TWI266145B - Chemically amplified photoresist composition, photoresist layer laminate, manufacturing method for photoresist composition, manufacturing method for photoresist pattern and manufacturing method for connecting terminal - Google Patents

Abstract

A chemically amplified positive photoresist composition which is stable and does not change its alkali solubility before radiation exposure, a photoresist layer laminate having a substrate and a layer of the photoresist composition laminated on the substrate, a manufacturing method of photoresist pattern by using the laminate, and a manufacturing method of connection terminals are provided. The photoresist composition comprises (a) a resin which changes its alkali solubility by an acid, (b) a compound which releases an acid by a radiation exposure thereon, and (c) a rust-preventive agent.

Description

(1) 1266145 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a method for producing a photoresist film composition of a 'chemically enhanced photoresist composition, a photoresist layer laminate', and a photoresist pattern. And a method of manufacturing the terminal for connection. In addition, it is a 'reinforced chemical type photoresist composition, a photoresist layer laminated body, and a photoresist composition which are suitable for the manufacture of the connection terminal used for the mounting of the circuit board of semiconductor or electronic component. Manufacturing Method 'The manufacturing method of the photoresist pattern and the manufacturing method of the terminal for connection. [Prior Art] Photographing, which is currently the mainstream of precision microfabrication technology, means that a photosensitive resin composition is applied to a surface of a workpiece to form a coating film, and a coating film pattern is obtained by photolithography. A technique in which electrons are formed by chemical etching, electrolytic etching, and/or electroplating as a light-shield, and various precision parts such as semiconductor packages are manufactured. In recent years, with the miniaturization of electronic devices, the high-density mounting technology of semiconductor packages is continuing to progress, and the pin-up film assembly (niouting) of the package is required, and the size of the package is miniaturized. The two-dimensional assembly technique of the flip chip method improves the assembly density of the three-dimensional assembly technique. In such a high-density assembly technique, the terminal for connection is, for example, a bump electrode (assembly terminal) such as a bump protruding on the package or a peripheral (peripheral (2) 1266145) terminal on the wafer. A metal post or the like to which the extended rewiring and the assembly terminal are connected is accurately placed on the substrate. The above-mentioned materials used in the optical manufacturing apparatus have photoresist. The photoresist system is, for example, used for forming a bump or a metal post caused by an electroplating step. A bump or a metal pillar, for example, a photoresist formed by forming a photoresist on a support, exposing it through a predetermined mask pattern, developing, forming a bump or a portion of the metal pillar selectively removed (peeled) The type is formed, and the removed portion (non-photosensitive portion) can be formed by embedding a conductor such as copper after plating, and can be formed by removing the photoresist pattern around it. In the case of the photoresist, for example, the photopolymerizable photosensitive resin composition for forming a bump or forming a wiring is described in the following Patent Documents 1 to 3. On the other hand, the photosensitive resin composition having a high sensitivity as compared with the photopolymerizable photosensitive resin composition is known as a chemically-resistant photoresist containing an acid generator. The characteristic of enhancing the chemical type resist is that the acid is generated by the irradiation of radiation (exposure), and the acid can be generated by the heat treatment after the exposure, and the base resin in the resin composition is Causes acid catalyst reaction, and changes its alkali solubility. When the chemical-type resist is reinforced by irradiation with radiation, the base which is insoluble in alkali is a positive type which is solubilized by alkali, and the one which is alkali-soluble is a negative type in which alkali is insolubilized. For example, Non-Patent Document 1 discloses a photoresist which combines a polyvinyl phenol of L.E. Bogan et al. and a melamine derivative in a representative example of enhancing a chemical type negative resist. However, the above-mentioned enhanced chemical type photoresist is used to form the photoresist layer. -6- 1266145 (3) The shape is used for a support such as a substrate, and a metal such as aluminum or copper is present in the photoresist layer. In the case where the action of the acid of the resin is hindered, there is a problem that the photoresist pattern characteristic of the required commercial accuracy cannot be obtained. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. 2000-39709 [Patent Document 3] # 曰本特开 2000-663 8 No. 6 [Non-patent Literature 1]

