KR20050006218A - Rust preventives and method of rust prevention with the same - Google Patents

Abstract

(1) a rust preventive agent comprising a copolymer of a hydrophilic or water-soluble polymerizable monomer (A) and a hydroxyphenylbenzotriazole compound monomer (B) having a polymerizable double bond-containing group as an active ingredient, and (2) the above ( A), (B), and general formula (1):

[R ¹ : hydrogen atom, C _1-8 alkyl group, carboxyl group, C _1-8 alkoxycarbonyl group, phenoxycarbonyl group, hydroxy group or halogen atom. R ² : A hydrogen atom, a hydroxyl group, an amino group, a halogen atom, or a metal atom.] A rust preventive agent containing the benzotriazoles (D) represented as an active ingredient. As an example of the said monomer (B), the compound represented by General formula (2) is contained. The rust preventive agent can be used as an aqueous solution without using an organic solvent, and is particularly effective for rust prevention of copper and its alloys.

Description

Antirust agent and rust prevention method using the same {RUST PREVENTIVES AND METHOD OF RUST PREVENTION WITH THE SAME}

In the past, various methods have been proposed for rust preventing metals. For example, the coating of other metals that are difficult to corrode on the metal surface with plating, the coating of the metal surface with paint, the method of chemically or electrochemically forming a film on the metal surface, and the like. Background Art A method of suppressing corrosion by preventing contact with the environment is known.

As rust inhibitors of metals, benzotriazoles are known. For example, Japanese Patent Application Laid-open No. Hei 10-265979 discloses an organic solvent dissolving composition of an acrylic copolymer containing a component derived from dialkylaminoalkyl (meth) acrylate. The anticorrosive composition for copper materials which added the benzotriazoles is disclosed. In addition, Japanese Patent Laid-Open No. 59-108099 discloses a metal corrosion inhibitor for lubricating oil at a high temperature containing 2-hydroxyphenylbenzotriazoles as an active ingredient.

Although benzotriazoles chelate bond with a metal surface to form a film and express a rust preventive effect, the prior art still has a problem to be solved practically. For example, since the film is generally thin, the rust preventive effect is not very satisfactory under severe circumstances. Moreover, when triazole is added to a resin as a rust preventive agent, it is easy to produce a bleed out phenomenon, and the stable effect is not acquired. In addition, when triazoles lack water solubility, they usually require an organic solvent for dilution, which increases the cost, problems in terms of work safety and waste liquid treatment, and also limits the types of solvents used. There are problems such as that. For example, 2'-hydroxyphenylbenzotriazoles have to be dissolved in an organic solvent in order to exhibit anti-rusting properties and to exhibit an rust-preventing effect.

Therefore, although the subject of this invention is a rust inhibitor containing a benzotriazole type compound, it can exhibit and maintain a rust prevention effect even in severe environment with respect to metals, and also under the conditions of the aqueous solution which does not contain an organic solvent substantially. A rust preventive agent which can be used and a rust prevention method using the same are provided.

The present invention relates to a rust preventive agent comprising a hydroxyphenylbenzotriazole-based copolymer as an active ingredient and a method for preventing corrosion of metals using the same.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, when the present inventors examined the rust prevention effect with respect to various benzotriazole compounds from practical use, the air obtained by copolymerizing a water-soluble or hydrophilic copolymerization monomer with hydroxyphenyl benzotriazole. The copolymer was found to be very useful as a rust preventive agent for metals due to its abundance of water solubility, thus completing the present invention.

That is, this invention relates to the following rust inhibitors and the rust prevention method using the same.

(1) A rust preventive agent comprising a copolymer of a water-soluble or hydrophilic polymerizable monomer (A) and a hydroxyphenylbenzotriazole compound monomer (B) having a polymerizable double bond-containing group as an active ingredient.

(2) A copolymer of a hydrophilic or water-soluble polymerizable monomer (A) and a hydroxyphenylbenzotriazole compound monomer (B) having a polymerizable double bond-containing group, and general formula (1):

[Wherein, R ¹ represents a hydrogen atom, a C _1-8 alkyl group, a carboxyl group, a C _1-8 alkoxycarbonyl group, a phenoxycarbonyl group, a hydroxy group or a halogen atom. R <^2> represents a hydrogen atom, a hydroxyl group, an amino group, a halogen atom, or a metal atom.] The rust preventive agent containing benzotriazole (D) shown as an active ingredient.

