CN1308487C - Rust preventives and method of rust prevention with the same - Google Patents
Rust preventives and method of rust prevention with the same Download PDFInfo
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- CN1308487C CN1308487C CNB038098202A CN03809820A CN1308487C CN 1308487 C CN1308487 C CN 1308487C CN B038098202 A CNB038098202 A CN B038098202A CN 03809820 A CN03809820 A CN 03809820A CN 1308487 C CN1308487 C CN 1308487C
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- rust
- preventive agent
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- benzotriazole
- hydroxyl
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Rust preventives 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 containing as the active ingredients the monomer (A), the monomer (B), and a benzotriazole (D) represented by the general formula (1): [wherein R1 is hydrogen, C1-8 alkyl, carboxyl, C1-8 alkoxycarbonyl, phenoxycarbonyl, hydroxyl, or halogeno; and R2 is hydrogen, hydroxyl, amino, halogeno, 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
Technical field
The present invention relates to a kind of the multipolymer of hydroxy-phenyl benzotriazole class as the rust-preventive agent of effective constituent and the rust-proofing method that uses its metal species.
Background technology
, got rusty in the past, proposed the whole bag of tricks in order to prevent metal species.For example, known on the metallic surface by plating etc. be covered with uncorruptible other metal method, with coating cover the method for metallic surface, on the metallic surface by chemical process or the film forming method of electrochemical method shape etc., suppress corroding method etc. by preventing that the metallic surface from contacting with the external corrosion environment.
Rust-preventive agent as metal species, known have a benzotriazole category, for example open in the flat 10-265979 communique, disclose the copper product composite corrosion inhibitor that in the organic solvent dissolution composition of the acrylic copolymer that contains the composition that comes from dialkyl aminoalkyl (methyl) acrylate, adds benzotriazole category the spy.In addition, open in the clear 59-108099 communique, disclose the metal inhibitor to the lubricating oil under the high temperature of 2 '-hydroxy-phenyl benzotriazole class as effective constituent the spy.
Benzotriazole category is by forming chelate bond with the metallic surface, and forms tunicle thus and show rust-proof effect, but in technology in the past, and also existing in actual applications needs the problem that solves.One of them is, because this tunicle is very thin usually, so may not necessarily satisfy rust-proof effect under severe environment.Also can enumerate when in resin, adding triazole species, be easy to produce and ooze out phenomenon, can not obtain stable effect as rust-preventive agent.Also exist when triazole species and lack when water-soluble, usually need to use the organic solvent of dilution usefulness, thereby this departmental cost is uprised, and having problems aspect operational secure context and the liquid waste disposal, have problems such as the solvent species that can use is restricted in addition.For example, 2 '-hydroxy-phenyl benzotriazole class lacks water-soluble, if will embody rust-proof effect, it is dissolved in the organic solvent, above-mentioned problem will occur when therefore using.
Summary of the invention
Therefore, problem of the present invention is the rust-preventive agent that contains benzotriazole compound, even can and keep rust-proof effect and substantially do not contain also operable rust-preventive agent under the aqueous solution condition of organic solvent and use the rust-proofing method of this rust-preventive agent for the metal species performance even its purpose is to provide under severe environment also.
In order to solve above-mentioned problem, the inventor etc. have carried out the research of rust-proof effect from application facet to various benzotriazole cpds, found that, be imbued with water-soluble by making water-soluble or hydrophilic copolymerization monomer and hydroxy-phenyl benzotriazole carry out the multipolymer that copolyreaction obtains, be suitable as very much the rust-preventive agent of metal species, so far finished the present invention.
That is, the present invention relates to following rust-preventive agent and its rust-proofing method of use.
(1) a kind of rust-preventive agent is characterized in that, contains the multipolymer of water-soluble or hydrophilic polymerizable monomer (A) and the hydroxy-phenyl benzotriazole compound monomer (B) with the group that contains the two keys of polymerizability as effective constituent.
(2) a kind of rust-preventive agent, it is characterized in that, contain water-soluble or hydrophilic polymerizable monomer (A) and the multipolymer of hydroxy-phenyl benzotriazole compound monomer (B) and the benzotriazole category of representing with general formula (1) (D) as effective constituent with the group that contains the two keys of polymerizability
[in the formula, R
1Expression hydrogen atom, C
1-8Alkyl, carboxyl, C
1-8Alkoxy carbonyl, phenyloxycarbonyl, hydroxyl or halogen atom, R
2Expression hydrogen atom, hydroxyl, amino, halogen atom or atoms metal].
(3) rust-preventive agent of record in above-mentioned (1) or (2) is characterized in that, above-mentioned hydroxy-phenyl benzotriazole compound monomer (B) is the hydroxy-phenyl benzotriazole compound with general formula (2) expression,
[in the formula, R
3, R
4And R
5Identical or different, expression contains group, hydrogen atom, the C of the two keys of polymerizability
1-8Alkyl, C
1-8Alkoxyl group, cyano group, hydroxyl, halogen atom, carboxyl or alkoxy carbonyl.Wherein, R
3, R
4And R
5In at least one be the group that contains the two keys of polymerizability].
(4) a kind of rust-proofing method of metal species is characterized in that, covers the rust-preventive agent of each record in above-mentioned (1)-(3) on the surface of metal species.
(5) a kind of rust-proofing method of metal species is characterized in that, in covering above-mentioned (1)-(3) on the surface in metal species during the rust-preventive agent of each record, uses in above-mentioned (1)-(3) rust-preventive agent of putting down in writing in each with the form of aqueous solution.
(6) rust-proofing method of record in above-mentioned (4) or (5), above-mentioned metal species is copper or copper alloy.
