JPH10176123A - Corrosuion-preventing composition containing soluble conductive polymer and method for preventing corrosion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a corrosion-preventing composition which is soluble both in water and in an organic solvent, shows good applicability to and coverage of a metal and can exhibit sufficient corrosion-preventing performance even when it is in the form of a very thin film by using an acid-group-containing self-doping soluble conductive polymer as the principal component. SOLUTION: This composition mainly consists of an acid-group-containing self-doping soluble conductive polymer. It is desirable that the self-doping soluble conductive polymer is a soluble conductive polymer having sulfo groups and/or carboxyl groups. It is desirable that such a conductive polymer is a conductive aniline polymer represented by the formula: [wherein 0<=y<=1; R1 to R18 , which are independent of each other, are each H, SO3 <-> , SO3 H, COOH or the like; at least one of R1 to R16 is selected among SO3 <-> , COOH, etc.; and the rate of the rings containing the acid groups is 20-100%]. This composition may contain a crosslinking compound in addition to the conductive polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anticorrosion composition containing a soluble conductive polymer as a main component and a method for preventing the corrosion. Since the anticorrosion composition used in the present invention is soluble in a solvent, particularly water and a water-containing organic solvent, it can be applied to a metal surface, coated easily, and protected.

[0002]

2. Description of the Related Art As a method of preventing corrosion of a metal surface, a method of coating the surface is generally adopted. The method of applying a polymer compound has a disadvantage that corrosiveness proceeds from a defective portion of the coating film. In addition, the method of applying a chromic acid compound exhibits a very excellent anticorrosion effect, but an alternative method is required from both environmental and health aspects. A method of controlling the potential of a metal to a constant value also exhibits an excellent effect, but requires an external power supply and a device for controlling the potential, and its application is naturally limited technically and economically.

Therefore, a method has been proposed in which a conductive polymer is coated to control the potential to keep the potential constant, thereby preventing corrosion. For example,
A method of coating polyaniline as a conductive polymer on a metal surface by electrolytic polymerization [J. Electrochem. S
oc. , 132, 1022 (1988)],
It is difficult to apply to large area metal surfaces.

Further, a method of dispersing powdered polyaniline in a polymer compound and coating the same on a metal surface (Japanese Patent Laid-Open No.
No. 3-199884) has been proposed, but the anticorrosion effect is insufficient due to uneven dispersion.

A method has been proposed in which undoped polyaniline is dissolved in a polar organic solvent such as N-methylpyrrolidone (Japanese Patent Laid-Open No. 28228/1991), but a step of doping with a protonic acid after coating is required. Industrially unsuitable.

A method in which an amine such as ammonia is added to dissolve polyaniline in a doped state in a polar organic solvent (Japanese Patent Application Laid-Open No. 03-285983) has been proposed, but it is industrially used because ammonia evaporates during drying. Can not. A method in which soluble polyaniline and a dopant dissolved in an organic solvent are coated on a metal surface (Japanese Patent Laid-Open No.
-320958) has been proposed, but is industrially complicated since it is necessary to add a dopant,
In addition, there are problems such as insufficient solubility of polyaniline. Further, since it is insoluble in water, only an organic solvent must be used as a solvent, which is not preferable from the viewpoint of global environmental problems.

A method for solubilizing doped polyaniline (Japanese Patent Application Laid-Open No. 08-92479) has been proposed. However, there are problems in industrial application such as insufficient solubility and solution stability. is there.

[0008]

As described above, in the technical field of the art, in preventing corrosion of metals, it is soluble in both water and organic solvents, and can be easily applied and coated. However, development of anticorrosion compositions that can exhibit sufficient anticorrosion performance has become an important issue.

The present invention overcomes the above-mentioned drawbacks of the conventional anticorrosive agent, is soluble in both water and organic solvents, has good coatability and coatability for metals, and has a very thin film. An object of the present invention is to provide an anticorrosion composition capable of exhibiting sufficient anticorrosion performance and an anticorrosion method thereof.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to develop an anticorrosion composition having the above-mentioned preferable properties, and as a result, a composition containing a specific soluble conductive polymer as a main component has been developed. They found a match and led to the present invention.

That is, a first aspect of the present invention relates to an anticorrosion composition comprising a self-doping soluble conductive polymer (a) having an acidic group.

A second aspect of the present invention is that a self-doping soluble conductive polymer (a) containing an acidic group is further added to a heat-crosslinkable or ultraviolet- or electron-beam-crosslinkable compound (b) and the acid-soluble polymer (a). The present invention relates to an anticorrosion composition comprising at least one compound (c) having at least two functional groups capable of reacting with a group (hereinafter also referred to as a crosslinkable compound (c)).

[0013] A third aspect of the present invention relates to an anticorrosion film formed by applying the anticorrosion composition containing the soluble conductive polymer on at least one surface of a substrate on which anticorrosion is to be applied.

