TWI228546B - Rust preventives and method of rust prevention with the same - Google Patents

Abstract

Rust preventives (1) containing as the active ingredient a copolymer of a hydrophilic or water-soluble polymerizable monomer (A) and a monomer (B) having hydroxyphenylbenzotriazole structure and a polymerizable double bond; and rust preventives (2) containing as the active ingredients the monomer (A), the monomer (B), and a benzotriazole (D) represented by the general formula (1) are disclosed: (1) [in which R1 is hydrogen, C1-8 alkyl, carboxyl, C1-8 alkoxycarbonyl, phenoxycarbonyl, hydroxyl, or halogen; and R2 is hydrogen, hydroxyl, amino, halogen, or a metal atom]. The monomer (B) includes compounds represented by the general formula (2). The rust preventives can be used in the form of aqueous solutions without using any organic solvent and are effective particularly in the rust prevention of copper and its alloys.

Description

1228546 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a rust inhibitor using a hydroxyphenylbenzotriazole copolymer as an effective component and a rust prevention method for metals using the same. [Prior art] In the past, various methods have been proposed for rust prevention of metals. For example, a method of coating a metal surface with another metal that is not easily corroded, a method of coating the metal surface with a paint, a method of forming a film chemically or electrochemically on the metal surface, and the like to prevent the metal surface Methods of suppressing corrosion by contact with an external corrosive environment are known. Known as metal-based rust inhibitors are benzotriazoles. For example, in Japanese Patent Application Laid-Open No. Hei 10-2 6 5 9 7 9, it is disclosed that the compounds contain a dialkylamino-derived (fluorene) A rust preventive composition for a copper material made of benzotriazoles is added to an organic solvent-soluble composition of an acrylic copolymer of a component of an alkyl acrylate. Further, in Japanese Patent Application Laid-Open No. 5-9-10809, a metal corrosion inhibitor for a high-temperature lubricating oil containing 2 ^ -hydroxyphenylbenzotriazoles as an active ingredient is disclosed. Although benzotriazoles can chelate with metal surfaces to form coatings to exert rust-preventive effects, the conventional technologies still have unresolved issues in practice. For example, because its coating is usually thin, its rust-preventive effect under severe conditions may not be satisfied, and this is one of them. In addition, a case where a three-sigma sigma as a rust preventive agent is added to a resin may cause a bleed-out phenomenon, and a stable effect cannot be obtained. In addition, in the case of poor water solubility of the tritium, the organic solvent for dilution is usually required. Therefore, it will increase the cost of 5 312 / Invention Specification (Supplement) / 92-07 / 92112016 1228546, resulting in safety in operation. There are problems in surface and wastewater treatment, and there are restrictions on the types of solvents that can be used. For example, 2 ^ -hydroxyphenylbenzotriazoles have poor water solubility. In order to exert the anti-rust effect, they must be dissolved in an organic solvent, and the above problems will occur in use. Therefore, the subject of the present invention is to provide a rust preventive agent and a rust preventive method using the rust preventive agent, which are those containing a benzotriazole-based compound, and are suitable for metals even under severe conditions. The rust preventive effect is exhibited and maintained, and it can be used even under the condition of an aqueous solution containing substantially no organic solvent. [Summary of the Invention] In order to solve the above problems, the present inventors reviewed the rust prevention effect of various benzotriazole compounds in practice and found that p-hydroxyphenylbenzotriazole is water-soluble or hydrophilic. The copolymer obtained by copolymerizing the copolymerizable monomers is rich in water solubility, and is very useful as a metal-based rust inhibitor. The present invention has been completed in 焉. That is, the present invention relates to the following antirust agents and methods for using them. (1) A rust preventive agent comprising: a water-soluble or hydrophilic polymerizable monomer (A); and a hydroxyphenylbenzotriazole compound monomer having a polymerizable double bond-containing group ( B) Copolymer as an active ingredient. (2) A rust preventive agent comprising: a water-soluble or hydrophilic polymerizable monomer (A); and a hydroxyphenylbenzotriazole compound monomer having a polymerizable double bond-containing group ( B) Copolymer and general formula (1): 6 312 / Invention Specification (Supplement) / 92-07 / 92112016 1228546 Chinese

C-based alkyl proton J, or sub-radical pro 0, gold or carbonyl oxygen pro benzene radical

Carboxyloxy group, hydroxy 8-Λ C atom of alkoxy group, hydrogen radical carboxyl group shown in Table 2, R is effective as D κίν azole triacene shown in the table, such as phenyl phenyl, and its agent is rust. The item of defense V) / 2 / IV or 2 / (V is generally regarded as the B / IV body compound azole triacene R5