Embodiment
At first, enumerate the substituent expression and the object lesson thereof of record in this manual.
So-called C
1-4Alkyl is represented straight chain shape or the branched-chain alkyl of carbonatoms 1-4, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl.
So-called C
1-8Alkyl is represented straight chain shape or the branched-chain alkyl of carbonatoms 1-8, except above-mentioned C
1-4Alkyl also can be enumerated n-pentyl, isopentyl, neo-pentyl, tert-pentyl, n-hexyl, heptyl or octyl group etc.
So-called C
1-18Alkyl is represented straight chain shape or the branched-chain alkyl of carbonatoms 1-18, except above-mentioned C
1-4Alkyl and C
1-8Beyond the alkyl, also can enumerate nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl etc.
So-called C
1-8Alkoxyl group is represented straight chain shape or the chain alkoxyl group of carbonatoms 1-8, can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy, n-pentyloxy, isopentyloxy, neopentyl oxygen, uncle's pentyloxy, positive hexyloxy, heptan oxygen base or octyloxy etc.
So-called alkoxy carbonyl is represented a straight chain shape or the chain alkoxy carbonyl of carbonatoms 1-8, can enumerate methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, n-butoxy carbonyl, tert-butoxycarbonyl, n-pentyloxy carbonyl, isopentyloxy carbonyl, neopentyl oxygen carbonyl, tert-pentyloxy carbonyl, positive hexyloxy carbonyl, heptan oxygen base carbonyl or carbonyl octyloxy etc.
So-called C
1-4Alkylidene group is represented a straight chain shape or the chain alkylidene group of carbonatoms 1-4, can enumerate methylene, ethylene, trimethylene, fourth support, methyl methylene, propylidene, 1-methyl trimethylene, 2-methyl trimethylene or ethyl ethylene etc.
So-called C
1-10Alkylidene group is represented a straight chain shape or the chain alkylidene group of carbonatoms 1-10, except above-mentioned C
1-4Alkylidene group also can be enumerated pentamethylene, hexamethylene, support in heptan, octamethylene, support in the ninth of the ten Heavenly Stems, decamethylene or 2,2-dimethyl trimethylene etc.
As halogen atom, can enumerate chlorine, bromine, fluorine, iodine.
As atoms metal, can enumerate alkali metal atom (sodium, potassium, lithium etc.), silver atoms etc.
As the above-mentioned multipolymer of the effective constituent of rust-preventive agent of the present invention be with water-soluble or hydrophilic polymerizable monomer (A) and hydroxy-phenyl benzotriazole compound monomer (B) with the group that contains the two keys of polymerizability as necessary monomeric multipolymer.
As above-mentioned polymerizable monomer (A), so long as contain free-radical polymerised group and be water-soluble or wetting ability, just have no particular limits at intramolecularly, for example can enumerate below the material shown in 1.-8..
1. vinylformic acid or methacrylic acid etc. (methyl) acrylic acid or the like; Unsaturated copolymerization carboxylic-acids such as toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, butenoic acid or maleic anhydride;
2. be selected from an alkali metal salt (sodium, potassium, lithium salts etc.), ammonium salt and aminocompound salt (dimethylamine, Trimethylamine 99, diethylamine, triethylamine, Monoethanolamine MEA BASF, diethanolamine, methyldiethanolamine, methyl isopropyl hydramine, dimethyl Monoethanolamine MEA BASF, trolamine etc.) a kind of of above-mentioned unsaturated copolymerization carboxylic-acid or more than two kinds;
3. use the vinylformic acid alkylene glycol ethers compound of general formula (3) expression,
[in the formula, R
6Expression hydrogen atom or C
1-4Alkyl, R
7Expression C
1-4Alkylidene group, R
8Expression hydrogen atom, C
1-4Alkyl or phenyl, m are represented the integer of 1-20].
4. by making halogenated hydrocarbons such as benzyl chloride, methyl chloride, monochloroethane, chloropropane, chlorobutane, bromotoluene, monobromethane, monobromethane, N-PROPYLE BROMIDE, n-butyl bromide, methyl iodide, benzyl iodide, iodoethane or iodopropane; Alkylating reagent and N such as sulfuric acid ester such as ethyl sulfate or methyl-sulfate, N-dimethylaminopropyl (methyl) acrylamide, N, N-dimethyl aminoethyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide, N, (methyl) acrylic amides such as N-diethylamino ethyl (methyl) acrylamide; (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) vinylformic acid N, N-diethylamino ethyl ester, acryloyl morpholine, 2-hydroxyl-hydroxyl acryloxy propyl group-N, N dimethylamine, 3-hydroxyl acryloxy propyl group-N, the resulting unsaturated copolymerization quaternary ammonium salt of N dimethylamine etc. (methyl) acrylic-amino alkyl esters effect;
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. vinylamide class such as N-vinyl formamide or N-vinyl acetamide;
8. acrylamide-2, unsaturated copolymerization sulfonic acid class and ammonium salts thereof such as 2 '-dimethyl propylene sulfonic acid, methacrylic acid 2-sulphur ethyl ester or methacrylic acid 3-sulphur propyl ester.
As acrylic compound, for example can enumerate (methyl) acrylic acid hydroxy alkyl ester classes such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxypropyl acrylate or (methyl) vinylformic acid 4-hydroxy butyl ester with above-mentioned general formula (4) expression; (methyl) acrylic acid alkoxy alkyl classes such as (methyl) vinylformic acid methoxyl group ethyl ester or (methyl) vinylformic acid ethoxy ethyl ester; (methyl) acrylic acid macrogol ester classes such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate or polyalkylene glycol diester; Alkoxyl group polyalkylene glycol diester classes such as methoxy poly (ethylene glycol) (methyl) acrylate or methoxyl group polypropylene glycol list (methyl) acrylate; (methyl) acrylic acid phenoxy group polyalkylene glycol diester classes such as phenoxy group polyoxyethylene glycol (methyl) acrylate or phenoxy group polypropylene glycol list (methyl) acrylate.