(3) The hydroxyphenylbenzotriazole compound monomer (B) is represented by the general formula (2):

[Wherein, R ³ , R ⁴ and R ⁵ are the same or different and include a polymerizable double bond containing group, a hydrogen atom, a C _1-8 alkyl group, a C _1-8 alkoxy group, a cyano group, a hydroxy group, a halogen atom, a carboxyl group or An alkoxycarbonyl group is shown. However, at least 1 of R <^3> , R <^4> and R <^5> is a polymerizable double bond containing group.] The rust preventive agent as described in said (1) or (2) which is a hydroxyphenyl benzotriazole compound represented by.

(4) The antirust method of metals characterized by coating the antirust agent in any one of said (1)-(3) on the surface of metals.

(5) The coating of the rust inhibitor according to any one of (1) to (3) above on the surface of metals, wherein the rust inhibitor according to any one of (1) to (3) above is used in the form of an aqueous solution. Antirust method of metals characterized by the above-mentioned.

(6) The antirust method according to the above (4) or (5), wherein the metals are copper or a copper alloy.

First, the display of the substituent described in this specification and its specific example are given.

C _1-4 alkyl group represents a linear or branched alkyl group having 1 to 4 carbon atoms, and is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group or tert- Butyl group is mentioned.

C _1-8 alkyl group represents a linear or branched alkyl group having 1 to 8 carbon atoms, and in addition to the C _1-4 alkyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n -Hexyl group, heptyl group, octyl group, etc. are mentioned.

A C _1-18 alkyl group represents a linear or branched alkyl group having 1 to 18 carbon atoms, and in addition to the C _1-4 alkyl group and the C _1-18 alkyl group, a nonyl group, decanyl group, undecanyl group, and dodecanyl group. And tridecanyl group, tetradecanyl group, pentadecanyl group, hexadecanyl group, heptadecanyl group or octadecanyl group.

C _1-8 alkoxy group refers to a linear or branched alkoxy group having 1 to 8 carbon atoms, which is a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, n- Pentyloxy group, isopentyloxy group, neopentyloxy group, tert-pentyloxy group, n-hexyloxy group, heptyloxy group, octyloxy group, etc. are mentioned.

The alkoxycarbonyl group represents a linear or branched alkoxycarbonyl group having 1 to 8 carbon atoms, and a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, etc. are mentioned.

A C _1-4 alkylene group represents a linear or branched alkylene group having 1 to 4 carbon atoms, and is methylene, ethylene, trimethylene, tetramethylene, methylmethylene, propylene, 1-methyltrimethylene, 2-methyltrimethylene or Ethyl ethylene and the like.

The C _1-10 alkylene group represents a linear or branched alkylene group having 1 to 10 carbon atoms, and in addition to the C _1-4 alkylene group, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene and deca Methylene or 2,2-dimethyltrimethylene and the like.

Examples of the halogen atom include chlorine, bromine, fluorine and iodine.

Examples of the metal atoms include alkali metal atoms (sodium, potassium, lithium, etc.), silver atoms, and the like.

The said copolymer which is an active ingredient of the rust preventive agent of this invention is a copolymer which makes a water-soluble or hydrophilic polymerizable monomer (A) and the hydroxyphenyl benzotriazole compound monomer (B) which has a polymerizable double bond containing group an essential monomer. to be.

As said polymerizable monomer (A), if it contains a radically polymerizable group in a molecule | numerator, and is water-soluble or hydrophilic, it will not specifically limit, For example, what is represented by the following (1)-(8) is mentioned.

(Meth) acrylic acid, such as (1) acrylic acid or methacrylic acid; Unsaturated copolymerizable carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid or maleic anhydride

(2) Alkali metal salts (sodium, potassium, lithium salts, etc.), ammonium salts and amino compound salts (dimethylamine, trimethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, methyl) of the above unsaturated copolymerizable carboxylic acids. Diethanolamine, methyl isopropanolamine, dimethyl monoethanolamine, triethanolamine, etc.)

③ Formula (3):

[Wherein, R ⁶ represents a hydrogen atom or a C _1-4 alkyl group. R ⁷ represents a C _1-4 alkylene group. R ⁸ represents a hydrogen atom, a C _1-4 alkyl group or a phenyl group. m represents an integer of 1 to 20.] alkylene glycol ether acrylate compound represented by