(2) [In the formula, R3, R4, and R5 represent the same or different polymerizable double bond containing group, a hydrogen atom 'Cu alkyl group, C] -8 alkoxy group, cyano group, hydroxyl group, halogen atom, Or alkoxycarbonyl; at least one of R3, R4, and R5 is a polymerizable double bond-containing group. ] The hydroxyphenylbenzotriazole compound shown. (4) A rust preventive method for metals, characterized in that the surface of the metal is coated with the rust preventive agent according to any one of (1) to (3) above. (5) A method for rust prevention of metals, characterized in that, when the surface of a metal is covered with the rust preventive agent according to any one of the items (1) to (3), the method (1) to (1) to (3) The rust preventive agent of any one of the items is used in the form of an aqueous solution 7 312 / Invention Specification (Supplement) / 92-07 / 92112016 1228546. (6) The rust prevention method according to the above item (4) or (5), wherein the aforementioned metal is copper or a copper alloy. [Embodiment] First, the representative of the substituents described in the present specification and specific examples thereof will be listed. The 1-4 alkyl group means a linear or branched alkyl group having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Second or third butyl.

Ci-8 alkyl group means a linear or branched alkyl group having 1 to 8 carbon atoms. In addition to the above alkyl groups of 1-4, examples include n-pentyl, isopentyl, and neo Amyl, tertiary amyl, n-hexyl, heptyl or octyl, etc.

Chu alkyl group means a linear or branched alkyl group having 1 to 18 carbon atoms. In addition to the above Ci-4 alkyl group and Ci-8 alkyl group, nonyl and decyl are also listed. Base, eleven base, twelve base, thirteen base, fifteen base, fifteen base, sixteen base, eighteen base, etc.

Ci-8's alkoxy group means a linear or branched alkoxy group having 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butane. Oxy, tertiary butoxy, n-pentyloxy, isopentyloxy, neopentyloxy, tertiary pentoxy, n-hexyloxy, heptyloxy or octyloxy and the like. The alkoxycarbonyl group represents a linear or branched alkoxycarbonyl group having 1 to 8 carbon atoms, and examples thereof include fluorenyloxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and Tributoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, tertiary pentyloxycarbonyl, n-hexyloxycarbonyl, heptyloxycarbonyl or octyl 8 312 / Invention Specification (Supplement) / 92-07 / 92112016 1228546 oxycarbonyl and the like.

Ci-4's alkylene group means a linear or branched alkylene group having 1 to 4 carbon atoms. Examples include methylene, ethylene, trimethylene, tetramethylene, and fluorenyl groups. Amidylene, propylene, 1-fluorenyltrimethylene, 2-methyltrimethylene, or ethylethylene. C1-!. The alkylene group means a linear or branched alkylene group having 1 to 10 carbon atoms. In addition to the Ci-4 alkylene group, examples include pentamethylene and hexamethylene , Hepta-methylene, octa-methylene, non-methylene, deca-methylene or 2,2-dimethyltrimethylene. Examples of the halogen atom include chlorine, bromine to fluorine, and iodine. Examples of the metal atom include an alkali metal atom (sodium, potassium, lithium, etc.), a silver atom, and the like. The aforementioned copolymer as an effective component of the rust preventive agent of the present invention is a water-soluble or hydrophilic polymerizable monomer (A) and a hydroxyphenylbenzotriazole compound monomer (B having a polymerizable double bond-containing group) ) As a copolymer of the necessary monomers. The polymerizable monomer (A) is not particularly limited as long as it contains a radical polymerizable group in the molecule and is water-soluble or hydrophilic. Examples thereof include the following ① to ①: ① acrylic acid Or (acryl) acrylic acid such as fluorenyl acrylic acid; unsaturated copolymerization of cis-butenedioic acid, trans-butenedioic acid, itaconic acid, citraconic acid, crotonic acid or cis-butenedioic anhydride Carboxylic acids; ② selected from alkali metal salts (sodium, potassium, lithium salts, etc.), ammonium salts and amino compound salts (dimethylamine, trimethylamine, diethylamine, 9312 / Invention Specification (Supplement) / 92-07 / 92112016 1228546 1 of the group of triethylamine, monoethanolamine, diethanolamine, methyldiethanolamine, fluorenylisopropanolamine, dimethylmonoethanolamine, triethanolamine, etc.) Or two or more; ③ With the general formula (3): H2C = C—c—0— (R7-0) m-R8 R6 〇 (3) [wherein R6 represents a hydrogen atom or a C1-4 alkane base. R7 represents an alkylene group of Cl-4. R8 is a hydrogen atom, an alkyl group of Ch, or a phenyl group. m is an integer from 1 to 20. ] Acrylic acid alkylene glycol ether compound; ④ N, N -dimethylaminopropyl (fluorenyl) acrylamide, N, N -dimethylaminoethyl (meth) acrylamide , N, N -diethylaminoethyl (fluorenyl) acrylamide and other (fluorenyl) acrylamide, and N, N -dimethylaminopropyl (fluorenyl) acrylate, N, N -Diethylaminoethyl (fluorenyl) acrylate, propenylmorpholine, 2-hydroxy-hydroxypropenylpropyloxy-N, N-dimethylamine, 3-hydroxypropenyl-N, N -Amino alkyl (meth) acrylates such as dimethylamine, which are benzyl chloride, methyl chloride, chloroethane, chloropropane, chlorobutane, iodopane, fluorenyl iodide, iodoethane Or alkylated reagents such as iodopropane and alkylated reagents such as diethylsulfuric acid or difluorenylsulfuric acid, and the unsaturated copolymerizable fourth-grade ammonium salts; Methyl ethyl ether, vinyl ether via ethyl vinyl scale or propyl vinyl bond, etc .; ⑥ vinyl ketene such as hydroxyethylketene, hydroxyethylketene or hydroxypropylketene; ⑦ N- Among the aforementioned polymerizable monomers (A), especially ① is selected from among the aforementioned polymerizable monomers (A). Acrylic acid such as acrylic acid and fluorenyl acrylic acid; unsaturated copolymers of cis-butenedioic acid, trans-butenedioic acid, itaconic acid, citraconic acid, crotonic acid or cis-butenedioic anhydride One or two or more of the group of alkali metal salts, ammonium salts, and amino compounds of polymerizable carboxylic acids; and acrylic acid compounds represented by the general formula (3) are preferred. In addition, it is copolymerized with one or more selected from the group consisting of alkali metal salts, ammonium salts, and amino compounds of the unsaturated copolymerizable carboxylic acids with a hydroxyphenylbenzotriazine compound (B). In the case of a copolymer as the aforementioned copolymer, one or two or more groups selected from the group consisting of alkali metal salts, ammonium salts and amino compounds of the unsaturated copolymerizable carboxylic acids may be used. After a copolymer of a saturated copolymerizable carboxylic acid and a hydroxyphenylbenzotriazole compound (B), 0.1 to 1.3 equivalents of one or two or more selected from the group consisting of an alkali metal salt, ammonium, and an amino compound are used. To make it react to make. Next, as for the hydroxyphenylbenzotriazole compound monomer (B) having a polymerizable double bond-containing group, as long as it has a polymerizable double bond-containing group at any substitutable position of hydroxyphenylbenzotriazole, Yes, it is not particularly limited, and examples thereof include the general formula (2) as described above.

