TW200428148A - Acid sensitive copolymer, positive photosensitive resist composition and the method for producing the print circuit boards from it - Google Patents

Abstract

The present provides a positive photosensitive resist composition which can use the high sensitive but cheap photo acid generator and can been exposed by the ultraviolet and been developed by the weakly base, and has high resolution and also can been correspond to the substrate having porous. The present invention comprises a positive photosensitive resist composition comprising the acid sensitive copolymer, wherein the said acid sensitive copolymer comprises the first constituent unit represented by the general formula (1) below, , (in the formula (1), X represents hydrogen or methyl) the secondary constituent unit represented by the general formula (2) below, , (in the formula (2), the R1 represents hydrogen or methyl, R2 represents C1-6 liner or branched non-substituted alkyl group, C1-6 liner or branched non-substituted alkyl group substituted by the carbonyl group, C1-6 liner or branched non-substituted alkyl group substituted by the halogen atoms, C1-6 liner or branched non-substituted alkyl group substituted by the cyano group or C1-6 liner or branched non-substituted alkyl group substituted by the dialkylamino group), the third constituent unit represented by the general formula (3) below, , (in the formula (3), R3 represents hydrogen or methyl, R4 represents hydrogen, halogen atoms, or C1-6 liner or branched non-substituted alkyl group, Y represents the hydrogen, C1-6 liner or branched non-substituted alkyl group or C1-6 liner or branched substituted alkyl group, Z represents represents the hydrogen, C1-6 liner or branched non-substituted alkyl group or C1-6 liner or branched substituted alkyl group, and the Y and Z can also form the cyclic structure).

Description

200428148 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to an acid-sensitive copolymer, and the resulting microcircuit can form an inexpensive positive-type photosensitive resist composition, electronic parts using the same, and Its manufacturing method. [Prior art] Current printed wiring boards and the like are manufactured by coating a photoresist on a substrate and mounting a photomask 'after the irradiation with near-ultraviolet light, and then drawing a circuit on the substrate. As a photoresist material used in the manufacture of printed circuit boards and the like, when it is mainly used as a negative type photoresist material, it is generally a composition composed of a polycarbonate resin, an ethylenically unsaturated compound, and a photopolymerization initiator. The printed substrate is coated with the composition on a substrate, and a photomask is installed to irradiate near-ultraviolet rays (hereinafter referred to as exposure). After curing the resin, it is immersed in a developing solution such as a 1% sodium carbonate aqueous solution to remove unexposed portions. The remaining photoresist material of the exposed portion forms a pattern. In addition to the photomask, uranium is engraved to form a printed substrate. However, in the case of a substrate that includes holes such as through-holes or circuit holes through the substrate, the photoresist material in the hole has a thick film, so unhardened portions remain even after exposure. Therefore, the photoresist material flows out of the hole during the development process. It may be difficult to use it for a negative photosensitive resist composition. The solution is a method of forming a pattern by protecting holes, such as ink for burial, in advance. However, the ink for burial cannot be dried by heat, which may result in poor productivity. In addition, in the negative type, it may be difficult to form a fine pattern of 50 μηΊ or less because the resin in the exposed portion is hardened. 200428148 On the other hand, a patterning method using a positive-type photosensitive resist material that can be applied to a substrate having through holes and the like and can be minutely processed has been widely used in the semiconductor field. However, the naphthoquinonediazide-based photosensitive material used in the semiconductor field has insufficient resolution when fine patterns are formed when it is used in printed circuit board applications. Furthermore, naphthoquinonediazide-based compounds are expensive, and there is a problem in terms of cost for printed circuit board applications. Positive photoresist materials of different benzoquinonediazide-based systems are photoresists composed of compounds or resins whose solubility has been proposed to be changed with respect to compounds that generate photoacids and alkaline water that is generated by the hydrolysis of acids. material. However, these photoresist materials have a small resolution and poor resolution regardless of the difference in solubility between the unexposed portion and the exposed portion. In the development, if an organic alkali agent such as a tetraalkylammonium hydride is used, the image will not be developed, or an expensive photoacid generator such as a key salt must be used. The pattern formation of the printed wiring board cannot be practical Offerings. Therefore, in recent years, there has been a demand for the development of inexpensive, high-performance positive-type photoresist materials, particularly for the manufacture of high-performance printed wiring boards. In addition, in the production of printed substrates and the like by pattern forming methods using negative-type photoresist materials, when near-ultraviolet light (300 to 450 nm) is used, substrates having through holes and the like are used at this wavelength. It is important to make fine processing. Photosensitive materials with a circuit width and a circuit interval of 10 μη or less are required. Furthermore, it is important that the developer can use a weakly alkaline developer represented by the 1% sodium carbonate aqueous solution currently used. In addition, it is important that printed circuit boards are inexpensive. That is, a high-resolution, inexpensive positive-type photoresist material is desired to be formed by exposure to near-ultraviolet light, and developed with a weakly alkaline developer, and high-resolution. 200428148 A basic polymer of a positive photosensitive photoresist is disclosed in Japanese Patent Application Laid-Open No. 8-1 0 1 5 0 7 as a copolymer of P-isopropenylphenol group and 2-tetrahydropiranyl acrylate, and containing Radioactive resin composition of a radioactive acid generator. Furthermore, in Japanese Patent Application Laid-Open No. 1 2-0 2 9 2 1 5, it is disclosed that a polymer skeleton includes a phenol group unit as a side lock and a polyacetal ester or a ketal ester which is reactive when photoactivated. A unit of polymer is a radiation-sensitive resin composition. However, when these resin compositions are used for ultra-fine processing for semiconductors and the like, they can be developed using an alkali developer solution such as a 2.38% tetramethylammonium aqueous solution. However, a printed circuit board can be used as the developer solution. In use, it may be difficult to dissolve in a 1% sodium carbonate aqueous solution. Therefore, it is necessary to further improve the use as a photoresist material for a printed circuit board. In view of the circumstances as described above, an object of the present invention is to provide a positive-type photosensitive photoresist material which can form fine patterns, but is inexpensive, and an acid photosensitive copolymer using the same. More specifically, even for substrates with through-holes, they provide near-ultraviolet light exposure and can be developed even with a weak base imaging solution such as a 1% sodium carbonate aqueous solution. They can form fine patterns and have high resolution. Positive photoresist material. [Summary of the Invention] In order to achieve the above-mentioned object, the present inventors intently reviewed the result of an intensive 'acid-sensitive polymer having a tritium structure is a highly sensitive and photoacid generator; = 4 is composed of 4 containing at least one kind in the molecule The 6-bis (trichloromethyl) -s-triple-based compound was found to obtain a cheap, yet highly sensitive positive-type photosensitive photoresist material to complete the present invention. That is, according to the present invention, -10- 200428148

(In the formula (2), R1 represents a hydrogen atom or a methyl group, and R2 represents a straight lock or branched unsubstituted radical having 1 to 6 carbon atoms, and a straight lock having 1 to 6 carbon atoms substituted by a hydroxyl group. Or branched alkyl groups, straight-chain or branched alkyl groups with 1 to 6 carbon atoms substituted with halogen atoms, straight-chain or branched alkyl groups with 1 to 6 carbon atoms substituted with cyano A dialkylamino group substituted with a linear or branched alkyl group having 1 to 6 carbon atoms) The third constituent unit represented by the following general formula (3): 11-200428148

Z (in formula (3), R3 represents a hydrogen atom or a methyl group, R4 represents a hydrogen atom, a halogen atom, or a straight-chain or branched unsubstituted radical having 1 to 6 carbon atoms; Y represents a hydrogen atom, Unsubstituted or branched unsubstituted alkyl with 1 to 6 carbon atoms or substituted or branched unsubstituted alkyl with 1 to 6 carbon atoms; Z is a straight or branched chain with 1 to 6 carbon atoms Unsubstituted alkyl or straight-chain or branched substituted alkyl having 1 to 6 carbon atoms; γ and z may also be combined to form a cyclic structure) (However, a, b, and c are composition ratios, and a is 0. .05 or more, 0.3 or less, b is from 0.1 to 0.7, c is a rational number from 0.2 to 0, 8 or less, and the sum of a, b, and c is 1). A second object is to provide a positive-type photosensitive photoresist composition having an acid generator and the above-mentioned acid-sensitive copolymer. In the case of an acid generator, a compound having at least one kind of 4,6-bis (trichloromethyl) -s-trioxo group has a more sensitive and cheaper preferable aspect. The acid generator is more preferably a compound represented by the following general formula (4). [Chemical formula 1 1] -12- (4) (4) 200428148 ρα3 R ~ i / CCI3 (In the formula (4), R5 represents a straight lock selected from trichloromethyl and 1 to 12 carbon atoms or Branched alkyl, straight or branched alkoxy with 1 to 12 carbon atoms, halogen atom, cyano, hydroxy, phenyl, hydroxyphenyl, nitrophenyl, alkphenyl, alkoxy Phenyl, alkylene glycol monoalkyl ether substituted phenyl, decyl, styryl, straight-chain or branched alkoxy substituted styryl, naphthyl 3, a straight-chain or branched alkoxy-substituted naphthyl substituent of 1 to 3 carbon atoms) The third purpose is to provide a positive-type photosensitive photoresist composition characterized by the above-mentioned acid generator relative to the above The acid-sensitive copolymer is 100 parts by mass and contains 0.5 to 20 parts by mass. A fourth object is to provide a method for manufacturing a printed circuit board, which is characterized in that, in the above-mentioned photoresist composition having a liquid specific gravity of 0. 8 0 0 to 0. 990, at least one surface is provided with a metal layer by impregnation A laminated board, a step of drying and uniformly coating a film of a photosensitive resin on a surface of the laminated board, a step of exposing through a photomask, a step of developing an exposed portion, and a step of etching a metal layer. A fifth object is to provide an electronic component 'which is manufactured by the above-mentioned manufacturing method. Best Mode for Carrying Out the Invention The acid-sensitive copolymer of the present invention contains the general formula (1), [0 0 2 4] -13- 200428148