④N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminoethyl (meth) (Meth) acrylamides such as acrylamide and N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, acryloyl morpholine, 2-hydroxy-hydroxy To (meth) acrylic acid aminoalkyl esters such as hydroxyacryloyloxypropyl-N, N-dimethylamine and 3-hydroxyacryloyloxypropyl-N, N-dimethylamine, benzyl chloride, methyl chloride, ethyl chloride Halogenated hydrocarbons such as propyl chloride, butyl chloride, benzyl bromide, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, methyl iodide, benzyl iodide, ethyl iodide or propyl iodide; Unsaturated copolymerizable quaternary ammonium bases obtained by reacting alkylation reagents such as sulfuric acid esters such as diethyl sulfuric acid or dimethyl sulfuric acid

(5) Vinyl ethers such as hydroxymethyl vinyl ether, hydroxyethyl vinyl ether or hydroxypropyl vinyl ether

(6) vinyl ketones such as hydroxymethyl vinyl ketone, hydroxyethyl vinyl ketone or hydroxypropyl vinyl ketone

(7) Vinylamides such as N-vinylformamide or N-vinylacetamide

(8) Unsaturated copolymerizable sulfonic acids such as acrylamide-2,2'-dimethylpropanesulfonic acid, 2-sulfoethyl methacrylate or 3-sulfopropyl methacrylate and ammonium salts thereof

As an acrylic acid compound represented by the said General formula (4), for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, or Hydroxyalkyl esters of (meth) acrylic acid, such as 4-hydroxybutyl (meth) acrylate; Alkoxyalkyl esters of (meth) acrylic acid such as methoxyethyl (meth) acrylate or ethoxyethyl (meth) acrylate; Polyethylene glycols of (meth) acrylic acid such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate or polyalkylene glycol esters; Alkoxy polyalkylene glycol esters such as methoxy polyethylene glycol (meth) acrylate or methoxy polypropylene glycol mono (meth) acrylate; Phenoxy polyalkylene glycol ester of (meth) acrylic acid, such as phenoxy polyethyleneglycol (meth) acrylate or phenoxy polypropylene glycol mono (meth) acrylate, is mentioned.

Among them, especially hydroxyethyl (meth) acrylate and methoxyethyl from the viewpoint of providing high water solubility to a copolymer obtained from the hydroxyphenylbenzotriazole compound (B) having a polymerizable double bond-containing group described below. (Meth) acrylate, polyethyleneglycol mono (meth) acrylate, methoxy polyethyleneglycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, or methoxy polyethyleneglycol (meth) acrylate is preferable. These polymerizable monomers (A) may be used independently and may use 2 or more types together.

The amount ratio of the polymerizable monomer (A) in the copolymer is not particularly limited and can be appropriately selected in a wide range, but is usually 5 to 99.9% by weight, preferably 10 to 99% by weight of the total amount of the copolymerization component. good.

Among the polymerizable monomers (A), alkalis of unsaturated copolymerizable carboxylic acids such as (meth) acrylic acid such as acrylic acid and methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride, etc. 1 type or 2 or more types chosen from the group of a metal salt, an ammonium salt, and an amino compound, (3) The acrylic acid compound represented by General formula (3) is preferable.

Moreover, the said copolymer is made into the copolymer which consists of 1 type (s) or 2 or more types chosen from the group of the alkali metal salt, ammonium salt, and amino compound of the said unsaturated copolymerizable carboxylic acids, and a hydroxyphenyl benzotriazole compound (B). In the case, instead of using one or two or more selected from the group of alkali metal salts, ammonium salts and amino compounds of the unsaturated copolymerizable carboxylic acids, the corresponding unsaturated copolymerizable carboxylic acids and hydroxyphenylbenzotriazole compounds After forming the copolymer of (B), you may manufacture by reacting 1 type, or 2 or more types chosen from the group of 0.1-1.3 equivalent alkali metal salt, ammonium, and an amino compound.

Next, the hydroxyphenylbenzotriazole compound monomer (B) having the polymerizable double bond-containing group is not particularly limited as long as it has a polymerizable double bond-containing group at any substitutable position of the hydroxyphenylbenzotriazole. For example, as described above, the general formula (2):

[Wherein, R ³ , R ⁴ and R ⁵ are the same or different and include a polymerizable double bond-containing group, a hydrogen atom, a C _1-8 alkyl group, a C _1-8 alkoxy group, a cyano group, a hydroxy group, a halogen atom, a carboxyl group Or an alkoxycarbonyl group. Provided that at least one of R ³ , R ^4, and R ⁵ is a polymerizable double bond-containing group.

Herein, the polymerizable double bond-containing group is not particularly limited as long as it is a group containing a polymerizable double bond of vinyl type. For example, General Formula (4):

[Wherein, R ⁹ represents a C _1-10 alkylene group. R ¹⁰ represents a hydrogen atom or a C _1-4 alkyl group. n represents the integer of 0 or 1. The polymeric double bond containing group shown by the following is mentioned.