[Wherein R3, R4 and R5 represent the same or different polymerizable double bond containing group, hydrogen atom, Ci-8 alkyl group, L-8 alkoxy group, cyano group, hydroxyl group, halogen atom, carboxyl group or alkane Oxycarbonyl; however, at least one of R3, R4 and R5 is polymerizable bis 12 312 / Explanation of the Invention (Supplement) / 92-07 / 92112016 1228546 oxy) phenyl] -5 -fluorenylbenzotrisial, Or [2-Ethyl-3-tert-butyl-5- (propenyloxyethoxycarbonylethyl) phenyl] benzotriazole and the like. These hydroxyphenylbenzotriazole compounds can be produced according to a known method, for example, the method described in Japanese Patent No. 2701 1 16. The hydroxyphenylbenzotriazole compound monomer (B) may be used alone or in combination of two or more. The amount ratio of the hydroxyphenylbenzotriazole compound monomer (B) in the aforementioned copolymer is not particularly limited, and can be appropriately selected in a wide range. However, the obtained copolymer has antirust properties and water solubility. In consideration of the use environment, purpose, and economy, it is generally suitable to be 0.0001 to 50% by weight of the total amount of the copolymerization component, and preferably 0.001 to 30% by weight. In order to improve the film-forming property and stability of the copolymer of the polymerizable monomer (A) and the hydroxyphenylbenzotriazole compound monomer (B), to prevent aggregation, precipitation, or gelation, and to seek water solubility and foaming It is preferred that the copolymer is composed of other polymerizable monomers (C) in combination with other polymerizable monomers (C), such as flexibility, adhesion, and adhesion. Examples of the other polymerizable monomer (C) include fluorene (meth) acrylate, ethyl (meth) acrylate, butyl (fluorenyl) acrylate, octyl (meth) acrylate, or (meth) ) Alkyl (fluorenyl) acrylates such as lauryl acrylate; cyclohexyl acrylate (fluorenyl), cyclohexyl (meth) acrylate, isofluorenyl (meth) acrylate, or (fluorenyl) acrylic acid (Meth) acrylate cycloalkyl esters such as cyclododecyl ester; caprolactone adducts of (fluorenyl) acrylic acid; hydroxy aromatic vinyls such as p-hydroxystyrene; 1-hexene, Olefins such as 1-octene, 1-decene, or styrene; vinyl acetate, vinyl propionate, or vinyl laurate; Jt acid vinyl esters; vinyl chloride, etc. 14 312 / Invention Specification (Supplement) / 92-07 / 92112016 1228546 These other polymerizable monomers (c) may be used alone or in combination of two or more. The amount ratio of the other polymerizable monomers in the copolymer is not particularly limited, and can be appropriately selected in a wide range. However, if the amount of the other polymerizable monomers exceeds 20% by weight, water solubility will be impaired. It is generally suitable to be 20% by weight or less of the total amount of the copolymer component, preferably 0.01 to 20% by weight, and more preferably 1 to 15% by weight. In the present invention, in order to further improve the rust prevention performance, one or two or more kinds of benzotriazoles (D) described below may be added to the copolymer. Examples of the benzotriazoles (D) include 1 fluorene-benzotriazole, 4-methyl-1 fluorene-benzotriazole, 4-mercapto-1 fluorene-benzotriazole, 4 -Fluorenyl-1fluorene-benzotriazole sodium salt, 5-fluorenyl-1fluorene-benzotriazole, benzotriazolebutyl ester, silver benzotriazole salt, 5-chloro-1fluorene-benzotriazole, 1-chlorobenzotriazole and the like. The amount ratio of the benzotriazoles (D) in the aforementioned copolymer can be appropriately selected within a wide range. However, it is generally used in an amount of 0 to 500 parts by weight based on 100 parts by weight of the copolymer. The degree is better. Next, a polymerization method of the aforementioned copolymer used as the rust preventive agent of the present invention will be described. Basically, it can be produced by a general polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, and the like. For example, when a solution polymerization method is used, the polymerizable monomer (A) and the hydroxyphenylbenzotriazole compound (B) may be polymerized in a solvent in the presence of a polymerization initiator, and if necessary, polymerized with other polymers. The monomer (C) may be copolymerized. As the solvent, a conventional one can be widely used, and examples thereof include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, and n-pentyl. Alcohol, Ethyl Fibrinolysin, Butyl Fibrinolysin, 1-Methoxy 15 312 / Instruction of the Invention (Supplement) / 92-07 / 