TW200916607A - Corrosion inhibitors or strippers containing substituted ketones or derivatives thereof and process for production of the same - Google Patents

Abstract

A corrosion inhibitor containing a substituted ketone capable of exerting high corrosion-inhibiting effect even against easily corrodible metals such as copper or a derivative of the ketone; an anticorrosive treatment fluid or anticorrosive preservation fluid, prepared by using the corrosion inhibitor; a corrosion -inhibiting resist stripper which contains both the ketone and a compound having resist stripping performance; and a resist stripping fluid prepared by using the stripper. The substituted ketone or derivative thereof according to the invention exhibits high corrosion-inhibiting effect even against highly corrodible metals such as copper and can be recovered from the waste liquor after use.

Description

200916607 IX. Description of the invention: H. The invention relates to an anti-Ivory 5 agent containing a substituted ketone compound or a derivative thereof, and an anti-corrosion treatment liquid or an anti-corrosion preservation solution which can be prepared by the anti-corrosion agent The substituted ketone compound is a compound which exhibits a high anticorrosive effect on a corrosive metal such as copper. Further, the corrosion inhibitor, the anticorrosive treatment liquid or the antipreservation solution of the present invention has an excellent feature of easily recovering the substituted ketone compound or a derivative thereof from the waste liquid as needed. The present invention further relates to a photoresist release agent having corrosion resistance or a photoresist release liquid which can be prepared from the release agent, which contains the compound and a compound having photoresist peeling properties. BACKGROUND OF THE INVENTION 15 pastes, 'copper, such alloys are widely used in forming electricity

The material is a metal film or a metal circuit in a process such as a wafer, a printed circuit board, or a liquid crystal material. Among the materials of the metal film and the metal wiring, for example, copper has an excellent resistance to electromigration and a low electrical resistance, and the value is relatively easy to oxidize and has a property of being perishable. , (4) The corrosion of the circuit will increase the resistance of the circuit. In order to prevent this phenomenon, it can be used for the insertion of + _, the formation of the circuit (especially the metal film and metal on the semiconductor integrated circuit, which belongs to the circuit) The anti-surname technology that forms the step) has received attention in recent years. Therefore, the corrosion inhibitor itself is required to have sufficient corrosion resistance under the various processes and conditions of use. For example, in the photo-resistive peeling step in the case of producing a printed circuit board, after the through-hole is formed by dry etching or the like on the metal film, the new metal circuit formed is simultaneously prevented in the step of removing the etching residue or the like ( In particular, copper circuits) corrosion is still an important technical issue. Heretofore, the use of a photoresist release agent having a compound having an anticorrosive property has been used as an improvement method of the above problems. Among the compounds exhibiting such anti-surname properties, for example, organic compounds such as aromatic hydroxy compounds such as hydroxybenzoic acid, carboxyl group-containing organic compounds such as acetic acid, citric acid, and succinic acid, and benzotriazole (BTA) Etc. has been used so far (for example, refer to the patent literature). Among them, benzotriazole is known to have strong coordination with metals and has excellent corrosion resistance. For example, 'there are reports that it is used in chemical mechanical polishing (CMP) processes, etc. Patent Document 2 and Patent Document 3). However, due to the increased ambition to reduce the environmental burden in recent years, chemical safety and waste reduction have been required for the waste liquid and waste of the factory. In particular, the CMP process will produce a large amount of waste liquid, which must be fully considered. 20 For example, the above-mentioned waste liquid treatment method is preferably isolated and recovered by distillation and liquid separation of waste liquid, or may be decomposed by microorganisms such as decomposing bacteria and treating bacteria, but the aforementioned benzotriazole and the like are known. Derivatives are difficult to recover from waste liquids and are difficult to biodegrade, and the current situation still has to rely on complicated and costly treatment methods. 200916607 On the other hand, for example, when the aromatic hydroxy compound and the carboxyl group-containing organic compound are used as an anticorrosive agent for a semiconductor device process, they may be separated and discharged from the discharged waste liquid and waste. Or distillation and other methods to isolate the shouting 'If you can reuse it, you can greatly reduce (10) the amount of discarded material and the amount of anti-corrosion agent. That is, compared with benzotriazole which is difficult to recover from waste liquid treatment, such soil use can be said to be excellent in reducing the environmental burden. On the contrary, even from the conventional anti-mystery An aromatic radical-based compound or an organic compound having a few groups or the like prepares a photoresist stripper and is similarly used in a process, and it is difficult to be sufficient for a metal such as copper which is highly venomous. (Patent Document 1) Japanese Laid-Open Patent Publication No. Hei. No. 3 (Patent Document 2) Japanese Laid-Open Patent Publication No. 3 (Patent Document 3) Japanese Patent Laid-Open No. 7〇9 Bulletin 15 [In the month of the month] 20 doses or = ::::provided; can be used from waste - stripping agent =::::: for a kind of photoresist with anti-pure energy containing the pottery and light called photoresist - the case Mao Ming people continue to study for the above purpose As a result, it was found that a substituted ketone compound represented by Formula 7 200916607 (Al), Formula (B1) and Formula (Cl) and/or a derivative thereof is a metal film, a metal circuit or the like which is composed of copper, aluminum or the like. The rot of the special metal article has an excellent anti-surname effect, and the present invention is finally completed.

Wherein R1 is a hydrocarbon group optionally having a substituent; R2&R3 is a hydrogen atom, a pixel atom or an optionally substituted hydrocarbon group; and R2 may optionally be bonded to R3 to form a ring of 4 to 6 membered rings. Further, R5 is a hydrocarbon group optionally having 10 substituents.

Wherein R 1 is an optionally substituted hydrocarbon group; R 2 and R 3 are a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group; further, R 2 may be bonded to R 3 to form 3 to 6 members. a cyclic structure of a ring; R6 is a hydrogen atom or a nicotinyl group optionally having a substituent; n = an integer of 2-6. <化3>