The polymerizable double bond-containing group represented by the general formula (4) may be bonded directly to any position of the hydroxyphenylbenzotriazole or via a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom. .

Specific examples of the hydroxyphenylbenzotriazole compound monomer (B) include 2- [2'-hydroxy-5 '-(acryloyloxy) phenyl] benzotriazole and 2- [2'-hydroxy-5' -(Methacryloyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(methacryloyloxy) phenyl] benzotriazole, 2- [2 '-Hydroxy-3'-methyl-5'-(acryloyloxy) phenyl] benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -5- Chlorobenzotriazole, 2- [2'-hydroxy-5 '-(acryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-( Methacryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy-3'-methyl-5 '-(acryloyloxyethyl) phenyl] benzotriazole, 2- [2'-hydroxy Oxy-3'-tert-butyl-5 '-(methacryloyloxyethyl) phenyl] -5-chlorobenzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxypropyl) Phenyl] -5-chlorobenzotriazole, 2- [2'-hydroxy-5 '-(acrylo Oxy-butyl) phenyl] -5-methyl benzotriazole, or [2-hydroxy -3-tert- butyl-5 (to an oxy-acryloyl-ethoxycarbonyl) phenyl] benzotriazole.

These hydroxyphenylbenzotriazole compounds can be manufactured according to a well-known method, for example, the method of Unexamined-Japanese-Patent No. 2701116. The hydroxyphenylbenzotriazole compound monomer (B) can be used individually by 1 type, and may use 2 or more types together.

The amount ratio of the hydroxyphenylbenzotriazole compound monomer (B) in the copolymer is not particularly limited and can be appropriately selected in a wide range, but considering the rust prevention performance, water solubility, use environment and purpose, and economic efficiency of the obtained copolymer In general, the content of the copolymer component is 0.0001 to 50% by weight, preferably 0.001 to 30% by weight.

In order to improve the film formation and stability of the copolymer of the polymerizable monomer (A) and the hydroxyphenylbenzotriazole compound monomer (B), to prevent aggregation, precipitation or gelation, and to achieve water solubility, foaming property, adhesiveness, adhesiveness, and the like. And other polymerizable monomer (C) are preferably used together to form a copolymer.

As another polymerizable monomer (C), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, or lauryl (meth) acrylate, etc. (Meth) acrylic-acid alkylesters; (Meth) acrylic acid cycloalkyl esters such as cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate or cyclododecyl (meth) acrylate; Caprolactone adducts of (meth) acrylic acid; hydroxy aromatic vinyls such as p-hydroxy styrene; Low olefins such as 1-hexene, 1-octene, 1-decene or styrene; Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, or a vinyl lauryl acid; Vinyl chloride etc. are mentioned.

These other polymerizable monomers (C) may be used individually by 1 type, and may use 2 or more types. The amount ratio of the other polymerizable monomer in the copolymer is not particularly limited and can be appropriately selected in a wide range. However, since the water solubility is impaired when the amount of the other monomers used exceeds 20% by weight, it is usually 20 The weight% or less, preferably 0.01 to 20% by weight, more preferably 1 to 15% by weight.

In the present invention, one or two or more of the following benzotriazoles (D) may be added to the copolymer in order to further improve characteristics such as rust prevention performance.

Examples of the benzotriazoles (D) include 1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, and 4-methyl-1H-benzotriazole sodium. Salt, 5-methyl-1H-benzotriazole, benzotriazole, butyl ester, benzotriazole silver salt, 5-chloro-1H-benzotriazole, 1-chlorobenzotriazole, etc. are mentioned.

Although the ratio of the benzotriazoles (D) in the said copolymer can be suitably selected in a wide range, Usually, it is preferable to use about 0-500 weight part with respect to 100 weight part of said copolymers.

Next, although the polymerization method of the said copolymer used as a rust preventive agent of this invention is demonstrated, it can basically manufacture according to normal polymerization methods, such as solution polymerization, emulsion polymerization, suspension polymerization, and the like.

For example, in the case of solution polymerization, a polymer monomer (A) and a hydroxyphenyl benzotriazole compound (B) are copolymerized with other polymerizable monomer (C) in the presence of a polymerization initiator in a solvent. I want you to.