92112016 1228546 Gyl-2-propanol, ethylene glycol, propylene glycol, diethylene glycol, Alcohols such as polyethylene glycol or polypropylene glycol; esters such as ethyl acetate, propyl acetate or butyl acetate; aliphatic hydrocarbons such as petroleum ether, hexane, or heptane; benzene, toluene, or two Aromatic hydrocarbons such as toluene; ketones such as acetone, methyl ethyl ketone or methyl isobutyl fluorenone; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, or dioxane; N, N-dimethylformamidine Amines such as amines. Among these solvents, a water-soluble solvent is particularly preferable when the required copolymer is used as an aqueous solution. Specific examples include methanol, ethanol, isopropanol, and ethyl solvents. Alcohols such as cellulose or 1-methoxy-2-propanol; ethers such as tetrahydrofuran or dioxane; and amines such as N, N-dimethylformamide. These solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, and can be appropriately selected in a wide range according to the characteristics and applications of the copolymer to be obtained. Generally, when the total amount of the copolymer component is 100 parts by weight, 1 to 1 can be used. 0 0 0 0 parts by weight. As the polymerization initiator, a conventional one can be widely used, and examples thereof include peroxides such as phenylhydrazone and dibutyl peroxide; and azo compounds such as azobisisobutyronitrile. The polymerization initiator may be used singly or in combination of two or more kinds. 1〜5 莫耳 ％。 The amount of the polymerization initiator is not particularly limited, and generally may be the entire copolymer component (total moles) of 0.1 to 5 mole%. This copolymerization reaction is usually carried out at a temperature ranging from room temperature to 200 ° C, and preferably at a temperature ranging from 40 to 140 ° C. It is generally suitable to complete the copolymerization at 1 to 50 hours, and to complete at 2 to 50 hours. ~ 2 4 hours is better. The molecular weight of the aforementioned copolymer can be obtained by a usual method, such as adding tetragasified carbon, lauryl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, 16 312 / Invention Specification (Supplement) / 92-07 / 92112016 1228546 Chain transfer agent such as octyl hydrothioacetate, thioglycerin, or polymerization blocking agent such as hydroquinone. The copolymer obtained in this way usually has a weight average molecular weight of 1 0 0 to 2 0 0 0 0, and preferably 2 0 0 to 1 5 0 0 0 0, if it is water-soluble and exudates over time For prevention and other considerations, 3 0 0 0 to 1 0 0 0 0 0 is preferred, and 5 0 0 0 to 5 0 0 0 0 is more preferred. The rust preventive agent of the present invention contains the aforementioned copolymer as an active ingredient. This copolymer is rich in water solubility and can be used in the form of an aqueous solution. If necessary, a dispersant, an emulsifier, or the like can be used as a dispersion or an emulsion. The above-mentioned aqueous solution refers to a solution made of water or a solution made of water as a main solvent. In the latter case, an organic solvent may be contained to the extent that it does not interfere with the solubility of the copolymer in water. For example, the solvent used in the production of the rust-preventive polymer may contain such a solvent so as not to hinder the rust-preventive effect. In the rust preventive agent of the present invention, other rust preventive agents, ultraviolet absorbers, near-infrared absorbers, and water-soluble matting agents may be added to the extent that the rust preventive effect of the copolymer is not impaired. , Oxidation inhibitor, fluorescent whitening agent, wetting agent, surface tension adjuster, pigment, dye, pigment, perfume, metal inactivator, nucleating agent, antistatic agent, flame retardant, slip agent, tackifier , Antifungal agent, preservative, oxygen absorbent or processing aid, or other additives that have traditionally been used in rust inhibitor compositions. Although the use concentration of the aforementioned copolymer in the rust preventive agent of the present invention varies slightly depending on the type of the copolymer, it is generally sufficient as long as it is greater than or equal to 0.0001% by weight, which is not particularly limited, but is preferably 0. 0 1 to 10% by weight is used, and 17 312 / Invention Specification (Supplement) / 92-07 / 92112016 1228546 0. 