Among these, from can be to reacting the viewpoint that the multipolymer that obtains is given highly water-soluble with hydroxy-phenyl benzotriazole compound (B), also preferred especially (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid methoxyl group ethyl ester, polyethyleneglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, polypropylene glycol list (methyl) acrylate or methoxy poly (ethylene glycol) (methyl) acrylate etc. with the group that contains the two keys of polymerizability.These polymerizable monomers (A) both can use separately, also can be used in combination more than two kinds.
Amount ratio to the polymerizable monomer in the above-mentioned multipolymer (A) is not particularly limited, and can suitably be selected from wide scope, but is generally the 5-99.9 weight % of copolymer composition total amount, preferred 10-99 weight %.
In above-mentioned polymerizable monomer (A), also especially preferably 2. be selected from an alkali metal salt, ammonium salt and aminocompound a kind of of unsaturated copolymerization carboxylic-acids such as vinylformic acid or methacrylic acid etc. (methyl) acrylic acid or the like, toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, butenoic acid, maleic anhydride or more than two kinds, 3. use the acrylic compound of general formula (3) expression.
Also have, when above-mentioned multipolymer is considered as by an alkali metal salt that is selected from this unsaturated copolymerization carboxylic-acid, when ammonium salt and aminocompound a kind of or material and hydroxy-phenyl benzotriazole compound (B) are formed more than two kinds multipolymer, also can make by the following method, promptly, replace being selected from an alkali metal salt of this unsaturated copolymerization carboxylic-acid, ammonium salt and aminocompound a kind of or more than two kinds, after the unsaturated copolymerization carboxylic-acid and hydroxy-phenyl benzotriazole compound (B) formation multipolymer with correspondence, with the normal an alkali metal salt that is selected from of 0.1-1.3, ammonium salt and aminocompound a kind of or react more than two kinds and finish manufacturing.
Also have, with regard to above-mentioned hydroxy-phenyl benzotriazole compound monomer (B) with the group that contains the two keys of polymerizability, so long as on the optional position that can replace of hydroxy-phenyl benzotriazole, have the group that contains the two keys of polymerizability, just be not particularly limited, as mentioned above, can enumerate the hydroxy-phenyl benzotriazole compound of representing with general formula (2).
[in the formula, R
3, R
4And R
5Identical or different expression contains group, hydrogen atom, the C of the two keys of polymerizability
1-8Alkyl, C
1-8Alkoxyl group, cyano group, hydroxyl, halogen atom, carboxyl or alkoxy carbonyl, wherein, R
3, R
4And R
5In at least one be the group that contains the two keys of polymerizability].
Here, with regard to the group that contains the two keys of polymerizability, so long as contain the group of the two keys of polymerizability of vinyl, just not restriction especially can be enumerated the group that contains the two keys of polymerizability of for example using general formula (4) expression.
[in the formula, R
9Expression C
1-10Alkylidene group, R
10Expression hydrogen atom or C
1-4Alkyl, n are represented 0 or 1 integer].
With the group that contains the two keys of polymerizability of above-mentioned general formula (4) expression, also can be directly or be connected in the optional position of hydroxy-phenyl benzotriazole by heteroatomss such as nitrogen-atoms, Sauerstoffatom, sulphur atoms.
As the object lesson of hydroxy-phenyl benzotriazole compound monomer (B), can be exemplified as 2-[2 '-hydroxyl-5 '-(acryloxy) phenyl] benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxy) phenyl] benzotriazole, 2-[2 '-hydroxyl-the 3 '-tertiary butyl-5 '-(methacryloxy) phenyl] benzotriazole, 2-[2 '-hydroxyl-3 '-methyl-5 '-(acryloxy) phenyl] benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxypropyl) phenyl]-the 5-chlorobenzotriazole, 2-[2 '-hydroxyl-5 '-(acryloxy ethyl) phenyl] benzotriazole, 2-[2 '-hydroxyl-the 3 '-tertiary butyl-5 '-(methacryloxyethyl) phenyl] benzotriazole, 2-[2 '-hydroxyl-3 '-methyl-5 '-(acryloxy ethyl) phenyl] benzotriazole, 2-[2 '-hydroxyl-the 3 '-tertiary butyl-5 '-(methacryloxyethyl) phenyl]-the 5-chlorobenzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxypropyl) phenyl]-the 5-chlorobenzotriazole, 2-[2 '-hydroxyl-5 '-(acryloxy butyl) phenyl]-the 5-Methylbenzotriazole, perhaps [the 2-hydroxyl-3-tertiary butyl-5-(acryloxy ethoxy carbonyl ethyl) phenyl] benzotriazole etc.
These hydroxy-phenyl benzotriazole compounds can be according to known method, and for example the method for No. 2701116 communique records of Japan's special permission is made.Hydroxy-phenyl benzotriazole compound monomer (B) can be used alone, and also can be used in combination more than two kinds.
Amount ratio to hydroxy-phenyl benzotriazole compound monomer (B) in the above-mentioned multipolymer is not particularly limited, can suitably be selected from wide scope, but consider the rustless property of gained multipolymer, water-soluble, environment for use and purpose, economy, be generally the 0.0001-50 weight % of copolymerization composition total amount, be preferably 0.001-30 weight %.