As a solvent, a conventionally well-known thing can be used widely, For example, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, n-pentanol, and ethylcell Alcohols such as sorb, butyl cellosolve, 1-methoxy-2-propanol, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol or polypropylene glycol; Esters such as ethyl acetate, propyl acetate or butyl acetate; Aliphatic hydrocarbons such as petroleum ether, hexane or heptane; Aromatic hydrocarbons such as benzene, toluene or xylene; Ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone; Ethers such as diethyl ether, dibutyl ether, tetrahydrofuran or dioxane; Amides, such as N, N- dimethylformamide, are mentioned.

Among these solvents, in consideration of using the target copolymer as an aqueous solution, it is preferable that the solvent is a water-soluble solvent, and specifically, methanol, ethanol, isopropanol, ethyl cellosolve, 1-methoxy-2-propanol, or the like. Ethers such as alcohols, tetrahydrofuran or dioxane, and amides such as N, N-dimethylformamide. These solvent may be used individually by 1 type, and may use 2 or more types together. Although the usage-amount of a solvent is not specifically limited, Although it can select suitably in a wide range according to various characteristics and uses of a copolymer to obtain, it is good to set it as 1-10000 weight part normally with 100 weight part of whole copolymer components.

As a polymerization initiator, a conventionally well-known thing can be used widely, For example, peroxides, such as benzoyl peroxide and dibutyl peroxide, azo type compounds, such as azobisisobutyronitrile, etc. are mentioned. A polymerization initiator can be used individually by 1 type, and may use 2 or more types together. Although the usage-amount of a polymerization initiator is not specifically limited, Usually, what is necessary is just to be 0.1-5 mol% of the copolymer component whole quantity (total mole number).

This copolymerization reaction can be normally performed in the temperature range of room temperature to 200 degreeC, Preferably it is 40-140 degreeC, and is usually completed in 1 to 50 hours, preferably 2 to 24 hours.

The molecular weight of the said copolymer is a conventional method, for example, carbon tetrachloride, lauryl mercaptan, n-dodecyl mercaptan, tert- dodecyl mercaptan, octyl thioglycolate, thioglycerol, hydroquinone, etc. It can adjust by adding the polymerization inhibitor.

The copolymer obtained in this way has a weight average molecular weight of 1,000 to 200,000, preferably 2,000 to 150,000, but in view of water solubility and prevention of bleed-out over time, it is preferably 3,000 to 100,000, more preferably 5,000 to 50,000.

The rust preventive agent of this invention contains the said copolymer as an active ingredient. Although the said copolymer is rich in water solubility and can be used in the form of an aqueous solution, it can be used in the form of a dispersion liquid and an emulsion liquid using a suitable dispersing agent, an emulsifier, etc. as needed. The above-mentioned aqueous solution means a solution containing water or water as the main solvent, and in the latter case, the organic solvent may be contained to such an extent that it does not prevent the dissolution of water into the copolymer. For example, you may contain the solvent used at the time of manufacture of a rust preventive polymer so that it may not affect an rust prevention effect.

In the rust inhibitor of the present invention, other rust inhibitors, ultraviolet absorbers, near-infrared absorbers, water-soluble quenchers, antioxidants, fluorescent brighteners, wetting agents, surface tension modifiers, pigments, and the like, so as not to impair the anti-corrosive effect of the copolymer as necessary. Dyestuffs, pigments, flavorings, metal deactivators, nucleating agents, antistatic agents, flame retardants, lubricants, thickeners, antifoaming agents, preservatives, oxygen absorbers or processing aids, or other conventionally added additives to rust inhibitor compositions You may also

Although the use concentration of the said copolymer in the rust preventive agent of this invention differs according to the kind of copolymer, it is usually 0.0001 weight% or more, and if it is more than the concentration, it will not specifically limit, but 0.001-10 weight %, Preferably it is preferable to use about 0.01 to 1 weight%. If the concentration is less than 0.0001% by weight, sufficient antirust effect cannot be expected.

Although the rust preventive agent of this invention is effective for the rust prevention of general metals (metals or alloys, such as copper and iron), it shows the outstanding antirust effect especially with respect to copper and a copper alloy.

In the antirust method of the present invention, for example, a solution containing the antirust agent of the present invention is coated on a metal surface that needs to be rust prevented, or sprayed or coated, or the metal is immersed in the solution, and then dried. It can carry out by coating.

Although the rust preventive agent of this invention can be preserve | saved in the state of a solution, in consideration of the circulation condition, you may use it as a concentrate and dilute with water to a predetermined density | concentration at the time of use.

According to the rust-preventing method of the present invention, the rust-preventive treatment can be performed very easily on metals, and the corrosion and corrosion can be significantly suppressed even under severe conditions such as in salt water, in an acidic phase, at high temperature and high humidity, or for a long period of outdoor exposure. Moreover, when used in the plastic housing of an electronic device, the effect equivalent to the electroless plating of nickel can be acquired.