According to a fourth aspect of the present invention, an anticorrosion composition containing the soluble conductive polymer is applied on at least one surface of a substrate to be subjected to anticorrosion to form a film. About the method.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. It is important that the anticorrosion composition of the present invention contains a self-doping soluble conductive polymer (a) having an acidic group. The soluble conductive polymer (a) of the present invention is not particularly limited as long as it is a self-doping type soluble conductive polymer having an acidic group, and for example, JP-A-61-197633.
JP, JP-A-63-39916, JP-A-Heisei 1-3
01714, JP-A-5-504153, JP-A-5-503954, JP-A-4-32848, JP-A-4-328181, JP-A-6-14
5386, JP-A-6-56987, JP-A-5-226238, JP-A-5-178889, JP-A-6-293828, JP-A-7-118
524, JP-A-6-32845, JP-A-6-32845
-87949, JP-A-6-256516,
Soluble conductive polymers disclosed in JP-A-7-41756, JP-A-7-48436, JP-A-4-268331 and the like are preferably used.

Specifically, unsubstituted and substituted phenylene vinylene, vinylene, thienylene, pyrrolylene,
Phenylene, iminophenylene, isothianaphthene, furylene, on the skeleton of a π-conjugated polymer containing a carbazolylene as a repeating unit or on a nitrogen atom in the polymer,
A soluble conductive polymer having a sulfonic acid group and / or a carboxylic acid group, or an alkyl group substituted with a sulfonic acid group and / or a carboxylic acid group or an alkyl group containing an ether bond is included. Among these, a soluble conductive polymer having a skeleton such as thienylene, pyrrolylene, iminophenylene, and isothianaphthene is particularly preferably used.

Preferred soluble conductive polymers (a) are as follows: General formula (1)

Embedded image (Wherein R _1, R ₂ are each independently, H, -SO ₃ ^-, -SO
^{_{3 H, -R 20 SO 3 -}} , -R 20 SO 3 H, -OCH 3, -
_{CH 3, -C 2 H 5,} -F, -Cl, -Br, -I, -
_{N (R 19) 2, -NHCOR} 19, -OH, -O -, -S
_{R 19, -OR 19, -OCOR 19} , -NO 2, -COO
_{H, -R 20 COOH, -COOR 19} , -COR 19,
Selected from the group consisting of -CHO and -CN, wherein:
R ₁₉ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, R ₂₀ is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R ₁ and R ₂ is -SO ₃ ^- ,- SO ₃ H, -R ₂₀ SO _{3
^{-, -R 20 SO 3 H,}} -COOH and -R ₂₀ CO
It is a group selected from the group consisting of OH. The ratio of the ring containing an acidic group is 20 to 100%. )

General formula (2)

Embedded image (Wherein R _3, R ₄ are each independently, H, -SO ₃ ^-, -SO
^{_{3 H, -R 20 SO 3 -}} , -R 20 SO 3 H, -OCH 3, -
_{CH 3, -C 2 H 5,} -F, -Cl, -Br, -I, -
_{N (R 19) 2, -NHCOR} 19, -OH, -O -, -S
_{R 19, -OR 19, -OCOR 19} , -NO 2, -COO
_{H, -R 20 COOH, -COOR 19} , -COR 19,
Selected from the group consisting of -CHO and -CN, wherein:
R ₁₉ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, R ₂₀ is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R ₃ and R ₄ is -SO ₃ ^- ,- SO ₃ H, -R ₂₀ SO _{3
^{-, -R 20 SO 3 H,}} -COOH and -R ₂₀ COOH
A group selected from the group consisting of The ratio of the ring containing an acidic group is 20 to 100%. )

General formula (3)

Embedded image (Each independently wherein R ₅ to R ₈ is, H, -SO ₃ ^-, -SO
^{_{3 H, -R 20 SO 3 -}} , -R 20 SO 3 H, -OCH 3, -
_{CH 3, -C 2 H 5,} -F, -Cl, -Br, -I, -
_{N (R 19) 2, -NHCOR} 19, -OH, -O -, -S
_{R 19, -OR 19, -OCOR 19} , -NO 2, -COO
_{H, -R 20 COOH, -COOR 19} , -COR 19,
Selected from the group consisting of -CHO and -CN, wherein:
R ₁₉ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, R ₂₀ is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R _{5 to} R ₈ is -SO ₃ ^- ,- SO ₃ H, —R ₂₀ SO ₃ ⁻ ,
-R is a ₂₀ SO ₃ H, a group selected from the group consisting of -COOH and -R ₂₀ COOH. The ratio of the ring containing an acidic group is 20 to 100%. )

General formula (4)

Embedded image (Each independently wherein _{R 9 ~R 13, H, -SO} 3 -, -SO
^{_{3 H, -R 20 SO 3 -}} , -R 20 SO 3 H, -OCH 3, -
_{CH 3, -C 2 H 5,} -F, -Cl, -Br, -I, -
_{N (R 19) 2, -NHCOR} 19, -OH, -O -, -S
_{R 19, -OR 19, -OCOR 19} , -NO 2, -COO
_{H, -R 20 COOH, -COOR 19} , -COR 19,
Selected from the group consisting of -CHO and -CN, wherein:
R ₁₉ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, R ₂₀ is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and at least one of R _{9 to} R ₁₃ is -SO ₃ ^- ,- SO ₃ H, —R ₂₀ SO ₃ ⁻ ,
-R is a ₂₀ SO ₃ H, a group selected from the group consisting of -COOH and -R ₂₀ COOH. The ratio of the ring containing an acidic group is 20 to 100%. )

And the general formula (5)

Embedded image (Wherein R ₁₄ represents —SO ₃ ⁻ , —SO ₃ H, —R ₂₀ SO ₃ ⁻ ,
-R ₂₀ SO ₃ H, selected from the group consisting of -COOH and -R ₂₀ COOH, wherein, R ₂₀ is alkylene, arylene or aralkylene group having 1 to 24 carbon atoms. A) a water-soluble conductive polymer containing at least one repeating unit selected from the group consisting of and having a molecular weight of 1000 or more, preferably 2000 or more.