General formula (2) (1) represents a hydrogen atom or a methyl group] [0 0 2 5] (2) [Chemical Formula 1] (In the formula (2), R1 represents a hydrogen atom or a methyl group, and R2 represents a carbon atom Straight-chain or branched unsubstituted alkyl groups of 1 to 6, straight-chained or branched alkyl groups substituted by hydroxyl groups, 1-6-chained straight-chained or branched alkyl groups, 1 to 6 carbon atoms substituted by halogen atoms Or branched alkyl, straight-chain or branched alkyl with 1 to 6 carbon atoms substituted with cyano, or straight-chained or branched alkyl with 1 to 6 carbon atoms substituted with dialkylamino Group) and general formula (3) [0 0 2 6] [Chem. 1 8] -14- 200428148

(In the formula (3), R3 represents a hydrogen atom or a methyl group, r4 represents a hydrogen atom, a halogen atom, or a straight-chain or branched unsubstituted group having 1 to 6 carbon atoms; Y represents a hydrogen atom, carbon Unsubstituted or branched unsubstituted alkyl groups having 1 to 6 carbon atoms or unsubstituted or branched substituted alkyl groups having 1 to 6 carbon atoms; Z is a direct locking or branched group having 1 to 6 carbon atoms Unsubstituted alkyl group or straight-chain or branched substituted alkyl group with 1 to 6 carbon atoms; ¥ and 2 can also be combined to form a cyclic structure). In the general formula (1), X represents a hydrogen atom or a methyl group. The methyl group has good developability and is preferred. The Ri system in the general formula (2) is a hydrogen atom or a methyl group. In addition, the 11 system in the general formula (2) is a straight-chain or branched unsubstituted, substituted, halogen-substituted, cyan-substituted, or dialkylamino-substituted alkyl group having 1 to 6 carbon atoms, specifically, Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, cyclohexyl, or cyclopentyl unsubstituted alkyl and hydroxyl groups. Methyl, mono-hydroxyethyl, 2-mono-hydroxyethyl, 2-mono-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3--hydroxy-n-propyl, χ ~ hydroxyisopropyl, 2,3 ~ dihydroxy-1 Hydroxy-substituted alkyl groups such as n-propyl, hydroxy-n-butyl, 2-hydroxy-n-butyl, 3 to n-hydroxyn-butyl, or 4-mono-n-butyl ester, trifluoromethyl, 2, 2, 2-trifluoroethyl , 2,2,2 2,2,2,2'-hexafluoroisopropyl, 2,2,3,4,4,4-hexafluorobutyl, 2-chloroethyl, chlorochloroethyl, 3 Halo-substituted alkyl groups such as monobromoethyl or heptafluoroisopropyl ester, cyano-substituted alkyl groups such as 2-cyanoethyl ester, or 2-15-200428148 mono (dimethylamino) ethyl, 3- (Dimethylamino) propyl or 3-monomethylamino neopentyl ester Alkylamino-substituted alkyl. Preferred are straight-chain or branched unsubstituted, hydroxy-substituted, halogen-substituted, cyan-substituted or dialkylamino-substituted alkyl groups having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n- Propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, 2-monohydroxyethyl, trifluoromethyl or 2, 2, 2-trifluoroethyl, and the like.

More preferred are straight-chain or branched unsubstituted, branched, unsubstituted, hydroxy-substituted, halogen-substituted, cyan-substituted, or dialkylamino-substituted alkyl groups. Specific examples include methyl, ethyl, n- Propyl, isopropyl, trifluoromethyl \ 2 once ethyl, trifluoromethyl or 2,2,2-trifluoroethyl etc.

The R system in the general formula (3) is a hydrogen atom or a methyl group. In addition, in the general formula (3), R4 represents a hydrogen atom, a halogen atom, or a branched unsubstituted alkyl group having 1 to 6 carbon atoms, and Z represents a hydrogen atom or a carbon atom of 1 to δ. Straight-chained or branched unsubstituted or substituted alkyl, and γ represents a hydrogen atom, a straight-chained or branched unsubstituted or substituted alkyl having 1 to 6 carbon atoms, or γ has a cyclic structure in combination with Z Also good. R4 is specifically a direct lock of a hydrogen atom, a fluorine atom, or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, or a third butyl group. Or branched unsubstituted alkyl, γ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, or third butyl, etc. Unsubstituted, hydroxy-substituted, halogen-substituted, cyan-substituted or dialkylamino-substituted alkyl, etc., ζ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl Or straight-chain or branched, such as tertiary butyl, etc., without -16-200428148 substitution, hydroxy substitution, halogen substitution, cyano substitution or dialkylamino substituted alkyl, etc. More specifically, the R 4, C, 0, Y, and Z portions of the alkoxyalkyl ester group of the general formula (3) are specifically represented as 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-second butoxyethyl, 2-ethoxy Ethyl, 2-n-propoxyethyl, 2-isopropoxyethyl, 2-n-butoxyethyl, 2-isobutoxyethyl, 2-second butoxyethyl, 1-methoxypropyl, 1-ethoxypropyl, 1-n-propoxypropyl, 1-isopropoxypropyl, 1-n-butoxypropyl, 1-isobutoxypropyl Group, 1-second butoxypropyl, 1-third butoxypropyl, 2-methoxypropyl, 2-ethoxypropyl, -n-propoxypropyl, 2-isopropyl Oxypropyl, 2-n-butoxypropyl, 2-isobutoxypropyl, 2-second butoxypropyl, 2-third butoxypropyl, 3-methoxypropyl , 3-ethoxypropyl, 3-n-propoxypropyl, 3-isopropoxypropyl, 3-n-butoxypropyl, 3-isobutoxypropyl, 3- Unsubstituted alkyl groups such as dibutoxypropyl and 3-tert-butoxypropyl, hydroxy-substituted alkoxyalkyl groups such as 1- (1-hydroxy) methoxyethyl, 1-methoxy Halogen-substituted alkoxyalkyl groups such as mono-2,2,2-trifluoroethyl, 1-trifluoromethoxy-2,2,2 monotrifluoroethyl, 1 mono (1 monocyano) methoxy Cyano-substituted alkoxyalkyl such as ethyl ester, dialkylamino-substituted alkoxyalkyl such as 1,1-dimethylaminomethoxyethyl, tetrahydrofuran-2-ylhydroxy, tetrahydropipe Unsubstituted cyclic ethers such as 2-monohydroxyesters, 2-methyltetrahydrofuran ~ 2-monohydroxy groups, alkyl-substituted cyclic ethers such as 2-methyltetrahydropiperan 2- 2-hydroxyesters, or Halogen-substituted cyclic ethers such as, 2-fluorotetrahydrofuran-2-17-200428148-ylhydroxy, 2-fluorotetrahydropiperan-2-ylhydroxyester, and the like. The general formulae (1), (2), or (3) may include not only a constituent unit of ifs but also two or more constituent units. In other words, if the stomach has two types of general formula (1), two or more types of general formula (2), and two types of copolymers represented by the general formula (3) of ^, there are four types of copolymers or & The copolymer of the above constitutional unit is also contained in the copolymer & of the present invention. Also, the copolymer of the present invention has a structure represented by the general formula (1), the general formula (2), and the general formula (3). The composition ratio of the unit is extremely important. When the total of the three constituent units becomes 1, the composition ratio of the general formula (1) is more than 0.05, more preferably 0. 15 or more, 0.3 or less, and 0 · Below 2 5 is the best. In addition, the composition ratio of the general formula (2) is more preferably 0.1 or more, 0. 15 or more is more preferable, and 0 '7 or less, and 0. 5 or less is more preferable. The composition ratio of the general formula (3) is more preferably 0.2 or more and 0.4 or more, and most preferably 0.8 or less and 0.7 or less. When two or more constituent units represented by the general formula (2) or the general formula (3) are used, the composition ratio is the total of the composition ratios of the constituent units individually. In addition, the composition ratio of the three constituent units can be measured by, for example, 1 Η — N M R and 13 C — N M R. The acid-sensitive copolymer used in the present invention, and the constituent units represented by the general formula (1), the general formula (2), and the general formula (3) are, for example, a random copolymerizer, and the 3 constituent units are alternately copolymerized. Polymerizers and block copolymerizers are also acceptable. The weight-average molecular weight (M w) of the acid-sensitive copolymer used in the present invention varies depending on the purpose of use of the copolymer. -18- 200428148 is preferably 3,000 or more, 4 Above 0,0 0 is more preferable, below 80,0 0 0 & is more preferable, and below 60,0 0 0 is most preferable. Moreover, molecular weight dispersion (where Mη is a number average molecular weight) is preferably 1.0 or more, 5.0 or less, more preferably 4.0 or less, and most preferably 3.0 or less. The weight average molecular weight and molecular weight dispersion can be measured by polyethylene conversion using, for example, a gel permeation layer method (GPPC). The copolymer used in the present invention contains a 4- (1-methylethenyl) phenol group and / or a 4-vinylphenol group, and a (meth) propionate ester represented by the general formula (5) The monomer mixture, the radical polymerization initiator and the solvent formed by the (meth) acrylic alkoxyalkyl esters represented by the general formula (6). The molar ratio of the monomers in the monomer mixture is determined. It is obtained by mixing and heating. H2 (ο 7 1r6icg = 0'rification &