(C1) R6 wherein 'R1 is an optionally substituted hydrocarbon group; R2 is a hydrogen atom, 2〇 halogen atom or a hydrocarbon group optionally having a substituent; further, R6 is a hydrogen atom or may optionally have a substituent Hydrocarbyl group. For example, the substituted ketone compound of the formula (1) of the present invention and its derivative 200916607 are used for processing a metal film metal circuit composed of copper, aluminum or alloys such as a semiconductor integrated circuit or a printed circuit board. Or when the composition contains one or more of copper and aluminum, it exhibits an excellent anti-corrosion effect. Therefore, the compound is suitably used as an anticorrosive agent and an anticorrosive treatment liquid using the same as 5 and an anticorrosive preservation solution. Further, 'for example, the substituted ketone compound of the present invention and its derivative can be prepared by mixing with a compound having a photoresist stripping property such as an alkanolamine (e.g., 2-aminoethanol) to have both corrosion resistance and The photoresist stripper having a photoresist stripping property can further prepare a photoresist stripping solution using the same; for example, in a photoresist stripping step when the substrate is used as a printed circuit board, thereby imparting a newly formed metal Excellent corrosion resistance of film or metal circuits. [Embodiment] The preferred embodiment of the present invention &lt;Aspect A: 10,000-i homo-ester compound&gt; 15 The derivative of the substituted ketone compound of the present invention which exhibits an anti-surrogate effect is exemplified by the following formula (A1) Lu-ketoester compound. <Chemical Formula 4> R1&gt;^^or5 (A1) wherein R 1 is an optionally substituted hydrocarbon group; R 2 and R 3 are a hydrogen atom 2 oxime, a _ atom, and optionally a hydrocarbon group; R 2 Optionally, it may be bonded to R to form a cyclic structure of a 4- to 6-membered ring; further, R5 is a hydrocarbon group optionally having a substituent. In the above formula, R1 is a hydrocarbon group which may have a substituent. The hydrocarbon group in R1 may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentylene group, a linear alkyl group having 1 to 2 carbon atoms such as a hexyl group or a hexyl group, or a branch having 3 to 12 carbon atoms. a linear alkyl group having 2 to 1 ring carbon atoms such as a chain alkyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group, which have an atomic number of 3 to 12, such as a cycloalkyl group, a vinyl group, an allyl group and a propenyl group; , isopropenyl, isoprenyl, and geranyl, such as a branched alkenyl group having 3 to 12 carbon atoms, a cyclopentenyl group, a cycloalkenyl group, and a cyclopentenyl group. An aliphatic group having 3 to 12 carbon atoms and an alkynyl group having 2 to 9 carbon atoms such as an ethynyl group and a propargyl group; an aromatic aliphatic group having 7 to 18 carbon atoms such as a benzyl group; An alkyl group (aralkyl group); and an aromatic group such as a stupid group, a phenyl group, and a naphthyl group. In addition, such groups contain various isomers. 10 The hydrocarbon group may optionally have a substituent. Examples of the substituent include a dialkylamino group having a carbon number of 丨~6 such as a fluorine atom and a gas atom, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a nitro group, a cyano group, and a dimethylamino group. An alkoxy group having 1 to 6 carbon atoms such as an oxy group, an ethyl sulfonyl group or the like, which is bonded to the alkyl group to form a carbonyl group, an alkoxycarbonyl group having 6 or more carbon atoms such as a methoxycarbonyl group, and a carbon atom number of 15 1 . ~6 of the burnt stone to buy sulfhydryl groups such as sulfhydryl and methylthio groups having 1 to 6 carbon atoms. Further, the substituents may have more than one or more of the hydrocarbon groups, but the total number of carbon atoms of the compound of the formula (A1) is preferably not more than 36 in consideration of the balance between fat solubility and water solubility. The tobacco group of R1 is preferably a linear alkyl group, a branched alkyl group, and a cycloalkanyl group, the aforementioned alkynyl group, a pro-arylene group, a phenyl group and a naphthyl group, and more preferably a linear chain having 1 to 6 carbon atoms. An alkyl group, a branched alkyl group having 3 to 6 carbon atoms, and a cycloalkyl group, an ethynyl group, a propargyl group, a benzyl group, a phenyl group and a naphthyl group. Further, the hydrocarbon group of 'R1 may optionally have a substituent. The substituent of Ri is preferably a halogen atom, a hydroxyl group, the above alkoxy group, the aforementioned dialkylamino group, the aforementioned 200916607 alkanesulfonyl group, the above-mentioned pendant oxy group and the aforementioned alkoxycarbonyl group, more preferably a fluorine atom, a gas atom or a hydroxyl group. , methoxy, dimethylamino, methanesulfonyl, 2-oxoxypropyl and iota-(indolylcarbonyl)methyl. Further, R1 may optionally be bonded to R2 or R3 to form a ring-like structure of 3 to 6 membered rings. Among the compounds represented by the formula (A1), such a compound may, for example, be ethyl 2-cyclohexanonecarboxylate. In the formula, R2 and R3 are a hydrogen atom, a halogen atom or a hydrocarbon group which may optionally have a substituent. Further, the substituent of the hydrocarbon group in R2 and R3 is synonymous with the above. Further, R2 may optionally be bonded to R3 to form a cyclic structure of a 3- to 6-membered ring such as a three-membered ring (cyclopropyl group) and a six-membered 10-ring (cyclohexyl group). The hydrocarbon group of R2 and R3 is preferably a hydrogen atom, a fluorine atom, the above linear chain, a branched alkyl group, a cycloalkyl group, the aforementioned alkynyl group, the aforementioned aralkyl group, a phenyl group, a naphthyl group, and a combination of R2 and R3. Cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. In the above, R2 and R3 are more preferably a hydrogen source, a fluorine atom, a linear alkyl group having 1 to 4 carbon atoms, a branched or cyclic alkyl group having 3 to 4 carbon atoms, or an ethynyl group. , propargyl, benzyl, phenyl, naphthyl and cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups of R2 and R3, and with a hydrogen atom, a methyl group, an ethyl group, a benzyl group and a combination R2 It is preferably a cyclopropyl group or a cyclobutyl group of R3. Further, the hydrocarbon group of r2 &amp; r3 may optionally have a substituent. The substituent of R3 and R4 is preferably a aryl atom, a hydroxy group, the aforementioned alkoxy group, the aforementioned dialkylamino group, the above-mentioned alkanesulfonyl group, the above-mentioned pendant oxy group, and the above alkoxycarbonyl group are more preferably a fluorine atom or a gas atom. Hydroxy, methoxy, dimethylamino, methanesulfonyl, 2-oxooxypropyl, methoxycarbonylindenyl. 11 200916607 wherein R is a hydrocarbon group synonymous with R1. In the above, R5 is preferably an aliphatic group and a phenyl group, more preferably an alkyl group having 1 to 6 carbon atoms and a stupid group. The formula (A1) of the present invention is as follows: "Qi/3" ketoester compound can be used as it is, and if it is not commercially available, the ketone-based brewing compound can be produced as disclosed in JP-A-2000-143590. Further, the 2-position modification of the scallops can be carried out as needed. For example, refer to Buii ρη'. The 2-position modified compound of the 3-keto-based compound was obtained by the method of 1.62, 4G72 (1989) and the like. 10 is as shown in the above formula (A1) which can be used as the anti-adhesive agent of the present invention; and the S-mercaptoester compound can be exemplified as follows. 3-sided oxy-butyrate, 3-formoxy-valerate, 3-oxo-hexanoic acid S曰, 3-sided oxy-heptanoate, 3-tert-oxyoctanoate, 3_sideoxy-phthalic acid ester, 3-sided oxy-phthalic acid ester, 3-sideoxy-deca-ester, 3-sideoxy-dodecanoic acid 15 §曰, 3_phenyl side oxygen -propionate, 4-phenyl-3-oxo-butyrate, 3-naphthyl-3-oxo-propionate, 4-naphthyl_3_sideoxy-butyrate ; 2 - methyl winter side oxy-butyric acid s, 2 - methyl _ 3 phenyl _ 3 side oxy propionate vinegar, 2 - methyl - 4 - phenyl - oxo - butyl Acid ester, 2,2-diindolyl_3_sideoxy-butyrate, 3-phenyl-2,2-dimethyl-3_sideoxy-propionate, 2,2-dimethyl Base_4_20 phenyl-3-sideoxy-butyric acid vinegar, 2-membered winter side oxy-butyric acid vinegar, 2-membered phenyl phenyl-3-oxo-propionate, 2_ Benzyl_4_phenyl_3 oxo-butyrate, 2,2-dihexyl-3- oxo-butyric acid, 2,2-di-2-yl phenyl winterside oxy- Propionate, 2,2-dibenzyl-4-yl-3-yloxy-butyrate; 3-(2-hydroxyphenyl)-3-oxo-propionate, 4-(2) _hydroxyphenyl)_3_sideoxy-butyric acid 12 200916607 ester, 2-methyl-3-(2-hydroxyl Phenyl)-3-oxo-propionate, 2-mercapto-4-(2-hydroxyphenyl)-3-butyrate, 2-benzyl-3-(2-hydroxyphenyl)- 3-sided oxy-propionate, 2-benzyl-4-(2-hydroxyphenyl)-3-oxo-butyrate; 3-(3,4-dihydroxyphenyl)-3- Sideoxy-propionate, 4-(3,4-dihydroxyphenyl)-3-oxo-5-butyrate, 2-methyl-3-(3,4-dihydroxyphenyl)- 3-sided oxy-propionate, 2-methyl-4-(3,4-dihydroxyphenyl)-3-oxo-butyrate, 2-benzyl-3-(3, 4- Dihydroxyphenyl)-3-oxo-propionate, 2-benzyl-4-(3,4-dihydroxyphenyl)-3-oxo-butyrate; 3-(3-oxime Oxy-4-hydroxyphenyl)-3-oxo-propionate, 4-(3-methoxy-4-hydroxyphenyl)-3-oxo-butyrate, 2-methyl-10 3-(3-methoxy-4-hydroxyphenyl)-3-oxo-propionate, 2-methyl-4-(3-indolyl-4-hydroxyphenyl)-3 - pendant oxy-butyrate, 2-benzyl-3-(3-decyloxy-4-hydroxyphenyl)-3-oxo-propionate, 2-benzyl-4-(3-曱oxy-4-hydroxyphenyl)-3-oxo-butyrate; 3-(3,4-dimethoxyphenyl)-3-oxo-propionate, 4-(3 , 4-dimethoxyphenyl)-3-oxo-butyrate, 2-methyl 15 -3-(3,4-dimethoxyoxyphenyl)-3-oxo-propionate, 2-mercapto-4-(3,4-dimethoxyphenyl)-3-sideoxy -butyrate, 2-benzyl-3-(3,4-dimethoxyphenyl)-3-oxo-propionate, 2-benzyl-4-(3,4-dimethyl Oxyphenyl)-3-oxo-butyrate; 3-(3,4-methylenedioxyphenyl)-3-oxo-propionate, 4-(3, 4- Nalylene dioxyphenyl)-3-oxo-butyrate, 2-mercapto 20 -3-(3,4-methylenedioxyphenyl)-3-oxo-propyl Acid ester, 2-methyl-4-(3,4-methylenedioxyphenyl)-3-oxo-butyrate, 2-benzyl-3-(3,4-methylene) Oxyphenyl)-3-oxo-propionate, 2-benzyl-4-(3,4-methylenedioxyphenyl)-3-oxo-butyrate; 3- (2-Hydroxyethylphenyl)-3-oxo-propionate, 4-(2-hydroxyethylphenyl)-3-oxo-butyrate, 2-methyl-3-( 2- 13 200916607 Hydroxyethylphenyl)-3-oxo-propionate, 2-methyl-4-(2-hydroxyethylphenyl)-3-oxo-butyrate, 2- Benzyl-3-(2-hydroxyethylphenyl)-3-oxo-propionate, 2-benzyl-4-(2-hydroxyethylphenyl)-3-oxo-butyric acid Ester; 3-(3-acetoxyphenyl)-3-oxo-propionic acid 4-(3-Ethyloxyphenyl)-3-oxo-5-butyrate, 2-mercapto-3-(3-ethyloxyphenyl)-3-oxo-propyl Acid ester, 2-methyl-4-(3-acetoxyphenyl)-3-oxo-butyrate, 2-benzyl-3-(3-acetoxyphenyl)-3 - pendant oxy-propionate, 2-benzyl-4-(3-acetoxyphenyl)-3-oxo-butyrate; 3-(4-fluorophenyl)-3- side Oxy-propionate, 3-(4-chlorophenyl)-3-oxo-propionate, 3-(4-bromophenyl)-3-oxo-propionate 10 and 3- (4-iodophenyl)-3-oxo-propionic acid vinegar; 3-(4-epoxyphenyl)-3-oxo-propionate, 3-(4-methanesulfonylbenzene) 3-)oxy-propionate, 3-(4-methylthiophenyl)-3-oxo-propionate, 3-(4-aminophenyl)-3-oxo -propionate, 3-(4-nitrophenyl)-3-oxo-propionate, 3-(4-cyanophenyl)-3-oxo-propionate; 3- The pendant oxy-heptane-1,5-dicarboxylic acid diester and the 2-sided oxy-15-propanone-1,3-dicarboxylic acid di S are intended. With respect to the /3-ketoester compound represented by the formula (A1) of the present invention, among the above, 4,4-dimethyl-3-oxo-valerate and 3-side oxygen are preferred. - Valeric acid vinegar, 3-oxo-pentane-1, 5-dicarboxylate, 3-(2-hydroxyphenyl)-3-oxo-propionate, 3-(2, 5 -dihydroxyphenyl)-3-oxo-propionate, 3-(3, 4-20 dihydroxyphenyl)-3-oxo-propionate, 2-pyryl-3-side oxygen Base-butyrate and 2-mercapto-3-oxo-butyrate. More preferred are, for example, 4,4-dimercapto-3-oxo-valerate, 3-o-oxy-pentane-1,5-dicarboxylic acid diester, 2-sided oxy-propane -1,3-dicarboxylic acid diester, 3-(2-hydroxyphenyl)-3-oxo-propionate, 2-benzyl-3-oxo-butyl 14 200916607 acid ester and 2- Mercapto-3-oxo-butyrate. &lt;Surface B: Dod-ketoguanamine compound&gt; The derivative of the substituted ketone compound exhibiting an anticorrosive effect of the present invention may be, for example, that R4 in the above formula (1) is a hydroxyalkylamine group and has the following formula ( The 5/5-ketoguanamine compound shown in B1). <化5&gt; Ο 0

(CH2)n-OH wherein 'R1 is a hydrocarbon group optionally having a substituent. R2 and R3 are a hydrogen atom, a halogen atom, and a hydrocarbon group which may optionally have a substituent. Further, R2 may optionally be bonded to R3 to form a cyclic structure of 3 to 6 membered rings. R6 is a hydrogen atom or a hydrocarbon group which may optionally have a substituent. n = an integer from 2 to 6. A commercially available product can be used as it is in the keto ketone ester compound represented by the formula (B1) of the present invention. In addition, a commercially available product can be obtained by reacting a corresponding diketene with an alkanol 15 amine represented by the formula (B3) by referring to, for example, JP-A-63-280048. The /3-ketoester compound represented by the formula (B2) is reacted with an alkanolamine represented by the formula (B3), and is obtained in a simple manner (Reaction formula [1]). <Chemical 6> Reaction formula [1]