In the crosslinking of these conductive polymers,
When sulfonic acid groups and carboxylic acid groups involved in doping are used for crosslinking, there is a disadvantage that if the number of crosslinking points is increased more than necessary, the anticorrosion property is significantly reduced. Therefore, it is preferable that the addition amount of the cross-linking agent is minimized. Specifically, based on the sulfonic acid group and / or carboxylic acid group of the soluble conductive polymer, 50 mol% or less,
Preferably 25 mol% or less, more preferably 10 mol%
Hereinafter, it is more preferable to use the compound (c) having a functional group in an amount equivalent to 5 mol% or less, since the decrease in corrosion resistance is small and the water resistance and the solvent resistance are practical.

On the other hand, when a conductive polymer having a sulfonic acid group or a carboxylic acid group which is not involved in doping is used, even if these sulfonic acid groups and carboxylic acid groups are used for crosslinking, there is no decrease in conductivity and corrosion resistance. It is convenient. For example, for doping of an aniline-based conductive polymer, it is theoretically sufficient that one sulfonic acid group or one carboxylic acid group exists for every two aromatic rings. Therefore, an acidic group such as a sulfonic acid group or a carboxylic acid group is added to the aromatic ring by 5
1% or more, preferably 60% or more, more preferably 70%
%, Particularly preferably 80% or more, the use of a soluble aniline-based conductive polymer enables theoretical crosslinking without lowering the conductivity and the anticorrosion property, and the compound (c) can be sufficiently added. The same can be achieved by using another conductive polymer having two or more sulfonic acid groups on the aromatic ring.

Among the above conductive polymers, the aniline conductive polymer (6) represented by the following general formula and having a sulfonic acid group and / or carboxylic acid group content of 20% or more with respect to the aromatic ring is most preferably used. .

Embedded image (Where 0 ≦ y ≦ 1 and R _{1 to} R ₁₈ are each independently
^{_{H, -SO 3 -, -SO 3}} H, -R 20 SO 3 -, -R 20 SO
_{3 H, -OCH 3, -CH 3} , -C 2 H 5, -F, -C
l, -Br, -I, -N ( R 19) 2, -NHCOR 19,
_{^{-OH, -O -, -SR 19,}} -OR 19, -OCO
R ₁₉ , -NO ₂ , -COOH, -R ₂₀ COOH, -CO
OR ₁₉ , —COR ₁₉ , —CHO and —CN, wherein R ₁₉ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, and R ₂₀ is a group having 1 to 2 carbon atoms.
4 is an alkylene, arylene or aralkylene group, wherein at least one of R _{1 to} R ₁₆ is —SO ₃ ⁻ , —S
_{O 3 H, -R 20 SO 3} -, a -R ₂₀ SO ₃ H, a group selected from the group consisting of -COOH and -R ₂₀ COOH. The ratio of the ring containing an acidic group is 20 to 100%. )

Here, an aniline-based conductive polymer having a sulfonic acid group and a carboxylic acid group content of at least 50% with respect to the aromatic ring is preferably used because of its very good solubility, more preferably at least 70%, more preferably at least 70%. Preferably 90%
As mentioned above, 100% of the polymer is particularly preferably used.

The substituent added to the aromatic ring preferably has an electron donating property in terms of anticorrosion and solubility, and specifically, is preferably an alkyl group, an alkoxy group, a halogen group, etc., and particularly preferably an aniline having an alkoxy group. Based conductive polymers are most preferred.

Among these combinations, the most preferred aniline-based conductive polymer is represented by the following general formula (7).

Embedded image Wherein A is one group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, an alkali metal salt thereof, an ammonium salt and a substituted ammonium salt, and B is a methyl group, an ethyl group, an n- Propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, dodecyl group, alkyl group such as tetracosyl group, methoxy group, ethoxy group, n-propoxy group, iso -Propoxy group, n-butoxy group, is
o-Butoxy group, sec-butoxy group, tert-butoxy group, heptoxy group, hexoxy group, octoxy group, dodecoxy group, alkoxy group such as tetracosoxy group, fluoro group, chloro group, halogen group such as bromo group Shows one selected group. x represents an arbitrary number of 0 to 1, n represents a degree of polymerization, and is preferably 3 or more. )

As the weight average molecular weight, those having a weight average molecular weight of 2,000 or more in terms of polyethylene glycol of GPC are preferably used because of their excellent anticorrosion properties, film formability and film strength, and those having a weight average molecular weight of 3,000 to 1,000,000 are more preferable. Those having a molecular weight of 5,000 to 500,000 are more preferable. Here, a polymer having a weight average molecular weight of 2000 or less has excellent solubility, but may have insufficient film-forming properties and anticorrosion properties, and a polymer having a weight average molecular weight of 1,000,000 or more has excellent corrosion protection properties. However, the solubility may be insufficient.