\ 1/5 / V \ — / 6 / c \ In the general formula (5) of the raw material monomer of the acid-sensitive copolymer used in the present invention, R6 represents a hydrogen atom or a methyl group, and R7 represents a carbon atom. Straight-chain or branched unsubstituted alkyl groups of 1 to 6, hydroxyl groups, -19-200428148 prime-substituted alkyl groups, cyano-substituted alkyl groups, or dialkylamino-substituted alkyl groups, specifically, for example, acrylic acid Methyl ester, ethyl acrylate, n-propyl acrylate, isopropyl propionate, n-butyl acrylate, isobutyl acrylate, second butyl acrylate, third butyl acrylate, cyclohexyl acrylate or cyclopentyl acrylate Acrylic unsubstituted alkyl esters, hydroxymethyl acrylate, 1-ethyl acrylate, 2-hydroxyethyl acrylate, 1-hydroxy n-propyl acrylate, 2-hydroxy-n-propyl acrylate, 3-hydroxy acrylate N-propyl ester, 1-hydroxyisopropyl acrylate, 2,3-dihydroxypropyl acrylate, 1-butyl acrylate, 2-hydroxy-n-butyl acrylate, 3-hydroxy-n-butyl acrylate, or 4-hydroxy acrylate Hydroxy-substituted alkyl esters of acrylic acid such as n-butyl ester, trifluoromethyl acrylate, acrylic acid 2,2,2-trifluoroethyl enoate, hexaisopropyl acrylate, 2,2,3,4,4,4 hexafluorobutyl acrylate, 2-chloroethyl acrylate, trichloroethyl acrylate, Acrylic halogen-substituted alkyl esters such as 3-bromoethyl acrylate or heptyl-2-propyl acrylate, cyano-substituted alkyl esters of acrylic acid such as 2-cyanoethyl acrylate, 2-mono (dimethylamino) acrylic acid Esters, 3- (dimethylamino) propyl acrylate or 3-dimethylamino neopentyl acrylate, dialkylamino substituted alkyl esters of acrylic acid, methyl methacrylate, ethyl methacrylate, etc. , N-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, third butyl methacrylate, cyclohexyl methacrylate Esters or cyclopentyl methacrylate, etc., unsubstituted alkyl methacrylates, methyl propionate, methyl ester, methyl propionate, methyl ethyl ester, 2-hydroxyethyl methacrylate, methyl 1-hydroxy-n-propyl acrylate, 2-hydroxy-n-propyl methacrylate, 3-hydroxy-n-propyl methacrylate 1, methacrylic acid 1 monohydroxyisopropyl ester, methacrylic acid 2, 3 -20-20 200428148 hydroxypropyl ester, methacrylic acid 1 monohydroxy n-butyl ester, methylpropionyl n-butyl ester, methacrylic acid 3 -Hydroxy-substituted alkyl methacrylates such as hydroxy-n-butyl or methyl mono-hydroxy-n-butyl, trifluoromethyl acid, methacrylic acid 2,2,2-trifluoroethyl ester, and hexafluoroisopropyl ester 2,2,3,4,4,4 methacrylic acid 2-chloroethyl hexafluoroacrylic acid, trichloroethyl methacrylate, methyl 3-bromoethyl or heptafluoro 2-methacrylate Methyl halide substituted alkyl esters such as esters, methyl cyano substituted alkyl esters such as 2-cyanoethyl methacrylate, methacrylic acid 2- (dimethylamino) methacrylic acid 3 _ (dimethylamino) Dialkylamino substituted methacrylates such as propyl or methacrylamidopentyl: R 7 in the general formula (5) is an unsubstituted alkyl group having 1 to 4 carbon atoms, A hydroxy-substituted alkyl group, a halogen-substituted alkyl alkyl group, or a dialkylamino group-substituted alkyl group. Preferred examples of the (meth) propyl group include methyl acrylate and ethyl acrylate. , Propyl, isopropyl acrylate, n-butyl acrylate, second butyl isobutyl acrylate, third butyl acrylate, cyclohexyl acrylate, pentyl ester, hydroxymethyl acrylate, 1-hydroxyethyl acrylate, 1 Hydroxyethyl ester, trifluoromethyl acrylate, 2,2,2 acrylate, hexafluoroisopropyl acrylate, 2,2,3,4,4,4 acrylate, 2-cyanoethyl acrylate, 2-acrylate Dimethylamine 3 methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methylpropyl, second methacrylate, methacrylic acid Tertiary butyl acrylate cyclohexyl, cyclopentyl methacrylate, methacrylic acid 2-acrylic acid 4 methacrylic acid butyl acrylate, methacrylic acid ethyl acrylate, methyl 3-dimethyl Esters and the like. Straight-locked or divided, cyano-substituted acrylates n-propyl enoate, propylene acrylate cycloacrylate 2-trifluoroethylene octafluorobutane I) ethyl ester, n-propyl ester, isobutyl acrylate, methylpropyl methyl ester , -21- 200428148 1 monohydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, trifluoromethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, hexafluoromethacrylate Isopropyl ester, 2,2,3,4,4,4 hexafluorobutyl methacrylate, 2-cyanoethyl methacrylate or 2- (dimethylamino) ethyl methacrylate. More preferably, R7 in the general formula (5) is a straight-chain or branched unsubstituted alkyl group having 1 to 3 carbon atoms, a hydroxy-substituted alkyl group, a halogen-substituted alkyl group, a cyan-substituted alkyl group, or a dialkylamino group. Examples of more preferred (meth) acrylic acid esters instead of alkyl groups include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, hydroxymethyl acrylate, 1-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 1-hydroxy-n-propyl acrylate, 1-hydroxy-isopropyl acrylate, 2,3-dihydroxypropyl acrylate, trifluoromethyl acrylate, 2,2,2-trifluoroethyl acrylate Esters, hexafluoroisopropyl acrylate, 2-chloroethyl acrylate, trichloroethyl acrylate, 3-bromoethyl acrylate, heptafluoro-2-acrylic acid acrylate, 2-cyanoethyl acrylate, and acrylic acid 2— ( Dimethylamino) ethyl ester, 3- (dimethylamino) propyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, methyl Hydroxymethyl acrylate, 1 hydroxyethyl methacrylate, 2 methacrylic acid Hydroxyethyl ester, 1-hydroxy-n-propyl methacrylate, 2-hydroxy-n-propyl methacrylate, 3-hydroxy-n-propyl methacrylate, 1-hydroxyisopropyl methacrylate, methyl 2,3-dihydroxypropyl acrylate, trifluoromethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2-chloroethyl methacrylate, Trichloroethyl methacrylate, -22-200428148 3-bromoethyl methacrylate, heptafluoro-isopropyl methacrylate, 2 monocyanoethyl methacrylate or 2-(dimethyl Amine) ethyl ester. Moreover, if the above (meth) acrylates are used singly or in combination of two or more kinds, in this case, two or more kinds of constituent units represented by the general formula (2) may be obtained randomly. Copolymerized copolymers. The composition ratio of the general formula (2) at this time is the total of the composition ratios of the constituent units represented by two or more general formulas (2). Another raw material of the acid-sensitive copolymer used in the present invention is an alkoxyalkyl (meth) acrylate represented by the general formula (6), where R8 represents a hydrogen atom or a methyl group, and R9 represents A hydrogen atom, a halogen atom or a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, and Z is a straight-chain or branched unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, Y represents hydrogen A straight or branched unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, and Y and Z may be combined to form a cyclic structure. Specific examples of the alkoxyalkyl (meth) acrylates include 1-methoxyethyl acrylate, 1-ethoxyethyl acrylate, 1-n-propoxyethyl acrylate, and 1-isopropyl acrylate. Propoxyethyl, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-butoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-n-acrylate Propoxyethyl, 2-isopropoxyethyl acrylate, 2-n-butoxyethyl acrylate, 2-isobutoxyethyl acrylate, 2-butoxyethyl acrylate, 1- Methoxypropyl, 1-ethoxypropyl acrylate, 1-n-propoxypropyl acrylate, 1-isopropoxypropyl acrylate, 1-n-butoxypropyl acrylate, 1-isobutyl acrylate Oxypropyl ester, acrylic acid 1-second butoxypropyl ester, acrylic acid 1-third butoxypropyl ester, propane 23-200428148 enoic acid 2-methoxypropyl ester, 2-ethoxypropyl acrylate , 2-n-propoxypropyl acrylate, 2-isopropoxypropyl acrylate, 2-n-butoxypropyl acrylate, 2-isobutoxypropyl acrylate, propyl Acid 2-second butoxypropyl, acrylic acid 2-third butoxypropyl, acrylic acid 3-methoxypropyl, acrylic acid 3-ethoxypropyl, acrylic acid 3-n-propoxypropyl, 3-isopropoxypropyl acrylate, 3-n-butoxypropyl acrylate, 3-isobutoxypropyl acrylate, 3-second butoxypropyl acrylate or 3-tertiary butoxypropyl acrylate Unsubstituted alkoxyalkyl acrylates such as esters, hydroxy-substituted alkoxyalkyl acrylates such as 1- (1-hydroxy) methoxyethyl acrylate, 1-methoxy-2, 2 acrylate -Trifluoroethyl or acrylic 1-trifluoromethoxy-1,2,2,2-trifluoroethyl and other halogen-substituted alkoxyalkyl acrylates, 1- (1-cyano) methoxyethyl acrylate Acrylic cyano-substituted alkoxyalkyl esters, etc., Acrylic dialkylamino-substituted alkoxyesters, such as 1,1-dimethylaminomethoxyethyl acrylate, tetrahydrofuran-2-yl hydroxyacrylate, or acrylic acid Unsubstituted cyclic oxalic acid esters of acrylic acid such as tetrahydropiperan-2-ylhydroxyester or 2-methyltetrahydrofuran-2-ylhydroxyacrylate or acrylic acid 2- Acrylic alkyl substituted cyclic oxalate such as methyltetrahydropiperan-2-yl hydroxy ester, etc. Acrylic halogen substituted cyclic oxalate, methacrylic acid such as 2-fluorotetrahydrofuran-2-yl hydroxy ester 1 monomethoxyethyl, methacrylic acid 1 monoethoxyethyl ester, methacrylic acid 1 mono-n-propoxyethyl ester, 1-isopropoxyethyl methacrylate, 1-n-butyl methacrylate Ethoxyethyl ester, 1 isobutoxyethyl methacrylate, 1 second butoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-n-propoxy