Wherein, R1 to R. And R6 is the same as the foregoing. Further, R5 is a ketone group which can be substituted with a substituent. n = 2 to 6 integer. 15 200916607 In the above formula (B1), R1 is a hydrocarbon group which may have a substituent. R2 and R are a hydrogen atom, a halogen atom and a hydrocarbon group which may have a substituent. Further, R may optionally be combined with R3 to form a cyclic structure of 3 to 6 membered rings. Further, R is a hydrocarbon group which may have a substituent, and R6 is a hydrogen atom or a hydrocarbon group which may optionally have a 5-substituent. A ring structure of a halogen atom, an optionally substituted nicotine group, and a 3 to 6 membered ring formed by combining R2 and R3, and a &lt;form A: dot ketoester compound&gt; Synonymous. η is the number of anthracene groups, and represents an integer of n=2 to 6. n should be 2 to 4 and more preferably 10. The ketone ester compound of the starting material of the formula (B2) can be directly used as a commercial product. Further, for example, a commercially available product can be manufactured as disclosed in Japanese Laid-Open Patent Publication No. 2000-143590. It can be further adjusted according to the needs of the 亍δ玄未- Guoji S compound 2 position modification. For example, the 2-position modified compound of the ketone-ester compound can be obtained by referring to Bull. 15 Soc. Chem. JaPan., Vo1.62 4072 (1989). The alkanolamines of the starting materials of the formula (B3) include, for example, 2-aminoethanol, diethanolamine, N-ethylaminoethanol, N-methylaminoethanol, N-methyldiethanolamine, and dimethyl. Aminoethanol, 2-(2-aminoethoxy)ethanol, and amino-2-indol-2-propanol. Further, the alkanolamines can also be used as a salt of a hydrochloride or the like or an organic solution such as an ethanol solution. The above alkanolamine is preferably 2-aminoethanol, diethanolamine or N-methylaminoethanol. As the aforementioned alkanolamine, a commercially available product can be used as it is. In addition, those who have no commercial products can refer to Rugamoto Tehiko 4_275933 and Synlett, (9) 1374~1378 (2006), and synthesize them for reuse. λ The amount of the calcinolamine relative to the keto vinegar compound 1 represented by the formula (B2) is preferably 〇'5 moles to (10) moles, more preferably 1.0 moles to 50 moles, and particularly preferably 5 For L2 Moer ~ 1 〇 Mo Er. The burdock has been passed, and the 0-ketoester compound represented by the formula (B2) is mixed with the formula (B3: the alcohol-alcoholamine is mixed in the presence or absence of the solvent, and the mixture is stirred and mixed, and the reaction is carried out. Further, the oxime compound of the above formula (Bi) is produced. The preparation of the bis-mercaptoamine compound represented by the formula (B1) is usually carried out in the absence of the solvent d, but the raw materials used are improved. A solvent may be suitably used for the purpose of solubility, etc. The solvent to be used is not particularly limited, but may be one column = aromatic hydrocarbons such as 1, formazan, diphenylbenzene, and cumene, and chlorobenzene. Benzene 1,3-dialdehyde benzene and hydrazine, 4-dioxene benzene and other _ aromatic hydrocarbons; Xiaotuo and Shishaojia smoldering and other nitriding hydrocarbons; N, N-dimethyl amide , N, N-methylammoniumamine, N-methyl-2-pyrrolidinone and other guanamines; i 3 dimethyl sulphate 03⁄4 1,3_diisopropyl-2-sodium sulphate a chain or branched ether such as isopropyl ether I2-methylmercaptoethane, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether-ethylene glycol monobutyl ether; dioxane, tetrahydrogen 2〇°夫°南南等环_趟趟 derivative; dimethyl (4) Class; dimethyl wind and other winds, - carbon sulfide; and water, etc. Among these solvents, guanamines, sub-categories and ureas are preferred, and N,N-dimethylformamide, team It is better to define the dimethyl ethanoamine, the cyanomethyl group, the ketone, the dimethyl hydrazide and the 1' 3-dimercapto-2- sulphate. In addition, the solvents can be used alone or present. The amount of the solvent used is preferably 0.01 to 100 ml, and more preferably 0.02 to 20 ml, and more preferably 0.03 to 3% of the ketoester compound lg represented by the formula (B2). 5.0 ml. 5 The reaction temperature is preferably -20 to 100 ° C, more preferably -10 to 80 ° C and particularly preferably 0 to 60 ° C. In addition, the reaction pressure is not particularly limited, but can also be under reduced pressure While the alcohol (R5OH, formula (B4)) produced by the reaction is distilled off, the production method of the present invention can be carried out in air, but it is preferably carried out in an inert gas such as nitrogen or argon. The reaction of the invention can also obtain the /5-ketoguanamine compound represented by the formula (B1) in the form of a crude product, but, for example, in this case, it can also be neutralized, extracted, filtered, concentrated after the reaction is completed. Distillation Separation and purification by a general method such as recrystallization, crystallization, column chromatography, etc. The /3-ketooxime 15 amine compound represented by the formula (B1) synthesized by the method of the present invention as described above is a fat in R1. In the case of a group, for example, the following may be mentioned. N-(2-hydroxyethyl)-3-oxo-butanamine, N-(2-hydroxypropyl)-3-oxo-butyl Indoleamine, N-(2-hydroxybutyl)-3-oxo-butamine, N-(2-hydroxyhexyl)-3-oxo-butanamine; N-(2-hydroxyethyl) -N-methyl-3-oxirane-butanamine, N-(2-propyl)-N-mercapto-3-oxo-butyric acid amine, N-(2- via butyl 20 -N-methyl-3-indolyl-butanamine, N-(2-hydroxyhexyl)-N-indolyl-3-oxo-butanamine; N-(2-hydroxyethyl) -N-phenyl-3-oxo-butylamine, N-(2-hydroxypropyl)-N-phenyl-3-oxo-butanamine, N-(2-hydroxybutyl) -N-phenyl-3-oxo-butylamine, N-(2-hydroxyhexyl)-N-phenyl-3-oxo-butanamine; N,N-bis(2-hydroxyl Ethyl)-3-oxo-butanamine, anthracene, Ν-β (2-hydroxypropyl)-3- 18 200916607 oxo-butylamine, N,N-bis(2-hydroxybutyl) --3-Alkyloxy-butanamine, N,N-bis(2-hydroxyhexyl)-3-oxo-butane ; N-(2-hydroxyethyl)-2-methyl-3-oxo-butanamine, Ν·(2-hydroxyethyl)-2,2-dimethyl-3-oxo- Butylamine, Ν-(2-hydroxyethyl)-2-benzyl-3-oxo-butanamine, Ν-(2-hydroxyethyl)-2, 2-5 dibenzyl-3- Oxyl-butylamine; hydrazine, hydrazine-bis(2-hydroxyethyl)-2-methyl-3-oxo-butanamine, N-(2-hydroxyethyl)-N-methyl -2-benzyl-3-sidedoxy-butanamine, N,N-bis(2-hydroxyethyl)-2-benzyl-3-oxo-butanamine; N-(2-hydroxyl Ethyl)-4,4-dimethyl-3-oxo-pentamidine; N-(2-ethyl)-3-oxo-pentamethyleneamine, N-(2-hydroxybutyl) -4,4-dimethyl-3-oxo-pentamidine, 10 N-(2-hydroxybutyl)-3-oxo-pentamethyleneamine, N-(2-hydroxyethyl) -N-methyl-4,4-dimercapto-3-indolyl-decylamine, N-(2-hydroxyethyl)-N-methyl-3-oxo-pentamethyleneamine, N , N-bis(2-hydroxyethyl)-4,4-dimethyl-3-oxo-pentamethyleneamine, hydrazine, N-bis(2-ethyl)-3-oxo-pentane Amine; N-(2-hydroxyethyl)-2-methyl-4, 4-dimercapto-3-oxo-pentamidine, N-(2-hydroxyethyl)-2-benzyl -4, 4-15 dimethyl-3-oxo-pentamidine, N-(2-hydroxyethyl)_2, 2-dimethyl-4,4-didecyl_3_ side Ketopentaamine, N-(2-hydroxyethyl)_2, 2_di-Butyl-4,4·dimethyl-3-oxo-pentamidine; N-(2-ethyl) _N_mercapto_3_sideoxy_pentamidine, N-(2-hydroxyethyl)-N-phenyl-3-yloxy-pentamethyleneamine, sense (2-hydroxyethyl)-N -mercapto-2-benzyl-3-indolyl-pentamidine, N_(2-hydroxyethyl)-N-20phenyl-2-benzyl-3_sideoxy-pentamidine, N,N - bis(2-hydroxyethyl)-2-mercapto•3-o-oxy-pentamidine, N,N-bis(2-hydroxyethyl)_2-benzyl_3_sideoxy_pentaquinone Amines, etc. Further, when R1 is an aromatic group, for example, the following may be mentioned. N-(2-hydroxyethyl)-3-phenyl-3-oxo-propionamine, N (2-hydroxypropyl 19 200916607)-3-phenyl-3-oxo-propionamide, N you hydroxybutyl)_3_phenyl_3_sideoxy-propanol, N-(2-hexyl)_3_phenyl! Side oxypropylamine; n (2-hydroxyethyl)-3-naphthyl-3-oxo-propionamine, N_(2-hydroxypropyl)3 naphthyl-3_ oxo-propionamide, N-(2-hydroxybutyl)_3_naphthyl_3_sideoxy-propionamine, 5 N-(2-hydroxyhexyl)-3-naphthyl-3-oxo-propionamide; N_ (2-hydroxyethyl)_2-mercapto-3-phenyl-3-oxo-propionamine, N-(2-ethyl)-2-benzyl-3-phenyl-3-oxo -propanamide, N-(2-hydroxyethyl)_2,2-dimethyl-3-phenyl-3-oxo-propionamide, N-(2-hydroxyethyl)-2, 2-dibenzyl-3-ylphenyl_3_sideoxy-propionamine; N-(2-hydroxyethyl)-N-methyl-3-phenyl-3-oxo-propionamide , 10 N-(2-ethyl)-N-phenyl-3-phenyl-3-oxo-propionamine; N-(2-ethyl)-N-methyl-2-methyl Benzyl-3-phenyl-3-oxo-propionamine, N-(2-diethylethyl)-N-methyl-2-pyryl-3-phenyl-3-oxo-propenylamine, N-(2-Ethyl)-N-phenyl-2-methyl-3-phenyl-3-oxo-propionamine, Nd!ethyl)-N-phenyl-2-carbyl -3-phenyl-3-oxo-propyl 15 amine, N, N-bis(2-lightethyl)-3-benz-3-oxo-propanamine, N, N-di (2~Hydroxyethyl)-2-methyl-3-phenyl-3-oxo-propionamide, N, N-di (2 -hydroxyethyl)-2-benzyl-3-phenyl-3-oxo-propionamine; N-(2-hydroxyethyl)-3-(2-hydroxyphenyl)-3-sideoxy -propanolamine, N-(2-hydroxyethyl)-2-mercapto-3-(2-hydroxyphenyl)-3-oxo-propionamide, N-(2-hydroxyethyl) -2-benzyl-3-(2-hydroxyphenyl 20-yl)-3-oxo-propionamine; N-(2-hydroxyethyl)-3-(3,4-dihydroxyphenyl)_3_ Sideoxy-propionamide, N-(2-hydroxyethyl)-3-(3,4-dihydroxyphenyl)-2-methyl-3-oxo-propanamide, N-(2 -hydroxyethyl)-3-(3,4-dihydroxyphenyl)_2-benzyl-3-oxo-propionamine; N-(2-hydroxyethyl)-3-(3-methoxy 4--4-hydroxyphenyl)-3-oxo-propionamine, N-(2-hydroxyethyl)-2-methyl-3-(3-methoxy-4- 20 200916607 hydroxyphenyl --3-Alkyloxy-propanamide, N-(2-hydroxyethyl)-2-benzyl-3-(3-methoxy-4-hydroxyphenyl)-3-oxo-propyl Indoleamine; N-(2-hydroxyethyl)-3-(3,4-dimethoxyoxyphenyl)-3-oxo-propionamide, N-(2-hydroxyethyl)-2- Mercapto-3-(3,4-dimethoxyphenyl)-3-oxo-propionamide, N-(2-hydroxyethyl)-2-benzyl 5 -3-(3,4 -dimethoxyphenyl)-3-oxo-propionamide; N-(2-hydroxyethyl)-3-(3,4-ylidenedioxyphenyl)-3 - pendant oxy-propanamide, N-(2-hydroxyethyl)-2-methyl-3-(3,4-methylenedioxyphenyl)-3-oxo-propionamide , N-(2-hydroxyethyl)-2-benzyl-3-(3,4-methylenedioxyphenyl)-3-oxo-propionamide; N-(2-hydroxyethyl) 3-(2-hydroxyethylphenyl)-3-oxo-propanyl 10 decylamine, N-(2-hydroxyethyl)-2-methyl-3-(2-hydroxyethylbenzene Benzyloxy-propylamine, N-(2-hydroxyethyl)-2-fyl-3-(2-hydroxyethylphenyl)-3-oxo-propionamide; N-(2-hydroxyethyl)-3-(3-acetoxyphenyl)-3-oxo-propionamide, N-(2-hydroxyethyl)-2-methyl-3- (3-Ethyloxyphenyl)-3-oxo-propionamide, N-(2-hydroxyethyl)-2-pyringyl-3-(3-ethyloxyphenyl)-3 - pendant oxy-15-propanolamine; N-(2-hydroxyethyl)-3-(4-fluorophenyl)-3-oxo-propionamide, N-(2-hydroxyethyl)- 3-(4-Phenylphenyl)-3-oxo-propionamide, n-(2-hydroxyethyl)-3-(4-bromophenyl)-3-oxo-propionamide, N-(2-hydroxyethyl)_3_(4_magnetic phenyl)-3-oxo-propionamine; N-(2-hydroxyethyl)-3-(4-epoxyphenyl)_3 _ pendant oxy-propionamine, N-(2-hydroxyethyl)-3-(4-methylsulfonylphenyl)_3_sideoxy-propionyl 20 amine, N_(2-hydroxyethyl) -3-(4- Thiophenyl)-3-oxo-propionamine, n-(2-hydroxyethyl)-3-(4-aminophenyl)-3-propionate, N-(2-hydroxyethyl -3-(4-cyanophenyl)-3-oxo-propionamine and the like. Further, when R is an aromatic aliphatic group, for example, the following may be mentioned as follows: 0 21 200916607 N-(2-ethyl)-4-phenyl-3-oxo-butylamine, N-(2 -propyl)-4-phenyl-3-oxo-butanamine, N-(2-hydroxybutyl)-4-phenyl-3-oxo-butanamine, N-(2- Hydroxyhexyl)-4-phenyl-3-oxo-butanamine; N-(2-hydroxyethyl)-4-naphthyl-3-yloxy-butanamine, N-(2-hydroxyl Propyl)-4-naphthyl-3-5 pendant oxy-butanamine, N-(2-hydroxybutyl)-4-naphthyl-3-oxo-butanamine, N-(2- Hydroxyhexyl)-4-naphthyl-3-yloxy-butanamine; N-(2-hydroxyethyl)-2-indolyl-4-phenyl-3-oxo-butanamine, N -(2-hydroxyethyl)-2-benzyl-4-phenyl-3-oxo-butanamine, N-(2-hydroxyethyl)-2,2-dimethyl-4-benzene 3-yloxy-butanamine, N-(2-hydroxyethyl)-2,2-dibenzyl-4-phenyl-3-oxo-10-butanamine; N-(2 -hydroxyethyl)-N-methyl-4-phenyl-3-oxo-butanamine, N-(2-diethylethyl)-N-phenyl-4-phenyl-3-yloxy- Styrene, N-(2-ethyl)-N-methyl-2-methyl-4-phenyl-3-oxo-butyric acid, N-(2-ethyl)-N -Phenyl-2-pyryl-4-phenyl-3-oxo-butanamine, N,N- (2-hydroxyethyl)-4-phenyl-3-oxo-butanamine, N,N-bis(2-hydroxyethyl)-2-15 methyl-4-phenyl-3- side Oxy-butanamine, N,N-bis(2-hydroxyethyl)-2-benzyl-4-phenyl-3-oxo-butanamine; N-(2-hydroxyethyl)- 4-(2-hydroxyphenyl)-3-oxo-butamine, N-(2-hydroxyethyl)-2-methyl-4-(2-hydroxyphenyl)-3-indolyl - Butanamine, N-(2-hydroxyethyl)-2-benzyl-4-(2-hydroxyphenyl)-3-oxo-butanamine; N-(2-hydroxyethyl)- 4-(3,4-dihydroxyphenyl)-3-oxoyl-2-azetamine, N-(2-hydroxyethyl)-4-(3,4-dihydroxyphenyl)-3- Oxyl-butylamine, N-(2-hydroxyethyl)-2-methyl-4-(3'4-dihydroxyphenyl)-3-oxo-butanamine, N-(2 -hydroxyethyl)-2-benzyl-4-(3,4-dihydroxyphenyl)-3-oxo-butanamine, N-(2-hydroxyethyl)-2-benzyl-4 -(3,4-dihydroxyphenyl)-3-oxo-butamine, N-(2-hydroxyethyl)-2-benzyl-4-(3,4-dihydroxybenzene 22 200916607 3-oxooxy-butanamine; N-(2-hydroxyethyl)-4-(3-methoxy-4-hydroxyphenyl)-3-oxo-butanamine, N- (2-Hydroxyethyl)-4-(3-methoxy-4-hydroxyphenyl)-2-indolyl-3-pentyloxy-butanamine, N-(2-hydroxyethyl) 2-methyl-4-(3-methoxy-4-hydroxyphenyl)-3-oxo-butamine, N-(2-hydroxyethyl)-2,2-di 5 Mercapto-4-(3-decyloxy-4-hydroxyphenyl)-3-oxo-butanamine, N-(2-hydroxyethyl)-2-benzyl-4-(3-methyl Oxy-4-hydroxyphenyl)-3-oxo-butamine, N-(2-hydroxyethyl)-2,2-dibenzyl-4-(3-decyloxy-4-hydroxyl Phenyl)-3-oxo-butylamine; N-(2-hydroxyethyl)-4-(3,4-dimethoxyphenyl)-3-oxo-butanamine, N -(2-hydroxyethyl)-2-methyl-4-(3,4-dimethoxyphenyl)-3-1 oxime oxo-butylamine, N-(2-hydroxyethyl) -2,2-dimercapto-4-(3,4-dimethoxyphenyl)-3-oxo-butanamine, N-(2-hydroxyethyl)-2-benzyl-4 -(3,4-dimethoxyphenyl)-3-oxo-butanamine, N-(2-hydroxyethyl)-2,2-dibenzyl-4-(3,4-di Methoxyphenyl)-3-oxo-butanamine; N-(2-hydroxyethyl)-4-(3,4-methylenedioxyphenyl)-3-oxo- Butanamine, N-(2-hydroxylethyl)-2-methyl-4-(3,4-methylenedioxyphenyl)-3-oxo-butanamine, N-( 2-hydroxyethyl)-2,2-dimercapto-4-(3,4-decyldioxyphenyl)-3-oxo-butanamine, N-(2- Ethyl)-4-(3,4-methylenedioxyphenyl)-2-benzyl-3-oxo-butanamine, N-(2-hydroxyethyl)-2,2- Dibenzyl-4-(3'4-methylenedioxyphenyl)-3-oxo-butanamine; N-(2-hydroxyethylamino)-4-(2-hydroxyethyl) Phenyl)-3-oxo-butylamine, N-(2-hydroxyethyl)-2-mercapto-4-(2-hydroxyethyl)phenyloxy-3-butanamine , N-(2-hydroxyethyl)-2,2-dimethyl-4-(2-hydroxyethylphenyl)-3-oxo-butanamine, N-(2-hydroxyethyl) -2-benzyl-4-(2-hydroxyethylphenyl)-3-oxo-butanamine, N-(2-hydroxyethyl)-2,2-dibenzyl-4-(2 -hydroxyethylphenyl)-3-oxo-butanamine; N-(2- 23 200916607, 'soil) 4 (3-acetoxyphenyl)-3-oxo-butylamine , N-(2-hydroxyethyl)methyl 4-(3-ethoxyindolyl)_3_sideoxy-butanamine, ^(2-hydroxyethyl)-2,2, - ώ甘- Monomethyl-4-(3-acetoxyphenyl)_3-o-oxy-butanamine, ethyl)_2_pyringyl_4_(3-ethyloxyphenyl) Brewing 5 amine hydrazine (2·34 ethyl)-2,2-dipyridyl-4-(3-acetoxyphenyl)-3-oxo-butanamine; Π # -(2- Red ethyl)-4-(4-fluorophenyl)-3-oxo-butylamine (2 soap ethyl)-4-(4-phenylphenyl)_3_sideoxy-butanamine, N (2hydroxyethyl) 4 (4_/ stinky)-3_sideoxy-butyl Amine and N-(2-ethyl)-4-(4-indolephenyl)_3_side gas-butamine; N-(2-ethyl)_4_(4_epoxy)_3_ 1〇-oxyl butylamine, N—(2′-ethyl)-4-(4-methyllithophenylphenyl)·3-sideoxybutanamine, Ν-(2_hydroxyethyl 4-(4-methylthiophenyl)-3-oxo-butanamine, N-(2- to-ethyl)-4-(4-amine-phenyl)-3-propionic acid Vinegar, N-(2-ethyl) 4 (4 cyanophenyl)-3-oxo-butanamine, and the like. ^Amino 'aminoenamide compound> The derivative of the substituted ketone compound which exhibits an anticorrosive effect of the present invention is more preferably an amine oxime oxime compound represented by the following formula (C1). <化7>