The thermally crosslinkable or ultraviolet (UV) or electron beam (EB) crosslinkable compound (b) is not particularly limited, but the following compounds are preferred.

As the thermally crosslinkable compound, epoxy resin,
Oligoester acrylate, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, phenol resin, unsaturated polyester resin, furan resin, polyimide, poly (p-hydroxybenzoic acid),
Polyurethane, maleic resin, melamine resin, urea resin and the like are preferably used.

As the UV or EB crosslinkable compound,
Liquid polybutadiene compound, unsaturated polyester compound, polyene-polythiol compound, cationic polymerizable compound, aminoalkite resin, urethane acrylate,
Acrylic base resins such as epoxy acrylate, polyester acrylate, polyether acrylate, acrylate monomer, acrylic oligomer and aqueous acrylate are preferably used.

As the polymerization initiator of the UV or EB crosslinkable compound, a radical polymerization initiator, a cationic polymerization initiator and the like are used. Examples of radical polymerization initiators include benzophenone, acetophenone, acenaphthenequinone and benzophenone derivatives, thioxanthone,
Benzoin ether, benzyl methyl ketal, α-hydroxyalkylphenone, α-aminoalkylphenone, acylphosphine oxide, and the like. Examples of the water-soluble radical polymerization initiator include 4- (2-hydroxyethoxy) phenyl ( 2-hydroxy-2-propyl) ketone, thioxanthone ammonium salt, benzophenone ammonium salt and the like. Examples of the cationic polymerization initiator include a Bronsted acid generating type such as a diaryliodonium salt and a triarylsulfonium salt, and a Lewis acid type such as an aryldiazonium salt and an iron arene complex. In addition, a cation and anion hybrid type is exemplified.

The crosslinkable compound (c) is not particularly limited as long as it has at least two functional groups in the molecule capable of reacting with a sulfonic acid group and / or a carboxylic acid group. A low molecular weight compound having at least two functional groups selected from the group consisting of a thiol group, an amino group, an epoxy group, and a functional group in which these functional groups are protected by a protecting group; A polymer compound having a repeating unit is preferably used.

In order to obtain a practically sufficient crosslink,
Since it is preferable that the crosslinkable compound (c) does not vaporize in a drying step after film formation, the crosslinkable compound (c) is not less than 30 ° C.
It preferably has a boiling point of 50 ° C or higher, more preferably 80 ° C or higher, particularly preferably 100 ° C or higher.

Examples of the crosslinkable compound (c) include low molecular weight compounds such as diols and polyols, disilanols and polysilanols, dithiols and polythiols, diamines and polyamines, epoxies, melamines and ureas, and sugars; Hydroxyl group, thiol group, silanol group, vinyl group having amino group or epoxy group, acrylic ester type, methacrylic ester type,
A polymer compound having at least one of acrylamide-based and methacrylamide-based monomers as a repeating unit may be used.

Specific examples of diols and polyols are listed on Jan. 30, 1986, published by Baifukan Co., Ltd., edited by The Society of Polymer Science, Polymer Data Handbook, Basic Edition, pp. 283-322, Table 23.1. The indicated compounds are used. Preferably, chain or cyclic aliphatic diols and polyols having a relatively low crosslinking temperature are used. As specific examples, ethylene glycol, propylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2 -Pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-
Hexanediol, 1,3-hexanediol, 1,4
-Hexanediol, 1,5-hexanediol, 1,
6-hexanediol, 2,3-hexanediol,
2,4-hexanediol, 2,5-hexanediol, diethylene glycol, triethylene glycol,
Tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, dipropylene glycol, tripropylene glycol, thiodiethanol,
3,6-dithio-1,8-octanediol, 3,6
9-trithio-1,11-dodecanediol, 1,2-
Cyclopentanediol, 1,3-cyclopentanediol, 1,4-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,5-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,5-cyclohexanedimethanol, o-methylolcyclohexanol, m-
Methylol cyclohexanol, p-methylol cyclohexanol, o-xylylene glycol, m-xylylene glycol, p-xylylene glycol, hydroquinone, bisphenol A, glycerin, trimethylolpropane, 1,2,3-butanetriol, 1, 2,4
-Butanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,2,5-pentanetriol, 2,3,4-pentanetriol,
Trimethylolethane, tetramethylolmethane, 1,
2,3-cyclohexanetriol, 1,2,4-cyclohexanetriol, 1,2,5-cyclohexanetriol, 1,3,5-cyclohexanetriol,
1,2,3-cyclohexanetrimethanol, 1,2,2
4-cyclohexanetrimethanol, 1,2,5-cyclohexanetrimethanol, 1,3,5-cyclohexanetrimethanol and the like can be mentioned.