Proceeding of SPIE, 1 0 8 6 巻, 3 4-47 (1 9 8 9) ' [Summary of the Invention] The present invention has been made to solve the above problems of the prior art. The subject of the invention is to provide a photoreceptive layer laminate which can form a high-precision photoresist pattern and which can be laminated on a support, a photoresist composition, a photoresist pattern, and a photoresist pattern. A manufacturing method of the type and a manufacturing method of the terminal for connection. [Means for Solving the Problems] As a result of intensive review, the inventors of the present invention have found that the above-mentioned problems can be solved by adding a rust inhibitor to a conventional reinforced chemical resist composition, and thus the present invention has been completed. -7- (4) 1266145 That is, the first aspect of the present invention contains a resin which changes solubility of an alkali by an acid, (b) a compound which is irradiated by radiation, and (c) rust prevention. An agent that enhances chemical light species. The second aspect of the present invention is a composite in which a support and a photoresist layer formed of a strong chemical resist composition are laminated. The third aspect of the present invention is a chemically enhanced type in which (a) a resin which changes in acid solubility, (b) an acid generated by radiation irradiation, and (c) a rust preventive agent. Photoresist group manufacturing method. A fourth aspect of the present invention includes a step of laminating the above-mentioned physico-type photoresist composition to a support to obtain a photoresist layer, and selectively irradiating the photoresist layer The photo-step and the method of manufacturing the photoresist pattern after the exposure step to obtain a photoresist pattern step. The fifth aspect of the present invention includes a method of manufacturing a terminal for connection in which a terminal for forming a connection is formed in a non-photoresist portion of a resist pattern obtained by a resistive pattern manufacturing method. Advantageous Effects of Invention According to the present invention, it is possible to obtain a stable-enhanced chemical-type resist composition in which the properties are not changed before irradiation of radiation, and a photoresist layer laminate in which a composition is laminated on a support, and the same is used. The light (a) is caused by the acid resistance to form the above-mentioned resistance-increasing layer layer, so that the exposed layer of the alkali-soluble compound is enhanced, and the photo-conductor is dissolved in the photo-resistance pattern - 8 - (5 1266145 Manufacturing method and method of manufacturing terminal for connection. [Best Mode of the Invention] Hereinafter, the present invention will be described in detail. When the chemically-resistant photoresist composition of the present invention is used, (a) a resin which changes solubility due to an acid, and (b) a compound which generates an acid by radiation irradiation plus (c) a rust preventive agent, It can be either positive or negative. The following description will be made by taking an example of a negative-type enhanced chemical resist composition (a) a resin which changes alkali solubility due to an acid, and a chemical-type resist composition which is a negative type, (a) acid A resin which changes the alkali solubility (hereinafter referred to as a component (a)), and a resin which is reduced in alkali solubility by an acid is generally not used as a resin which is a base resin which is a negative-type chemically-resistant photoresist. It is particularly limited, and it can be used arbitrarily from the conventional materials in view of the light source used for exposure. For example, an acid aldehyde lacquer resin as a main component is generally widely used because of its good characteristics. The component (a) is particularly preferably selected from the group consisting of (a) g-formaldehyde lacquer resin and (b) one or more resins having a basic composition of a polymer such as 7C. Because it is easy to control the coating properties and development speed. (A) phenolic enamel resin (hereinafter referred to as (meth) component), for example, an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "benzene-9-(6) 1266145 phenol)") and an aldehyde It can be obtained by addition condensation condensation under an acid catalyst. In this case, examples of the phenol to be used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol. , p-butyrrol, 2,3-xylenol, 2,4-dimethylphenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-two Cresol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, gallicol , phloroglucinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, $-naphthol and the like. Further, examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like. < The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid or the like can be used as the acid catalyst. The above phenolic enamel resin is preferably a mass average molecular weight of from 3,000 to 10,000, preferably from 6,000 to 9000, more preferably from 7,000 to 8,000. When the mass average molecular weight is less than 30,000, the film tends to become thin after development, and when the mass average molecular weight exceeds 10,000, the residue tends to remain after development, which is not preferable. In the case of a polymer having a (i) hydroxystyrene structural unit (hereinafter referred to as a (B) component), for example, hydroxystyrene such as p-hydroxystyrene or α-methylhydroxystyrene may be mentioned. a radical polymer or an ionic polymer formed by a hydroxystyrene unit such as α-alkylhydroxystyrene or the like, or the above-mentioned hydroxystyrene constitutes a mono-10-(7) 1266145 Copolymers formed by other constituent units. The ratio of the hydroxystyrene constituent unit in the polymer is preferably 1% by mass or more, more preferably 10% to 30% by mass. When the ratio of the hydroxystyrene structural unit is less than 10% by mass, the developability is lowered and the resolution tends to be lowered. Further, the mass average molecular weight of the component (B) is preferably 500 or less, more preferably 2 to 4,000. In this system, when the mass average molecular weight exceeds 5,000, the resolution tends to decrease. The constituent unit (b) of the above (B) may contain a monomer which forms a constituent unit other than the constituent unit of the above hydroxystyrene. The monomer is preferably a monomer in which a hydroxyl group of a hydroxystyrene unit is substituted with another group or a monomer having a ?