(C1) wherein 'R is a thiol group which may have a substituent. R2 is a gas atom, a halogen atom or a hydrocarbon group which may have a substituent. Further, R6 is a hydrogen atom or a hydrocarbon group which may optionally have a substituent. The alkyne oxime compound of the formula (C1) may be a /3-ketoester compound represented by the formula (C2) or a 5-ketodecylamine compound represented by the formula (C4) and an alkanol represented by the formula (C3). The amine reaction is carried out (reaction formula [2] and reaction formula [3]). 24 20 200916607 <化8> Reaction formula [2] Ο ο

R7-oh wherein 'R1 is a hydrocarbon group optionally having a substituent. R2 is a hydrocarbon group optionally having 5 hydrogen atoms and a substituent. R3 is a hydrogen atom. R5 is a hydrocarbon group optionally having a substituent. R6 is a hydrogen atom or a hydrocarbon group which may have a substituent, and R7 is a hydrogen atom or a substituent synonymous with R5. n = 2 to 6 integer. <Chemical 9> Reaction formula [3]

Wherein 'R1 to R7 and η are synonymous with the above. In the amine olefinamide compound represented by the formula (C1) of the present invention, R2 is a hydrogen atom and a hydrocarbon group which may have a substituent, and R6 is a hydrogen atom or a hydrocarbon group which may optionally have a substituent. η is the number of anthracene groups and represents an integer from 2 to 6. η is preferably 2 to 4 15 and more preferably 2. As described above, the raw material of the amino olefinamide compound represented by the formula (C2) in the above reaction formula [2] can be exemplified by the compound of the 5-keto group S represented by the formula (Α1), r2 or R3. Any one is a hydrogen atom. Further, as the ketone ester compound of the starting material represented by the formula (C2), a commercially available product can be used as it is. Further, a commercially available product can be obtained by, for example, Bul1. Soc. Chem. Japan" Vol_62 4072 (1989), etc., to obtain a 2-modified compound of the /3-ketoester compound. The above reaction formula [3] The raw material 25 of the amine oxime amide compound represented by the formula (C4) is a hydrogen atom of the ketone oxime compound represented by the above formula (B1), wherein the caliper 2 or & 3 is a hydrogen atom. A commercially available product can be directly used as the ketone decylamine compound of the starting material (C4). Alternatively, those not commercially available may be synthesized and used according to the above reaction formula π]. 5 % (C3) Amine can be scaled as 2_aminoethanol, diolamine, N-ethylaminoethanol, N-methylaminoethanol, N-methyldiethanolamine: dimercaptoethanol, 2_(2 amine Further, the anthracylamine may be used as an organic solution such as a salt of a hydrochloride or an ethanol solution, etc. - Aminoethanol, diethanolamine or N-methylaminoethanol. Commercially available products can be used as the above-mentioned alkanolamine. In addition, those without a commercial product can refer to 曰本特开2004-275933 and Synlett., (9) 1374-1378 (2006 ), the other synthetic use. 15, the amount of pre-Wei coffee (four) in · 2) (4) ketone-based compound or formula (4) compound 丨 Mo Er, Yi Tao $ Mo Er, Mo and 1.0 Mo ~ Mo More preferably, it is 2 moles to 1 mole. The amine olefin amine compound represented by the above formula (C1) is a ketone oxime compound represented by the formula (C2) or a keto oxime compound represented by the formula (C4). The product of the above-mentioned formula (C1) is usually produced by a method in which the oxime amine is mixed in the presence or absence of the lanthanum, for example, by a reaction such as a reaction. In the absence of a solvent, the ridge can be used for the purpose of improving the solubility of the raw materials used, etc. The solvent used is not particularly limited, but for example, 26 200916607 The following solvents are suitable for use. Halogenated aromatic hydrocarbons such as aromatic hydrocarbons such as benzene, toluene, xylene and cumene; chlorobenzene, 1,2-dichlorobenzene, 1,3-diphenylbenzene, and 1,4-diphenylbenzene; Nitrobenzenes such as nitrobenzene and nitromethane; amides such as N,N-dimercaptocaramine, N, N-5 dimercaptoacetamide, N-methyl-2-pyrrolidone ;1,3-dimethyl-2 -Ureas such as imidazolidinone and 1, 3-diisopropyl-2-imidazolidinone; isopropyl ether, 1,2-dimethoxyethane, diethylene glycol monomethyl ether, diethylene glycol Chain or branched ethers such as monoethyl ether and diethylene glycol monobutyl ether; ether derivatives of cyclic ethers such as dioxane and tetrahydrofuran; and hydrazines such as dimethyl sulfoxide; dimethyl hydrazine;飒10; carbon disulfide; and water, etc. Among these solvents, guanamines, sulfoxides and ureas are preferred, and N, N-dimercaptocaramine, N, N-didecyl hydrazine Amine, N-methyl-2-pyrrolidone, dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone are more preferred. Further, these solvents may be used singly or in combination of two or more. The amount of the solvent is preferably 0.01 to 100 ml, more preferably 0.02 to 20 m, more preferably 0.03 to the ketoester compound represented by the formula (C2) or the ketone ketone amide compound lg of the formula 15 (C4). 5·0πύ. The reaction temperature is preferably -20 to 100 ° C, more preferably -10 to 80 ° C, and particularly preferably 0 to 60 ° C. Further, the reaction pressure is not particularly limited, but it can be carried out by distilling off the alcohol or water (R7〇H, formula (C5)) produced by the reaction under reduced pressure. Further, the production method of the present invention can be carried out in the air, but it is preferably carried out in an inert gas such as nitrogen or argon. By the reaction of the present invention, the amine olefinamide compound represented by the formula (C1) can also be obtained in the form of a crude substance, but at this time, after the reaction, by, for example, neutralization, extraction, filtration, concentration, distillation, Recrystallization, crystallization, column chromatography, etc., were isolated and purified by a method of 27, 2009,607. The above-described formula (ci) is a compound of the formula (ci), which is represented by the formula (ci), which is represented by the formula (4), and the above formula (referred to as the (four) group. Among the compounds exemplified as the compound, a compound obtained by using a compound material of any of r2 2 R as a hydrogen atom. &lt;Formation of the anti-surge agent&gt; The use of the anti-corrosion treatment liquid and the anti-button preservation liquid is not particularly limited. For the above-mentioned applications, for example, copper, or such alloys used in a process such as a semiconductor integrated circuit and a printed circuit board are used. The metal film, the metal wiring, or the constituent component having one or more kinds of copper and aluminum are included in the composition. The preferred use of the anti-surge agent of the present invention may be, for example, a metal film used on a semiconductor substrate (especially It is a step of the anti-surname processing of the copper film. 15 Further, in terms of the preferred use of the anti-money treatment liquid of the present invention, for example, the method of applying copper, aluminum or the alloy circuit is applied. In the cleaning step of the LSI substrate or the printed circuit board, or the rinsing step of the CMP weaving, etc. For the purpose of anti-money treatment, the use of the anti-chain preservation solution of the present invention may be, for example, a surface treatment of a metal film or a storage solution of a semiconductor wafer after processing the circuit substrate in a CMp process, etc. The anti-thaw treatment is used for the purpose, and the best one is, for example, the case where the metal crucible or the circuit uses copper in the above case. The anti-surplus agent of the present invention can directly use the above formula (A1), The compound of the formula (B1) and the formula (3) may be used alone, or two or more of these compounds may be mixed and used in the application of 28 200916607. Further, for example, the agent may also be treated with water and/or an organic solvent as an anti-corrosion treatment. Liquid or anti-corrosion preservation solution. In addition, it may be mixed with an acid or a base which does not decompose the compound, pH adjustment to improve water solubility, or to prevent degradation of the corrosion inhibitor itself, 5 mixing of an oxidizing agent, etc., depending on the conditions of use and It is used as an anti-corrosion agent, an anti-corrosion treatment liquid and an anti-corrosion preservation liquid for use as an additive. The organic solvent usable in the anti-corrosion agent type only needs to be of the formula (A1), formula (B1) and formula (C) of the present invention. 1) The compound shown may be reacted without particular limitation. Suitable solvents include aromatic hydrocarbons such as benzene, toluene, diphenylbenzene and isopropyl 10 benzene; chlorobenzene, 1,2-di Halogenated aromatic hydrocarbons such as chlorobenzene, 1,3-dichlorobenzene and 1, 4-dichlorobenzene; nitrophenylnitrile aromatic hydrocarbons; quinones such as dimethyl sulfoxide; dimethyl sulfone , sulfones such as diethyl hydrazine, bis(2-hydroxyethyl) sulfone and tetradecyl sulfone; hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-diethylacetamide, hydrazine- Amidoxime such as methyl-2-pyrrolidone, anthracene-hydroxyindol-2-pyrrolidone and anthraquinone-hydroxyethyl 15-yl-2-pyrrolidone; 1, 3-dimethyl-2-imidazolidinone, 1 , 3-diethyl-2-imidazolidinone and urea such as 1,3-diisopropyl-2-imidazolidinone; isopropyl bond, 1,2-dimethoxyethane, bisaki, a bond such as tetrazo-α-fusan; an alcohol such as methanol, ethanol, n-propanol, n-butanol, isopropanol or ethylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol, diethylene glycol monoterpene ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol monoterpene ether Esters of polyhydric alcohols, ethylene glycol monoethyl ether acetate and the like ether or ester derivatives. Further, these organic solvents may be used singly or in combination of two or more. Among these organic solvents, lower alcohols, sulfoxides and ureas are preferred, 29 200916607 and ethanol, n-propanol, n-butanol, isopropanol, dimercapto sulfoxide and 1,3-dimethyl -2-Mi. It is better to sit on the ketone. In the corrosion inhibitor of the present invention, the concentration of the compound represented by the formula (A1), the formula (B1) and the formula (C1) can be appropriately set depending on the use and purpose, but it is preferably 〇·〇1% by mass to 805% by mass. It is preferably from 1% by mass to 60% by mass, and particularly preferably from 1.0% by mass to 40% by mass. Further, when it is mixed with a compounding agent such as a pH adjusting agent or an antioxidant, compatibility with the compounding agent and/or dispersibility should be considered. In the anticorrosive treatment liquid of the present invention, the concentration of the compound represented by the formula (A1), the formula (B1) and the formula (C1) can be appropriately set depending on the use and purpose, but for example, 10 is used for the substrate on which the metal wiring is formed. The cleaning treatment and the anti-corrosion treatment are preferably 0.01% by mass to 80% by mass, more preferably (u% by mass to 6% by mass%, and particularly preferably 1.0% by mass to 40% by mass. The anticorrosive treatment liquid of the present invention) In the above range, it is preferable from the viewpoints of the anti-corrosion effect, the substrate cleaning time, and the amount of the washing waste liquid (environmental burden). Further, for example, the anti-corrosion treatment liquid 15 of the present invention may be used in addition to the foregoing. In the rinsing step after the CMP process or the CMP process, for example, the cleaning process of the anti-corrosion preservation solution of the present invention can be temporarily used as a solution for holding the wafer between the cleaning process for removing the abrasive particles and the like. 2. In the corrosion protection liquid of the present invention, the spread/index of the δ substance represented by the formula (A1), the formula (B1) and the formula (C1) may be appropriately set depending on the purpose and purpose, but is preferably 〇(1)% by mass. ~80% by mass, more preferably ai mass%~6〇% by mass 'and especially ι When the corrosion protection liquid of the present invention is in the above range, it is preferable from the viewpoints of the anti-corrosion effect, the anti-abrasive time of 30 200916607 2, and the amount of the waste liquid to be washed (environmentally negative milk, etc.) When the material of the metal film or the metal circuit is copper, the corrosion protection liquid of the present invention exhibits a better anti-corrosion effect. &lt; Release agent form&gt; The formula (A1), formula (B1) and formula (C1 of the present invention) The compound shown, for example, may be prepared by a method such as a compound having a photoresist stripping property such as an alkoxylamine (2. amino alcohol or the like) to prepare a light having both anti-surge property and photoresist peeling property. Further, the compound of the formula (Al), the formula (B1) and the formula (Cl) may be used in combination of two or more kinds. In the present invention, the "photoresist stripper" is used. Refers to: the anti-corrosion of the pre-recorded metal species, and for example, the photoresist stripping step when the printed substrate is used is used to strip excess photoresist film and various debris from the article containing the photoresist film. The agent having the aforementioned peeling property may, for example, be a hydroxyl group. Or an alkanol 15 amine or a hydrogen fluoride salt, etc., but preferably an alkanolamine. Specifically, the aforementioned alkanolamine compound may, for example, be 2-aminoethanol, diethanolamine, N-ethylaminoethanol, N _ mercaptoaminoethanol, N-methyldiethanolamine, dimethylaminoethanol, 2-(2-aminoethoxy)ethanol, amidino-2-propanol, diethanolamine, etc., and preferably 2 _ Aminoethanol, diethanolamine, ν-μ methylaminoethanol. For example, the photoresist stripper of the present invention may be added with an antioxidant for the purpose of preventing deterioration of the release agent itself, or for the purpose of improving solubility. Further, an amphiphilic compound or a rhomodulating agent which is miscible with an acid, a base, water, an organic solvent or other compounding component is added. 