Specific examples of dithiols and polythiols are described in the aforementioned Polymer Data Handbook, Basic Edition, p.
347-349. The compounds shown in Table 25.2 are used. As a specific example, 4-ethylbenzene-1,3-
Dithiol, 1,2-ethanedithiol, 1,8-octanedithiol, 1,1-cyclohexanedithiol,
1,2-cyclohexanedithiol, 1,1-cycloheptanedithiol, 1,1-cyclopentanedithiol, 1,3-diphenylpropane-2,2-dithiol, 2,6-dimethyloctane-2,6-dithiol,
2,6-dimethyloctane-3,7-dithiol, 2,
4-dimethylbenzene-1,3-dithiol, 4,5-
Dimethylbenzene-1,3-dithiol, 3,3-dimethylbutane-2,2-dithiol, 2,2-dimethylpropane-1,3-dithiol, 1,3-di (p-methoxyphenyl) propane-2,2- Dithiol, 3,4-
And dimethoxybutane-1,2-dithiol.

Specific examples of diamines and polyamines are described in the aforementioned Polymer Data Handbook, Basic Edition, p.
1-255. The compounds shown in Table 21.1 are used. As specific examples, ethylenediamine, N-methylethylenediamine, N, N'-dimethylethylenediamine, N-ethylethylenediamine, N-methyl-N'-
Ethyl ethylene diamine, N, N′-diethyl ethylene diamine, N-propyl ethylene diamine, N-isopropyl ethylene diamine, N-butyl ethylene diamine, N, N′-dibutyl ethylene diamine, N-pentyl ethylene diamine, N-heptyl ethylene diamine,
N-octylethylenediamine, 1,2-diaminopropane, N, N′-dimethyl-1,2-diaminopropane, 2,3-diaminobutane, 1,3-diamino-2-
Methylpropane, pentamethylenediamine, 2,3-diaminopentane, 2,4-diaminopentane, 1,3-
Diamino-2-methylbutane, 1,4-diamino-2-
Methylbutane, hexamethylenediamine, 1,4-diaminoheptane, heptamethylenediamine, 2,3-diaminoheptane, 1,6-diaminooctane, octamethylenediamine, 2,3-diaminooctane, nonamethylenediamine, decamethylenediamine, Undecamethylenediamine, dodecamethylenediamine, 1,12-diaminooctadecane, 1,2-diaminocyclohexane,
1,3-diaminocyclohexane, 1,4-diaminocyclohexane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4-amino-2
-Methylaminotoluene, 4-amino-2-ethylaminotoluene, 3-amino-4-methylbenzylamine,
Naphthylenediamine- (1,2), naphthylenediamine- (1,3), naphthylenediamine- (1,4), naphthylenediamine- (1,5), naphthylenediamine-
(1,6), naphthylenediamine- (1,7), naphthylenediamine- (1,8), naphthylenediamine-
(2,3), naphthylenediamine- (2,6), naphthylenediamine- (2,7), 4,4′-diaminostilbene, bis- (4-aminophenyl) acetylene, ethylene glycol-bis (2 -Aminophenyl ether), 2,2′-diaminodiphenyl ether, 2,
2'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl disulfide, hydroquinone-bis (4-aminophenyl ether), 4,4'-diaminodibenzyl sulfide, 2,4- Diaminonaphthol- (1), 2-oxybenzidine, 4,4'-diaminodiphenylcarbinol, 4,4'-diamino-3'-oxy-3-methyldiphenyl, 4,4'-diamino-2-oxytrioxy Phenylmethane, 4,4'-diaminotriphenylcarbinol, 3,5-diaminocatechol, 2,5-diamino-9,10-dioxyphenanthrene, 4,6-diaminopyrogallol, 4,6-diamino-2- Methylfluoroglucin and the like.

Specific examples of epoxies are described in the Polymer Data Handbook, Basic Edition, pp. 194-195, Table 1.
The compounds shown in 8.1 and 2 are used. As specific examples, 1,3-diglycidyl-5,5-dimethylhydantoin, 1,3-diglycidyl-5-methyl-5
-Ethylhydantoin, glycerol diglycidyl ether, N, N'-diglycidyl-5,5-dimethylhydantoin, polypropylene glycol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and the like.

Specific examples of melamine and ureas include:
The Polymer Data Handbook, Basic Edition, p237-2
38 The compounds shown in Tables 20.1 and 2 are used. As specific examples, melamine, N ² , N ⁴ , N ⁶ −
Trimethyl melamine, N ⁴ - methyl -N ² - ethyl melamine, benzoguanamine, N ² - phenyl melamine, N
^2, N ^4, N ⁶ - triethyl melamine, N ^2, N ⁴ - diphenyl ^{melamine, N 2, N 4, N} 6 - tri - (2-chlorophenyl) ^{melamine, N 2, N 4, N} 6 - triphenyl melamine ^{, N 2, N 4, N} 6 - tri -p- tolyl ^{melamine, N 2, N 4, N} 6 - tri -α- naphthyl ^{melamine, N 2, N 4, N} 6 - tri -β- naphthyl melamine, hexa Methoxymethylolmelamine, urea, thiourea, guanidine, semicarbazide, monoformylurea,
Biuret, guanyl urea, monomethylol urea, oxalyl urea, ethylene urea, ethylene thiourea, monoacetyl urea, carbonyl diurea, dienantilidene triurea and the like.