-unsaturated double bond. Other bases which may be substituted for the hydroxyl group of the above-mentioned hydroxystyrene structural unit ‘β is an alkali dissolution inhibiting group which is not dissociated by an acid. The base dissolution inhibiting group which is not dissociated by an acid may, for example, be a substituted or unsubstituted phenylsulfonyloxy 'substituted or unsubstituted naphthosulfonyloxy group, a substituted or unsubstituted phenylcarbonyloxy group, Substituted or unsubstituted naphthylcarbonyloxy group and the like. Specific examples of the substituted or unsubstituted benzenesulfonyloxy group include a phenylsulfonyloxy group, a chlorobenzenesulfonyloxy group, a methylbenzenesulfonyloxy group, and an ethylphenyloxy group. The propyl sulfonyloxy group, the methoxybenzenesulfonyloxy group, the ethoxy group wall oxy group, the propoxy sulfonyloxy group, the acetaminophen benzene sulfonyloxy group and the like are preferred. Specific examples of the substituted or unsubstituted naphthosulfonyloxy group, neatsyloxy, chloronaphthalenesulfonyloxy, methylnaphthalenesulfonyloxy, 2-methylsulfonyloxy-propyl Naphthalenesulfonyloxy, methoxynaphthalenesulfonyloxyethoxynaphthalenesulfonyloxy, propoxynaphthalenesulfonyloxy, acetaminonaphthalenesulfon-11. (8) 1266145 S-based oxygen Base is better. Further, in the above-mentioned examples, the substituted or unsubstituted phenylcarbonyloxy group and the substituted or unsubstituted naphthalenecarbonyloxy group are preferably those in which the substituted unsubstituted sulfonyloxy group is replaced by a mineral oxygen group. . Among them, an acetamidophenylsulfonyloxy group or an ethenylnaphthalenesulfonyloxy group is preferred. Further, specific examples of the monomer having a ^,/5-unsaturated double bond may, for example, be styrene, chlorostyrene, chloromethylstyrene, vinyltoluene or α-methylstyrene. Monomer, methyl acrylate, methyl bis-formic acid methyl ester, phenyl methacrylate acrylate monomer, acetic acid B _, φ benzoic acid ethylene and other vinyl acetate monomers, etc. good. a copolymer obtained from hydroxystyrene and styrene, for example, a poly(4-hydroxystyrene-styrene) copolymer, a poly(4-hydroxystyrene-methyl styrene) copolymer, etc., which can exhibit high At the same time as the resolution, the heat resistance is also high. Further, the component (a) may contain other resin components for the purpose of appropriately controlling physical and chemical properties. For example, a (propylene) propylene resin or a (butyl) vinyl resin can be exemplified. Φ (propylene) propylene-based resin: a propylene-based resin which is a component (c), and is not particularly limited as long as it is an alkali-soluble propylene-based resin, and particularly contains a constituent unit derived from a polymerizable compound having an ether bond. It is preferred that the constituent unit derived from the polymerizable compound having a carboxyl group is used. The polymerizable compound having an ether bond can be exemplified by 2-methoxyethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate -12- 0) 1266145 ester, 3-methoxy Butyl (meth) acrylate, ethyl carbitol (methyl) propyl acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, four a (meth)acrylic acid derivative such as hydroquinone (meth) acrylate or the like having an acid bond and an vinegar bond, preferably a 2-methoxyethyl acrylate or a methoxy triethylene group. Alcohol acrylate. These compounds may be used alone or in combination of two or more. Examples of the polymerizable compound having a carboxyl group include a monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid, a dicarboxylic acid such as maleic acid, fumaric acid or itaconic acid, and 2-methylpropene. Mercaptooxyethyl succinic acid, 2-methylpropenyl oxyethyl maleic acid, 2-methylpropenyl oxyethyl fumarate, 2-methylpropenyl oxyethyl A compound having a carboxyl group and an ester bond, such as hexahydrofumaric acid, is preferably acrylic acid or methacrylic acid. These compounds may be used alone or in combination of two or more. (butyl) vinyl resin: a (butyl) component vinyl resin, a poly(ethylene lower alkyl ether), an ethylene lower alkyl ether represented by the following general formula (I), or a mixture of two or more thereof obtained by polymerization Made of (co)polymer. Η C II 6 CIOIR Η N) / I—I / (\ (The above general formula (Ο, R6 represents a linear or branched bond of the carbon number 1 to 5). General formula (I) In the case of a linear or branched chain of -1 to 5 carbon atoms of 1 to 5, the alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an i-propyl group or an n-butyl group. i - butyl, n-pentyl, i-pentyl, etc. Among these alkyl groups, a methyl group, an ethyl group, an i-butyl group is preferred, and a methyl group or an ethyl group is preferred. Particularly preferred poly(ethylene lower alkyl ether), poly(vinyl methyl ether), poly(vinyl ethyl ether). Further, component (a) contains a mixed resin of (a) component and (b) component. In the case, the sum of the (a) component and the (b) component is 100 parts by mass, the (meth) component is 50 to 98 parts by mass, preferably 55 to 95 parts by mass, and the (b) component is 50 to 2 mass. The portion is preferably 45 to 5 parts by mass. (b) The compound which is produced by irradiation of radiation to the acid (b) component used in the present invention is an acid generator which can be directly or indirectly caused by light. The compound is not particularly limited, and specific examples thereof include 2,4-bis(trichloromethyl)-6-[2-(2-furanyl)vinyl]-s-three-plow, 2, 4 Bis(trichloromethyl)-6-[2-(5-methyl-2-oxafuryl)vinyl]-s-three tillage, 2,4-bis(trichloromethyl)-6-[2- (5-ethyl-2-furyl)vinyl]-s-trimorphine, 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furanyl)vinyl ]-s - three tillage, 2,4 double (trichloromethyl)-6 - [2 - (3,5-dimethoxyphenyl)vinyl])-s-three tillage, 2,4 pair (trichloromethyl)-6-[2 - (3,5-diethoxyphenyl)vinyl]-s-three tillage, 2,4-bis(trichloromethyl)-6-[2-( 3,5-dipropoxyphenyl)vinyl]-s-triazine, 2,4-bis-14-(11) 1266145 (trichloromethyl)-6-[2 - (3-methoxyl- 5-ethoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)vinyl] —s — three, 2 ,4-bis(trichloromethyl)-6-[2-(3,4-monomethylenedioxyphenyl)vinyl]-s-three-plowed, 2,4-bis(trichloromethyl)- 6-(3,4-methylenedioxyphenyl)-s-three tillage, 2,4-bis-trichloromethyl-6-(3-bromo-tetramethoxy)phenyl-s-three Plough, 2,4-bis-trichloromethyl- 6-(2-bromo-tetramethoxy)phenyl-s-trisyl, 2,4-di-mono-trichloromethyl-6-(2-bromo 4-1,4-methoxystyrylphenyl-s-three tillage, 2,4-bis-trichloromethyl-6-(3-bromo-tetramethoxy)styrenephenyl-s-three tillage ,2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)> 1,3 '5-three tillage, 2 —( 4 —methoxynaphthyl)-4,6 — double (trichloromethyl)-1,3,5-trimorphine, 2 —[2-(2-furyl)vinyl]- 4,6-bis(trichloromethyl)-1,3,5-three Plowing, 2-[2-(5-methyl-2-furanyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2 — [2— (3 ,5-dimethoxyphenyl)vinyl]-4,6 - bis(trichloromethyl)-1,3,5-three tillage, 2-[2_(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1 , 3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, three (1,3 -Dibromopropyl)-1,3,5-triazine, tris(2,3-dibromopropyl)-1,3,5-three tillage, etc., halogen-containing three-till compounds and three (2,3- Halogenated three-till compound -15- 1266145 of the following general formula of dibromopropyl)isocyanate

