TW200307058A - 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

200307058 (1) 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 rust inhibitor. [Prior art] In the past, various methods for rust prevention of metals have been proposed. For example, a method of coating a metal surface with other metals that are not easily corroded, a method of coating a metal surface with a paint, a method of forming a film on a metal surface chemically or electrochemically, etc. Methods of suppressing corrosion by contacting with an external corrosive environment are known. As metal-based rust inhibitors, benzotriazoles are known. For example, Japanese Patent Application Laid-Open No. Hei 10-2 6 5 9 7 9 discloses that it contains a dialkylamino group (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 an alkyl acrylate component. 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. 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 triazoles, an organic solvent for dilution is usually required. Therefore, 5 312 / Invention Specification (Supplement) / 92-07 / 92112016 200307058 causes an increase in cost and safety in operation. There are problems in surface and wastewater treatment, and the types of solvents that can be used are also limited. For example, 2 ^ -hydroxyphenylbenzotriazoles are poor in water solubility. In order to exert the anti-rust effect, they must be dissolved in an organic solvent, and the above problems will be encountered 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 copolymerization of the copolymerization 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 200307058

[In the formula, R1 represents a hydrogen atom, an alkyl group of Cl-8, a carboxyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, a radical or a halogen atom of Cl-8; R2 represents a hydrogen atom, a hydroxyl group, an amino group, a halogen atom or a metal atom ;] The benzotriazoles (D) shown as active ingredients. (3) The rust preventive agent according to the above item (1) or (2), wherein the aforementioned triphenylphenylbenzotriazole compound monomer (B) is represented by the general formula (2) ··

[In the formula, R3, R4 and R5 represent the same or different polymerizable double bond containing group, hydrogen atom, Cl-8 alkyl group, Cl-8 alkyloxy group, cyano group, warp group, halogen atom, carboxyl group or An alkoxycarbonyl group; however, at least one of R3, R4, and R5 is a polymerizable double bond-containing group. ] As a hydroxyphenylbenzotriazole compound. (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) above, the method (1) to (1) to (3) The rust preventive agent according to any one of the items is used in the form of an aqueous solution 7 312 / Invention Specification (Supplement) / 92-07 / 92112016 200307058. (6) The rust prevention method according to the above (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.

Ci-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 Ci-4 alkyl group, examples include n-pentyl, isopentyl, and new Amyl, third pentyl, n-hexyl, heptyl or octyl, and the like.

Ci-u alkyl group means a linear or branched alkyl group having 1 to 18 carbon atoms. In addition to the above-mentioned Cl-4 alkyl group and Cl-8 alkyl group, nonyl groups are also listed. , Decyl, undecyl, twelve, thirteen, fourteen, fifteen, sixteen, seventeen or eighteen.

Ci-8 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 means 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, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, heptyloxycarbonyl or octyl 8 312 / Description of the Invention (Supplement) / 92-07 / 92112016 200307058 Oxycarbonyl and others. The alkylene group of C i-4 represents a linear or branched alkylene group having 1 to 4 carbon atoms, and examples thereof include methylene, ethylene, trimethylene, tetramethylene, and fluorenyl groups. Methylene, propylene, 1-methyltrimethylene, 2-methyltrimethylene or ethylethylene. C i i. The alkylene group refers to 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 and the like. Examples of the halogen atom include chlorine, bromine ', fluorine, and iodine. Examples of the metal atom include an alkali metal atom (sodium, potassium, lithium, etc.), a silver atom, and the like. The copolymer of the active ingredient 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 include those represented by the following ① to ⑧: ① acrylic acid Or (meth) acrylic acid such as methacrylic 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 200307058 1 of the group of