System film, stability for the multipolymer that improves above-mentioned polymerizable monomer (A) and hydroxy-phenyl benzotriazole compound monomer (B), prevent cohesion, precipitation or gelation, thereby obtain water-soluble, whipability, binding property, adaptation etc., preferably combination is used other polymerizable monomer (C) and is constituted multipolymer.
As other polymerizable monomer (C), can enumerate as (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) Octyl acrylate or (methyl) lauryl acrylates; (methyl) vinylformic acid cycloalkyl ester classes such as (methyl) cyclohexyl acrylate, (methyl) vinylformic acid methyl cyclohexane ester, (methyl) isobornyl acrylate or (methyl) vinylformic acid cyclo-dodecyl ester; (methyl) acrylic acid caprolactone affixture; Aromatic hydroxyl vinyl such as para hydroxybenzene ethene;-olefines such as 1-hexene, 1-octene, 1-decene or vinylbenzene; Vinyl carboxylates classes such as vinyl acetate, propionate or vinyl laurate; Vinylchlorid etc.
These other polymerizable monomers (C) both can be used alone, and also can use more than two kinds.The amount ratio of other polymerizable monomer in the above-mentioned multipolymer is not particularly limited, can suitably be selected from wide scope, if but other monomeric usage quantity surpasses 20 weight %, then can damage water-soluble, so usually below 20 weight % of copolymerization composition total amount, preferred 0.01-20 weight %, more preferably 1-15 weight %.
Among the present invention,, also can add a kind of in the following benzotriazole category (D) or more than two kinds to above-mentioned multipolymer in order further to improve characteristic such as rustless property.
As above-mentioned benzotriazole category (D), can be exemplified as for example 1H-benzotriazole, 4-methyl isophthalic acid H-benzotriazole, 4-carboxyl-1H-benzotriazole, 4-methyl isophthalic acid H-benzotriazole sodium salt, 5-methyl isophthalic acid H-benzotriazole, benzotriazole butyl ester, benzotriazole silver salt, 5-chloro-1H-benzotriazole, 1-chlorobenzotriazole etc.
The amount of the benzotriazole category in the above-mentioned multipolymer (D) still usually with respect to the above-mentioned multipolymer of 100 weight parts, is used about 0-500 weight part than can suitably being selected from wide scope.
Below, describe for polymerization process as the above-mentioned multipolymer of rust-preventive agent of the present invention, can make according to common polymerization processs such as for example solution polymerization, letex polymerization, suspension polymerizations basically.
For example, under the situation that adopts solution polymerization process, exist in solvent under the condition of polymerization starter, other polymerizable monomer (C) that make polymer monomer (A) and hydroxy-phenyl benzotriazole compound (B), adds as required carries out copolymerization and gets final product.
As solvent, known in the past material can be used widely, for example alcohols such as water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, isopropylcarbinol, Pentyl alcohol, ethyl cellosolve, ethylene glycol butyl ether, 1-methoxyl group-2-propyl alcohol, ethylene glycol, propylene glycol, glycol ether, polyoxyethylene glycol or polypropylene glycol can be exemplified as; Ester classes such as vinyl acetic monomer, propyl acetate or N-BUTYL ACETATE; Aliphatic hydrocarbons such as sherwood oil, hexane or heptane; Benzene, toluene or dimethylbenzene etc. are aromatic hydrocarbon based; Ketones such as acetone, methylethylketone or methyl iso-butyl ketone (MIBK); Ethers such as diethyl ether, dibutyl ether, tetrahydrofuran (THF) or two _ alkane; N, amidess such as dinethylformamide.
In these solvents, consider and in aqueous solution, use the target multipolymer, so preferred water miscible solvent, specifically, can be exemplified as methyl alcohol, ethanol, Virahol, ethyl cellosolve or 1-methoxyl group-alcohols such as 2-propyl alcohol, ethers such as tetrahydrofuran (THF) or two _ alkane, N, amidess such as dinethylformamide.These solvents both can be used alone, and also can be used in combination more than two kinds.The usage quantity of solvent is restriction especially not, can suitably be selected from wide scope according to the various characteristics and the purposes of the multipolymer that will obtain, and when usually multipolymer composition total amount being considered as 100 weight parts, is preferably the 1-10000 weight part.
Known in the past material can be used widely as polymerization starter, for example azo compounds such as superoxide such as benzoyl peroxide, dibutyl superoxide, Diisopropyl azodicarboxylate etc. can be exemplified as.Polymerization starter can be used alone, also can two kinds to be used in combination.The usage quantity of polymerization starter is restriction especially not, is generally the 0.1-5 mole % of copolymerization composition total amount (total mole number).
This copolyreaction is carried out in room temperature～200 ℃, preferred 40-140 ℃ temperature range usually, finishes in 1-50 hour, preferred 2-24 hour usually.
The molecular weight of above-mentioned multipolymer can for example add the method for polymerization retarders such as chain-transfer agents such as tetracol phenixin, lauryl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, Thiovanic acid monooctyl ester, thioglycerol or quinhydrones by usual method to be regulated.
The weight-average molecular weight of the multipolymer that obtains thus is generally 1000-200000, preferred 2000-150000, consider water-soluble, prevent along with oozing out of time etc., be preferably 3000-100000, more preferably 5000-50000.
Contain above-mentioned multipolymer as effective constituent in the rust-preventive agent of the present invention.This multipolymer is imbued with water-soluble, can use with the form of aqueous solution, can also use suitable dispersion agent, emulsifying agent etc. to use with the form of dispersion liquid, emulsion as required.So-called aqueous solution is meant water or is the solution of primary solvent with water in above-mentioned, under latter event, is not hindering water also can contain organic solvent in to the scope of the solvency action of above-mentioned multipolymer.For example, in the scope that does not influence rust-proof effect, also can contain the solvent that when making the rust-preventing characteristic polymkeric substance, uses.