R3 丫, R2 Ο (wherein, R1 to R3 represent each, which may be the same or different, and the halogenated compound base) α - (p-toluenesulfonyloxyimino)-phenylacetonitrile, α - (benzene expansion醯-based oxyimino)- 2,4-dichlorophenylacetonitrile, α-(phenylsulfonyloxyimino)- 2,6-monochlorophenylethane, α-(2-chlorobenzenesulfonate)醯 methoxyiminoimido)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, a compound of the following general formula; [Chemical 3]

R4^c=no—so2r5 CN (wherein R4 represents a monovalent to trivalent organic group, R5 represents a substituted, unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, and η represents a nature of 1 to 3 The term "aromatic compound group" as used herein means a group of a compound exhibiting a specific physicochemical property in an aromatic compound, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group or a heterocyclic group such as a furyl group or a thienyl group. The ring may have one or more suitable substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group, etc. Further, R5 is particularly preferably an alkyl group having 1 to 4 carbon atoms, and may be exemplified as A- 16-(13) 1266145, ethyl, propyl, butyl. In particular, R4 is an aromatic compound group, and R5 is preferably a lower alkyl compound. In the above general formula, the acid generator is When n=l, R4 is a compound of a phenyl group, a methylphenyl group, a methoxyphenyl group, and R5 is a methyl group, and specifically, α-(methylsulfonyloxyimino group) ) 1-phenylacetonitrile, α - (methylsulfonyloxyimino)-1 mono(p-methylphenyl)acetonitrile, α — (Methylsulfonyloxyimino)-l-(p-methoxyphenyl)acetonitrile. When η=2, the acid generator represented by the above general formula may specifically be represented by the following chemical formula. Acid generator.) -17- 1266145 (14) [Chemical 4]

=N—Ο一S—CH3 d; N °2

C2H5—S—〇—N 〇2 =C—C=N-CN Ό Ό一 S~C2H5 〇2 C4H9—S—〇—N=C 〇2 *

;=N—〇~S—CF〇 iN

F〇C—S_O~N=C

i,N bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2, 4- dimethylphenylsulfonyl) diazomethane diazomethane such as diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrile N-toluenesulfonate, dinitrobenzyl tosylate, nitric acid sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate, etc.; ninthyl phenol trimethoprim (mesylate) ), gallic phenol trimethylbenzene-18-1266193137231 patent application Chinese manual revision page (15): sulfonate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxy amber Amine, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxybutylimide, N-methylsulfonyloxyphthalimide, etc. Sulfonate; N-hydroxyphthalimide, trifluoromethanesulfonate such as N-hydroxyphthalimide; diphenyl iodine hexafluorophosphate, (4-methoxyphenyl) Phenyl iodide Methanesulfonate, bis(p-tert-butylphenyl) iodine trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate , (for tertiary butylphenyl) diphenyl sulfonium trifluoromethanesulfonate and other key salts; benzoin tosylate, α-methylbenzoin tosylate and other benzoin tosylate; other In the case of the component (b) such as a diphenyl iodonium salt, a triphenyl sulfonium salt, a phenyldiazonium salt or a benzyl carbonate, the compounds may be used singly or in combination of two or more. In the composition of the present invention, the content of the component (b) is preferably in the range of from 1 to 20 parts by mass based on 1 part by mass of the component (a). When the content of the component (b) is less than 1 part by mass, the sensitivity is insufficient. When the content is more than 20 parts by mass, a uniform photoresist composition cannot be obtained, and the developability is also lowered. The content of the component (b) is preferably in the range of 5 to 15 parts by mass in consideration of sensitivity, uniformity and development of the photoresist composition, and the like. The metal rust agent of the component (c) is not particularly limited as long as it can prevent corrosion with respect to the metal atom used for the substrate or the wiring, but tributylamine can be suitably used. Pentylamine, benzotris-19- 1266145 (16) Benzene combined with J, 5 azoles} t

Formula I can be exemplified by the following formula: wherein R1 and R14 represent independently hydrogen atoms, substituted or unsubstituted hydrocarbon groups having 1 to 10 carbon atoms, carboxyl group, amino group, hydroxyl group, cyano group, methyl group, sulfonate. a mercaptoalkyl group or a sulfonyl group; Q may be a hydrocarbon group having a hydrogen atom 'hydroxyl group' substituted or unsubstituted and having 1 to 10 carbon atoms (however, the structure may have a mercapto bond, an ester Bonding), aryl, or representing the following formula (III) [Chem. 6] Κ:

Rj—Ν' r9 (III)

(In the formula (III), R7 represents an alkylene group having 1 to 6 carbon atoms; and R8 and R9 each independently represent a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group; a benzotriazole-based compound represented by the group]. The "hydrocarbon group" is an organic group formed by a carbon atom and a hydrogen atom. In the present invention, in the definition of the above-mentioned group Q, Ri3, and Rm, the hydrocarbon group may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, or may have a saturated or unsaturated bond, and may be a straight chain or a branch. Any of the chains. The substituted hydrocarbon group '-20- 1266145 (17) can be exemplified by, for example, a hydroxyalkyl group, an alkoxyalkyl group or the like.

Further, in the case of the substrate formed by C11, in the above general formula (Π), the Q is particularly preferably a group represented by the above formula (ΙΠ). Among them, in the formula (III), R8 and R9 are preferably selected from each other, and a hydroxyalkyl group or an alkoxyalkyl group having 1 to 6 carbon atoms is preferred. Further, in the case where at least one of R8 and R9 is an alkyl group having 1 to 6 carbon atoms, the physical properties of the benzotriazole-based compound having a relevant composition are such that the other component which dissolves the compound due to lack of water solubility is in the treatment liquid. The situation exists in the case and can be used properly. Further, in the above general formula (I), in the case of Q, those which exhibit water solubility can be suitably used. Specifically, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (that is, 'methyl, ethyl, propyl, isopropyl), a transalkyl group having 1 to 3 carbon atoms, a hydroxyl group, etc. In the case of having an inorganic material layer (for example, 'poly-cracked film, amorphous ruthenium film, etc.) on the substrate, it is preferable in terms of its corrosion resistance.