triethylamine, monoethanolamine, diethanolamine, methyldiethanolamine, methylisopropanolamine, difluorenylmonoethanolamine, triethanolamine, etc.) Or two or more; ③ With the general formula (3): Η2〇 = ^ — C—0— (R7-〇) m-R8 R6 〇 (3) [wherein R6 represents a hydrogen atom or a b-4 alkane base. R7 represents an alkylene group of Ci-4. R8 is a hydrogen atom, a Ci-4 alkyl group, or a phenyl group. m is an integer from 1 to 20. ] Acrylic acid alkylene glycol ether compound; ④ N, N -diamidoaminopropyl (fluorenyl) acrylamide, N, N -dimethylaminoethyl (meth) acrylamide (N) N-diethylaminoethyl (fluorenyl) acrylamide and other (meth) acrylamide, and N, N-dimethylaminopropyl (meth) acrylate, N, N -Diethylaminoethyl (meth) acrylate, propylene morpholin, 2-meryl-mercaptopropoxypropyloxy-N, N-dimethylamine, 3-hydroxypropenyl-N (N-dimethylamine) amino alkyl (meth) acrylates, etc., benzyl chloride, methyl chloride, gas ethane, chloropropane, chlorobutane, iodopane, fluorenyl iodide, iodine Halogenated hydrocarbons such as ethane or iodopropane, and alkylating agents such as sulfuric acid esters such as diethylsulfuric acid or difluorenylsulfuric acid, and the unsaturated copolymerizable fourth-grade ammonium salts thereof; ⑤ Vinyl ethers such as hydroxyethyl vinyl ether, hydroxyethyl vinyl ether, or hydroxypropyl vinyl ether; ⑥ Ethyl ketones such as hydroxyethyl vinyl ketone, hydroxyethyl ketene, or hydroxypropyl ketene; ⑦ N- Vinylamines such as methanamine or N-ethyleneacetamide; 10 312 / Explanation of the Invention (Supplement) / 92-07 / 92112016 200307058 Acrylamido-2, 2'-dimethylpropanesulfonic acid Unsaturated copolymerizable sulfonic acids such as 2-sulfoethyl methacrylate or 3-sulfopropylfluorenyl acrylate and their ammonium salts; as the acrylic compound represented by the aforementioned general formula (4), Examples are: 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, or 4-hydroxybutyl (meth) acrylate Hydroxyalkyl esters of (meth) acrylic acid such as esters; alkoxyalkanes of (fluorenyl) acrylic acid such as methoxyethyl (fluorenyl) acrylate or ethoxyethyl (fluorenyl) acrylate Base esters; polyethylene glycol mono (fluorenyl) acrylates, polypropylene glycol mono (fluorenyl) acrylates, or polyalkylene glycol glycols (fluorenyl) acrylic acid polyethylene glycols; methoxy Alkoxy polyalkylene, such as propylene glycol (fluorenyl) acrylate or methoxy polypropylene glycol mono (fluorenyl) acrylate Ethylene glycol esters; phenoxy polyethylene glycol (meth) acrylate or phenoxy polypropylene glycol mono (meth) acrylate and other phenoxyalkylene glycol esters. Among these, from the viewpoint of imparting high water solubility to a copolymer prepared with a hydroxyphenylbenzotriazole compound (B) having a polymerizable double bond-containing group described below, hydroxyethyl is particularly preferred. (Fluorenyl) acrylate, methoxyethyl (fluorenyl) acrylate, polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol (fluorenyl) acrylate, polypropylene glycol mono (methyl Base) acrylate or methoxy polyethylene glycol (meth) acrylate and the like are preferred. These polymerizable monomers (A) may be used alone or in combination of two or more kinds. The amount ratio of the polymerizable monomer (A) in the aforementioned copolymer is not particularly limited, and can be appropriately selected in a wide range. Generally, it is suitable to be 5 to 99.9% by weight of the total amount of the copolymerization component. 10 to 99% by weight is preferred. 11 312 / Invention Specification (Supplement) / 92-07 / 92112016 200307058 Among the aforementioned polymerizable monomers (A), ① is particularly selected from (fluorenyl) acrylics such as acrylic acid and methacrylic acid; cis-butene Alkali metal salts, ammonium salts, and amino compounds of unsaturated copolymerizable carboxylic acids such as diacids, transbutenedioic acid, itaconic acid, citraconic acid, crotonic acid, and cis-butenedioic anhydride. One kind or two or more kinds; and ③ the acrylic compound represented by the general formula (3) is preferable. 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 hydroxyphenylbenzotriazole 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 the 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, Ci-8 alkoxy group, cyano group, hydroxyl group, halogen atom, carboxyl group or alkane An oxycarbonyl group; however, at least one of R3, R4, and R5 is a polymerizable double 12 312 / Description of the Invention (Supplement) / 92-07 / 92112016 200307058 bond-containing group. A hydroxyphenylbenzotrisigma compound represented by]. Here, the so-called polymerizable double bond-containing group is not particularly limited as long as it is a group containing an ethylene-based polymerizable double bond, and examples thereof include the following general formula (4): R10-(R9) n ——〇C——C = CH2