In rust-preventive agent of the present invention, in the scope of the rust-proof effect that does not damage above-mentioned multipolymer, also can add other rust-preventive agent, UV light absorber, near infrared ray absorption, water-soluble matting agent, antioxidant, fluorescent bleaches, wetting agent, surface tension modifier, pigment, dyestuff, pigment, spices, metal passivator as required, make nuclear agent, static inhibitor, fire retardant, lubricant, thickening material, mould inhibitor, inhibiter, oxygen absorbent or processing aid and other additive that in the past in antirust agent composition, added etc.
The working concentration of the above-mentioned multipolymer in the rust-preventive agent of the present invention is more or less different according to the kind difference of this multipolymer, but be generally more than the 0.0001 weight %, need only at this more than concentration, just have no particular limits, preferred working concentration is about 0.001-10 weight %, more preferably about 0.01-1 weight %.If working concentration less than 0.0001 weight % then can not obtain enough rust-proof effects.
Rust-preventive agent of the present invention is antirust effective to general metal species (metal or alloys such as copper, iron), and particularly can demonstrate good rust-proof effect for copper and copper alloy.
Rust-proofing method of the present invention can be implemented by the following method, for example on the antirust metallic surface of needs, cover by the solution that is coated with, atomizer spray contains rust-preventive agent of the present invention, perhaps with this metal impregnation after this solution etc. is handled, the method that its drying is covered is implemented.
Rust-preventive agent of the present invention can be preserved with the state of solution, but considers the facility of circulation, also can manage to make it to form concentrated solution, when using then more according to the rules concentration water dilute.
If adopt rust-proofing method of the present invention, can carry out antirust processing to metal species very easily, even in salt solution, in the many wet environments of acid gas phase medium and high temperature or under the mal-condition of long-term outdoor exposure, also can significantly suppress to get rusty and even corrode.In addition, when being used for the plastics system shell of electronics, can obtain the effect identical with the electroless plating of nickel.
Embodiment
Below, by enumerating embodiment and test example, specify the present invention further." part " or " % " unless specifically stated otherwise below also having, expression " weight part " or " weight % " respectively.
Embodiment 1
In four-hole boiling flask, add 100 parts of Virahols with agitator, thermometer, condenser and the funnel that drips, in being warming up to 80 ℃ process, with dripping 20 parts of 2-[2 '-hydroxyl-5 '-(methacryloxyethyl) phenyl in 2 hours] mixture of benzotriazole, 80 parts of methoxy polyethylene glycol methacrylate-styrene polymers (the repeat number m ≈ 8 of ethylene glycol) and 0.3 part of Diisopropyl azodicarboxylate, kept 4 hours down at 80 ℃ again, obtain the target multipolymer, thereby made the rust-preventive agent of forming by the aqueous isopropanol (solid component content 50.8%) of this multipolymer.The weight-average molecular weight of measuring according to gel permeation chromatography (hereinafter referred to as GPC) of this multipolymer is 43100.Except that desolvating, add deionized water by the solution decompression that contains above-mentioned multipolymer in residue, modulation contains the aqueous solution (solid component content 30%) of above-mentioned multipolymer, thus the rust-preventive agent that acquisition is made up of aqueous solution.
Embodiment 2
To having agitator, thermometer, add 100 parts of 1-methoxyl group-2-propyl alcohol in the four-hole boiling flask of the condenser and the funnel that drips, in being warming up to 80 ℃ process, with 30 parts of 2-[2 '-hydroxyl-5 '-(methacryloxyethyl) phenyl of dropping in 2 hours] benzotriazole, 70 parts of methoxy polyethylene glycol methacrylate-styrene polymers (m ≈ 7), 0.3 the mixture of part Diisopropyl azodicarboxylate and 1 part of n-dodecyl mercaptan, kept 4 hours down at 80 ℃ again, obtain the target multipolymer, thereby make the rust-preventive agent of forming by the 1-methoxyl group-2-propanol solution (solid component content 51.2%) of this multipolymer.
Embodiment 3
To having agitator, thermometer, add 100 parts of 1-methoxyl group-2-propyl alcohol in the four-hole boiling flask of the condenser and the funnel that drips, in being warming up to 80 ℃ process, with 30 parts of 2-[2 '-hydroxyl-3 '-tertiary butyl-5 '-(methacryloxyethyl) phenyl of dropping in 2 hours] benzotriazole, 50 parts of methoxy polyethylene glycol methacrylate-styrene polymers (m ≈ 7), 20 parts of vinylformic acid, 0.3 the mixture of part Diisopropyl azodicarboxylate and 1 part of n-dodecyl mercaptan, kept 4 hours down at 80 ℃ again, obtain the target multipolymer, thereby make the rust-preventive agent of forming by the 1-methoxyl group-2-propanol solution (solid component content 49.7%) of this multipolymer.The weight-average molecular weight of measuring according to GPC of this multipolymer is 5900.