In the case of a benzotriazole-based compound, specifically, for example, benzotriazole, 5,6-dimethylbenzotriazole, fluorene monohydroxybenzotriazole, fluorene monomethylbenzopyrene, 1 Monoaminobenzotriazine, 1 phenylbenzotriazine, 1 monomethyl benzodiazole, 1 benzotriazole carboxylic acid methyl, 5-benzotriazole carboxylic acid, 1 A Oxygen-benzotriazole, 1-(2,2-dihydroxyethyl)-benzobisazole, 1-(2,3-dihydroxypropyl)benzotriazole, or "Ilkamate" series in Chiba Specially used by specialty chemical companies, for example 2'2~{[(4-methyl-1H-benzotriazole-!-yl)methyl]imino}diethanol, 2, wide -U(5-methyl-1H-benzodioxin-l-yl)methyl]imino}diethanol, 2, — {[(4-a-21 - 1266145 (18) yl- 1H- Benzotriazole-1-yl)methyl]imidopyridinium di-ethane, or 2,2 {[(4 monomethyl-1H-benzotriazol-1-yl)methyl]imido] Dipropane and the like. Among these, 1-(2,3-dihydroxypropyl)-benzotriazole, 2,2,-{[(4-methyl-1H-benzotriazol-1-yl)methyl] Imino]diethanol, 2,2-{{(5-methyl-1H-benzotriazol-1 mono)methyl]imino}diethanol can be suitably used. One type or two or more types of benzotriazole-based compounds can be used. In the above sulfur-containing compound, dithiodiglycerol [S (CH2CH(OH)CH2(OH)) 2], bis(2,3-dihydroxypropylthio)ethene [CH2CH2 (SCH2CH (OH) CH2) can be exemplified. ( OH ) ) 2],3 -(2,3 -dihydroxypropylthio)-sodium 2-methylpropanesulfonate [CH2 ( OH ) CH ( OH) CH2SCH2CH ( CH3 ) CH2S03Na], 1 -thioglycerol [HSCH2CH(OH) CH2 ( OH ) ], 3 - thiol-sodium 1-propane sulfonate [HSCH2CH2CH2S03Na], 2-thiol-ethanol [HSCH2CH2 (OH)], thioacetic acid [HSCH2C02H], and 3 —Hexylthio-1-propanol [HSCH2CH2CH20H], 1,3,5-three tillage-2,4,6-trithiol. Among these, 1-monothioglycerol, 1,3,5-three tillage-2,4,6-trithiol, thioacetic acid, and the like can be suitably used. One or two or more kinds of the components (c) can be used. The component (c) is preferably in the range of 0.01 to 5 parts by mass, more preferably in the range of 0.1 to 1 part by mass, per 100 parts by mass of the component (a). When the content of the component (c) is less than 〇. 质量1 parts by mass, there is a case where a high-precision photoresist pattern cannot be obtained, and when it exceeds 5 parts by mass, the adhesion between the photoresist pattern and the substrate is lowered. Hey. -22- 1266145 (19) In the case where the chemical-resistant resist composition is a negative type, in addition to the above components, a crosslinking agent is further contained. The crosslinking agent used in the present invention is not particularly limited, and a crosslinking agent for any of the well-known chemically-reactive negative-type photoresist compositions can be suitably used. For example, a melamine resin, a urea resin, a guanamine resin, a glycoluril-a waking resin, an amber amide-formaldehyde resin, an ethylene urea-formaldehyde resin, etc., but particularly an alkoxymethylation can be used. An alkoxymethylated amino resin such as a trihydroamine resin or an alkoxymethylated urea resin can be suitably used. The alkoxymethylated amino resin is, for example, a condensate obtained by reacting a polyamine or urea with a formalin in a boiling aqueous solution, such as methyl alcohol, ethyl alcohol, propanol, butanol or isopropanol. The lower alcohol is etherified, and then the reaction liquid is cooled and precipitated to be produced. In the above alkoxymethylated amino resin, specifically, a methoxymethylated melamine resin, an ethoxymethylated melamine resin, a propoxymethylated melamine resin, a butoxymethylated melamine resin, and the like may be mentioned. Oxymethylated® resin, ethoxymethylated urea resin, propoxymethylated urea resin, butoxymethylated urea resin. The alkoxymethylated amino resins may be used singly or in combination of two or more. In particular, the alkoxymethylated melamine lipoester has a small dimensional change with respect to the change in the amount of irradiation of the radiation, and is preferable because a stable photoresist pattern can be formed. Among them, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethyl t hydrazine polyamine resin and butoxymethylated melamine resin are preferred. The crosslinking agent is preferably contained in an amount of from 1 to 30 parts by mass based on 1 part by mass of the total of the components (a), (b) and (c). Crosslinking agent-23- 1266145 (20) When the amount is less than 1 part by mass, the plating resistance, chemical resistance, and adhesion of the obtained film may be lowered or the shape of the formed bump may be poor. When the amount exceeds 30 parts by mass, development failure occurs during development, which is not preferable. In the reinforced chemical-type resist composition of the present invention, an additive having a blending property, such as an additive resin for improving the performance of the photoresist film, a plasticizer, can be added in a range that does not impair the essential characteristics. , adhesive additives, stabilizers, colorants, surfactants and the like. Further, in the reinforced chemical resist composition of the present invention, an organic solvent can be suitably blended for viscosity adjustment. Specific examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, and the like; ethylene glycol, ethylene glycol monoacetate, Diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or Polyvalent alcohols such as monophenyl ether and derivatives thereof; dioxane-like cyclic ethers; and methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, ethyl pyruvate An ester of methyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate or the like. These may be used singly or in combination of two or more. The amount of the solvent used is, for example, a spin coating method, and in order to obtain a film thickness of preferably 20 // m or more, the solid content concentration in the reinforced chemical resist composition is from 30% by mass to 65% by mass. The range is good. In the case where the solid content concentration is less than 30% by mass, it is difficult to obtain an appropriate thick film in the production of the terminal for connection. When the content exceeds 65 mass%, the composition of the composition -24-1266145 (21) is significantly deteriorated. In the processing difficulty, a uniform photoresist film cannot be obtained by the spin coating method. Next, an example of a positive-type enhanced chemical resist composition will be described. 增强 A chemical-type resist composition is a positive type, and a crosslinking agent is not required. Further, (the bismuth component and the (c) component are the same as the negative one, and the component (a) is a resin which can improve the alkali solubility due to the acid. The component (a) can generally be used as a positive type to enhance chemical chemistry. The resin used for the base resin of the type of photoresist is not particularly limited, and can be used arbitrarily according to the light source for exposure, for example, a propylene resin as a main component and at least a part of a hydroxyl group thereof. An alkali-dissolving inhibitor-substituted material which may be dissociated by an acid or a polymer having a hydroxystyrene structural unit as a main component, and at least a part of a hydroxyl group thereof may be substituted by an alkali-dissolving inhibiting group which is dissociated by an acid. In terms of the component (a), it may be composed of a polymer having a (i) hydroxystyrene constituent unit similar to the above negative type, and a resin selected from the group consisting of a (propylene) propylene resin, and a hydroxyl group thereof. At least one part can be exemplified by a base dissolution inhibiting group which is dissociated by an acid. This is because the coating speed is controlled, and the development speed is easy. In the dissolution of the alkali due to the action of acid The base group may, for example, be a tertiary alkyloxy group selected from a tertiary butoxy group, a tertiary pentyloxy group or the like; a cyclic acetaloxy group such as a tetrahydropyranyloxy group or a