As a specific example of the saccharide, September 30, 1993
Published by Nihon Maruzen Co., Ltd., edited by The Chemical Society of Japan, revised 4th edition Chemical Handbook, Basic Edition, pI-519-523, structural formula 18.1-
The compounds shown in 18.105 are used. As specific examples, erythritol, D-erythrulose, D-
Erythrose, D-threose, D-arabinose, β
-D-arabinose, β-L-arabinose, D-xylulose, L-xylulose, D-xylose, α-D
-Xylose, 2-deoxy-D-ribose, 2-deoxy-β-D-ribose, D-lyxose, α-D-lyxose, α-L-lyxose, D-ribulose, D-
Ribose, D-arabitol, ribitol, D-altrose, β-D-altrose, D-allose, β-D
-Allose, D-idose, D-galactose, α-D
-Galactose, β-D-galactose, α-L-galactose, D-quinobose, α-D-quinobose, D-
Glucose, α-D-glucose, β-D-glucose, D-growth, L-sorbose, D-tagatose,
D-talose, α-D-talose, 2-deoxy-D-
Examples include glucose, D-fucose, D-psicose, D-fructose, galactitol, D-glucitol, D-mannitol and the like.

Compounds in which the functional groups of these compounds are protected by protective groups such as ether, ester, acetal, and hemiacetal, and the aforementioned Polymer Data Handbook, Basic Edition, p194-207, Table 18.1-1
The compound represented by 8.13, in which a hydroxyl group or the like is generated by ring opening, can also be used as the crosslinkable compound (c). The transfer of all of the crosslinkable compounds described in the above publications is omitted here, but the contents of the above publications are incorporated herein by reference.

The monomer (A) constituting the polymer compound as the crosslinkable compound (c) includes vinyl monomers, acrylic monomers, methacrylic monomers, acrylamide and methacrylamide monomers, vinylamine monomers, and silanol group-containing monomers. And a monomer (A) such as a monomer. As vinyl monomers,
Vinyl alcohol, allyl alcohol, vinylamine,
Allylamine and the like can be mentioned.

As acrylic monomers, 2-hydroxyethyl acrylate, 2- (2-hydroxyethoxy) ethyl acrylate, 2-hydroxycyclohexyl acrylate, (1-hydroxycyclohexyl) methyl acrylate, 2- (2-hydroxy-1, 1-dimethylethoxy) -1,1-dimethylethyl acrylate, 2-hydroxy-3-sulfopropyl acrylate, 2-hydroxy-3-piperidinopropyl acrylate, 2-hydroxy-3-phenylethyl acrylate, 2-hydroxy- 3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-
Hydroxy-3- (propenyloxy) propyl acrylate, 2-hydroxy-3-propoxypropyl acrylate, 2-hydroxy-2-methylpropyl acrylate, 2-hydroxy-2-methoxypropyl acrylate, 3-hydroxy-2- (methoxymethyl ) -4
-Pentenyl acrylate, glycidyl acrylate,
Examples thereof include 12-hydroxydodecyl acrylate, 13-hydroxytridecyl acrylate, 18-hydroxyoctadecyl acrylate, and 24-hydroxytetracosyl acrylate.

Examples of the methacrylic monomer include 2-hydroxyethyl methacrylate, 3-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, 12-hydroxydodecyl methacrylate, 13-hydroxytridecyl methacrylate, 18-hydroxyoctadecyl methacrylate, 24 -Hydroxytetracosyl methacrylate and the like.

The acrylamide and methacrylamide monomers include N- (2-hydroxyphenyl) methacrylamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxypropyl) acrylamide, N- (1,1- Dimethyl-2-hydroxyethyl) acrylamide, N- (1-ethyl-2-hydroxyethyl) acrylamide, N- (1,1-dimethyl-
3-hydroxybutyl) acrylamide, N- [1,1
-Bis (hydroxymethyl) ethyl] acrylamide,
N, N-bis (2-hydroxyethyl) acrylamide, 1-acrylamide-1-deoxy-D-glucitol, N- (2-hydroxyethyl) methacrylamide, N- (2-hydroxypropyl) methacrylamide, N- ( 1,1-dimethyl-2-hydroxyethyl)
Methacrylamide, N- (2,2-dimethyl-2-hydroxyethyl) methacrylamide, N- (1-ethyl-
2-hydroxyethyl) methacrylamide, N- (1,
1-dimethyl-3-hydroxypropyl) methacrylamide, N- [1,1-bis (hydroxymethyl) ethyl] methacrylamide, N- [2-hydroxy-1,1
-Bis (hydroxymethyl) ethyl] methacrylamide, N- (1,1-dimethyl-3-hydroxybutyl)
Methacrylamide, N- (2-hydroxyethyl) -N
-Methyl methacrylamide, 1-methacrylamide-1
-Deoxyglucitol methacrylamide, N- (hydroxymethyl) acrylamide, N- (hydroxymethyl) methacrylamide, 12-hydroxydodecylmethacrylamide, 13-hydroxytridecylmethacrylamide, 18-hydroxyoctadecylmethacrylamide, 24-hydroxy Tetracosyl methacrylamide,
N, N-dimethylhydroxypropylamine-N-acryloylimide and the like.