Embodiment 4
To having agitator, thermometer, add 100 parts of 1-methoxyl group-2-propyl alcohol in the four-hole boiling flask of the condenser and the funnel that drips, in being warming up to 80 ℃ process, with 30 parts of 2-[2 '-hydroxyl-3 '-tertiary butyl-5 '-(methacryloxyethyl) phenyl of dropping in 2 hours]-the 5-chlorobenzotriazole, 65 parts of methoxy polyethylene glycol methacrylate-styrene polymers (m ≈ 7), 5 parts of 4-methacryloxies-2,2,6, the mixture of 6-tetramethyl piperidine and 0.3 part of Diisopropyl azodicarboxylate, keep down copolyreaction is finished at 80 ℃ again, thereby make the 1-methoxyl group-2-propanol solution (solid component content 50.8%) of rust-preventing characteristic multipolymer.The weight-average molecular weight of measuring according to GPC of this multipolymer is 35900.After this copolymer solution removal of solvent under reduced pressure, adding deionized water and modulate solid component content in residue is 30% the aqueous solution, thereby obtains the rust-preventive agent of aqueous solution.
Embodiment 5
To having agitator, thermometer, add 250 parts of 1-methoxyl group-2-propyl alcohol in the four-hole boiling flask of the condenser and the funnel that drips, 30 parts of 2-[2 '-hydroxyl-5 '-(methacryloxyethyl) phenyl] benzotriazole, 60 parts of ammonium methacrylates, 10 parts of methacrylic acid 2-hydroxyl ethyl esters, 0.5 the mixture of part Diisopropyl azodicarboxylate and 2 parts of n-dodecyl mercaptans, under nitrogen atmosphere, stir on one side on one side and be warming up to 60 ℃, under this temperature, kept about 12 hours, obtain the target multipolymer, thereby make the rust-preventive agent of forming by the 1-methoxyl group-2-propanol solution (solid component content 29.1%, percent polymerization 100%) of this multipolymer.The weight-average molecular weight of measuring according to GPC of this multipolymer is 43100.After this copolymer solution removal of solvent under reduced pressure, adding deionized water and modulate solid component content in residue is 30% the aqueous solution, thereby obtains the rust-preventive agent of aqueous solution.The pH of this rust-preventive agent is 6.9.
Embodiment 6
To having agitator, thermometer, add 250 parts of tetrahydrofuran (THF)s in the four-hole boiling flask of the condenser and the funnel that drips, 30 parts of 2-[2 '-hydroxyl-5 '-(methacryloxyethyl) phenyl] benzotriazole, 60 parts of methacrylic acids, 10 parts of methacrylic acid 2-hydroxyl ethyl esters, 0.5 the mixture of part Diisopropyl azodicarboxylate and 2 parts of n-dodecyl mercaptans, after one side is stirred under nitrogen atmosphere and is warming up to 60 ℃ on one side, kept about 12 hours, obtain the target multipolymer, thereby make the rust-preventive agent of forming by the tetrahydrofuran solution (solid component content 29.1%, percent polymerization 100%) of this multipolymer.Then, add 25% ammonia soln so that pH reaches 6-7, at room temperature stir 3 hours after, removal of solvent under reduced pressure, adding deionized water and modulate solid component content in residue is 30% the aqueous solution, thereby obtains the rust-preventive agent of aqueous solution.The weight-average molecular weight of measuring according to GPC of this multipolymer is 41100.
Embodiment 7
To having agitator, thermometer, add 480 parts of tetrahydrofuran (THF)s in the four-hole boiling flask of the condenser and the funnel that drips, 72 parts of 2-[2 '-hydroxyl-5 '-(methacryloxyethyl) phenyl] benzotriazole, 24 parts of methyl methacrylates, 96 parts of vinylformic acid, 48 parts of methacrylic acid 2-hydroxyl ethyl esters, 0.5 the mixture of part Diisopropyl azodicarboxylate and 2 parts of n-dodecyl mercaptans, after one side is stirred under nitrogen atmosphere and is warming up to 60 ℃ on one side, kept about 12 hours, obtain the target multipolymer, thereby make the rust-preventive agent of forming by the tetrahydrofuran solution (solid component content 33.5%, percent polymerization 100%) of this multipolymer.Then, add 25% ammonia soln so that pH reaches 6-7, at room temperature stir 3 hours after, removal of solvent under reduced pressure adds deionized water in residue and the solid component content of modulating multipolymer is 30% the aqueous solution, thereby obtains the rust-preventive agent of aqueous solution.The weight-average molecular weight of measuring according to GPC of this multipolymer is 36900.
Test example 1 (rust prevention test)
Make test film as described below: (JIS specification C1020P after 0.5 * 30 * 70mm) the surface finish, impregnated in 0.5% hydrochloric acid 5 minutes, washes then 1 minute with copper coin to use No. 320 sand paper.
Experimental liquid 1: add deionized water in the 1-methoxyl group-2-propanol solution that is obtained by embodiment 2, the modulation solids component is the rust-preventive agent of 0.18% aqueous solution, as experimental liquid 1.
Experimental liquid 2: add deionized water in 30% aqueous solution that is obtained by embodiment 7, the modulation solids component is the rust-preventive agent of 0.15% aqueous solution, as experimental liquid 2.
Comparison test liquid 1: use the 1% benzotriazole aqueous solution as rust-preventive agent.
Comparison test liquid 2: 1% acetone soln that uses 2-(2-hydroxy-5-methyl base phenyl) benzotriazole (チ ヌ PVC Application P, Japanese チ バ ガ イ ギ-society's system) is as rust-preventive agent.
Above-mentioned test film be impregnated in experimental liquid 1, experimental liquid 2, comparison test liquid 1 and the comparison test liquid 22 minutes respectively under 20 ℃, by air-supply 60 ℃ dry 30 minutes down.On each test film of handling, spraying 5% salt solution is 24 hours under 35 ℃, the confirmation form surface state.In addition, with contact resistance value instrument ロ レ ス -MP (Mitsubishi Chemical's system, detector: 2 the probe modes) resistance value before and after the experiment with measuring.Measurement is carried out 2 positions.Also have, carry out the salt solution spraying too for the material that on the copper coin surface, has carried out the nickel electroless plating as a reference and handle, and the confirmation form surface state.