methacrylate Ethyl ester, 2-isopropoxyethyl methacrylate, 2-methacrylate 2--24-200428148 n-butoxyethyl ester, 2-isobutoxyethyl methacrylate acid 2-second butoxy Ethyl ester, methacrylic acid 1-methoxyacrylic acid 1-ethoxypropyl ester, methacrylic acid 1: ester, methacrylic acid 1-isopropoxypropyl ester, methacryloxypropyl ester, methyl Acrylic acid 1 isobutoxypropyl, methyl a second butoxypropyl, methacrylic acid 1-the third butoxyacrylic acid 2-methoxypropyl Esters, 2-methacrylic acid 2-n-propoxypropyl, 2-propyl methacrylate, 2-n-butoxypropyl methacrylate, methyl-propoxypropyl, methacrylic acid 2 — second butoxypropyl acid 2 — third butoxypropyl ester, methacrylic acid 3 — methoxyacrylic acid 3 — ethoxypropyl ester, methacrylic acid 3-ester, methacrylic acid 3 —iso Propoxypropyl, methacryloxypropyl, 3-isobutoxypropyl methacrylate, methyl-2ndoxypropyl or methylmethacrylic acid 3 Alkoxyalkyl esters, methacrylic acid-substituted methacrylates and other hydroxy-substituted methacrylates, methacrylic acid 1 -methoxy-2,2,2-trifluoroethanoic acid 1 -3 Acid-halogen-substituted alkoxyalkyl esters such as fluoromethoxy-1,2,2-trifluoroethyl esters, cyano-substituted alkoxyalkyl methacrylates such as methacrylate Methylpropylamino substituted alkoxyalkyl esters such as 1,1-dimethylaminomethoxyethyl, tetrahydrofuryl methacrylate or tetrahydropiperan methacrylate-2- Unsubstituted cyclic oxalate such as hydroxyester, 2-methyltetramethacrylate, methacrylpropyl, methyl-n-propoxypropionic acid, 1-n-butylacrylic acid, 1-propylpropyl, methoxypropyl Esters, 1- (1-co-oxyalkyl esters of 2-isopropoxyenoic acid 2-iso, methacryl propyl ester, methyl n-propoxy propionate 3-n-butyl acrylate 3-yl propyl ester, etc. Or methacrylic acid methacrylic acid 1 monocyano) methyl, methacrylic acid dialkyl 2-yl hydroxy methacrylic hydrogen furan 2 -25- 200428148-hydroxyhydroxy ester or methacrylic acid 2- methyl Alkyl methacrylic acid substituted cyclic oxalic acid esters such as tetrahydropiperanyl 2-yl hydroxyester, or fluorine substituted cyclic methacrylic acid esters such as 2-monofluorotetrahydrofuran 2-yl hydroxyester Esters and so on. Moreover, if the above (meth) acrylic alkoxyalkyl esters are used singly or in combination of two or more kinds, in this case, two or more kinds of constituent units represented by the general formula (3) can be obtained. It is a structured copolymer that is randomly copolymerized. The composition ratio at this time is the total of the composition ratios of the constituent units represented by two or more general formula (3). In the case of '4-vinylphenol-based, (meth) acrylic, and alkoxyalkyl (meth) acrylate, the stabilizer contains a basic compound such as potassium hydroxide or a polymerization inhibitor. In this case, it is preferable to use a general refining operation such as recrystallization or distillation to remove the stabilizer, and it is particularly preferable to use a commercially available product without refining operation. The amount of these 4-vinylphenol-based, (meth) acrylic esters and (meth) acrylic alkoxyalkyl esters is preferably based on the composition ratio of the desired co-hydrate, relative to The total amount of these monomers is 1 mole part, 4 vinyl phenol based systems are preferably more than 0.05 mole parts, more preferably more than 0.5 mole parts, and less than 0.3 mole parts. The best is less than 0.25 mol. In addition, (meth) acrylates are preferably 0.2 mol parts or more. ◦ .15 mol parts or more is more preferable, 0.7 mol parts or less is preferable, and less than 0.5 mol parts. For the best. Furthermore, the (meth) guanylenol ethyl vinegars are more preferably 0.2 mol parts or more, more preferably Q. 4 mol parts or more, and 0.8 mol parts or less are preferred, and 0. 7 moles or less is best. -26- 200428148 Further, when there are two kinds of 4-vinylphenol groups, it is preferable that the total mole number is within the above range, and when two or more kinds of (meth) propionic acid esters are used. It is preferable that the total number of moles is within the above range. When the number of alkoxyalkyl (meth) acrylates is two or more, the total number of moles is preferably within the above range. Examples of the radical polymerization initiator in the method of the present invention include: azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanenitrile, and azo Bis-2-fluorenylpropane hydrochloride, azobisisobutyric acid dimethyl, azobisisobutylphosphonium hydrochloride or 4,4'-azobisbis-4-cyanocyanuric acid, etc. Azo-based initiators, benzamyl peroxide, 2,4-dichlorobenzyl peroxide, di-tert-butyl peroxide, lauryl peroxide, ethenyl peroxide, Oxidized diisopropyl dicarbonate, cumene hydroperoxide, tertiary butyl hydroperoxide, dicumene peroxide, P-capane hydroperoxide, pinane hydroperoxide, Methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxy dicarbonate, third butyl peroxy laurate, di-third butyl peroxy phthalate Peroxide initiators such as dibenzyloxy ester or 2,5-dimethylhexane-2,5-dihydroperoxide, or benzamyl peroxide-N, N-dimethyl peroxide Aniline or peroxodisulfite Redox-based initiators such as sodium bicarbonate. Among these, azo-based initiators or peroxide-based initiators are preferred, and azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, Azobiscyclohexanenitrile, azobisisobutyric acid dimethyl, benzoyl peroxide, 2,4-chlorochlorobenzoyl peroxide, monoperoxide-27- 200428148 tributyl , Lauryl peroxide, diisopropylperoxydicarbonate or acetamyl peroxide. The radical polymerization initiators as described above can be used singly or in combination of two or more kinds simultaneously or sequentially. These amounts are used relative to 4-vinylphenol-based compounds, (meth) acrylic acid esters represented by the general formula (5), and (a The total amount of acryloyloxyalkyl esters used is preferably 0.001 mol times or more, more preferably 0.001 mol times or more, and 0. 〇〇 It is more preferably 5 mol times or more, on the other hand, it is preferably 0.1 mol times or less, and most preferably 0.05 mol times or less. The total amount of the radical polymerization initiator used may be the same amount as the amount of "g" at the start of heating and the full amount is added. After the heating is started, the whole amount or a part may be used. • The solvent used in the method of the present invention can be used if it does not hinder the reaction, specifically, for example: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cycloheptanone or γ -Ketones such as butyrolactone, alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, third butyl alcohol, η-octanol, 2-ethylhexanol or η-lauryl alcohol , Alcohols such as ethylene glycol, propylene glycol or diethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether , Diethylene glycol methyl ethyl ether, tetrahydrofuran or dioxane and other ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl acid, 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 Esters such as vinegar, isobutyl acetate, n-pentyl acetate, ^ -hexyl acetate, methyl propionate, ethyl propionate, or methyl butyrate, 2 monooxypropionate 28-200428148 methyl ester, Ethyl 2-oxypropionate, n-propyl 2-oxypropionate, isopropyl 2-oxypropionate, ethyl 2-oxy- 2 -methylpropionate or 2-oxy-1- Monooxycarbonates such as methyl methyl butyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, or 3- Alkoxy carbonates such as methyl ethoxypropionate, celestel acetate, methyl celestrate acetate, ethyl celestrate acetate, butyl celestrate acetate, etc. Xanthusyl esters, aromatic hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as trichloroethylene, chlorobenzene or dichlorobenzene, or dimethylacetamido, dimethylformamidine Amido, N-methylacetamido, N-methyl D-pyrrolidone, N-N-dimethylimidazolidone, and other amines and the like. 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, celex acetate, methyl celex acetate, ethyl cel Luthulone acetate, butylcelulose acetate or toluene. These solvents may be used alone or in combination of two or more. In addition, the use of a solvent such as M Ut is more preferable if the reaction solution is a homogeneous phase, and the WT is a uniform plural phase. The amount of the solvent used varies depending on the type or amount of the base polymerization initiator used, the molecular weight of the desired copolymer * 4 and the like, and is different from the total amount of the monomer mixture 10 0 parts by mass, preferably 5 parts by mass or more, more than 20 parts by mass, more preferably 50 parts by mass or more, on the other hand, 0.00 parts by mass of 29-200428148 parts are preferred, 5 It is more preferable that the content is less than or equal to 1,000 parts by mass, and the most preferable is less than or equal to 1,000 parts by mass. Moreover, it is most preferable that the concentration of the copolymer formed after the polymerization reaction is adjusted to an amount of 25 to 75 mass% regardless of the concentration, that is, 3 to 4 0 0 with respect to 100 parts by mass of the monomer mixture. Range of parts by mass.