31 200916607 In addition, the photoresist stripper can be used to prepare a photoresist stripping solution by using water, an organic solvent or a mixed solvent thereof, thereby being used for the photoresist stripping step in the same manner as the above-mentioned photoresist stripping agent. Various wastes and residues are used for photoresist stripping. 5 10 15 20 The photoresist stripper having anti-corrosion property of the present invention can be prepared by mixing only the compounds of the formula (A1), the formula (B1) and the formula (Cl), which are compounded with a photoresist stripping energy. For example, nitrogen may be used as a photoresist stripper by using water, an organic solvent or a mixed solution of the above. Further, the organic solvent used is synonymous with the money solvent which can be used for preparing the above-mentioned anti-surname agent and the anti-removal solution and the anti-dumping liquid using the same. The light of the hair of the month and the formula of the formula (3) and the formula (the formula (3) is preferably 0.01% by weight to 255% by weight and more preferably 0.1% by weight to 15% by weight relative to the total amount of the photoresist stripper. %, and particularly preferably from 1.0% by weight to 10% by weight. It is quite suitable from the viewpoints of anti-corrosion effect, substrate cleaning time, and cleaning waste (circle ^ burden) in the above-mentioned Fan Yige. The concentration of the compound having the photoresist etch-off property is more than 5% by weight, more preferably from 5% by weight to 75% by weight, based on the total amount of the resist release agent, and is preferably from 10% by weight to 75% by weight. When the solvent is mixed to prepare the photoresist stripper of the present invention, the ϊ ϊ ϊ can be appropriately adjusted to the concentration of the compound of the above formula (Α1), formula (Β1)-), and the compound having the photoresist stripping property. It falls within the above range. The photoresist or stripper can reach the sound and the effect of the anti-corrosion effect. At the same time, for example, in the above-mentioned photoresist stripping step, 32 200916607 can more effectively remove the substrate from the substrate. The film of the photoresist is peeled off and the residue is removed. The photoresist stripping of the present invention The agent or the photoresist stripping liquid exhibits an excellent anticorrosive effect especially when the material of the metal film or the metal wiring is copper. &lt;Recycling of a compound or a derivative thereof&gt; 5 Further, for example, Extracting, filtering, and concentrating 'steamed crane, tube chromatography, etc.--the method of recovering the waste from the above-mentioned sister's step materials (4) receiving materials (4) Longzhizhi's intention to replace the difficult compound or its derivative. &lt;Anti-corrosion Method for evaluating performance> One of the preferred uses of the compound of the formula (A1), the formula (B1) and the formula (C1) of the present invention, that is, the light which can be used in the above-mentioned photoresist peeling step or the like The method for preparing the resist stripping solution and the method for evaluating the corrosion resistance are exemplified as follows, and the order thereof is explained. 1. A commercially available metal foil, a metal plate or a metal wire is used as the test metal I5 sheet, which is in accordance with the order of the water, The water-repellent material surface is washed with a metal surface for pre-treatment, and is dried and weighed. V &gt; 2. at least one selected from the compounds of the formula (A1), formula (B1) or formula (C1) of the present invention. 1 compound as a corrosion inhibitor component, alkanolamine as a photoresist stripper component, and water The organic solvent is mixed and mixed to prepare a photoresist stripping solution - 20. The prepared photoresist stripping solution is set to, for example, a temperature at which a photoresist stripping step can be performed, and then the test metal sheet is immersed in the solution. After taking a test piece of metal for a certain period of time, the amount of metal (concentration) eluted into the resist stripper is measured by, for example, Inductively Coupled Plasma Mass Spectrometry (33 200916607 ICP-MS). 4. From the measured value of the amount (concentration) of the eluted metal, the metal corrosion degree is calculated as the erosion degree value by the following mathematical formula [I], and quantitative evaluation is performed. 5 [Number 1] Mathematical formula [I] Invasiveness value (ppb/mg) = dissolved metal concentration (ppb) / metal weight before test (mg) The smaller the corrosion degree value, the better the corrosion prevention effect. Further, using a benzotriazole having the same effect as a control compound, a compound having a smaller degree of corrosion can be judged to be a compound having an excellent anticorrosive effect which has hitherto not been obtained. Hereinafter, the present invention will be more specifically described by way of examples. EXAMPLES &lt;Example A: /3-ketoester compound&gt; 15 Example A-1 (Photoresist stripping solution for preparation test; (4-mercapto-3-latyloxy-pentanoic acid ethyl ester) 2 g of 4-methyl-3-oxo-pentanoic acid ethyl ester used as an anticorrosive agent in a mixture of 2-aminoethanol and ultrapure water (weight ratio: 3/l), mixed at room temperature The test stripper was prepared. 20 Example A-2 (Side degree of erosion: 4-mercapto-3-oxo-pentanoic acid ethyl ester) Commercially available copper wire (weight: 1900 mg) at 50 ° C After immersing in lwt% sodium hydroxide aqueous solution for 1 minute and lwt% sulfuric acid aqueous solution for 1 minute, it was washed with ultrapure water and then dried to carry out copper foil pretreatment. Next, the copper foil was 34 200916607 70°. C was immersed in the test release agent prepared in Example A and allowed to stand for 1 hour. Thereafter, the copper foil was removed from the test release agent, and the dissolved copper concentration was measured by inductively coupled plasma mass spectrometry (ICP-MS). The measured value is expressed as the invasiveness value by the above formula (I), and is 1·8 ppb/mg. 5 Further, the intrusion degree is measured twice, and each is 1.6 ppb/mg and 1.9 ppb/mg. Average of 3 times 1.8 ppb/mg. Example A-3 (Resistance stripping solution for preparation test; 3-sideoxy-benzyl butyrate) Mixture of 2-aminoethanol and ultrapure water (weight ratio: 3/) l) 40g, 10 parts of 3-layer oxy-butyric acid benzyl ester of the corrosion inhibitor component were mixed at room temperature to prepare a photoresist stripping solution for the test. Example A-4 (Measurement of corrosion degree: 3-side oxygen Base-butyric acid benzyl ester) Commercially available copper wire (weight: 1900 mg) was immersed in a 1 wt% aqueous solution of 15% sodium hydroxide for 1 minute, 1 wt% aqueous sulfuric acid solution for 1 minute at 50 ° C, and then washed with ultrapure water. The copper wire was dried and subjected to a copper wire pretreatment. Then, the copper wire was immersed in the test photoresist release agent prepared in Example A-3 at 70 ° C, and stirred for 1 hour. Thereafter, the film was peeled off from the test. The copper wire was removed by the agent, and the dissolved copper concentration was measured by inductively coupled plasma mass spectrometry (ICP-MS). The measured value was expressed as the invading value according to the above formula 20 (I), which was 2.2 ppb/mg. Similarly, two intrusion measurements were performed, each of which was 1.9 ppb/mg and 2.1 ppb/mg, and the average of three times was 2.1 ppb/mg. Example A-5 (Resistance stripping solution for modulation test: 3-side) oxygen -butyric acid (3-methylbutyl ester)) 35 200916607 In a mixture of 2-aminoethanol and ultrapure water (weight ratio: 3/l) 40g, the 3-side oxygen of the corrosion inhibitor component is mixed at room temperature. 2 g of butyl-butyric acid (3-methylbutyl ester) to prepare a photoresist stripping solution for the test. Example A-6 5 (Determination of corrosion: 3-sided oxy-butyric acid (3-methylbutyl ester) The commercially available copper wire (weight: 1900 mg) was immersed in a lwt% sodium hydroxide aqueous solution at 50 ° C for 1 minute, and a lwt% sulfuric acid aqueous solution was used for 1 minute, and then washed with ultrapure water and then dried to carry out copper wire. Set processing. Next, the copper wire was immersed in the test photoresist release agent prepared in Example A-5 at 70 ° C, and stirred for 1 hour and 10 hours. Thereafter, the copper wire was removed from the test photoresist stripper, and the dissolved copper concentration was measured by inductively coupled plasma mass spectrometry (ICP-MS). The measured value is expressed as the invasive value according to the above formula (I) and is 2.7 ppb/mg. Further, in the same manner, the degree of erosion measurement was further performed twice, each of which was 2.5 ppb/mg and 1.6 ppb/mg, and the average value of the third time was 2.3 ppb/mg. 15 Example A-7 (Photoresist stripping solution for preparation test; 3-sideoxy-isobutyl butyrate) 40 g of a mixture of 2-aminoethanol and ultrapure water (weight ratio: 3/l) The test resist resist stripping solution was prepared by mixing 2 g of 3-oxyloxy-butyrate isobutylate of the corrosion inhibitor component at room temperature. 20 Example A-8 (Determination of erosion: 3-sided oxy-isobutyl butyrate) Commercially available copper wire (weight: 1900 mg) was immersed in a 1 wt% sodium hydroxide aqueous solution at 50 ° C for 1 minute, lwt After 1 minute of the sulfuric acid aqueous solution, it was washed with ultrapure water and dried, and the copper wire was pretreated. Next, the copper wire was immersed in the test photoresist stripper prepared in Example A-7 at 70 36 200916607 °C, and stirred for 1 hour. Thereafter, the copper wire was removed from the test photoresist stripper, and the dissolved copper concentration was measured by inductively coupled plasma mass spectrometry (ICP-MS). The measured value is expressed as the invading value according to the above formula (I) and is 3.0 ppb/mg. 5 In addition, the degree of erosion measurement was further performed twice, each of 2.4 ppb/mg and 1.8 ppb/mg, and the average of three times was 2.4 ppb/mg. Example A-9 (Photoresist stripping solution for preparation test: 3-sided oxy-3-phenyl-butyric acid ethyl ester) A mixture of 2-aminoethanol and ultrapure water (weight ratio: 3/l In 40 g, 10 g of 3-oxooxy-3-phenyl-butyric acid ethyl ester of the corrosion inhibitor component was mixed at room temperature to prepare a photoresist stripping solution for testing. Example A-10 (Measurement of Degree of Erosion · 3-Phenoxy-3-phenyl-butyrate Ethyl Ester) A commercially available copper wire (weight: 1900 mg) was impregnated at 50 ° C in 1 wt% of sodium hydroxide hydroxide After the aqueous solution was dried for 1 minute and 1 wt% sulfuric acid aqueous solution for 1 minute, it was washed with ultrapure water and dried, and the copper wire was pretreated. Next, the copper wire was immersed in the test photoresist release agent prepared in Example A-9 at 70 ° C, and stirred for 1 hour. Thereafter, the copper wire was removed from the test photoresist stripper, and the dissolved copper concentration was measured by inductively coupled plasma mass spectrometry (ICP-MS). The measured value is expressed as the invasiveness value according to the above formula 20 (I) and is 3.2 ppb/mg. Further, in the same manner, the degree of aggression was measured twice, each of which was 1.4 ppb/mg and 2.6 ppb/mg, and the average value of the third time was 2.4 ppb/mg. Example A-11 (Resistance stripping solution for preparation test: 2-sided oxy-propane-1, 3-dicarboxylic acid II 37 200916607 A mixture of 2-aminoethanol and ultrapure water (weight ratio: 3 /1) In 4 〇g, 2 g of an anticorrosive component and 2 g of propane d,3-dicarboxylic acid dimethyl ester were mixed at room temperature to prepare a photoresist stripping solution for testing. 5 Example A-12 (Measurement of degree of erosion: 2-sided oxy-propane-1, dimethyl phthalate) Commercially available copper wire (weight: 190 〇 mg) was immersed in 1 wt% of sodium sulphate solution After a minute and 1 wt% aqueous sulfuric acid solution, the mixture was washed with ultrapure water and dried to carry out copper wire pretreatment. Then, the copper wire was impregnated at 7〇1〇C in Example A-11. Test photoresist stripper, stirring