Above-mentioned test-results has been shown in table 1 and table 2.
[table 1]
| The situation of getting rusty | The variable color situation | |
| Experimental liquid 1 | Do not have | Do not have |
| Experimental liquid 2 | Do not have | Do not have |
| Comparison test liquid 1 | Get rusty comprehensively | Become China ink comprehensively |
| Comparison test liquid 2 | Do not have | Do not have |
| The nickel plating is handled | Do not have | Do not have |
[table 2]
| Resistance value | Before the brine spray | Behind the brine spray |
| Experimental liquid 1 | All below 0.1 Ω | All below 0.5 Ω |
| Experimental liquid 2 | All below 0.1 Ω | All below 0.5 Ω |
| Comparison test liquid 1 | All below 0.1 Ω | 3.0Ω，140Ω |
| Comparison test liquid 2 | All below 0.1 Ω | 0.3Ω，1.2Ω |
| The nickel plating is handled | All below 0.1 Ω | All below 0.5 Ω |
As can be known from the above results,, demonstrated better rust-proof effect, and demonstrated and the identical effect of nickel plating processing though rust-preventive agent concentration of the present invention is lower than the benzotriazole as the representative rust-preventive agent of copper.
Test example 2
Make test film as described below: (JIS specification C1020P after 0.5 * 30 * 70mm) the surface finish, impregnated in 5% sulfuric acid 1 minute, washes then 1 minute with copper coin to use No. 1500 sand paper.
Above-mentioned test film be impregnated under 20 ℃ respectively among following experimental liquid 3-6 and the comparison test liquid 1-2 after 5 minutes, washed 30 seconds, remove the water droplet on test film surface by air-supply after, 60 ℃ dry 30 minutes down.
Each test film of handling was placed in the constant temperature and humidity cabinet that is adjusted into 60 ℃ of temperature, humidity 85% 114 hours.With contact resistance value instrument ロ レ ス -MP (Mitsubishi Chemical's system, detector: 2 the probe modes) sheet resistance value before and after the experiment with measuring.Measure 5 positions, and its mean value as sheet resistance value.Test-results is shown in Table 4.
Experimental liquid 4: with respect to 30% aqueous solution, 5 weight parts that obtain by embodiment 6, add 1 part of 1H-benzotriazole after, add deionized water, making solids component is the aqueous solution of 250ppm, as experimental liquid 4.
Experimental liquid 5: with respect to 30% aqueous solution, 3.3 weight parts that obtain by embodiment 6, add 1 part of 1H-benzotriazole after, add deionized water, making solids component is the aqueous solution of 200ppm, as experimental liquid 5.
Experimental liquid 6: with respect to 30% aqueous solution, 1.7 weight parts that obtain by embodiment 6, add 1 part of 1H-benzotriazole after, add deionized water, making solids component is the aqueous solution of 150ppm, as experimental liquid 6.
Comparison test liquid 3: use the 100ppm1H-benzotriazole aqueous solution as rust-preventive agent.
Comparison test liquid 4: use the 250ppm1H-benzotriazole aqueous solution as rust-preventive agent.
Experimental liquid and comparison test liquid are shown in Table 3.
[table 3]
| Composition is than (ppm) | ||
| Embodiment 6 (solids component), ppm | The 1H-benzotriazole | |
| Experimental liquid 4 | 150 | 100 |
| Experimental liquid 5 | 100 | 100 |
| Experimental liquid 6 | 50 | 100 |
| Comparison test liquid 3 | 0 | 100 |
| Comparison test liquid 4 | 0 | 250 |
[table 4]
| Sheet resistance value (m Ω) | Increment rate (%) | ||
| Before the test | After the test | ||
| Experimental liquid 4 | 41.3 | 71.2 | 72.4 |
| Experimental liquid 5 | 29.6 | 30.8 | 4.1 |
| Experimental liquid 6 | 29.7 | 44.8 | 50.8 |
| Comparison test liquid 3 | 35.7 | 107.7 | 201.7 |
| Comparison test liquid 4 | 26.3 | 87.2 | 231.6 |
Can demonstrate synergy when as can be known from the above results, rust-preventive agent of the present invention and benzotriazole category rust-preventive agent are used in combination.
Utilizability on the industry
As mentioned above, contain hydrophily or water miscible polymerizable monomer (A) as active ingredient in the antirust agent of the present invention and have the copolymer of the hydroxy-phenyl benzotriazole compound monomer (B) of the group that contains the two keys of polymerism, antirust especially effective to metal species (particularly copper and alloy thereof). This antirust agent can be used as aqueous solution and uses, thus compare with the antirust agent of organic solvent class, with low cost, have security, liquid waste processing is easy, therefore be very beneficial for using.
Claims (6)
1. a rust-preventive agent is characterized in that, contains the multipolymer of wetting ability or water miscible polymerizable monomer (A) and the hydroxy-phenyl benzotriazole compound monomer (B) with the group that contains the two keys of polymerizability as effective constituent.
2. rust-preventive agent as claimed in claim 1 is characterized in that, also contains the benzotriazole category (D) that useful general formula (1) is represented as effective constituent,
In the formula, R
1Expression hydrogen atom, C
1-8Alkyl, carboxyl, C
1-8Alkoxy carbonyl, phenyloxycarbonyl, hydroxyl or halogen atom, R
2Expression hydrogen atom, hydroxyl, amino, halogen atom or atoms metal.