II (4) 〇 [wherein, R9 represents an alkylene group of Cl-, and R1Q represents an alkyl group of Ci-4. n is an integer of 0 or 1. The polymerizable double bond represented by] contains a group. The polymerizable double bond represented by the general formula (4) contains a group, and can be directly bonded or bonded to any position of hydroxyphenylbenzotriazole through a hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom. . Specific examples of the hydroxyphenylbenzotriazole compound monomer (B) include 2- [2'-hydroxy-5 /-(propenyloxy) phenyl] benzotriazole, 2- [ 2, -hydroxy-5 '-(methacryloxy) phenyl] benzotriazole, 2- [2 ~ hydroxy-3'-third-butyl-5'-(methacryloxy) Phenyl] benzotriazole, 2- [2, -hydroxy-3'-fluorenyl-5 '-(propenyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-5,- (Methacryl 醯 propoxy) phenyl] -5 -chlorobenzotriazole, 2- [2'-hydroxy-5 '-(propylene 醯 ethoxy) phenyl] benzotriazole, 2- [ 2'-Cyclo-3'_third butyl_5 / _ (fluorenylpropanylethoxy) phenyl] benzotriazole, 2- [2'-hydroxy-3 ... fluorenyl-5 ' -(Acrylic acid ethoxy) phenyl] benzotriazole, 2- [2'-hydroxy-3'-third butyl-5 '-(methacrylic acid ethoxy) phenyl] -5- Chlorobenzotriazole, 2- [2'-Hydroxy-5 '-(methacryl propylpropoxy) phenyl] -5 -chlorobenzotrityl, 2-L2, -Cyclo-5'-( Propidium 13 312 / Description of the Invention (Supplement) / 92-07 / 92112016 200307058 Oxy) phenyl] -5 -fluorenylbenzotriazole, or [2-hydroxy-3-tert-butyl-5 -(Acrylic acid Ethoxycarbonylethyl) phenyl] benzotriazole. These hydroxyphenylbenzotriazole compounds can be produced according to a known method, for example, a method described in Japanese Patent No. 2701 1 116. 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 it 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 adhesiveness, adhesion, and adhesion. Examples of the other polymerizable monomer (C) include methyl (fluorenyl) acrylate, ethyl (fluorenyl) acrylate, butyl (fluorenyl) acrylate, octyl (fluorenyl) acrylate, or (fluorenyl) ) Alkyl (meth) 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 esters; (fluorenyl) acrylic caprolactone adducts; hydroxy aromatic vinyls such as p-hydroxystyrene; 1-hexene, Olefins such as 1-octene, 1-decene, or styrene; vinyl carboxylates such as vinyl acetate, vinyl propionate, or vinyl laurate; vinyl chloride and the like. 14 312 / Invention (Supplement) / 92-07 / 92112016 200307058 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, the water solubility will be impaired. In general, it is preferable to make the copolymer component less than 20% by weight of the total amount of the copolymer, and preferably 0.1 to 20% by weight, and more preferably 1 to 15% by weight. In the present invention, in order to prevent The rust performance is further improved, and one or more of the benzotriazoles (D) described below may be added to the copolymer. Examples of the benzotriazoles (D) include 1 fluorene-benzo Triazole, 4-fluorenyl-1fluorene-benzotriazole, 4-carboxy-1fluorene-benzotriazole, 4-methyl-1fluorene-benzotrituna salt, 5-methylamino-1fluorene-benzotriazole Pyrene, benzotributene vinegar, benzotrisigma-silver salt, 5-chloro-1pyrene-benzotripyrene, I-chlorobenzotrisigma etc. Benzotriazoles in the aforementioned copolymers (D) The amount ratio can be appropriately selected within a wide range, but it is generally preferred to use the amount of 0 to 500 parts by weight based on 100 parts by weight of the aforementioned copolymer. The polymerization method of the aforementioned copolymer used for the rust agent will be described, and basically, it can be produced by a general polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, etc. For example, when a solution polymerization method is used, In the presence of a polymerization initiator, the polymerizable monomer (A) and the hydroxyphenylbenzotriazole compound (B) may be copolymerized with other polymerizable monomers (C) as necessary. 