Examples of the vinylamine-based monomer include the aforementioned Polymer Data Handbook, Basic Edition, p.
Examples include the monomers shown in Table 15.1, and specific examples include vinylethylamine, vinylbutylamine, vinyldodecylamine, vinylbenzylamine, and vinylcyclohexylamine.

Specific examples of the silanol group-containing monomer include those obtained by hydrolyzing a silyl group-containing monomer such as an ethylenically unsaturated alkoxysilane and an ethylenically unsaturated acyloxysilane to obtain a silanol group-containing monomer. Specific examples of ethylenically unsaturated alkoxysilanes include acrylate alkoxysilanes (for example,
γ-acryloxypropyltrimethoxysilane, γ-
Acryloxypropyltriethoxysilane) and methacrylatealkoxysilane (for example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltris (2-methoxyethoxy) silane). . Specific examples of the ethylenically unsaturated acyloxirane include acrylatoacetoxysilane, methacrylate acetoxysilane, ethylenically unsaturated acetoxysilane (for example, acrylatopropyltriacetoxysilane, methacrylatepropyltriacetoxysilane) and the like. Can be

In addition to the above monomers, other monomers (B) copolymerizable with the above monomers can also be used. The other copolymerizable monomer (B) is not particularly limited, but is preferably a vinyl monomer, a vinyl ether monomer, an acrylic monomer, a methacrylic monomer,
Acrylamide and methacrylamide monomers are exemplified. As the vinyl monomer, the monomers shown in the aforementioned Polymer Data Handbook, Basic Edition, pp. 79-81, Table 6.1 are preferably used. Specific examples include vinyl acetoacetate, allyl acetoacetate, vinyl acetate,
(2-ethoxyethoxy) vinyl acetate, vinyl isobutyrate, vinyl butyrate and the like.

As the vinyl ether-based monomer, the monomers shown in the aforementioned Polymer Data Handbook, Basic Edition, pp. 85-89, Table 7.1 are preferably used. As a specific example, alkyl vinyl ether (as an alkyl group, Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t
tert-butyl, dodecyl, tridecyl, octadecyl, tetracosyl and the like. ) Alkenyl vinyl ether (as alkenyl group, vinyl, allyl, 1-
Methyl allyl, 2-methyl allyl (methallyl), 3-methyl allyl and the like are mentioned. ), Alkynyl vinyl ether (as alkynyl group, ethynyl (acetylenyl), prop-1-ynyl, prop-2-ynyl, but-2-yl)
-Nil, but-2-ynyl, but-3-ynyl and the like. ), Aralkyl vinyl ethers (aralkyl groups include benzyl, p-methylbenzyl, etc.), phenyl vinyl ethers, oxyalkyl vinyl ethers (oxyalkyl groups as 2-hydroxyethyl, 3-hydroxypropyl, 3-hydroxybutyl, -Hydroxybutyl, 5-hydroxypentyl,
12-hydroxydodecyl, 24-hydroxytetracosyl, diethylene glycol mono, triethylene glycol mono, 2-methoxyethyl, 2-ethoxyethyl,
Acetoxymethyl, 2-acetoxyethyl and the like can be mentioned. ), Meso-1,2-diphenylethylene glycol methyl vinyl ether, m-phenylene bis (ethylene glycol) divinyl ether, aminoalkyl vinyl ether (as an aminoalkyl group, 2-aminoethyl, 2-dimethylaminoethyl, 2-diethylaminoethyl, 2-n-butylaminoethyl, 5-diethylaminopentyl, 12-diethylaminododecyl, 24-
Examples include diethylaminotetracosyl and diethanolamine mono. ), Thioalkyl vinyl ether (as thioalkyl group, 2-methylthioethyl, 2-ethylthioethyl, 2-n-propylthioethyl, 2-n-
Butylthioethyl, 2-n-dodecylthioethyl, 2-
n-tetracosylthioethyl and the like. ), 2-
And cyanoethyl vinyl monomers.

Examples of the acrylic monomer include the aforementioned Polymer Data Handbook, Basic Edition, pp. 106-113, Table 1.
The monomers shown in 0.1 are preferably used. Specific examples include 2-acetoacetoxypropyl acrylate, ethyl acrylate, 1-ethylpropyl acrylate, 2-ethylhexyl acrylate, oxiranylmethyl acrylate, and cyanomethyl acrylate. ,
1,1-dimethylethyl acrylate, trimethylsilyl acrylate, nonyl acrylate, phenyl acrylate, hexyl acrylate, methyl acrylate,
Examples thereof include 1-methylethyl acrylate, 1-methoxyethyl acrylate, and 2-methoxyethyl acrylate.

As the methacrylic monomers, the monomers shown in the aforementioned Polymer Data Handbook, Basic Edition, pp. 122-125, Table 11.1, are preferably used. Specific examples thereof include 1-acetylethyl methacrylate,
Acetylmethyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoxypropyl methacrylate, n-amyl methacrylate, iso-amyl methacrylate, tert-amyl methacrylate, allyl methacrylate, allyloxymethyl methacrylate, i
so-butyl methacrylate, ethyl methacrylate,
Examples thereof include dimethylaminoethyl methacrylate, stearyl methacrylate, nonyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxybutyl methacrylate, vinyl methacrylate, n-butyl methacrylate, methyl methacrylate, and 1-methyl amyl methacrylate.