tetrahydrofuranyloxy group; a chain acetaloxy group such as ethoxyethyloxy or methoxypropoxy; a cyclohexyloxy group of cyclohexyloxy, cyclopentyloxy-25-(22) 1266145; 1-methyl a mono-alkyl-cycloalkyloxy group such as a cyclohexyloxy group, a 1-ethylcyclohexyloxy group, a 1-methyladamantyloxy group, a 1-ethyladamantyloxy group or the like, and an alkyl group. Further, at least one of a polycycloalkyloxy group and the like is preferable. Further, the component (a) may be appropriately controlled by physical and chemical properties, and may contain other resin components. For example, the above-mentioned components may be mentioned. (A) phenolic enamel resin, (butyl) vinyl resin in the above negative examples, the cross-linking agent and (a) component, (b) component and (c) component, other components may be The reinforced chemical resist composition of the present invention is not particularly limited as long as it is on the support, but is preferably 20//m or more, more preferably 20 to 150//m. It is suitable for the formation of a photoresist layer of 30 to 120 / / m, and particularly preferably a film thickness of 55 to 75 / / m. Further, since the photoresist composition contains a rust inhibitor, it is particularly at least It is suitable to form a photoresist layer on one of the surface of the side using a copper support. φ Next, the photoresist layer lamination system of the present invention is coated on the support with the above-mentioned enhanced chemical type photoresist composition. The support layer is not particularly limited, and a conventional one can be used, and examples thereof include a substrate for an electronic component or a shape formed by a predetermined wiring pattern. For example, a metal substrate such as ruthenium, tantalum nitride, titanium, molybdenum, palladium, titanium tungsten, copper, chromium, iron, or aluminum, or a glass substrate can be used. For the material of the wiring pattern, for example, copper can be used. Tin, chrome, aluminum, -26- 1266145 (23) Nickel, gold, etc. In particular, in the case of a substrate or a wiring pattern or the like, copper is used in a part of the surface of at least the upper side of the support, and it is known that the effect of the enhanced chemical resistance of the contact portion with the copper is hindered by copper. A development defect is generated in a part of the film, and a rust inhibitor is added to obtain a stable photoresist layer laminate, and a good development profile can be obtained. In the preparation of the chemistive resistive composition of the present invention, for example, the above components may be mixed not only by a usual method, but also by a dissolver, a homogenizer, a roll mill, or the like. The disperser is dispersed and mixed. Further, after mixing, a sieve, a membrane filter or the like is further used for filtration. The photoresist layer laminate of the present invention can be produced, for example, in the following manner. Namely, a solution of the enhanced chemical resist composition prepared as described above is applied onto a substrate, and the solvent is removed by heating to form a desired coating film. As the coating method on the substrate to be processed, a method such as a spin coating method, a roll coating method, a mesh printing method, or a coater method (a p p i i c a t 〇 r) method can be employed. The prebaking conditions of the coating film of the composition of the present invention differ depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but are usually 70 to 130 ° C, preferably 80 to 120. °C, about 2~60 minutes. The film thickness of the photoresist layer is not particularly limited, but is preferably 20 // m or more, more preferably 20 to 150/m, still more preferably 30 to 120 #m, and still more preferably 55 to 75 / The range of /m is expected. When the photoresist layer laminate thus obtained is used to form a photoresist pattern, for example, in the case of using a negative-type enhanced chemical type photoresist, the obtained light -27-1266145 (24) resist layer is transmitted through the predetermined pattern. A type of reticle that selectively illuminates (exposed) radiation, such as ultraviolet light or visible light having a wavelength of 3 5 0 to 500 nm. In terms of the source of such radiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, gas-gas lasers, and the like can be used. Here, the term "radiation line" means ultraviolet light, visible light, far ultraviolet light, X-ray, electronic wire, etc. The amount of radiation exposure may vary depending on the type of each component in the composition, the film thickness of the coating film, and the like, for example, in the case of using an ultrahigh pressure mercury lamp, it is 1 0 0 to 2 0 0 m J / c. M2. Then, after the exposure, heating by a known method promotes the generation and diffusion of the acid, and the alkali solubility of the exposed photoresist layer can be changed. Next, for example, a predetermined alkaline aqueous solution is used as a developing solution, and an unnecessary portion is dissolved and removed to obtain a predetermined photoresist pattern. As the developer, an aqueous solution of a base such as sodium hydroxide or potassium hydroxide can be used. Further, an aqueous solution containing a water-soluble organic solvent such as methanol or ethanol or an appropriate amount of a surfactant may be used as a developing solution in the aqueous solution of the above-mentioned base. The development time varies depending on the type and composition ratio of each component of the composition, and the dry film thickness of the composition varies, but it is usually 1 to 30 minutes, and the development method can be a spin method, a dipping method, a dipping method, a spray developing method, or the like. Any of them. After development, it is washed with running water for 30 to 90 seconds, and it can be dried using an air gun or an oven. Then, in the non-resistance portion (the portion removed by the alkali developing solution) of the photoresist pattern thus obtained, for example, a conductor such as a metal can be buried by electroplating or the like, and 28-(25) 1266145 can be formed to form a metal cylinder. Or a terminal for connection such as a bump. The size of the non-photosensitive portion in which the terminals for connection are formed is preferably 5 to 200 / / m in width and 10 to 200 / / m in depth. According to the composition of the present invention, a photoresist pattern having an aspect ratio of 2 or more can be formed favorably, whereby a non-resistive pattern having an aspect ratio of 2 or more can be formed. If the composition of the present invention is used, it is also possible to form a photoresist pattern having an aspect ratio of 1 及 and a non-resistive pattern formed therefrom. The formation of the non-resistive part of the size of 2 5 // m or so is not to add a rust preventive agent as it is intended, and it can also form a highly practical thing, such as the above-mentioned high-precision width and height. The non-resistive part cannot form a practical thing in a conventional method. However, in this case, the formation of the high-precision non-resistive portion can be achieved by the use of a rust preventive. Further, the plating treatment method is not particularly limited, and various conventional methods can be employed. In the case of electroplating solutions, especially solder plating, copper plating solutions can be used just right. The residual photoresist pattern is finally removed by using a stripping solution or the like according to a certain method. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples. The resin component was synthesized in accordance with the following synthesis examples. [Synthesis Example 1] Synthesis of <(A-1) phenolic enamel resin> -29- (26) 1266145 Mix m-cresol with p-cresol at a mass ratio of 60:40, add formaldehyde water, use The oxalic acid catalyst is condensed according to a conventional method to obtain a cresol novolac lacquer resin. The fractionation treatment was carried out with respect to this resin, and the low molecular field was cut to obtain a phenolic enamel resin having a mass average molecular weight of 8,000. This resin was made into (A - 1 ). [Synthesis Example 2] <Synthesis of a polymer having (A-2) hydroxystyrene constituent unit> A flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank was replaced with nitrogen, and then charged as a solvent of propylene glycol A. The base ether acetate was stirred. Thereafter, &lt;, the temperature of the solvent was raised to 80 °C. 2' 2 &gt; - azoisobutyronitrile was placed in the dropping polymerization catalyst, and the constituent unit was charged. The hydroxystyrene unit was 75 mass% and the styrene unit was 25 mass%, and the polymerization catalyst was stirred until dissolved. Thereafter, the solution was uniformly dropped in the flask for 3 hours', followed by polymerization at 80 ° C for 5 hours. Thereafter, the mixture was cooled to room temperature to obtain a resin which was a component (A). The resin was subjected to a fractionation treatment to obtain a resin having a mass average molecular weight of 3, yttrium (A-2). [Synthesis Example 3] Synthesis of <(A - 3 ) propylene-based resin> In addition to the constituent unit system, 2-methoxyethyl acrylate 130 parts by mass of 'benzyl methacrylate 5 parts by mass, and acrylic acid 20 mass Parts -30- 1266145 (27) Other than the same as in Synthesis Example 2, a resin (A-3) having a mass average molecular weight of 20,000 was obtained. [Synthesis Example 4] <Synthesis of (A-4) Vinyl Resin> A methanol solution of poly(ethyl methacrylate) (mass average molecular weight: 50,000) (manufactured by Tokyo Chemical Industry Co., Ltd., concentration) using a rotary evaporator 50% by mass) was subjected to solvent substitution in propylene glycol monomethyl ether acetate to obtain a solution (A - 4 ) having a concentration of 50% by mass. [Synthesis Example 5] <(A-5) Synthesis of Resin which Increases Solubility to Alkali by Effect of Acid> In addition to the constituent unit, adamantane acrylate constituent unit 50% by mass, and 2-ethoxyB A resin (A-5) having a mass average molecular weight of 25,000 was obtained in the same manner as in Synthesis Example 2 except that the acrylate structural unit was 50% by mass. [Examples 1 to 9] [Comparative Example 1] <Adjustment of Reinforcing Chemical Type Photoresist Composition for Thick Film> After each component shown in Table 1 was mixed with propylene glycol monomethyl ether acetate to form a homogeneous solution, Filtration was carried out through a membrane filter having a pore size of 1 // m to obtain a chemically-enhanced positive photoresist composition for a thick film. Further, the contents of the symbols of the respective components shown in Table 1 are as follows. -31 - 1266145 (28) (B - 1 ): Compound represented by the following chemical formula [Chemical 8] C4H9 -S-〇-N = = N -〇-^- G4H9 °2 CN\^ CN °2 (C — 1) 1,3,5 - three tillage 2,4,6-trithiol (C-2) 1 -thioglycerol (C-3) tripentylamine (D-1) crosslinker: hexamethoxy The hydrazine triamine (trade name: Nikaluck Mw-100, manufactured by Sanwa Chemical Co., Ltd.) The following evaluation was carried out on the obtained chemically-resistant positive-type photoresist composition for thick film. • The photosensitive film is formed on a wafer of 5 inches in thickness, and a film having various film thicknesses is formed. The pattern for resolution measurement is transmitted through the mask, and a stepper (NSR-2005ilOD, manufactured by Nikon Co., Ltd.) is used at 100 to 1 The range of 0,000 mJ/cm2 is divided and exposed. This was developed with a developing solution (trade name: PMER series, P-7G, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Thereafter, it was washed with running water, and nitrogen gas was blown to obtain a pattern-like cured product. This was observed by a microscope to form a pattern having an aspect ratio of 2 or more, and the exposure amount of the residue could not be determined, that is, the exposure amount necessary for the formation of the pattern. Developability - 32 - 1266145 (29) Using a rotator on a 5 inch copper sputter wafer, the composition was applied to a film thickness of about 20/m, and applied at 1800 rpm for 25 seconds, at 1 1 〇 ° C, pre-baked on the hot plate for 6 minutes to form a thick film photoresist laminate. A photoresist laminate having a coating film having a film thickness of about 65 // m was formed in the following manner. The film was applied at 800 rpm for 25 seconds, pre-baked on a hot plate at 110 Torr for 1 minute, and further coated at 800 rpm for 25 seconds, and then pre-baked at 12 ° C for 12 minutes to form thick film light. The barrier layer is combined. Further, a photoresist laminated system having a coating film having a film thickness of about 120 / / m was formed as follows. After coating at 800 rpm for 25 seconds, pre-bake 1 minute on a hot plate at 10 ° C, and then 25 seconds at 500 rpm, pre-bake 1 minute on a hot plate at 110 ° C, and then at 5 After 20 seconds of coating at 00 rpm, 20 minutes pre-baking was performed at 110 ° C to form a thick film photoresist laminate. The thick film resist laminate obtained above was passed through a mask using a stepper (NSR-2005ilOD, manufactured by Nikon Co., Ltd.), and each of the layers was passed through a mask at a range of 100 to 10,000 mJ/cm 2 . UV exposure. After the exposure, the mixture was heated at 70 ° C for 5 minutes, and developed with a developing solution (trade name: PMER series, P-7G, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Thereafter, it was washed with running water and subjected to nitrogen blowing to obtain a patterned cured product. This was examined by a microscope, and the development and resolution were determined by the following evaluation criteria. A: A pattern having an aspect ratio of 2 or more is formed by the exposure amount of any of the above-mentioned cases where the residue cannot be determined. C: The pattern with an aspect ratio of less than 2 does not form 'or the residue is identified as -33-1266145 (30). In addition, the aspect ratio is displayed (the height of the photoresist on the pattern + the width of the photoresist on the pattern). • The resist shape has a substrate having a patterned cured product obtained by "developing and resolution evaluation" as a test piece, and the state of the patterned cured product formed on the test piece is observed, and the pattern-shaped cured product is observed. The shape was judged by the following evaluation criteria: 矩形A: Rectangular photoresist pattern is available. B: A rectangular photoresist pattern having only an inverse tapered shape is available. C: Rectangular photoresist pattern is not available. • Shading The pattern-shaped cured product was formed on the copper sputtering crystal circle in the same manner as in the "development and resolution evaluation", and the shape of the photoresist pattern was visually observed. A: A photoresist pattern can be formed. C: Residual film is produced. The examples of the examples 1 to 9 and the photoresist composition prepared in the comparative example were evaluated by the respective tests described above. The result is shown in 袠2. Further, in Example 3, the film thickness change was evaluated. -34- (31) 1266145 [Table 1] (Unit: parts by mass) Example Comparative Example 1 2 3 4 5 6 7 8 9 1 A- 1 90 70 70 70 70 70 60 70 A-2 20 20 20 20 20 90 10 20 A-3 10 A-4 10 A-5 100 B-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 C- 1 0.3 0.1 0.3 1 0.3 0.3 0.3 C-2 0.3 C-3 0.3 D- 1 10 10 10 10 10 10 10 10 10 -35- (32) 1266145 Comparative Example 'Ο 1 1 1 实施 Example ON ιη 3000 &lt;&lt;&lt; 00 ν〇1000 &lt;d &lt;&lt; Ό 1000 &lt;&lt;&lt; Ό 1000 &lt;&lt;&lt; νο 1000 &lt;&lt;&lt; 寸 ν〇1000 &lt;&lt;&lt; m rH 1500 &lt; m &lt; (T) Ό 1000 &lt;&lt;&lt; cn &lt;&lt;&lt;&lt; τ-Η ν〇1000 &lt;&lt;&lt; Film thickness sensitivity (mJ/cm2) developable resist shape HD &lt;