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-pentanol. , Ethyl lysinolysin, butyl lysinolysin, 1-methoxy 15 312 / Invention Specification (Supplement) / 92-07 / 92112016 200307058 2-propanol, ethylene glycol, propylene glycol, diethylene glycol, poly Alcohols such as ethylene 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 xylene Aromatic hydrocarbons; ketones such as acetone, ethyl ethyl ketone or methyl isobutyl ketone; Ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc .; N, N _ dimethylformamide, and other amines. Among these solvents, the required copolymer is used as an aqueous solution. In consideration, a water-soluble solvent is particularly preferable. Specific examples include alcohols such as methanol, ethanol, isopropanol, ethylcellolysin, and 1-methoxy-2-propanol; tetrahydrofuran Or ethers such as dioxane; amines such as N, N-dimethylamidamine. These solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited. It can be appropriately selected in a wide range according to the characteristics and uses of the copolymer to be obtained. Usually, when the total amount of the copolymer component is 100 parts by weight, 1 to 100 parts by weight can be used. 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. The amount of the polymerization initiator to be used is not particularly limited, and it may be generally from 0. 1 to 5 Mo. ° / 〇 for the entire copolymer component (total moles). The 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 the reaction at 2 to 50 hours. ~ 2 4 hours is better. The molecular weight of the aforementioned copolymer can be added by a common method such as adding carbon tetrachloride, lauryl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, 16 312 / Invention Specification (Supplement) / 92-07 / 92112016 200307058 It can be adjusted by 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 considerations such as prevention, 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. The 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 so-called aqueous solution refers to a solution made of water or a solution made of water as the main solvent. In the latter case, an organic solvent may be contained to such an extent that the solubility of the copolymer in water is not hindered. 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 added to the rust inhibitor composition. Although the use concentration of the aforementioned copolymer in the rust preventive agent of the present invention is slightly different depending on the type of the copolymer, it is usually only required to be greater than or equal to 0. 0 0 1% by weight, and there is no particular limitation. 0. 0 1 to 10% by weight is used, and 17 312 / Invention Specification (Supplement) / 92-07 / 92112016 200307058 0. 1 to 1% by mass is preferable. If the use concentration is less than 0.0001% by weight, a sufficient antirust effect cannot be expected. The rust preventive agent of the present invention is effective for rust prevention 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 the 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. 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. Moreover, it can also be used in a plastic case of an electronic device, and the same effect as that of the recorded electroless ore can be obtained. (Example) 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 was placed in a 4-necked flask equipped with a stirrer, thermometer, cooler, and 18 312 / Invention Specification (Supplement) / 92-07 / 92112016 200307058 dropping funnel, and the temperature was raised. To 80 ° C, and within 2 hours, 20 parts of 2- [2 / _Cyclo-5 _- (methylpropylsulfonyl ethoxy) phenyl] benzotriazole, A mixture of oxypolyethylene glycol (fluorenyl) 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, and prepare 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 copolymer, and deionized water was added to the residue to prepare an aqueous solution (solid content: 30%) containing the copolymer, to obtain a rust preventive 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 (fluorenyl) acrylate were added dropwise. (M% 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. 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 '-(methacrylic acid) ethoxy] phenyl] benzotriazole and methoxypolyethylene were added dropwise. Diol (fluorenyl) 19 312 / Invention Specification (Supplement) / 92-07 / 92112016 200307058 Acrylate (m = 7) 50 parts, acrylic part 20 parts, azobisisobutyronitrile 0 · 3 parts and n A mixture of 1 part of dodecanethiol was kept at 80 ° C for 4 hours to obtain the desired copolymer, and a 1-methoxy-2-propanol solution of the copolymer (solid content 4 9 7%). The average weight molecular weight of this copolymer by gel chromatography analysis (hereinafter referred to as GPC) was 590 ° (Example 4). 