The polymerization method of the acid-sensitive copolymer used in the present invention is not particularly limited. If the method is based on a 4-vinylphenol group, a (meth) acrylate represented by the general formula (5), or a general formula (6) As shown in the method of effectively mixing and contacting the (meth) propionic acid alkoxyalkyl esters, a radical polymerization initiator, and a solvent, etc., any method may be used, even if it is a fractionation method. Type, semi-return type or continuous flow type can be used. For example, to summarize these compounds, a method of inserting a reaction vessel to start heating or a method of inserting a monomer, a radical polymerization initiator, and a solvent continuously or intermittently and at least a part of the solvent into the reactor is generally used. Wait.

In these methods, the 4-vinylphenol-based, (meth) acrylic and (meth) acrylic acid alkoxyalkyl esters present in the reaction system from the start of heating to the end of the method of the present invention The total concentration of the compounds is preferably adjusted to 20% by mass or less, and the reaction is preferably performed. Specifically, it is based on the consumption of the polymerization of 4-vinylphenol-based, (meth) acrylates and alkoxyalkyl (meth) acrylates, the amount of new monomers formulated, and the polymerization initiation A method in which agents, solvents, etc. are incorporated into a continuous or intermittent reaction system. More specifically, for example, a method in which such monomers and a radical polymerization initiator are continuously or intermittently charged in a reaction system after the reactor is charged with only a solvent, the solvent in the reactor and the free Method for loading radical polymerization initiator -30 · 200428148 Single or continuous loading of reaction system into single reaction system, reactor with part of solvent and monomer after radical polymerization initiator And residual solvents and radical polymerization initiators are continuously or intermittently charged into the reaction system, or a part of the monomers, radical polymerization initiators and solvents remaining in the reactor are charged. The monomer, the radical polymerization initiator, and the solvent are continuously or intermittently charged into the reaction system, and the like. In the method for producing an acid-sensitive copolymer used in the present invention, a polymerization reaction is performed by heating. Regardless of the temperature at which the polymerization is carried out, the heating temperature differs by 40 ° depending on the desired degree of polymerization, composition, and molar ratio of the polymer, and the type or amount of the radical polymerization initiator and solvent used. Above C, preferably above 5 ° C, more preferably 50 t: Above is more preferable, above 60 ° C is best, on the other hand, below 250 ° C is best, 180 ° It is preferably below C, more preferably below 160 ° C, and most preferably below 150 ° C. The polymerization reaction time also varies depending on the degree of polymerization, composition, and molar ratio of the desired polymer, and the type or amount of the radical polymerization initiator and solvent used. However, it is preferably 0. 01 hours or more, on the other hand, it is preferably 40 hours or less, and most preferably 20 hours or less. Further, if necessary, the reaction may be performed under reflux, reduced pressure, normal pressure, or increased pressure. In particular, the reaction behavior is better because the heat of reaction is more efficient in removing heat under reflux. In addition, it is preferable to perform it in an inert gas atmosphere such as nitrogen or M gas, and it is also possible to perform it in the presence of a molecular acid such as air. -31- 200428148 Furthermore, in the method for producing an acid-sensitive copolymer used in the present invention, a phenol-based compound may be used in accordance with the purpose of increasing the recovery amount of the copolymer or changing the arrangement of the copolymer constituent units. And other additives. A solution containing the above copolymer (photoresist raw material), 0.05 to 0.3 mol parts of 4 monovinylphenol-based, 0.001 to 0.5 mol parts of (methyl) Acrylates, alkoxyalkyl (meth) acrylates of 0.2 to 0.8 mol parts and less, and a copolymer raw material containing the total mol number of 1 mol part or the above-mentioned copolymer raw materials when heated After heating, it can be concentrated or diluted as needed. The concentration of unreacted 4-vinylphenol-based photoresist raw material is 50 mass ppb to 0.5 mass% with respect to unreacted (meth) acrylic acid. The concentration of the photoresist material of the ester is 5 mass p pm to 5 mass%, and the photoresist material of the unreacted (meth) acrylic alkoxyalkyl ester is 200 mass p P b to 2 mass. %, And the total concentration of the photoresist raw material of these unreacted monomers and the acid-sensitive copolymer produced is 25 to 75% by mass. The solution coating characteristics and coating film of the photoresist material are used. The viewpoints of dominance and the like are preferable. After the polymerization reaction is completed, the reaction mixture can be used to separate the formed copolymer by a general method such as a solvent extraction method, a Shen Dian method, or a thin film evaporation method. In addition, if necessary, a copolymer of the target substance and a solution containing the produced copolymer may be used as a photoresist material. In addition, when the positive photosensitive resist of the present invention is used, the dissolution rate of the copolymer is 1.5 μπΐ / min or less before exposure, preferably 1.2 μπΐ / min or less after exposure, 2.5 μΓη / min or more after exposure, and It is more preferable that there is a large change at 3 μm / min or more. -32- 200428148 The measurement of the dissolution rate is a mixed solution of 30% by weight of the copolymer and 1% by weight of a photoacid generator such as naphthalenediamine trifluorosulfonate, etc., on a copper-clad laminated board or the like. The coating was formed on a substrate with a coating film having a thickness of 5 μm when the solvent was removed by heating, such as a spin coater or a bar coater. The coating film-based imaging solution on the substrate was measured for the complete dissolution time in a 1% sodium carbonate aqueous solution to determine the dissolution rate before exposure. After the exposure, the dissolution rate is the same as that after the film is coated on the substrate. The film is coated with light at a wavelength of 3 65 nm per 200 m J / cm 2. The measurement solution is completely dissolved in a 1% sodium carbonate aqueous solution. It depends on time. The present invention relates to a positive-type photosensitive photoresist composition including the above-mentioned acid-sensitive copolymer, an acid generator, and a solvent. The acid generator is a compound having at least one kind of 4,6-bis (trichloromethyl) -s-dioxo group in one molecule, which is local-sensitive and inexpensive. The positive photosensitive resist composition of the present invention can be exposed to near-ultraviolet light and developed with weak alkali, and has a high resolution. It may also correspond to a substrate including a through hole. In particular, when an acid generator has at least one type of 4,6-bis (trichloromethyl) -s-triple group, the exposure can be reduced to 10 mj / cm2, and the line width is It is possible to form a fine pattern of 10 μm and a line interval of 10 μm. Examples of the photoacid generator having at least one kind of 4,6-bis (trichloromethyl) -s-triple group in one molecule include compounds represented by the following general formula (4). [Chem. 1 5] • 33- 200428148 cci3 l = \