Time. Thereafter, the copper wire was removed from the test photoresist stripper, and the dissolved copper concentration was measured by inductively coupled plasma mass spectrometry (ICP-MS). According to the above formula (I), the measured value is expressed as the degree of erosion, and is 26 ppb/mgD. In addition, the measurement of the degree of erosion is performed twice, and each of them is 2.8 ppb/mg 15 and 2.5 PPb/mg. 2_6PPb/mg. Example A-13 (Resistance stripping solution for preparation test: 4,4-dimethyl- 3_sideoxy-pivalate) A mixture of 2-aminoethanol and ultrapure water (weight ratio: 3 / l) 40 g of 2, 4-dimethyl-3-oxo-pentanoic acid methyl ester 2 g of an anticorrosive component was mixed at room temperature to prepare a photoresist stripping solution for testing. Example A-14 (Measurement of Degree of Erosion: 4,4-Dimethyl_3_Phenoxy-Pentanoate) A commercially available copper wire (weight: 1900 mg) was impregnated at 50 ° C in 1 wt% NaOH 38 200916607 After a minute of sodium solution and 1 wt% aqueous sulfuric acid solution, it was washed with ultrapure water and dried, and the copper wire was pretreated. Next, the copper wire was immersed in the test photoresist release agent prepared in Example A-13 at 7 〇 C, and pj was stirred. Thereafter, the copper wire was removed from the test photoresist stripper, and the dissolved copper concentration was measured by inductively coupled plasma mass spectrometry (ICP-MS). The measured value is expressed as the degree of erosion according to the above mathematical formula (1) and is 丨8 ppb/mg. Example A-15 (Resistance stripping solution for preparation test: 2_methyl_3_sideoxy-butyric acid ethyl ester) A mixture of 2-aminoethanol and ultrapure water (weight ratio: 3/1) In 4 〇g, 10 g of 2-methyl-3-nonanthracene-butyrate ethyl ester of the corrosion inhibitor component was mixed at room temperature to prepare a photoresist stripping solution for testing. Example A-16 (Measurement of corrosion degree: 2-methyl-3-oxooxy-ethyl butyrate) Commercially available copper wire (weight: 1900 mg) was 50. (: After immersing in a lwt% aqueous solution of 15% sodium hydroxide for 1 minute and an aqueous solution of iwt% sulfuric acid for 1 minute, it was washed with ultrapure water and dried to carry out copper wire pretreatment. Next, the copper wire was 7〇. C was immersed in the test photoresist stripper prepared in Example a-15, and after stirring lj, day ^°, 'copper wire was removed from the test photoresist stripper to inductively coupled plasma mass spectrometry (ICP-MS) The dissolved copper concentration was measured, and the measured value was expressed as the degree of erosion according to the above formula 20 (1), and was 2.3 ppb/mg. Further, the etching degree was measured twice, and each was i.8 ppb/mg and 2.3 ppb/mg. 'The average value of 3 times is 2.lppb/mg. Example A-17 (Resistance stripping solution for preparation test: 2_benzyl_3_sideoxy-ethyl butyrate) 39 200916607 In 2-aminoethanol In a mixed liquid of 30 g and 10 g of ultrapure water, 2 g of 2-benzyl-3-oxo-butyric acid ethyl ester as an anticorrosive component was mixed at room temperature to prepare a photoresist stripping solution for testing. Example A-18 5 (Isolation degree of corrosion: 2-benzyl-3-oxo-butyric acid ethyl ester) Commercially available copper wire (weight: 1900 mg) was immersed in a 1 wt% sodium hydroxide aqueous solution at 50 ° C for 1 minute, lwt% After the sulfuric acid aqueous solution was washed for 1 minute, it was washed with ultrapure water and then dried to carry out copper wire pretreatment. Then, the copper wire was immersed at 70 ° C in the test photoresist stripper prepared in Example A-17. After stirring for 1 hour and 10 hours, the copper wire was removed from the test photoresist stripper, and the dissolved copper concentration was measured by inductively coupled plasma mass spectrometry (ICP-MS). The measured value was used as the invading name according to the above mathematical formula (1). The degree value is 2.0 ppb/mg. Further, the etching degree measurement is performed twice in the same manner, each of which is 2.8 ppb/mg and 3.2 ppb/mg, and the third average value is 2.7 ppb/mg. 15 Example A-19 (Recovery of 2-benzyl-3-oxooxybutyric acid ethyl ester) Ethyl acetate was added to the resist stripping solution used in Example A-18, and the organic layer was separated and the organic layer was dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off, and 2-benzyl-3-oxooxybutyric acid ethyl ester 20 and 2-aminoethanol were recovered as a mixture. &lt;Example B; /3-ketodecylamine compound&gt; B-1 (Synthesis of N-(2-hydroxyethyl)-4,4-dimethyl-3-oxo-pentamethyleneamine) 4, 4- 2 in a 50 ml eggplant flask under nitrogen atmosphere A -3- 40 200916607 15.82g (100mmol) of methyloxy-valerate and 9.16g (150mmol) of 2-aminoethanol, and stirred for 16 hours while maintaining the temperature below 30 ° C. After the reaction, the reaction solution was concentrated. The obtained yellow oily concentrate was purified by a ruthenium dioxide gel column chromatography (eluent: ethyl acetate) to obtain N-(2-hydroxyethyl)-4, which was obtained as a 5-color oil. 4-dimercapto-3-oxo-pentamidine 10.96 g (yield: 59%). The analytical data of the obtained above compounds are shown below. 1 H-NMR spectrum (300 MHz » CDC13) (5 ppm; 1.18 (s &gt; 9H), 3.07 (t, 1H, J = 5.4 Hz), 3.42~3.47 (m, 2H), 3.52 (s, 10 2H) , 3.70~3.75 (m, 2H), 7.48 (brs, 1H).