〇 1 to 1% by mass is preferable. If the use concentration does not reach 0. Ο Ο Ο 1% by weight, a sufficient antirust effect cannot be expected. The anti-recording agent of the present invention is effective for preventing rust of general metals (metals such as copper and iron or alloys), and particularly has excellent effects on copper and copper alloys. The rust prevention method of the present invention can be treated by, for example, coating the surface of a metal to be rust-proofed with a solution containing the rust inhibitor of the present invention, coating with a spray, or dipping the metal into the solution. Then, it is made to dry and coat. The rust preventive agent of the present invention can be stored in a solution state, but it can also be used as a concentrated liquid in consideration of distribution, and it can be diluted with water to a set concentration during use. By using the rust prevention method of the present invention, the rust prevention treatment of metals can be performed very easily, even under severe conditions such as salt water, acid gas phase, high temperature and humidity, or long-term outdoor exposure, Can also significantly inhibit rust and even corrosion. In addition, it can be used in a plastic case of an electronic device, and the same effect as that of the recorded non-electric key can be obtained. (Examples) Next, the present invention will be described more specifically with reference to examples and test examples. In addition, in the following description, "part" or "%" means "part by weight" or "% by weight" unless otherwise specified. (Example 1) 100 parts of isopropanol were placed in a 4-necked flask equipped with a stirrer, thermometer, cooler, and 18 312 / Invention Manual (Supplement) / 92-07 / 92112016 1228546 dropping funnel, and the temperature was raised. Between 2 to 80 ° C, 20 parts of 2- [2'-hydroxy-5 ... (fluorenyl propylene ethoxy) phenyl] benzotriazole and fluorenyl polyethylene were added dropwise within 2 hours. A mixture of diol (meth) acrylate (repeated number m and 8 of ethylene glycol) of 80 parts and 0.3 parts of azobisisobutyronitrile, and then kept at 80 ° C for 4 hours to obtain the desired Copolymer, to obtain an antirust agent composed of an isopropanol solution (solid content of 50.8%) of the copolymer. The average weight molecular weight of this copolymer by gel chromatography analysis (hereinafter referred to as G P C) was 4 3 100. The solvent was distilled off under reduced pressure from the solution containing the aforementioned copolymer, and deionized water was added to the residue to prepare an aqueous solution (solid content: 30%) containing the aforementioned copolymer to obtain a rust inhibitor composed of an aqueous solution. (Example 2) 100 parts of 1-methoxy-2-propanol was placed in a 4-necked flask equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, and the temperature was raised to 80 ° C. Between 2 hours, 30 parts of 2-[2 '-hydroxy-5'-(fluorenylpropene ethoxy) phenyl] benzotriazole and methoxypolyethylene glycol (meth) acrylate were added dropwise. (M and 7) A mixture of 70 parts and 0.3 parts of azobisisobutyronitrile and 1 part of n-dodecanethiol, and then kept at 80 ° C for 4 hours to obtain the desired copolymer, which was obtained. A rust preventive composed of a 1-methoxy-2-propanol solution of the copolymer (solid content 51.2%). (Example 3) 100 parts of 1-methoxy-2-propanol was placed in a 4-necked flask equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, and the temperature was raised to 80 ° C. Between 2 hours, 30 parts of 2-[2 '-hydroxy-3'-third butyl-5'-(methacryl fluorenylethoxy) phenyl] benzotriazole and methoxypolyethylene were added dropwise. Diol (Methyl) 19 312 / Invention Specification (Supplement) / 92-07 / 92112016 1228546 50 parts of acrylic acid S (m and 7), 20 parts of acrylic acid, 0.3 parts of azobisisobutyronitrile, and 10 parts A mixture of 1 part of dioxanethiol was held at 80 ° C for 4 hours to obtain the desired copolymer, and a 1-methoxy-2-propanol solution (solid content 4 9. 7%). The average weight molecular weight of this copolymer by gel chromatography analysis (hereinafter referred to as GPC) was 5 9 0 ° (Example 4). 