cci3 (4) (In the formula (4), R5 represents a trichloromethyl group, a straight-chain or branched unsubstituted alkyl group having 1 to 12 carbon atoms, and a straight group having 1 to 12 carbon atoms. Locked or branched alkoxy, halogen atom, cyano, hydroxyl, phenyl substituted with hydroxy, phenyl substituted with halogen, phenyl substituted with nitro, straight-locked or Branched unsubstituted alkyl-substituted phenyl, straight-chained or branched alkoxy-substituted phenyl, 1--3 carbons Diol monophenyl ether ether substituted phenyl, decyl, styryl, styryl substituted with straight-chain or branched alkoxy substituted with 1 to 3 carbon atoms, naphthyl, carbon atom A substituent of a straight-chain or branched alkoxy-substituted naphthyl group having a number of 1 to 3) The photoacid generator represented by the general formula (4) can be specifically exemplified; 2,4,6—three (three (Chloromethyl) -s-trimethyl, 2-methyl-4, 6-bis (trichloromethyl) -s-trimethyl, 2-ethyl-4, 6-bis (trichloromethyl) —S —trioxo, 2-propyl-4,6 —bis (trichloro Base) -s-triphenyl, 2-isopropyl-4,6-bis (trichloromethyl) -s-trisyl, 2-butyl-1,6-bis (trichloromethyl)- s — triple well, 2-methoxy-4,6 —bis (trichloromethyl) —s —trigenyl, 2 —ethoxy—4,6 —bis (trichloromethyl) —s — Trioxo, 2-propoxy-4,6-bis (trichloromethyl) -s-trioxyl, 2-isopropoxy-4,6-bis (trichloromethyl) -s-tri Well group, 2-but • 34- 200428148 oxy-4,6-bis (trichloromethyl) -s-tri well group, 2-chloro-4, 6-bis (trichloromethyl) -s-tri Well group, 2-bromo-4,6-bis (trichloromethyl) -s-triple group, 2-cyano-4, 6-bis (trichloromethyl) -s-triple group, 2-hydroxy —4,6 —bis (trichloromethyl) —s —trisyl, 2— (4-methoxyphenyl) —4,6—bis (trichloromethyl) —s —trigenyl, 2 — (4 —ethoxyphenyl) — 4,6 —bis (trichloromethyl) —s —trisyl, 2 — (4 —propoxyphenyl) — 4,6 —bis (trichloromethyl) base —S — triple well, 2 — (4-isopropoxyphenyl) — 4, 6, bis (trichloromethyl) — s — triple well, 2 — (4-butoxyphenyl) — 4,6 —bis (trichloromethyl) —s —triphenyl, 2 — (3-methoxyphenyl) —4,6 —bis (trichloromethyl) —s_trisyl, 2 — (3-Chloro-4—methoxyphenyl) -4,6-bis (trichloromethyl) -s-trimethyl, 2- (3-bromo-4 4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-trisyl, 2- (3-methoxyphenyl) -4,6-bis (trichloromethyl) -s-trisyl, 2- (3 , 4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -s-trisyl, 2- (3,5-dimethoxyphenyl) -4,6-bis ( Trichloromethyl) —s —triphenyl, 2 — (4-hydroxyphenyl) — 4,6-bis (trichloromethyl) — s —trimethyl, 2 — (4-nitrophenyl) — 4,6 —bis (trichloromethyl) -s —tricotyl, 2 — (4-monoethylene glycol monomethyl ether phenyl) —4,6 —bis (trichloromethyl) —s —trigon Base, 2 — (4 a Glycol monoethyl ether phenyl) -4,6-bis (trichloromethyl) -s-triple, 2- (4-propanediol monomethyl ether phenyl) -4,6-bis (trichloro (Methyl) —s —trioxo, 2 — (4-propanediol monoethyl ether phenyl) — 4,6 —bis (trichloromethyl) —s —triphenyl, 2 — (3,4 —methyl) Dioxy-35 · 200428148 phenyl) -4,6-bis (trichloromethyl) -s-trisyl, 2- (2,3-methyldioxyphenyl) -4,6-bis ( Trichloromethyl) -s-trisyl, 2- (2-methoxystyrene) -4,6-bis (trichloromethyl) -s-tris, 2- (3-methoxy (Styrene) -4,6-bis (trichloromethyl) -s-trisyl, 2- (4-monomethoxystyrene) -4, 6-bis (trichloromethyl) -s-tris Group, 2 — (4 — 2 — (4 —methoxy-α-naphthyl) —4,6—bis (trichloromethyl) —s—triple group, 2— [2— (5 —methyl Furan-2-yl) vinyl] -4, 6-bis (trichloromethyl) -s-trisyl, 2- [2- (furan-2-yl) vinyl] -1 4,6-bis (trichloromethyl) -s-trisyl, 2- [2- (5-methylfuran-2-yl) ethynyl] -4,6-bis (trichloromethyl) One s-trisyl, 2- (α-naphthyl) 4,6-bis (trichloromethyl) -s-trisyl, 2- (β-naphthyl) -4,6-bis (dichloro (Methyl) -s-dioxo, 2- (4-methoxy-α-naphthyl), 4-, 6-bis (trichloromethyl) -s-trisyl, 2- (3-methoxy -Α-naphthyl) -4, 6-bis (trichloromethyl) -s-triple, 2- (4-ethoxy-α-naphthyl) -4,6-bis (trichloromethyl) Group)-s-two well group, 2-(4-propoxy-α-naphthyl)-4, 6-bis (trichloromethyl)-s_ triple well group, 2-(4-isopropyloxy -Α-naphthyl) —4,6 —bis (trichloromethyl) —s—triple group, 2 — (4-butoxy-α-naphthyl) —4,6—bis (dichloromethyl) Base)-s-two coercion and other examples. It can be used alone or in combination. Among these, a photoacid generator having an absorption peak 値 λιη ax in the range of 300 to 450 nm is particularly preferable in the case of an ultraviolet exposure machine used for circuit exposure using a printed wiring board. i-line peak 値 3 6 5 nm has an absorption peak -Xmax at -36- 200428148, with 2-(4 -methoxymethoxy 6 -bis (trichloromethyl) -s-triplet group, 2-(4 1-naphthyl) -4,6-bis (trichloromethyl) -s-tris (4) methyldioxyphenyl) -4,6-bis (trichloromethyl), 2-(3 —Bromo—4 —methoxyphenyl) —4,6 methyl) —s—trimethyl, 2- (2-methoxyphenyl 4,6—bis (trichloromethyl) —s—tri Zylenyl, 2- (phenylvinyl) -4,6-bis (trichloromethyl) -s-mono (4-methoxyphenylethynyl) -4,6-bis (tris-tris) Well group, 2- (4-hydroxyphenyl) -4,6 ~ yl) -s-tri well group, 2- (4-ethylene glycol monoethyl 4,6-bis (trichloromethyl) -s —Three groups are particularly good. The blending amount of the photoacid generator is 100 parts by mass with respect to the acid sensitivity. In order to make the pattern formation well, the amount is preferably at least parts by mass, and more preferably at least 0.2 parts by mass. Good, 20 is better, and 10 parts by mass or less is the best. It is better than 0 · 0 5 mass produced by light irradiation When the acid becomes less, the pattern formation may be difficult to produce. On the other hand, when the amount is more than 20 parts by mass, the light may diffuse to the unexposed portion due to light irradiation, and the resolution may be reduced. Furthermore, for the purpose of increasing sensitivity, If necessary, ketone-based, anthraquinone-based, thioxanthone-based photosensitizers, or sensitizing pigments such as fragrant cyanine-based, fluorene-based, and fluorene-based sensitizers can also be used. Further, the concentration of the copolymer after heating Concentration is less than 2 or it is diluted when more than 75% by mass to adjust the concentration of the copolymer in the thick resistive raw material. For example, a photoresistive raw material is loaded into 5 groups)-4, methoxy-ex, 2-(3, The total amount of —s — three coaxes, one pair (trichloroethanyl), one 3-methoxytrifluorenyl group, two methyl groups, and one bis (phenyl trichloroformate) monomer is recognized as 0.5. When the content is less than the mass part, the tendency tends to grow. Too much acid, with benzophenone ketone system, 5 mass%. About the light tin plated tin plate -37- 200428148 fine flat tin plated plate It can be measured by entering a hot-air dryer, heating and resolving the pan from which the solvent has been removed. The positive-type photosensitive light of the present invention can be measured. In the composition, the pattern after exposure is confirmed by the reason of the conformity of the pattern position and the position of the through hole, etc., and the hue of the coating film can be changed by the acid generated by the exposure, and the color of the acidic region can be added Η Indicators such as methyl orange, methyl red, methyl blue violet, dinitrophenol group, thymol blue, bromophenol blue and the like.