Mass spectrum (CI-MS) · m/z = 188 [M + +1]. Example B-2 (Reducing agent for preparation test: (N-(2-hydroxyethyl)-4, 4-dimethyl-) 3-sided oxy-pivalamidine) 15 In a mixture of 2-aminoethanol and ultrapure water (weight ratio: 3M) 40g, N-(2-hydroxyethyl) mixed with an inhibitor component at room temperature -4,4-Dimethyl-3-oxo-pentamethyleneamine 2 g, the test photoresist stripping solution was prepared. Example B-3 (Measurement of erosion degree; N-(2-hydroxyethyl)-4 , 4-dimethyl-3-oxo-pentamethyleneamine) 20 The commercially available copper foil was immersed in a 1 wt% aqueous sodium hydroxide solution at 50 ° C for 1 minute, and a 1 wt% aqueous sulfuric acid solution was used for 1 minute. The pure copper was washed and dried, and the copper foil was pretreated. Then, the copper wire was immersed in the test photoresist stripping agent prepared in Example B-2 at 70 UC, and stirred for 1 hour. The photoresist was removed by a photoresist stripper, and the dissolved copper concentration was measured by inductively coupled plasma mass spectrometry 41 200916607 (ICP-MS). The measured value was expressed as an erosion degree value according to the above formula (1), and was 6 ppb/mg. Example B-4 (Synthesis of N-(2-hydroxyethyl)-3-phenyl-3-oxo-propionamine) 5 in a nitrogen ring Next, in a 20 ml eggplant type flask equipped with a stirrer and a thermometer, 3-phenyl-3-oxo-methyl propionate 1718 § (4〇111111〇1) and 2-aminoethanol 4.89 g (80 mmol) were mixed. The mixture was stirred for 16 hours while maintaining a temperature of 30 = c or less. After the completion of the reaction, the obtained reaction liquid was concentrated to obtain a yellow oil-like concentrate. The obtained concentrate was then subjected to a cerium oxide gel column chromatography (dissolving 10 liquids). : (ethyl acetate) was purified to give a pale yellow crystal of N-(2-hydroxyethyl)-3-phenyl-3-ylidene-propanamine 2.11 g (yield: 25.5%). The analytical data are as follows: iH-NMR spectrum (300 MHz, CDCl3) (5 ppm: 2.54 (t, 1H, J = 5.4 Hz), 3.48 to 3.53 (m, 2H), 3.75 to 3.80 (m, 2H), 4.00 (s) , 15 2H), 7.50~7.66 (m, 4H), 7.98~8.02 (m, 2H).

Mass spectrum (CI-MS): m/z = 208 [M + + 1] · Melting point: 73 to 76 ° C. Example B-5 (Preparation of stripping liquid: (2-hydroxyethyl)-3-phenyl- 3-sided oxy-propionamide) 20 In the mixture of 2-aminoethanol and ultrapure water (weight ratio: 3/l) of 40g of the stripper component, the corrosion inhibitor component is added at room temperature (2- 2 g of hydroxyethyl)-3-phenyl-3-oxo-pentamidine was prepared to prepare a stripper. Example B-6 (Isolation degree of corrosion: (2-hydroxyethyl)-3-phenyl-3-oxo-propionamide) 42 200916607 Commercially available copper foil was immersed at 1% by weight at 50 ° C After the sodium hydroxide aqueous solution was used for 1 minute and the lwt% sulfuric acid aqueous solution was used for 1 minute, it was washed with ultrapure water and dried, and the copper foil was pretreated. Next, the copper wire was immersed in the peeling liquid of Example B-5 at 70 ° C, and allowed to stand for 1 hour. Thereafter, the copper foil was removed from the stripping solution, and the concentration of copper dissolved in the liquid was measured by inductively coupled plasma mass spectrometry (ICP-MS). The measured value was expressed as an invading value according to the above formula (I), and the result was 5 ppb/mg. Example B-7 (Recovery (2-3⁄4 ethyl)-3-phenyl-3-oxo-propylamine) 10 Ethyl acetate was put into the stripping solution used in Example B-6, and the liquid was separated and pumped. Lift the organic layer. The obtained organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated, and then 2-(hydroxyethyl)-3-phenyl-3-oxo-propanamine and 2-aminoethanol were recovered as a mixture. Comparative Example 1 15 (Test piece: copper foil; no anti-corrosion compound) Except that the compound having an anticorrosive action, that is, the yS-ketoguanamine compound represented by the formula (B1), was not used, and Example B-5, The same operation and evaluation were carried out in Example B-6, and the result was 198 ppb/mg. Comparative Example 2 20 (Test piece: copper foil; compound having anti-corrosion effect · benzotriazole) Except that benzotriazole was used as a compound having an anticorrosive action, it was carried out in the same manner as in Example B-5 and Example B-6. The same operation and evaluation gave a result of 15 ppb/mg ° &lt;Example C: Amineneamine compound&gt; 43 200916607 Example ci (Synthesis of N-(2-hydroxyethyl)-3-(2-hydroxyethyl) Amino)-4,4-dimethyl-2-pentenylamine) 4,4-dimethyl-3-5-oxo-valeric acid mixed in a 5 〇ml eggplant flask under nitrogen atmosphere 30.00 g (190 mmol) of methyl ester and 30.00 g (491 mmol) of 2-aminoethanol were stirred at 70 ° C for 4 hours. After the completion of the reaction, the reaction mixture was concentrated, and the obtained oily white oil was purified on silica gel column chromatography (eluent: ethyl acetate) to give N-(2-hydroxyethyl) as a colorless oil. ?-(2-hydroxyethylamino)-4,4-dimethyl-2-pentenylamine 43.76 g (10%: 59%).