100 parts of 1-methoxy-2-propanol was placed in In a 4-necked flask of a blender, thermometer, cooler, and dropping funnel, 2-[2 '-Thryl-3' -Third-butyl- 5 '-(fluorenyl propylene ethoxy) phenyl] 30 parts of 5-chlorobenzotriazole, 65 parts of methoxy polyethylene glycol (meth) acrylic acid (πι and 7), A mixture of 5 parts of 4-methylpropoxy-2,2,6,6_tetramethylpiperidine and 0.3 parts of azobisisobutyronitrile, and then kept at 80 ° C for 4 hours to complete the copolymerization By reaction, a rust-preventive agent composed of a 1-methoxy-2propanol solution (solid content 50.8%) was prepared. The average weight molecular weight of this copolymer via GPC was 3,590. After the solvent of the copolymer was distilled off under reduced pressure, deionized water was added to the residue to prepare an aqueous solution with a solid content of 30% to obtain a rust preventive for an aqueous solution. (Example 5) In a 4-necked flask equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, 250 parts of 1-methoxy-2-propanol and 2- [2'-hydroxy-5,-( 30 parts of methacrylic acid, ethoxy) phenyl] benzotriazole, 60 parts of ammonium methacrylate, 10 parts of 2-hydroxyethylfluorenyl acrylate, 0.5 parts of azobisisobutyronitrile, and n A mixture of 2 parts of dodecanethiol, with stirring under a nitrogen environment, rises 20 312 / Invention Manual (Supplement) / 92-07 / 92112016 1228546 Temperature to 60 ° C, keep at this temperature for about 1 2 Hours, the desired substance was obtained, and a rust inhibitor composed of a 1-methoxy-2propanol solution of the copolymer (solid 29.1%, polymerization rate 100%) was prepared. The GPC weight average molecular weight of this copolymer was 4 3 1 0 0. After the solution of the copolymer was distilled off under reduced pressure, deionized water was added to the residue to prepare a solid I-containing aqueous solution to obtain an antirust agent for an aqueous solution. The pH of this rust inhibitor was (Example 6). In 4 bottles equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, 250 parts of tetrahydrofuran, 2-[2 '-hydroxy-5'-( A mixture of 30 parts of methyl fluorenylethoxy) phenyl] benzotriazole, 60 parts of fluorenyl acrylic acid, 10 parts of ethyl fluorenyl acrylate, 0.5 parts of azobisisobutyronitrile, and 2 parts of n-decathiol, After heating up under stirring in a nitrogen environment, it was kept for about 12 hours to obtain the desired copolymer, and a total tetrahydrofuran solution (solid content: 29.1%, polymerization rate: 100%) was prepared. Rust inhibitor. Then, a 25% aqueous ammonia solution was added to make it pΗ6 ~ 7, and after stirring for 3 hours, the solvent was distilled off under reduced pressure, and the residue was added with sub-water to prepare an aqueous solution with a solid content of 30% to obtain Aqueous solution rusting agent. The average weight molecular weight of this copolymer via GPC was 4 1 (Example 7) In 4 bottles equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, 480 parts of tetrahydrofuran, 2-[2 '- Hydroxy-5 '-(methylfluorenylethoxy) phenyl] benzotriazole 72 parts, methyl methacrylate 24 acrylic acid 96 parts, 2-hydroxyethylfluorenyl acrylate 48 parts, azobis 312 / Explanation of the invention (Supplement) / 92-07 / 92112016 Copolymerization content via solvent 30% 6.90% calcined propylene 2-hydroxydioxane 6 (TC polymer formed at room temperature to prevent 100 ° calcined propylene) A mixture of dilute portions, isobutyl 21 1228546 nitrile 0.5 parts and 2 parts of n-dodecanethiol, heated to 60 ° C under stirring in a nitrogen environment, and maintained for about 12 hours to obtain the desired polymer, A rust inhibitor composed of a tetrahydrofuran solution of the copolymer (solid content 33, polymerization rate 100%) was prepared. Then, 25% ammonia water was added to dissolve into pΗ 6 ~ 7, and stirred at room temperature. After 3 hours, the solvent was depressurized, and the residue was added with deionized water to prepare a liquid with a solid content of 30% to obtain an antirust agent for an aqueous solution. The average molecular weight of the product through GPC was 3 6900. (Test Example 1)-Antirust test surface of another copper plate (JIS standard C1020P, 0.5 X 3 0 x 70mm), after grinding with a number of sandpaper, It was immersed in 0.5% hydrochloric acid for 5 minutes, and then washed with water for 1 minute as a test piece. Test solution 1: The 1-methoxy-2 -propane obtained in Example 2 was dissolved in deionization. Water, prepared as an agent of a water-based solution with a solid content of 0.18%, to prepare a test solution 1. Test solution 2: A 30% aqueous solution obtained in Example 7 was added with de-water to prepare a solid content of 0.15%. The antirust agent of the aqueous solution is used as the test solution 2. Comparative test solution 1: 1% benzotriazole is used as the rust inhibitor. Comparative test solution 2: 2-(2-meridyl-5-methyl 1% acetone of phenyl) benzo (Tinuvin P, manufactured by Giba-Geigy Japan) was dissolved as a rust inhibitor.