Furthermore, in the positive photosensitive resist composition of the present invention, a solvent may be further added for reasons such as improvement in coating properties.

Examples of such solvents include, for example, acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, or methyl-2-n Ketones such as amyl ketone, ethanol, η-propanol, isopropanol, 1-butanol, 2-butanol, 3-methoxybutanol, 3-methyl-1 -methoxybutanol, Alcohols such as 1-methoxy-2-propanol or 1-ethoxy-2-propanol, polyols such as ethylene glycol, propylene glycol, or dipropylene glycol, ethylene glycol vinyl ester, propylene glycol, and glycol Monomethyl ether, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl Polyol derivatives such as ether, dimethyl ether or diethyl ether, cyclic ethers such as tetrahydrofuran or dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, Methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl esters such as ethyl 3-methoxypropionate, third butyl acetate or third butyl propionate, etc., benzene, Toluene or di Aromatic hydrocarbons such as benzene or chlorobenzene or dichlorobenzene original halogenated aromatic hydrocarbons. -38- 200428148 Among these, ketones, alcohols, polyhydric alcohols, polyhydric alcohol derivatives, cyclic ethers, esters or aromatic hydrocarbons are preferred, and acetone and methyl ethyl are more preferred. Ketone, methyl isobutyl ketone, cyclohexanone, ethanol, isopropanol, ethylene glycol dimethyl 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. In addition, the positive-type photosensitive resist composition of the present invention may be added with, for example, styrene and acrylic acid, methacrylic acid, or maleic anhydride, because of improvement in developability, storage stability, heat resistance, etc., as necessary. Copolymers, copolymers of olefins and maleic anhydride, vinyl alcohol copolymers, vinylpyrrolidone polymers, and the like. The addition amount of these optional components is generally 30 parts by mass or less, and preferably 5 parts by mass or less, based on 100 parts by mass of the acid-sensitive copolymer. In addition, if necessary, color pigments, color dyes, thermal polymerization inhibitors, tackifiers, shakers, leveling agents, defoamers, coupling agents, etc. may be blended. When the positive photoresist material obtained above is used as an etching photoresist for forming a circuit pattern on a printed wiring board, first adjust the viscosity to suit the coating method as necessary, and then the main printed circuit board or package substrate, flexibility A copper-clad laminated substrate for a printed circuit board or a copper-clad laminated substrate for forming a through-hole is coated by a method such as screen printing, curtain coating, roll coating, spray coating, dip coating, or the like, particularly Supports extremely thin substrates (substrate thickness: 0 · 1 mm or less) without affecting the surface shape and can be applied to the end surface, but can be reliably applied to the inner surface of through holes. Furthermore, dozens of substrates can be processed at once The processing efficiency is extremely excellent. Since the shake time of one tablet is greatly shortened, the coating method by the dip coating method is particularly good. -39- 200428148 At this time, the liquid specific gravity of the positive photosensitive resist composition of the present invention uses a solvent with a small specific gravity in order to increase the drying speed, and the substrates are not adhered to each other due to the residual solvent (residual viscosity). It is preferably below 0.99 0, and most preferably below 0.950. The lower limit is preferably 0.800 or more, and more preferably 0.850 or more. Then, after coating, it is 50 to 120 t: it is heated and dried for 5 to 30 minutes and the solvent contained in the volatile composition is exposed to contact and exposed to form a positive-type photosensitive film layer having no stickiness. Next, a mask having a predetermined pattern is attached to the film, and the mask is exposed to near-ultraviolet light (300 to 450 nm), and then developed with an alkali developing solution such as a 1% sodium carbonate aqueous solution. The desired pattern can be formed on the printed substrate. In the past, a positive-type photosensitive photoresist composition using a photoacid generator was used to activate the catalytic action of an acid after exposure. Therefore, most of them are subjected to heat treatment. However, the positive-type photosensitive photoresist composition in this case, especially The heat treatment after exposure is unnecessary, and heat treatment is also possible. Since sufficient development can be performed, the heat treatment step can be omitted. In addition, there is no problem even if heat treatment is performed. On the other hand, only the exposed portion is developed with a positive-type photosensitive photoresist that can be dissolved and removed with an aqueous alkali solution, and an etched photoresist may remain on a portion that is not irradiated with light such as in a through hole. A copper-plated laminated substrate with a predetermined photoresist pattern on the copper surface. The connector etches the copper surface with an acidic etchant, and removes the photoresist pattern with a strong alkaline aqueous solution such as sodium hydroxide or potassium hydroxide to form the predetermined circuit pattern. . The positive-type photosensitive resist composition of the present invention can be suitably used for the production of electronic parts such as a printed circuit board, a landless printed circuit board, a flexible printed circuit board, and a printed circuit board for packaging. -40-200428148 When a fine pattern is formed by using the positive photosensitive resist material of the present invention and a substrate having through holes, it can be island-free (丨 a n d} e s s). In the case of the negative type, in order not to harden the inside of the through hole, the inside of the through hole is impregnated with the etching solution when the etchant is immersed, and the internal plating is corroded and broken. In the dry film method, when there is no adhesion around the through hole, the etching solution is impregnated internally in the same way, which causes the plating to rot and break. Therefore, this material is the only material that can achieve landless. [Embodiments] (Examples) The present invention is further explained by the following examples, but the present invention is not limited by these examples. In addition, there is no special prohibition, and reagents and the like use commercially available high-purity products. First, examples of the acid-sensitive copolymer used in the present invention will be described. (Example 1) A stirrer, a thermometer, a cooling pipe, and a 500 ml dropping funnel were installed, and a four-necked flask with an internal volume of 1,000 ml was charged with 200 ml of tetrahydrofuran. The water bath was refluxed at an elevated temperature of 80 ° C. In addition, a 1,000-mL conical flask was charged with 4-mono (1-methylvinyl) phenol group (hereinafter abbreviated as PIPE), which was purified by crystallization from a 2-ethylhexanol solution. Grams (0.75 moles), distilled refined methyl acrylate 1 29 grams (1.50 moles) and acrylic acid 1 ethoxyethyl ester 2 16 grams (1.5 0 moles), as a radical polymerization initiator 16.4 g (0.10 mole) of azobisisobutyronitrile and 200 ml of tetrahydrofuran as a solvent. • 41- 200428148 After the solution was stirred and dissolved, the whole amount was transferred to the dropping funnel 2 times, and the reflux state in the four-necked flask was dropped at a continuous rate. The internal temperature at the initial stage of the reaction was 72 ° C, but the internal temperature was raised during the polymerization and was 80 ° C after 8 hours. In addition to continuing to stir the water bath, after processing for 2 hours until it was cooled to room temperature (25 ° C), the polymerization reaction solution was placed in a 5 liter beaker and 2 liters of n-hexane were deposited to precipitate the polymer. After filtering and separating the polymer in Shen Dian, it was dissolved again in 400 ml of tetrahydrofuran, charged into 2 liters of n-hexane, and the solid was extracted. This filtration, separation, and precipitation operation was repeated twice. After final filtration and separation, it was dried under reduced pressure at 100 mm Hg and 1000 ° C for 2 hours to obtain 356 g of a white polymer. As a result of the obtained quot-NMR analysis, 13C-NM R analysis, and elemental analysis, the obtained white polymer had a feed ratio of the intended copolymer raw material approximately the same as the molar ratio. As a result of GPC analysis of polyethylene as a standard, the weight average molecular weight (Mw) was 1 5,000, and the molecular weight dispersion (Mw / Mn) was 1.8 5. When the obtained copolymer is dissolved in each solvent of methyl ethyl ketone and cyclohexanone, the copolymer is dissolved in each solvent at 50% by weight or more. After the obtained copolymer was dissolved in methyl ethyl ketone, it was coated on a copper-clad laminated substrate having a dry film thickness of 5 μm using a bar coater, and heated at 80 ° C for 10 minutes. To form a film. When immersed in a 1.0 wt% sodium carbonate aqueous solution (alkali developer), the coating on the copper-clad laminated substrate was dissolved within 3 minutes. That is, the dissolution rate of the obtained copolymer was 1.5 µτη / min or less. -42- 200428148 In addition, the obtained copolymer was dissolved in methyl ethyl ketone, and a solution of naphthalenedimethylimide trifluorosulfonate (Green Chemical NAI-105) 1% by weight was added thereto, and the solution was dried. The next 5 μm copper-clad laminated substrate was coated with a bar coater and heated at 80 ° C for 10 minutes to form a film. An exposure device was used for manufacturing a general printed circuit board, and after 200 mJ / cm2 was irradiated with near-ultraviolet light (300 to 450 nm), the coating film was completely dissolved within 2 minutes when immersed in a 1.0 wt% sodium carbonate aqueous solution. That is, the dissolution rate of the obtained copolymer was 2.5 μm / min or more. After the obtained copolymer was dissolved in methyl ethyl ketone, it was coated on a quartz plate with a dry film thickness of 1 μm using a spin coater, and heated at 1000 ° C. for 10 minutes to form a film. When the transmittance was measured by a UV-visible spectrophotometer at 3 65 nm, the transmittance was 98% or more. (Examples 2 to 10) In Example 1, the methyl acrylate used in Example 1 was changed to that shown in Table 1, or the acrylic acid 1 monoethoxyethyl ester was changed to that shown in Table 1. The other conditions are completely the same as in Example 1. The reaction and post-treatment were performed in the same manner. The weight average molecular weight (M w) and the molecular weight dispersion (M w / M η) of the obtained copolymer were measured in the same manner as in Example 1. In addition, the dissolution rate was evaluated in the same manner as in Example 1 for the solvent solubility and the alkali developing solution. These analysis results and evaluation results, and the results of Example 1 are shown in Table 1. (Comparative Example 1) The feed amount of PI IP E used in Example 1 was changed to 2 5 1 · 9 g (1.88 mol), and the feed amount of methyl acrylate was changed to 1 6 1 · 8 g (1.88 mol) was used, except for 1-ethoxyethyl acrylate, to perform the same reaction, post-treatment, analysis and evaluation as in Example 1. -43- 200428148 Table 1 shows the analysis results and evaluation results of the feed mole ratio, the obtained copolymer, and the results of Examples 1 to 10. (Comparative Example 2) The feed amount of PIPE used in Example 1 was changed to 4 56 g (3.40 mol), and the feed amount of 1 monoethoxyethyl acrylate was changed to 55 g (0.5 38 moles), except that methyl acrylate was used, the reaction, post-treatment, analysis and evaluation were performed in exactly the same manner as in Example 1. Table 1 shows the analysis results and evaluation results of the feed mole ratio and the obtained copolymer. The results of Examples 1 to 10 and Comparative Example 1 are shown in Table 1. (Comparative Example 3) The feed amount of methyl acrylate used in Example 1 was changed to 26 g (0.3 mol), and the feed amount of 1 monoethoxyethyl acrylate was changed to 400 g (2 · 8 mol), except that the feed amount of PI IP was used, the reaction, post-treatment, analysis, and evaluation were performed in exactly the same manner as in Example 1. Table 1 shows the analysis results and evaluation results of the feed mole ratio, the obtained copolymer, and the results of Examples 1 to 10. (Comparative Example 4) The feed amount of PI P E used in Example 1 was changed to 61 g (0.46 mol), and the feed amount of methyl acrylate was changed to 3 1 5 g (3. 66 mol) and the amount of monoethoxyethyl acrylate were changed to 66 g (0.46 mol), and the same reaction, post-treatment, analysis, and evaluation as in Example 1 were performed. Table 1 shows the analysis results and evaluation results of the feed mole ratio, and the obtained copolymer. The results of Examples 1 to 10 are shown in Table 1. -44- 200428148 [Table 1] Example polymerization reaction (composition Morse ratio) Polymerization results PIPE a ugly) methyl acrylate type b (meth) acrylate alkoxyalkyl ester type C Mw Mw / Mn solvent solubility ( Disintegration rate of alkali imaging solution before acid treatment (" m / minute) Dissolution rate of alkali imaging solution after acid treatment (" m / minute) 1 0.20 methyl acrylate 0.40 1-ethoxyethyl acrylate 0.40 15,000 1.85 > 50 < 1.5 > 2.5 2 0.20 methyl acrylate 0.20 1-ethoxyethyl acrylate 0.60 18,500 1.87 > 50 < 1.5 > 2.5 3 0.20 methyl acrylate 0.40 1-ethoxy acrylate Ethyl 0.40 20,800 1.97 > 50 < 1.5 > 2.5 4 0.20 n-butyl acrylate 0.40 1-ethoxyethyl acrylate 0.40 25,900 1.94 > 50 < 1.5 > 2.5 5 0.20 methyl acrylate 0.40 acrylic 1- Methoxyethyl 0.40 15,600 1.83 > 50 < 1.5 > 2.5 6 0.20 Methyl acrylate 0.40 Acrylic acid butoxyethyl 0.40 19,300 1.92 > 50 < 1.5 > 2.5 7 0.25 Methyl acrylate 0.25 Acrylic 1 -Isopropoxyethyl 0.50 20,100 1.86 > 50 < 1. 5 > 2.5 8 0.20 methyl methacrylate 0.30 1. isopropoxyethyl 0.50 25,300 1.82 > 50 < 1.5 > 2.5 9 0.15 methyl methacrylate 0.25 1-isopropoxy methacrylate Ethyl 0.60 21,400 2.13 > 50 < 1.5 > 2.5 10 0.25 n-butyl methacrylate 0.15 1-isopropoxyethyl methacrylate 0.60 18,500 2.19 > 50 < 1.5 > 2.5 Comparative Example 1 0.50 Methyl acrylate 0.50 1-ethoxyethyl acrylate 10,800 1.89 > 50 ^ 0.5 ^ 0.5 Comparative Example 2 0.90 Methyl acrylate 1-ethoxyethyl acrylate 0.10 13,900 1.85 > 50 ^ 0.5 ^ 0.5 Comparative Example 3 Acrylic acid Methyl ester 0.1 1-ethoxyethyl acrylate 0.9 78,900 3.4 > 50 > 2.5 > 2.5 Comparative Example 4 0.10 Methyl acrylate 0.8 1-ethoxyethyl acrylate 0.10 38,300 2.2 > 50 < 1.5 ^ 0.5