Mass spectrum (CI-MS) · m/z = 231 [M + +1]. Example C-2 (Resistance stripping solution for preparation test · · N-(2-hydroxyethyl)-3-(2-hydroxyl Ethylamino)-4,4-dimethyl-2-pentenylamine) 15 in a mixture of 2~ aminoethanol and ultrapure water (weight ratio: 3/l) 40g, added at room temperature 2 g of N-(2-hydroxyethyl)-3-(2-hydroxyethylamino)-4,4-dimethyl-2-pentenylamine as a corrosion inhibitor was prepared to prepare a test stripper. Example C-3 (Determination of corrosion: N-(2-hydroxyethyl)-3-(2-hydroxyethylamino)-4,4-dimethyl 20 -2-pentanol) The copper wire (weight: 1900 mg) was immersed in a 1 wt% sodium hydroxide aqueous solution at 5 CTC for 1 minute, and a lwt% sulfuric acid aqueous solution was used for 1 minute, and then washed with ultrapure water and then dried to carry out copper wire pretreatment. Next, the copper wire was immersed in a test photoresist stripper prepared in Example C-5 at 70 C, and stirred at 1 small 44 200916607. Thereafter, the copper wire was removed from the test photoresist stripper, and the dissolved copper concentration was measured by inductively coupled plasma mass spectrometry (ICP-MS). The measured value is expressed as the invading value according to the above formula (I) and is 2.3 ppb/mg. Example C-4 5 (Synthesis of N-(2-lightethyl)-3-(2-ethylamino)-2-butanamine) 2-Amino group at 25 ° C under nitrogen atmosphere Ethanol l〇.〇〇g (l〇〇mm〇l) was stirred with N-(2-hydroxyethyl)-3-oxo-butanamine i 4.50 g (100 mmol) for 1 hour. After the completion of the reaction, the Mass spectrum (CI-MS) of the reaction liquid was measured, and the production of N-(2-ethyl)-3-(2-ethylamino)_2-butyric acid was determined. 1 〇 Mass spectrum (CI-MS): m/z = 189 [M + + 1]. Example C-5 (Modulation s type test resist stripping solution; N-(2-ethyl)_3_(2_ Ethylamino)-2-butylimamine) In a mixture of 2-aminoethanol and ultrapure water (weight ratio: 3/i) 4 〇g, 15 at room temperature, adding anti-corrosive ingredients Ν· 2 g of (2-hydroxyethyl)-3_(2-hydroxyethylamino)-2-butanamine was prepared to prepare a photoresist stripper for testing. Example C-6 (Measurement of Invasion Degree··N-(2-Ethyl) Winter (2_Ethylamino) 2_Butylamine) Commercially available copper wire (weight: BOOmg) was 2〇 Aqueous solution! Minutes [% aqueous solution of sulfuric acid! After a minute, the copper wire was washed with ultrapure water and the copper wire was pretreated. Next, the copper wire was stained with 7 〇 U in the test light produced by the example of the example, and the time was disturbed. Thereafter, the steel wire was removed from the test photoresist stripper to measure the dissolved steel concentration by inductive electric mass spectrometry (ICP_MS). The measured value is expressed as an erosion degree value according to the above-mentioned mathematical formula 45 200916607 (1), and is 1.5 ppb/mg. Comparative Example 3 (Test piece. Copper wire, compound having no anti-money effect) The same operation as in Examples 5 A-1 and C-2 was carried out except that the compound having an anticorrosive effect was not used, and no anti-insect was obtained. A photoresist stripper for testing compounds. The same operation as in Examples A-2 and C-3 was carried out three times, and the results were 211 ppb/mg, 79 ppb/mg, and 97 ppb/mg, respectively, and the average value of three times was 129 ppb/mg. Comparative Example 4 10 (Test piece. Copper wire, compound having anti-money effect: benzotriene) The same as Examples A-1 and C-2 except that benzotriazole was used as the compound having an anticorrosive action. The photoresist stripper was prepared and evaluated in the same manner as in Examples A-2 and C-3. The result was 3.7 ppb/mg. Comparative Example 5 15 (Test piece: copper wire; compound having peeling property: 2-ethanolamine) The photoresist stripping was prepared in the same manner as in Examples A-1 and C-2 except that 2-ethanolamine was used as the compound having peeling properties. The liquid was subjected to the same s evaluation as in Examples VIII and C-3. The result was 27.6 ppb/mg. As is apparent from the results of the above examples, the degree of corrosion of the substituted ketone 20 compound and its derivative used in the examples was smaller than that of the existing stupid triazole, i.e., exhibited an excellent anticorrosive effect. Further, after the degree of corrosion is measured, the substituted hydrazine compound of the present invention or a derivative thereof can be recovered from the waste liquid of the used photoresist stripping liquid. Industrial Applicability 46 200916607 As described above, according to the present invention, an anti-surplus agent, an anti-Immune treatment solution or an anti-corrosion preservation solution containing the formula (A1), the formula (B1) and the formula (C1) can be obtained. a compound of at least one of a substituted ketone compound and a derivative thereof; and a photoresist stripper or a photoresist stripper having both anti-corrosion properties and photoresist peeling properties, comprising the compound and a photoresist Peeling properties of the compound. For example, the photoresist stripper or the photoresist stripper of the present invention is used in a process such as a semiconductor integrated circuit and a printed circuit board, and is excellent in corrosive metals such as copper, aluminum, or the like. Prevent corrosion effects. 10 [Simple description of the diagram] (none) [Description of main component symbols] (none) 47

Claims (1)

200916607, the scope of the patent application: A defensive agent 'containing a ketone ester compound represented by the formula (A1); &lt;Chemical 1&gt; R1^〇R5 (A1) wherein R 1 is an optionally substituted hydrocarbon group; R 2 and R 3 are a hydrocarbon group which may optionally have a hydrogen atom, a _ atom, and optionally a substituent; R 2 may optionally R3 combines to form a cyclic structure of a 3- to 6-membered ring; further, 'R5 is a hydrocarbon group optionally having a substituent. 2. 10 kinds of anti-surplus agents 'containing yS-keto acid amine compound represented by formula (B1); &lt;Chemical 2&gt; 〇〇R1 15 3. *?C^N-(CH2)n-OH R2 R3 R6 Wherein R1 is an optionally substituted hydrocarbon group; R2 and R3 are a hydrogen atom, a dentate atom, and optionally a hydrocarbon group; and R may optionally be bonded to R3 to form a 3 to 6 member ring. a cyclic structure; R 6 is a hydrogen atom or a hydrocarbon group optionally having a substituent; n = an integer of 2 to 6. An anticorrosive agent containing an amin〇enamide compound represented by the formula (c丨); &lt;Chemical 3&gt; (B1) HO, R1 0, n^V^n~0H H R2 (C1) In the formula, R1 is a hydrocarbon group which may have a substituent; R2 is a hydrogen atom: a hydrogen atom which may optionally have a substituent; and further, / is a hydrogen atom or a hydrocarbon group which may optionally have a substituent. 48 20 200916607 4. ^Anti-touch treatment solution or anti-(4) storage solution, containing: For example, please contact the anti-narrative agent of any one of items 1 to 3 with water, organic solution or a mixed solution of these. 5. If the patent is covered by any of the items (1) of items 1 to 3, it is used to prevent the object rot 14 ' and the item has more than _ and more. 6. For example, if the anti-surname treatment liquid or the anti-survival preservation liquid of the applicant's patent scope is used, it is used to prevent the item from being used, and the product has more than two types of copper and the composition of the composition. 1〇7· “(4) agents of Item No. 1 to Item 3 of the material, which are used for the anti-residue treatment of the metal film or metal wiring on the semiconductor integrated circuit. 8·If the scope of patent application is 4 Item anti-treatment liquid or anti-money preservation liquid, which is used for the anti-touch treatment of metal film or metal wiring on the semiconductor integrated circuit. 9' kinds of photoresist stripping agent, containing: selected from the patent application scope At least one of the compounds of the formula (Α1), the formula (Β1), and the formula (C1); and the compound having a release property. 10. A photoresist stripping solution containing: The photoresist stripping agent of the ninth item; and the water, the organic solution or the mixed solution of the above. The photoresist stripping agent according to claim 9 of the patent scope, wherein the compound having the peeling property is an alkanolamine. The photoresist stripper according to claim 11, wherein the alkanolamine comprises a group selected from the group consisting of 2-aminoethanol, diethanolamine, N-ethylaminoethanol, methylaminoethanol, and N-mercapto Diethanolamine, dimethylaminoethyl yeast, 2_(2_ 49 200916607 amino ethoxy) ethanol A compound of 1 or more of 1-amino-2-propanol and triethanolamine. 13. The photoresist stripper according to claim 9 of the patent application, which is used for preventing the article from being rotted and having the component One of copper and lyon is on 5. 14. The photoresist stripping liquid according to claim 10 of the patent application is used for preventing corrosion of articles, and the article has one or more of copper and aluminum in the constituent components. The photoresist stripper of claim 9 which is used for the anti-corrosion treatment of the metal film or the metal wiring on the semiconductor 10 integrated circuit. 16. The photoresist stripping liquid according to claim 10 of the patent application is used An anti-corrosion treatment of a metal film or a metal wiring on a semiconductor integrated circuit. 17. A method for manufacturing an anti-shoe agent, the method comprising: the anti-money agent comprising: selected from any one of items 1 to 3 of the patent application scope. At least one compound of the compound represented by the formula (A1), the formula (B1) and the formula (C1): 15. A method for producing a photoresist stripper comprising: the photoresist stripper comprises: Formula (A1), formula (B1) and formula of any one of items 1 to 3 At least one of the compounds of the formula (C1); and a compound having a release property. 20 19. An anticorrosive agent according to any one of claims 1 to 3, which contains the patent application scope 4 items of anti-corrosion treatment solution and anti-corrosion preservation solution, or the photoresist stripping agent according to claim 9 or the photoresist stripping solution of item 10, which is determined by inductively coupled plasma mass spectrometry (ICP) -MS) Determine the amount of metal that has been dissolved, and then use the formula [I], and 50 200916607 to indicate the degree of dissolution as the degree of erosion value; &lt;Number 1&gt; Mathematical formula [I] Invasion #degree value (ppb/mg) = concentration of dissolved metal (ppb) / gold before test 5 genus weight (mg) 51 200916607 VII. Designation of representative figure: (1) The representative figure of the case is: (No). (2) A brief description of the symbol of the representative figure: (none) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none) 4