₃ ) ₂ and C═O. A copolymer comprising at least a first structural unit represented by the following formula (2), a second structural unit represented by the following formula (3), and a third structural unit represented by the following formula (4, wherein the molar composition ratio of a, b, c is a: 0.05 to 0.3, b: 0.5 to 0.9, c: 0.01 to 0.4, and the sum of a, b, and c is 1). <Formula 2> <Formula 3> In the formula, R ⁶ represents a hydrogen atom or a methyl group; R ⁷ is a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, a straight or branched alkyl group having 1 to 6 carbon atoms substituted with a hydroxy group, and a straight or branched carbon group having 1 to 6 carbon atoms substituted with a halogen atom C1-C6 linear or branched alkyl group substituted with an alkyl group, a cyano group, or a C1-C6 linear or branched alkyl group substituted with a dialkylamino group is shown. <Formula 4> In the formula, R ⁸ represents a hydrogen atom or a methyl group; R ⁹ represents a hydrogen atom, a halogen atom or a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms; Z represents a hydrogen atom, a straight or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight or branched substituted alkyl group having 1 to 6 carbon atoms; Y represents a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms or a linear or branched substituted alkyl group having 1 to 6 carbon atoms; Y and Z may combine to form a ring structure. The laminated plate whose at least one surface is a metal layer is immersed in the positive type photosensitive resist composition which further contains a solvent in the composition as described in any one of Claims 3, 5, and 6, and is 0.800-0.950 The film | membrane is uniformly coat | covered by the surface of a laminated board, and the inner wall of a hole, and then it exposes and develops, The manufacturing method of the printed wiring board characterized by the above-mentioned. The electronic component manufactured by the manufacturing method of Claim 8.