-45- 200428148 (Example 11) The acid-sensitive copolymer (A) obtained in Example 1 was dissolved in 30% by weight of methyl ethyl ketone, and then 100% by weight of the acid-sensitive copolymer, Add 2-(4-methoxyphenyl)-4, 6-bis (trichloromethyl)-s-trioxo (A-1) as a photoacid generator, 3 parts by weight, coloring dye UV-Β 1 ue 2 3 6 (manufactured by Mitsui Chemicals Co., Ltd.) 0.5 parts by weight was dissolved to prepare a positive-type photosensitive photoresist composition capable of being dip-coated. The positive photosensitive resist composition has a specific gravity of 0.9 1 3. Another method is to attach a copper foil with a thickness of 9 μm to a thickness of 0.5 mm on both sides of the FR-4 copper-clad laminated substrate. Use an NC cobalt tip (drill) to open a hole of 0. 2 mm 0 and apply 9 μ by a well-known method. m copper power ore. The obtained positive photoresist composition was used on both sides of the substrate containing the through hole, and after drying, it was coated with a dip coating having a film thickness of 4 μm, and then dried at 80 ° C. for 10 minutes to be non-sticky. The inner surface of the through hole of 0.2 mm 0 is covered with a photoresist material. Then, a model pattern having a line / space = 2 0/2 0 μm and a pattern film of 0.35 mm 4 land were adhered to the coating surface, and irradiated with 50 kJ / cm 2 with an ultra-high pressure mercury lamp of 3 kw. After that, heat treatment was performed, and immediately sprayed with a temperature-adjusted developing solution of a 1.0 wt% sodium carbonate aqueous solution at 30 t, followed by washing with water to perform a test of the development of the photosensitive photoresist film. The connector 'was etched with a copper chloride-based well-known copper etching line, and the photoresist material was spray-peeled with a 3.0 wt% caustic soda aqueous solution, washed with water, and dried. Then, the circuit formation state of the land and the copper in the through hole were observed. State of plating. The characteristic evaluation of the positive photosensitive resist film was performed by the following characteristic evaluation method. The results are shown in Table 2. -46- 200428148)) The floating price of the price of the test method is as follows: · Specific weight C specific film thickness: using an eddy current type simple film thickness meter (Esox pu M P 3 0; Forth Qia Yisi such as (Made by Mei Duo). Developability: 30 ° C, using 1.0% by weight sodium carbonate aqueous solution, spray development under a pressure of 0 · 18 P a for 60 seconds, and judge the composition residues of the exposed part. ◦ No residue. X Residue Resolution: Use a mask with a pattern of line width of 20 μm and a spacing of 20 μm to perform a predetermined exposure and development. After confirming the pattern, use a 200-times micro-mirror. Or judge. 〇When the line width and spacing are both 20 μm. △ Even when a pattern is formed, the line width and spacing are both 20 μm. X The complete pattern cannot be formed, and the pattern is not completely developed. Etching resistance ······························································································································· · · · · · · · The substrate on which the development is finished, copper chloride etching solution at 50 ° C, sprayed at a pressure of 0 · 2 Pa, after the etching is completed, the photoresist material may be peeled off by spraying with a 3.0 wt% caustic soda solution, and washed. After processing and drying, confirm the state of the circuit formation on the land and the state of the copper plating in the through hole, and then make a judgment. 〇 Case where the copper surface in the pattern and the through hole is not eroded at all △ Case where the copper surface in the pattern and the through hole is partially eroded 1 2 ~ 1 4) • 47- 200428148 Example 1 2- (4-monomethoxyphenyl)-4,6-bis (difluoromethyl) -s-dioxo ( a — 1) to 2 — (3,4-methyldioxyphenyl) —4,6—bis (trichloromethyl) —s—trigenyl (A-2), or 2— (4 Monomethoxyphenylvinyl) -4,6-bis (dichloromethyl) -s-triazine (A-3), or 2- (4-methoxy-α-naphthyl)- Except for 4,6—bis (trichloromethyl) —s—trioxo (A—4), the other conditions were completely treated in the same manner as in Example 1 to evaluate the characteristics of the positive photosensitive photoresist film. The results of these evaluations are shown in Table 2 together with the results of Example 1. 0 (Example 15) The acid-sensitive copolymer (b) obtained in Example 8 T was dissolved in 30% by weight of formic acid. After ethyl ethyl ketone, 2- (4-monomethoxyphenyl) -4,6-bis (trichloromethyl)-as a photoacid generator was added to 100 parts by weight of the acid-sensitive copolymer. s —Sangen-based (A-1) 3 parts by weight, coloring dye UV-B 1 ue 2 3 6 (Mitsui Chemical Co., Ltd.) 0.5 parts by weight, dissolved to produce a positive photosensitive resist composition capable of dipping coating Thing. The specific gravity of the positive photosensitive resist composition was 0.936. This positive-type photosensitive resist composition was treated in the same manner as in Example 11 to evaluate the characteristics of the positive-type photosensitive resist film. The results of these evaluations are shown in Table 2 together with the results of Example 11. (Example 16) Except for 2- (4-monomethoxyphenyl) -4,6-bis (trichloromethyl) -s-trigenyl (A —1) instead of 2 — (3,4-methyldioxyphenyl) —4,6-bis (tri-48- 200428148 chloromethyl) -S-trimethyl (A-2) and others The conditions were treated in the same manner as in Example 15 to evaluate the characteristics of the positive photosensitive resist film. The results of these evaluations are shown in Table 2 together with the results of Example 11. (Comparative Example 5) A positive-type photosensitive resist composition was produced in the same manner as in Example 11 except that the acid-sensitive copolymer (R) obtained in Comparative Example 1 was used. The positive-type photosensitive resist composition had a specific gravity of 0 · 9 1 0. This positive-type photosensitive resist composition was treated in the same manner as in Example 11 to evaluate the characteristics of the positive-type photosensitive resist film. These evaluation results are shown in Table 2 together with the results of Example 1 1. (Comparative Example 6) A positive-type photosensitive resist composition was produced in the same manner as in Example 11 except that the acid-sensitive copolymer (S) obtained in Comparative Example 2 was used. The specific photosensitive resist composition had a specific gravity of 0.924. This positive-type photosensitive photoresist composition was treated in the same manner as in Example 11 to evaluate the characteristics of the positive-type photosensitive photoresist film. The results of these evaluations are shown in Table 2 together with the results of Example 11. (Comparative Example 7) Except that 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s ~ triswell group was changed to α, α as a photoacid generator in Example 11 Except for the substitution of -dichloro-4-phenoxyacetone ketone (a-5), the other conditions were treated in the same manner as in the complete example, and the characteristics of the positive photosensitive resist film were evaluated. The results of these evaluations are shown in Table 2 together with the results of Example 11. -49- 200428148 In addition, the following shows the evaluation method of the film characteristics of the positive photosensitive resist composition, and Table 2 shows the results of the characteristics evaluation of the examples and comparative examples. (Comparative Example 8) A positive-type photosensitive photoresist composition was produced in the same manner as in Example 11 except that the acid-sensitive copolymer (T) obtained in Comparative Example 3 was used. The positive-type photosensitive resist composition had a specific gravity of 0 · 9 2 0. This positive-type photosensitive resist composition was treated in the same manner as in Example 11 to evaluate the characteristics of the positive-type photosensitive resist film. The results of these evaluations are shown in Table 2 together with the results of Example 1'1. (Comparative Example 9) A positive-type photosensitive resist composition was produced in the same manner as in Example 11 except that the acid-sensitive copolymer (U) obtained in Comparative Example 4 was used. The specific gravity of the positive-type photosensitive resist composition was 0.924. This positive-type photosensitive resist composition was treated in the same manner as in Example 11 to evaluate the characteristics of the positive-type photosensitive resist film. The results of these evaluations are shown in Table 2 together with the results of Example 11. [Table 2] Example Acid-sensitive composition Acid generator type Acid generator combined weight part Specific gravity film thickness (Development resolution resolution Etching resistance surface example 11 A Al 3.0 0.913 4.1 〇〇〇B example 12 A A-2 3.0 0.914 4.3 〇 Example 13 A A-3 3.0 0.913 4.4 〇 Example 14 A A-4 3.0 0.910 4.1 〇 Example 15 B Al 3.0 0.936 3.8 〇〇〇_ Implementation Example 16 B A-2 3.0 0.934 4.2 〇0 〇 Comparative example 5 R Al 3.0 0.910 4.0 XX a comparative example S Al 3.0 0.924 4.1 XX —- Comparative Example 7 A A-5 3.0 0.903 3.9 XX one comparative example 8 T Al 3.0 0.920 4.1 X (the unexposed part also dissolves) X Comparative Example 9 U Al 3.0 0.924 4.2 XX-50-50200428148 Industrial Applicability According to the present invention, it can form a high sensitivity to near-ultraviolet light and The photoresist pattern with excellent high resolution is used as a positive etching resist, and can be used in the field of fine circuit processing of printed wiring boards. Furthermore, because the positive type does not require exposure in the through hole, it can also be used for through-hole substrates, and because it can be developed by the most common ® @Sodium, it can be used without changing the printed wiring board processing equipment. . The material of the acid-sensitive copolymer of the present invention is a combination of commercially available photoacid generators that are inexpensive and can provide relatively inexpensive positive-type photoresist materials. [Schematic description]: None -51-

Claims (1)

〇〇428l48 ， Applicable patent scope: i. Monobasic acid sensitive copolymer, which includes the second constitutional unit represented by the following general formula (1), and the second constitution represented by the following general formula (2) Unit and the third constituent unit represented by the following general formula (3), wherein the first constituent unit represented by the general formula (1) is [Chemical Formula 1] 0H (In formula (1), X represents a hydrogen atom or a methyl group) The second constituent unit represented by the general formula (2) is [Chemical Formula 2] (In formula (2), R1 represents a hydrogen atom or a methyl group, R2 represents a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, and a straight-chain branch having 1 to 6 carbon atoms substituted with a hydroxyl group. Locked or branched alkyl group, straight-chain or branched alkyl group having 1 to 6 carbon atoms substituted with halogen atoms, straight-chain or branched alkyl group with 1 to 6 carbon atoms substituted with cyano or A straight-chain or branched alkyl group having 1 to 6 carbon atoms substituted with a dialkylamino group), and the third constituent unit represented by the general formula (3) is [Chem. 3] -52- 200428148 z (In formula (3), R3 represents a hydrogen atom or a methyl group, R1 represents a hydrogen atom, a halogen atom, or a straight-chain or branched unsubstituted radical having 1 to 6 carbon atoms, and γ represents a hydrogen atom 2. Unsubstituted alkyl or straight-chained or branched unsubstituted alkyl groups with 1 to 6 carbon atoms or substituted or substituted radicals with direct-locked or branched carbon groups with 1 to 6 carbon atoms; Z represents a direct-locked or branched carbon chain with 1 to 6 carbon atoms Unsubstituted branched or branched straight or branched substituted alkyl with 1 to 6 carbon atoms; γ and Z may also be combined to form a cyclic structure), (However, a, b, and c are composition ratios, a It is a rational number of 0.05 or more and 0.3 or less, b of 0.1 or more and 0.7 or less, and c of 0.2 or more and 0.8 or less, and the sum of a, b, and c is 1). 2 · —A type of positive photosensitive photoresist composition, which contains 1,000 parts by weight of the acidic copolymer of the first item in the scope of the patent application, and 4,6—double ( Trichloromethyl) -s-triple-based compound: 0.05 to 20 parts by weight. 3. The positive-type photosensitive photoresist composition according to item 2 of the patent application, wherein the acid generator is represented by the following general formula (4), [Chem. 4] • 53-1 200428148 or branched alkoxy, halogen atom, cyano, hydroxy, phenyl, phenyl, nitrophenyl, alkphenyl, alkoxyphenyl, butanediol monoalkyl ether -Substituted phenyl, decyl, styryl, straight-locked or branched alkoxy-substituted styryl, naphthyl, straight-locked or branched alkoxy or Branched alkoxy substituted naphthyl substituents). 4 · A method for manufacturing a printed circuit board, which is characterized in that the specific gravity of the liquid is adjusted to 0. 8 0 0 to 9 9 0, the positive feeling of any one of the items 2 or 3 of the patent application scope; 7t photoresist The composition includes a step of applying a photosensitive resin uniformly on the surface of the laminated board by dipping and drying at least one surface of the laminated board having a metal layer, a step of exposing through a photomask, a step of developing, and etching. Steps of metal layer. -54- 200428148 柒 Designated representative map: (1) The designated representative map in this case is: None. (II) Brief description of the component representative symbols in this representative diagram: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: None of the chemical formulas in this invention can represent the invention of this case alone, so it is not listed A chemical formula representing the features of the invention.