3. as claim 1 or 2 described rust-preventive agent, it is characterized in that above-mentioned hydroxy-phenyl benzotriazole compound monomer (B) is the hydroxy-phenyl benzotriazole compound with general formula (2) expression,
In the formula, R
3, R
4And R
5Identical or different, expression contains group, hydrogen atom, the C of the two keys of polymerizability
1-8Alkyl, C
1-8Alkoxyl group, cyano group, hydroxyl, halogen atom, carboxyl or alkoxy carbonyl, wherein, R
3, R
4And R
5In at least one be the group that contains the two keys of polymerizability.
4. the rust-proofing method of a metal species is characterized in that, covers each described rust-preventive agent among the claim 1-3 on the surface of metal species.
5. the rust-proofing method of metal species as claimed in claim 4 is characterized in that, when covering among the claim 1-3 each described rust-preventive agent on the surface of metal species, uses each described rust-preventive agent among the claim 1-3 with the form of aqueous solution.
6. as claim 4 or 5 described rust-proofing methods, wherein above-mentioned metal species is copper or copper alloy.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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|---|---|
| JP (1) | JPWO2003093534A1 (en) |
| KR (1) | KR20050006218A (en) |
| CN (1) | CN1308487C (en) |
| AU (1) | AU2003234992A1 (en) |
| HK (1) | HK1076492A1 (en) |
| TW (1) | TWI228546B (en) |
| WO (1) | WO2003093534A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106146420A (en) * | 2016-08-11 | 2016-11-23 | 重庆大学 | The synthesis of the water miscible potassium salt derivant containing two or three BTA rings of one class and application |
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| JP2005240073A (en) * | 2004-02-24 | 2005-09-08 | Toshiba Corp | Plating film deposition method, electromagnetic wave shielding material and casing |
| WO2008062543A1 (en) * | 2006-11-20 | 2008-05-29 | Hitachi, Ltd. | Permanent magnet rotating electrical machine |
| JP4862049B2 (en) * | 2006-12-08 | 2012-01-25 | 日立オートモティブシステムズ株式会社 | Permanent magnet rotating electric machine |
| JPWO2014156361A1 (en) * | 2013-03-28 | 2017-02-16 | 古河電気工業株式会社 | Surface treatment electrolytic copper foil |
| WO2014156362A1 (en) * | 2013-03-28 | 2014-10-02 | 古河電気工業株式会社 | Surface-treated copper foil |
| EP3680296A4 (en) * | 2017-09-05 | 2021-04-07 | Nippon Shokubai Co., Ltd. | Binder composition, rigid body , and method for manufacturing rigid body |
| CN108251827A (en) * | 2018-01-25 | 2018-07-06 | 胡旭日 | A kind of anti-oxidation liquid of Chrome-free of lithium ion battery electrolytic copper foil and anti-oxidation technique |
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|---|---|---|---|---|
| JPS52154836A (en) * | 1976-06-18 | 1977-12-22 | Mitsubishi Heavy Ind Ltd | Water-soluble film-forming rustproof compositions |
| CN1107470A (en) * | 1994-08-19 | 1995-08-30 | 辽宁省化工研究院 | Method for preparing benzotriazole aliphatic amine derivative |
| CN1236778A (en) * | 1999-03-24 | 1999-12-01 | 徐道如 | Process for synthesizing methyl benzotriazazole |
| JP2000080821A (en) * | 1998-09-03 | 2000-03-21 | Harumatsu Oda | Tent or net having expanding function to be installed to match diameter of post by forming part of semicircular tent or net to be attached to post into cylindrical shape and passing cord therethrough |
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| JP3187388B2 (en) * | 1999-06-04 | 2001-07-11 | 株式会社日本触媒 | Composition for paint |
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2003
- 2003-04-25 JP JP2004501667A patent/JPWO2003093534A1/en active Pending
- 2003-04-25 AU AU2003234992A patent/AU2003234992A1/en not_active Abandoned
- 2003-04-25 KR KR10-2004-7017531A patent/KR20050006218A/en not_active Application Discontinuation
- 2003-04-25 WO PCT/JP2003/005329 patent/WO2003093534A1/en active Application Filing
- 2003-04-25 CN CNB038098202A patent/CN1308487C/en not_active Expired - Fee Related
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52154836A (en) * | 1976-06-18 | 1977-12-22 | Mitsubishi Heavy Ind Ltd | Water-soluble film-forming rustproof compositions |
| CN1107470A (en) * | 1994-08-19 | 1995-08-30 | 辽宁省化工研究院 | Method for preparing benzotriazole aliphatic amine derivative |
| JP2000080821A (en) * | 1998-09-03 | 2000-03-21 | Harumatsu Oda | Tent or net having expanding function to be installed to match diameter of post by forming part of semicircular tent or net to be attached to post into cylindrical shape and passing cord therethrough |
| CN1236778A (en) * | 1999-03-24 | 1999-12-01 | 徐道如 | Process for synthesizing methyl benzotriazazole |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146420A (en) * | 2016-08-11 | 2016-11-23 | 重庆大学 | The synthesis of the water miscible potassium salt derivant containing two or three BTA rings of one class and application |
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| CN1650049A (en) | 2005-08-03 |
| AU2003234992A1 (en) | 2003-11-17 |
| JPWO2003093534A1 (en) | 2005-09-08 |
| TW200307058A (en) | 2003-12-01 |
| KR20050006218A (en) | 2005-01-15 |
| TWI228546B (en) | 2005-03-01 |
| HK1076492A1 (en) | 2006-01-20 |
| WO2003093534A1 (en) | 2003-11-13 |
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