100 parts of 1-methoxy-2-propanol was placed in In a 4-necked flask with a blender, thermometer, cooler, and dropping funnel, 2-[2, -hydroxy-3'-tert-butyl-5 was added dropwise between 2 hours and 80 ° C. '-(Fluorenylpropene ethoxy) phenyl] -5 -chlorobenzotriazole 30 parts, ethoxy polyethylene glycol (fluorenyl) acrylic acid S purpose (m4 7) 65 parts, 4- A mixture of 5 parts of fluorenylpropoxy- 2,2,6,6-tetramethylpiperidine and 0.3 parts of azobisisobutyronitrile, and then kept at 80 ° C for 4 hours to complete the copolymerization reaction An anti-rust agent composed of a 1-methoxy-2propanol solution (solid content: 50.8%) of the anti-rust copolymer 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 an antirust agent 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 fluorenylpropene 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 (Supplements) / 92-07 / 92112016 200307058 to 60 ° C, and keep at this temperature for about 1 2 Hours, the desired product was obtained, and a rust inhibitor composed of a 1-methoxy-2propanol solution (solid 29.1%, polymerization rate 100%) of the copolymer 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 a rust preventive 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'-( Mixture of 30 parts of fluorenylfluorene ethoxy) phenyl] benzotriazole, 60 parts of fluorenyl acrylic acid, 10 parts of ethyl methacrylate, 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 the total tetrahydrofuran solution (solid content: 29.1%, polymerization rate: 100%) was prepared. Anti-recording agent. 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 41 (Example 7). Into 4 bottles equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, 480 parts of tetrahydrofuran and 2- [2, -hydroxy-5 were placed. '-(Methylfluorenylethoxy) phenyl] benzotriazole 72 parts, methyl methacrylate 24 acrylic acid 96 parts, 2-hydroxyethyl methacrylate 48 parts, azobis312 / Invention specification ( (Supplement) / 92-07 / 92112016 The copolymerization content is passed through a solvent of 30%, 6.90, and propylene 2-hydroxydioxane at 60 ° C. It is formed by polymer at room temperature and is prevented from leaving at 100 °. 21 200307058 A mixture of 0.5 parts of nitrile 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, which is obtained by the copolymerization An anti-rust agent consisting of a tetrahydrofuran solution (solid content 33, polymerization rate 100%). Then, 25% ammonia water was added to dissolve into pΗ 6 ~ 7, and after stirring at room temperature for 3 hours, the solvent was depressurized, and the residue was added with deionized water to prepare a solution with a solid content of 30% to obtain Rust inhibitor for aqueous solutions. The copolymer has a GPC average weight molecular weight of 3 6900. (Experiment Example 1)-Anti-rust test The surface of a copper plate (JIS standard C1020P, 0.5 x 30 x 70mm) was ground with sandpaper and then immersed in 0.5% hydrochloric acid for 5 minutes, then washed for 1 minute, This was used as a test piece. Test solution 1: Test solution 1 was prepared by dissolving 1-methoxy-2-propane obtained in Example 2 in deionized water to prepare an aqueous solution having a solid content of 0.18%. Test solution 2: Deionized water was added to the 30% aqueous solution obtained in Example 7 to prepare a rust inhibitor of an aqueous solution with a solid content of 0.15%, and used as test solution 2. Comparative test solution 1: 1% benzotriazole was used as a rust inhibitor. Comparative Test Solution 2: 1% acetone in 2- (2-hydroxy-5-fluorenylphenyl) benzo (Tinuvin P, manufactured by Giba-Geigy Japan) was used 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 applied and rust-proof ions were used to test three saliva as the test solution. Blow down 22 200307058 and air dry for 30 minutes. The treated test piece was sprayed with 5% saline at 35 ° C for 24 hours to confirm the surface state. The resistance value before and after the test was measured using a contact resistance meter, Rolester MP (manufactured by Mitsubishi Chemical Corporation, probe: 2 probe type). The measurement was performed at two points. For reference purposes, a salt spray treatment was also performed on the surface of the copper plate with nickel electroless plating, 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 Full black comparison test solution 2 No nickel-free plating treatment No No [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 or less. 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 or 1.2 Ω Nickel plating treatment All of them are 0.1 Ω or less, and any of them are 0.5 Ω or less. From the above results, it can be known that although the benzotriazole, which is a representative rust inhibitor of the copper of the rust inhibitor of the present invention, has a relatively low concentration, However, it showed a better anti-rust effect, and showed 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 1500 23