Example

Next, an Example and a test example are given and this invention is demonstrated further more concretely.

In addition, below, what is "part" or "%" shows a "weight part" or "weight%", respectively, unless there is particular notice.

Example 1

Into a four-necked flask equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, 100 parts of isopropanol were added and heated to 80 ° C, followed by 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotria. A mixture of 20 parts of sol, 80 parts of methoxypolyethylene glycol methacrylate (repeated water of ethylene glycol (m) # 8) and 0.3 part of azobisisobutyronitrile was added dropwise over 2 hours, and further maintained at 80 ° C for 4 hours. Thus, the target copolymer was obtained, and the rust preventive agent which consists of the isopropanol solution (solid content 50.8%) of the said copolymer was manufactured. The average weight molecular weight of the copolymer by gel permeation chromatography (hereinafter referred to as GPC) was 43,100. The solvent was distilled off under reduced pressure from the solution containing the said copolymer, deionization was added to the residue, the aqueous solution containing this copolymer (solid content 30%) was prepared, and the rust preventive which consists of aqueous solutions was obtained.

Example 2

100 parts of 1-methoxy-2-propanol was added to a four-necked flask equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, and heated to 80 ° C., followed by 2- [2'-hydroxy-5 '-(methacryloyl). A mixture of 30 parts of oxyethyl) phenyl] benzotriazole, 70 parts of methoxy polyethylene glycol methacrylate (m ≒ 7), 0.3 parts of azobisisobutyronitrile and 1 part of n-dodecyl mercaptan was added dropwise over 2 hours. Then, the mixture was kept at 80 ° C. for 4 hours to obtain a target copolymer, to prepare a rust preventive comprising a 1-methoxy-2-propanol solution (51.2% solids content) of the copolymer.

Example 3

100 parts of 1-methoxy-2-propanol was placed in a four-necked flask equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, and heated to 80 ° C., followed by 2- [2'-hydroxy-3'-tert-butyl-5 30 parts of '-(methacryloyloxyethyl) phenyl] benzotriazole, 50 parts of methoxy polyethylene glycol methacrylate (m ≒ 7), 20 parts of acrylic acid, 0.3 parts of azobisisobutyronitrile and n-dodecyl The mixture of 1 part of mercaptans was dripped over 2 hours, and it hold | maintained again at 80 degreeC for 4 hours, and obtained the target copolymer, and the rust preventive which consists of a 1-methoxy- 2-propanol solution (solid content 49.7%) of the said copolymer Prepared. The average weight molecular weight of the copolymer by GPC was 5,900.

Example 4

100 parts of 1-methoxy-2-propanol was placed in a four-necked flask equipped with a stirrer, a thermometer, a cooler, and a dropping funnel, and heated to 80 ° C., followed by 2- [2'-hydroxy-3'-tert-butyl-5 '-(Methacryloyloxyethyl) phenyl] -5-chlorobenzotriazole 30 parts, methoxy polyethylene glycol methacrylate (m'7) 65 parts, 4-methacryloyloxy-2,2,6 A mixture of 5 parts of, 6-tetramethylpiperidine and 0.3 parts of azobisisobutyronitrile was added dropwise over 2 hours, and the mixture was further maintained at 80 ° C for 4 hours to terminate the copolymerization reaction to thereby prevent 1-methoxy of the rust-resistant copolymer. A 2-propanol solution (solid content 50.8%) was prepared. The average weight molecular weight of the copolymer by GPC was 35,900. After distilling a solvent off under reduced pressure from this copolymer solution, deionized water was added to the residue, the solid content 30% aqueous solution was prepared, and the rust inhibitor of the aqueous solution was obtained.

Example 5

250 parts of 1-methoxy-2-propanol, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotria in a four-necked flask equipped with a stirrer, thermometer, cooler and dropping funnel A mixture of 30 parts of sol, 60 parts of ammonium methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 0.5 parts of azobisisobutyronitrile and 2 parts of n-dodecyl mercaptan was added and stirred at 60 ° C under a nitrogen atmosphere. The temperature was raised to about 12 hours, the target copolymer was obtained, and a rust preventive agent composed of a 1-methoxy-2-propanol solution (solid content 29.1%, polymerization rate 100%) of the copolymer was prepared. The average weight molecular weight of the copolymer by GPC was 43,100. After distilling a solvent off under reduced pressure from this copolymer solution, deionized water was added to the residue, the solid content 30% aqueous solution was prepared, and the rust inhibitor of the aqueous solution was obtained. The pH of the rust preventive agent was 6.9.