The above test pieces were immersed in test solution 1, test 2, comparative test solution 1 and comparative test solution 2 respectively at 20 ° C for 2 minutes at 60 ° C 312 / Invention Specification (Supplement) / 92 -07/92112016 A total of 5% of the liquid on one side was distilled off the water-soluble level 320, and the solution was added and the anti-rust ion was used as the test solution. The test solution was blown under 22 1228546 and air-dried for 30 minutes. The treated test piece was sprayed with 5% saline for 24 hours to confirm the surface state. The resistance value before and after the test was measured using a contact resistance meter, Rollesite MP (Mitsubishi Chemical Corporation needle: 2 probe type). The measurement was performed at two points. In addition, for reference 4, a salt solution was also applied to a person who had been electrolessly plated with nickel on the surface of a copper plate, and the surface condition was confirmed. The test results are shown in Tables 1 and 2. [Table 1] Test condition 1 for rust and discoloration condition 1 No test solution 2 No comparison test solution 1 Comprehensive recording Fully blackened comparison test solution 2 None Nickel-free plating treatment No None [Table 2] Resistance value saline spray Test solution 1 after pre-saline spray is 0. Any one below 0.1 Ω is 0.5 Ω below. Any test solution 2 is 0. Any one below 1 Ω is 0.5 Ω or less. Any one of the comparative test solution 1 is less than 0.1 Ω 3. 0 Ω, 140 Ω Any one of the comparative test solution 2 is less than 0.1 Ω 0. 3 Ω, 1. 2 Ω Nickel plating treatment All of them are 0.1 Ω or less. Any of them are 0.5 Ω or less. From the above results, it can be known that the benzotriazole, which is a representative agent of the copper of the rust preventive agent of the present invention, has a relatively low concentration, but It shows better anti-fruit and shows the same effect as nickel plating. (Test Example 2) The surface of a copper plate (JIS standard C1020P, 0.5 x 30 x 70mm) was coated with electricity at 312 / Invention Specification (Supplement) / 92-07 / 92112016 3 50 ° C, used for exploration, and sprayed to prevent rust. 1500 23 1228546 No. sandpaper was ground, immersed in 5% sulfuric acid for 1 minute, and then washed with water for 1 minute as a test piece. The test pieces were immersed in test liquids 3 to 6 and comparative test liquids 1 to 2 shown below. After being immersed for 5 minutes at 20 ° C, they were washed with water for 30 seconds, and the test pieces were blown through air. After the water droplets on the surface were removed, it was dried at 60 ° C for 30 minutes. Each of the treated test pieces was left in a constant temperature and humidity tank adjusted to a temperature of 60 ° C and a humidity of 85% for 114 hours. The resistance values before and after the test were measured with a contact resistance meter, Rollesite MP (manufactured by Mitsubishi Chemical Corporation, probe: 2 probe type). The measurement was performed at 5 points. The average value was used as the surface resistance value. The test results are shown in Table 4. Test solution 4: After adding 1H-benzotriazole to 5 parts by weight of the 30% aqueous solution obtained in Example 6, deionized water was added to prepare an aqueous solution having a solid content of 250 ppm. Test solution 5: After adding 3H parts of 3% by weight aqueous solution obtained in Example 6 to 1H-benzotriazole, deionized water was added to prepare an aqueous solution with a solid content of 200 ppm. Test solution 6: After adding 1H-benzotrisigma to 30 parts of the 30% aqueous solution obtained in Example 6, deionized water was added to prepare an aqueous solution with a solid content of 150 ppm. Comparative Test Solution 3: A 1 p-benzotriazole aqueous solution of 100 p p m was used as a rust inhibitor. Comparative test solution 4: A 1Η-benzotriazole aqueous solution of 250 p p m was used as a rust inhibitor. 24 312 / Invention Specification (Supplement) / 92-07 / 92112016 1228546 The test solution and comparative test solution are shown in Table 3. [Table 3] Component ratio (ppm) Example 6 (solid content), ppm 1 Pyrene-benzotriazole test solution 4 150 100 Test solution 5 100 100 Test solution 6 50 100 Comparative test solution 3 0 100 Comparative test solution 4 0 250 [Table 4] Surface resistance value (m Ω) Increase rate (%) Test solution before test 4 41.3 71.2 72.4 Test solution 5 29.6 30. 8 4.1 Test solution 6 29.7 44. 8 50.8 Comparative test solution 3 35.7 107.7 201.7 Comparative test solution 4 26.3 87.2 231.6 From the above results, it can be seen that the rust preventive of the present invention exhibits a synergistic effect when used in combination with a benzotriazole-based rust preventive. (Industrial Applicability) As described above, the rust preventive agent of the present invention contains a hydroxyphenylbenzene containing a polymerizable monomer (A) which is hydrophilic or water-soluble and a group containing a polymerizable double bond. A copolymer of a benzotriazole compound monomer (B) as an active ingredient is extremely effective in preventing rust of metals (especially copper and its alloys). Since this rust inhibitor can be used as an aqueous solution, it is cheaper, safer, and easier to treat waste liquid than organic solvent-based rust inhibitors, which is very advantageous in practice. 25 312 / Invention Specification (Supplement) / 92-07 / 92112016