312 / Instruction of the Invention (Supplement) / 92-07 / 92112016 200307058 After grinding, sandpaper was immersed in 5% sulfuric acid for 1 minute, and then washed with water for 1 minute 'as a test piece. The above test pieces were immersed in the tests shown below, liquids 3 to 6 and comparative test liquids 1 to 2, respectively, after being immersed at 20 ° C for 5 minutes, and then washed with water for 30 seconds, and the test was carried out by blowing air. After the water droplets on the surface of the sheet were removed, it was dried at 60 ° C for 30 minutes. Each treated test piece was placed in a constant temperature and humidity tank adjusted to a temperature of 60 ° C and a humidity of 85% for 4 hours. The resistance value before and after the test was 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: 5 parts by weight of a 30% aqueous solution obtained in Example 6 was added with 1 fluorene-benzotrifluorene, and then deionized water was added to prepare an aqueous solution having a solid content of 250 ppm. Test solution 5: After adding 3% by weight of a 30% aqueous solution obtained in Example 6 to 1H-benzotrisigma, deionized water was added to prepare an aqueous solution having a solid content of 200 ppm. Test solution 6: After adding 1H-benzotriazole to 1.7 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 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 200307058 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 Liquid 3 35.7 107.7 201.7 Comparative test liquid 4 26.3 87. 2 231.6 From the above results, it can be seen that the rust preventive agent of the present invention can exhibit a multiplicative effect when used in combination with a benzotriazole-based rust preventive agent. (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)

200307058 Hydrophilic benzene or basic hydroxy water has a parent group containing 8 · ^ * ·:: The chain has a bi-sexual bond, and is concentrated in the presence of: ΠΓΤ sign and encirclement, special A Fanqi (A Lee, Please prevent the rustiness of the body. It is a kind of one-spot, one-spot pick-up effect. It is useful for crops to gather together. \ Ly B κί \ Single body compound oxazole triphenylphenyl water or benzene based water. The base has: a bond-containing bi-system, 'combined with the polysaccharide A, its (A, body agent, single rust-proof, anti-combination type, a two-solubility formula, and B / (V A single compound of azole triacene R \ / nir2 [wherein R1 represents a hydrogen atom, an alkyl group of Cl-8, a carboxyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, a hydroxyl group or a halogen atom of Cl-8; R2 represents A hydrogen atom, a hydroxyl group, an amino group, a halogen atom, or a metal atom;] the benzotriazole (D) as an active ingredient. 3. The rust preventive agent according to item 1 or 2 of the scope of patent application, wherein the aforementioned hydroxyl group The phenylbenzotriazole compound monomer (B) is represented by the general formula (2): (2) [wherein R3, R4 and R5 represent the same or different polymerizable double bond containing group, hydrogen atom, Ci-8 alkyl group, Ci-8 alkoxy group, cyano group, hydroxyl group, i atom, A carboxyl group or an alkoxycarbonyl group; however, at least one of R3, R4, and R5 is a polymerizable double 26 312 / Explanation of the Invention (Supplement) / 92-07 / 92112016 200307058 bond containing group; and a triphenylphenylbenzene shown in [] And two σ sitting compounds. 4. A method for rust prevention of metal, characterized in that the surface of metal is coated with an rust preventive agent according to any one of claims 1 to 3. 5. A rust-proof method for metals, characterized in that when the surface of a metal is covered with an anti-rust agent according to any one of claims 1 to 3, the scope of patents 1 to 3 will be applied The rust preventive agent according to any one of the items is used in the form of an aqueous solution. 6. The rust prevention method according to item 4 or 5 of the scope of application, wherein the aforementioned metal is copper or a copper alloy. 27 312 / Invention Specification (Supplement) / 92-07 / 92112016 200307058 柒. Designated Representative Map: (1) The designated representative map in this case is: (). (2) Brief description of the component representative symbols of this representative map: None T. J. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. 312 / Invention Specification (Supplement) / 92-07 / 92112016