Example 6

250 parts of tetrahydrofuran, 30 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotriazole, in a four-necked flask equipped with a stirrer, a thermometer, a cooler and a dropping funnel, meta A mixture of 60 parts of acrylic acid, 10 parts of 2-hydroxyethyl methacrylate, 0.5 parts of azobisisobutyronitrile and 2 parts of n-dodecyl mercaptan was added thereto, and the mixture was heated to 60 ° C. while stirring under a nitrogen atmosphere. It hold | maintained for 12 hours, the target copolymer was obtained, and the rust preventive agent which consists of a tetrahydrofuran solution (29.1% of solid content, 100% of polymerization rate) of the said copolymer was manufactured. Next, an aqueous 25% ammonia solution was added to pH 6-7 and stirred at room temperature for 3 hours, the solvent was distilled off under reduced pressure, deionized water was added to the residue to prepare a 30% aqueous solution of a solid component to obtain an aqueous solution rust inhibitor. . The average weight molecular weight of the rust inhibitor by GPC was 41,100.

Example 7

480 parts of tetrahydrofuran, 72 parts of 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] benzotriazole, in a four-necked flask equipped with a stirrer, a thermometer, a cooler and a dropping funnel, meta A mixture of 24 parts of methyl methacrylate, 96 parts of acrylic acid, 48 parts of 2-hydroxyethyl methacrylate, 0.5 parts of azobisisobutyronitrile and 2 parts of n-dodecyl mercaptan was added thereto, and the mixture was stirred at 60 ° C. under a nitrogen atmosphere. After the temperature was raised, the mixture was held for about 12 hours to obtain a target copolymer, to prepare a rust preventive agent comprising a tetrahydrofuran solution (solid content 33.5%, polymerization rate 100%) of the copolymer. Next, an aqueous 25% ammonia solution was added to pH 6-7 and stirred at room temperature for 3 hours, the solvent was distilled off under reduced pressure, deionized water was added to the residue to prepare a 30% aqueous solution of a solid component to obtain an aqueous solution rust inhibitor. . The average weight molecular weight of the rust inhibitor by GPC was 36,900.

Test Example 1 (Antirust Test)

After polishing the surface of a copper plate (JIS standard C1020P, 0.5 * 30 * 70mm) using the abrasive paper No. 320, it immersed in 0.5% hydrochloric acid for 5 minutes, and wash | cleaned with water for 1 minute after that as the test piece.

Test solution 1: Deionized water was added to the 1-methoxy-2-propanol solution obtained in Example 2, and the rust inhibitor of the aqueous solution of 0.18% of solid content was prepared, and it was set as the test solution 1.

Test solution 2: Deionized water was added to the 30% aqueous solution obtained in Example 7, the rust preventive agent of the aqueous solution of 0.15% of solid content was prepared, and it was set as the test solution 2.

Comparative Test Solution 1: An aqueous 1% benzotriazole solution was used as a rust preventive agent.

Comparative Test Solution 2: A 1% acetone solution of 2- (2-hydroxy-5-methylphenyl) benzotriazole (tinuvin P, manufactured by Nihon Chiba Co., Ltd.) was used.

The said test piece was immersed in test liquid 1, test liquid 2, comparative test liquid 1, and comparative test liquid 2, respectively for 20 minutes at 20 degreeC, and it dried for 30 minutes at 60 degreeC by air blow. Each treated specimen was sprayed with 5% saline at 35 ° C. for 24 hours to confirm the surface state. In addition, the electric resistance value before and behind a test was measured with the contact resistance value meter Lorester MP (made by Mitsubishi Kagaku, the probe: 2 probe system). The measurement was performed at two places. In addition, for the electroless plating on the surface of the copper plate as a reference, the saline spray treatment was similarly performed to confirm the surface state.

The test results are shown in Table 1 and Table 2.

Calling situation Discoloration situation Test solution 1 none none Test solution 2 none none Comparative Test Solution 1 Front side Front black side Comparative Test Solution 2 none none Nickel Plating none none

Electric resistance value Before salt spray After salt spray Test solution 1 0.1Ω or less 0.5Ω or less Test solution 2 0.1Ω or less 0.5Ω or less Comparative Test Solution 1 0.1Ω or less 3.0Ω, 140Ω Comparative Test Solution 2 0.1Ω or less 0.3Ω, 1.2Ω Nickel Plating 0.1Ω or less 0.5Ω or less

From the above results, it can be seen that the rust preventive agent of the present invention has a lower concentration than benzotriazole, which is a typical rust preventive agent of copper, and exhibits better rust preventive effect, and has an effect equivalent to that of nickel plating.