-36- (33) 1266145 It is understood from the results of Table 2 that in the examples relating to the present invention, any of the evaluations was good. [Industrial Applicability] As described in detail above, according to the present invention, there is provided a stable chemical-resistant resist composition which does not change in alkali solubility before irradiation of radiation, and a photoresist composition layer The photoresist layer laminate to be used in the support, the photoresist pattern manufacturing method and the terminal manufacturing method for the connection are used. Therefore, the present invention is extremely useful industrially.

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Claims (1)

(1) 1266145 X. Patent application scope 1. A chemical-reinforcing photoresist composition characterized by containing (a) a resin which changes alkali solubility due to an acid, and (b) an acid generated by radiation irradiation. Compound and (c) rust inhibitor. 2. The reinforced chemical-type resist composition according to claim 1, wherein the support is a thick film resist layer having a thickness of 20 to 150/m. The reinforced chemical resist composition according to the first aspect of the invention, wherein the (C) rust inhibitor is selected from the group consisting of an aromatic hydroxy compound, a benzotriazole compound, and a triterpenoid compound. And one or more kinds of sulfur compounds. 4. The reinforced chemical resist composition according to claim 3, wherein the '(C) rust inhibitor is selected from the group consisting of tributylamine or triamylamine, 1 thioglycerol, 1, 3 One or more of 5 - tris - 2, 4, 6 - trithiol. 5. The reinforced chemical resistive composition according to claim 1, wherein the user of the photoresist layer is formed on the support of copper on at least a portion of the upper surface. 6. A photoresist layer laminate comprising: a support, and a reinforced chemical resistive composition according to any one of claims 1 to 5 Resistance layer. The method for producing a chemistive-type resist composition according to any one of claims 1 to 5, wherein (a) a resin which changes alkali solubility due to an acid' (b) is irradiated Wire-irradiated compounds -39-1266145 (2) and (c) anti-emulsions are mixed. 8. A method for producing a photoresist pattern, comprising: affixing a chemistive resist composition according to any one of claims 1 to 5 to a support to obtain a photoresist The laminating step of the layer laminate is the same as the exposure step of selectively irradiating the radiation in the photoresist layer laminate, and the developing step after the exposure step to obtain a photoresist pattern. A method for producing a terminal for connection, which comprises forming a terminal for connecting a conductor by using a non-resistive portion of a photoresist pattern obtained by the method for manufacturing a photoresist pattern according to claim 8 of the patent application. The steps. 10. The method of manufacturing a terminal for connection according to claim 9, wherein the aspect ratio of the photoresist portion is 2 or more. -40-