Claims (1)

1228546 9¾ U The scope of patent application: 93. 6.-Replacement of this 1. A rust inhibitor, characterized by using hydrophilic or water-soluble polymerizable monomer (A), and the general formula (4): 10 R (4) • (R9) n — 〇—C—C = CH2 〇 [wherein R9 represents an elongation group of C represents a hydrogen atom or an alkyl group, and η is an integer of 0 or 1] A copolymer of a hydroxyphenylbenzotriazole compound monomer (B) containing a vinyl polymerizable double bond-based group is used as an active ingredient. The total content of the copolymer (A) is 5 to 9 9. 9 weight of the above (B) the content of the component is 0 · 0 0 0 1 ~ 50 0 weight ° / 0 poly sex soluble water or sex water is related to the anti-rust agent in the zhengte • Ifrui species 1 2 body unisexual formula Ο R1 丨 Plant R9) CNO 〇H2 CII -C Chinese formulae epithelial or protonazine bond amphiphilic polyethene ethylenic chain containing the indicated 1J integer II or ο is The η group is synthesized with a \ ly B / ϊ \ monomeric compound and an azole tris (phenylphenyl hydroxy) group ( 1 of the formula R n \\ / nir2 Ν 26 3 26 \ General file \ 92 \ 92112016 \ 92112016 (replacement) -1 1228546 [In the formula, R 1 represents a hydrogen atom, a Ci-8 alkyl group, a carboxyl group, and C] -8 alkyl, phenoxycarbonyl, hydroxyl or halogen atoms; R2 represents a hydrogen atom, a hydroxyl group, a halogen atom or a metal atom; the benzotriazoles (D) represented by] as the active ingredient, in the total amount of the copolymer The content of the component (A) is 5 to 99.9% by weight, the content of the component (B) contains 0. 0 0 0 1 to 50% by weight, and the content of the benzotriazole (D) is relative to the copolymer 1 0 0 The weight part is 0 to 500 weight part. 3. The rust preventive agent according to item 1 or 2 of the patent application scope, wherein the prophenylphenylbenzotriazole compound monomer (B) is represented by the general formula (2) ·· Oxycarbonyl, amine, the above amount is the above-mentioned hydroxyl [Wherein R3, R4 and R5 represent the same or different polymerizable double bond containing a hydrogen atom, an alkyl group of C 1-8, an alkoxy group of C-8, a cyano group, a hydroxyl group, a halogeno carboxyl group or an alkoxy group A carbonyl group; however, at least one of R3, R4, and R5 is a polymer bond-containing group; 4. A metal rust prevention method, characterized in that the metal surface is covered with a rust preventive agent according to any one of claims 1 to 3. 5. A metal rust prevention method, characterized in that When the metal surface is covered with the rust preventive agent of any one of the patent scopes 1 to 3, it is used in the form of the rust preventive system solution of any one of the patent scopes 1-3. 326 \ Overall files \ 92 \ 92112016 \ 92112016 (replacement) · 1 type, sub type, and double type 0 cover with water 27 1228546 6. For example, the rust prevention method of item 4 or 5 of the scope of patent application, wherein The metals are copper or copper alloys. 326 \ Total files \ 92 \ 92112016 \ 92112016 (replace) -1 28