Test Example 2

After polishing the surface of a copper plate (JIS standard C1020P, 0.5 * 30 * 70mm) using the 1,500 grind paper, it immersed in 5% sulfuric acid for 1 minute, and wash | cleaned with water for 1 minute after that as the test piece.

The test piece was immersed for 5 minutes at 20 ° C. in test solution 3 to 6 and comparative test solution 1 to 2 shown below, and then washed with water for 30 seconds, and after removing water droplets on the surface of the test piece by air blow, for 30 minutes at 60 ° C. Dried.

Each treated specimen was left to stand in a constant temperature and humidity chamber adjusted to a temperature of 60 ° C. and a humidity of 85% for 114 hours. The surface electrical resistance value before and after the test was measured by the contact resistance value meter Lorester MP (made by Mitsubishi Kagaku, probe: two probe method). The measurement point was performed at five places and made the average value into surface electrical resistance value. The test results are shown in Table 4.

Test solution 4: 1 part of 1H-benzotriazole was added to 5 parts by weight of the 30% aqueous solution obtained in Example 6, followed by addition of deionized water to prepare a test solution 4 as an aqueous solution having a solid content of 250 ppm.

Test solution 5: 1 part of 1H-benzotriazole was added to 3.3 parts by weight of the 30% aqueous solution obtained in Example 6, followed by addition of deionized water to prepare a test solution 5 as an aqueous solution having a solid content of 200 ppm.

Test solution 6: 1 part of 1H-benzotriazole was added to 1.7 parts by weight of the 30% aqueous solution obtained in Example 6, followed by addition of deionized water to an aqueous solution having a solid content of 150 ppm.

Comparative Test Solution 3: A 100 ppm aqueous solution of 1H-benzotriazole was used as a rust preventive agent.

Comparative Test Solution 4: 250 ppm aqueous 1H-benzotriazole solution was used as a rust preventive agent.

Table 3 shows a list of test solutions and comparative test solutions.

From the above result, it turns out that the rust inhibitor of this invention shows synergy effect by using together with a benzotriazole type rust inhibitor.

As described above, the rust inhibitor of the present invention contains a copolymer of a hydrophilic or water-soluble polymerizable monomer (A) and a hydroxyphenylbenzotriazole compound monomer (B) having a polymerizable double bond-containing group as an active ingredient. It is very effective for rust prevention of metals (especially copper and its alloy). The present rust preventive agent is very advantageous in practical use in terms of being able to be used as an aqueous solution, in terms of cost being lower than that of an organic solvent rust preventive agent, having stability, and easy waste liquid treatment.

Claims (6)

A rust preventive agent comprising a copolymer of a hydrophilic or water-soluble polymerizable monomer (A) and a hydroxyphenylbenzotriazole compound monomer (B) having a polymerizable double bond-containing group as an active ingredient. A copolymer of a hydrophilic or water-soluble polymerizable monomer (A) with a hydroxyphenylbenzotriazole compound monomer (B) having a polymerizable double bond-containing group, and general formula (1): [Wherein, R ¹ represents a hydrogen atom, a C _1-8 alkyl group, a carboxyl group, a C _1-8 alkoxycarbonyl group, a phenoxycarbonyl group, a hydroxy group or a halogen atom. R <^2> represents a hydrogen atom, a hydroxyl group, an amino group, a halogen atom, or a metal atom.] The rust preventive agent containing benzotriazole (D) shown as an active ingredient. The hydroxyphenylbenzotriazole compound monomer (B) according to claim 1 or 2 is represented by the general formula (2): [Wherein, R ³ , R ⁴ and R ⁵ are the same or different and include a polymerizable double bond containing group, a hydrogen atom, a C _1-8 alkyl group, a C _1-8 alkoxy group, a cyano group, a hydroxy group, a halogen atom, a carboxyl group or An alkoxycarbonyl group is shown. However, at least one of R ³ , R ⁴ and R ⁵ is a polymerizable double bond-containing group.] A rust preventive agent characterized by the above-mentioned. The antirust method of metals is coat | covered with the surface of metals. In coating the rust inhibitor according to any one of claims 1 to 3 on the surface of metals, the rust preventive agent according to any one of claims 1 to 3 is used in the form of an aqueous solution. Antirust method. The antirust method according to claim 4 or 5, wherein the metals are copper or a copper alloy.