As the acrylamide and methacrylamide monomers, the monomers shown in the aforementioned Polymer Data Handbook, Basic Edition, pp. 128-137, Table 12.1, are preferably used. Specific examples thereof include acrylamide, methacrylamide , N-methylacrylamide, N-ethylacrylamide, N-iso-propylacrylamide, Nn-butylacrylamide, N-
sec-butylacrylamide, N-iso-butylacrylamide, N-tert-butylacrylamide,
N- (1,1-dimethylbutyl) acrylamide, N-
n-octylacrylamide, N-dodecylacrylamide, N, N-dimethylhydroxypropylamine-N
-Methacryloylimide, N-methylmethacrylamide, N-ethylmethacrylamide, Nn-butylmethacrylamide, N-tert-butylmethacrylamide, N-allylmethacrylamide, N, N-dimethylacrylamide, N, N-diethyl Acrylamide, N,
N-dibutylacrylamide, N, N-diisobutylacrylamide, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (n
-Propoxymethyl) acrylamide, N- (iso-
Propoxymethyl) acrylamide, N- (n-butoxymethyl) acrylamide, N- (iso-butoxymethyl) acrylamide, N- (allyloxymethyl) acrylamide, N-[(2-cyanoethyl) oxymethyl] acrylamide, N, N '-Methylenebismethacrylamide, N- (2-dimethylaminoethyl) acrylamide, N- (2-diethylaminoethyl) acrylamide, N- (4-dimethylaminobutyl) acrylamide, N- (3-dimethylaminopropyl) methacrylamide , N- (2,2-dimethyl-3-dimethylaminopropyl) methacrylamide, N- (3-methylaminopropyl) methacrylamide, 2-acrylamidopropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2- acrylic Amide-n-hexanesulfonic acid,
N-formylacrylamide, N-acetylacrylamide, N- (2-oxopropyl) acrylamide, N
-(1-methyl-2-oxopropyl) acrylamide, N- (1-iso-butyl-2-oxopropyl)
Acrylamide, ethyl-2-acrylamide acetate, diethyl-N-acryloylimino bis acetate, acryloyl dicyandiamide, methacryloyl dicyandiamide and the like can be mentioned.

Among the other copolymerizable monomers (B), preferred are methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate and tetracosyl methacrylate, methyl acrylate and ethyl acrylate. And acrylates such as butyl acrylate, dodecyl acrylate and tetracosyl acrylate. Further, a monomer having an anionic group may be used in order to improve the adhesiveness to the base material and the like. It is omitted that all of the compounds described in the above publications are transcribed here, but the contents of the publications are incorporated herein by reference.

The copolymerization ratio of the monomer (A) in the copolymer is not particularly limited, but is preferably at least 0.01 mol%, more preferably at least 0.1 mol%, further preferably at least 1 mol%, particularly preferably. Is at least 5 mol%.

The polymer compound as the crosslinkable compound (c) is used in the form of a solution by dissolving it in a solvent or in the form of an emulsion by dispersing it in a suitable solvent. A general resin commonly used for such a dispersion may be added to the emulsion. Various binders may be mixed and used as needed. Examples of the binder used include resins such as acrylic resins, methacrylic resins, polyester resins, vinyl chloride resins, vinyl acetate resins, and ethylene resins.

The anticorrosion composition containing the soluble conductive polymer of the present invention comprises a soluble conductive polymer (a) or, in addition to the soluble conductive polymer (a), a thermally crosslinkable or ultraviolet or electron beam crosslinkable compound (b) and a crosslinkable compound. As a main component, at least one or more selected from the acidic compounds (c);
The composition is dissolved in the solvent (d) as required.

Specifically, the soluble conductive polymer (a) is dissolved in a solution of the thermally crosslinkable or ultraviolet or electron beam crosslinkable compound (b) or a solution obtained by dissolving it in a suitable solvent (d). Or a composition obtained by dispersing; a solution obtained by dissolving the crosslinkable compound (c) in an appropriate solvent (d) or an emulsion obtained by dispersing the soluble conductive polymer (a). Dissolving or dispersing a soluble conductive polymer (a) in a solution obtained by dissolving a thermally crosslinkable or ultraviolet or electron beam crosslinkable compound (b) and a crosslinkable compound (c) in a suitable solvent (d); It is a composition obtained by the above.

The solvent (d) is a soluble conductive polymer (a)
It is preferable to use different ones for dissolving in a solvent and for dispersing in a solvent.

When dissolving the soluble conductive polymer (a), the solvent (d) may be a soluble conductive polymer (a), a heat-crosslinkable or ultraviolet or electron beam crosslinkable compound (b) and / or a crosslinkable compound (c). Is not particularly limited as long as it is a solvent that dissolves, water, methanol, ethanol, propanol, iso-propanol, alcohols such as butanol, ethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether,
Ethylene glycols such as diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether and the like Propylene glycols, ethyl lactate, dimethylformamide, dimethylacetamide, N
-Methylpyrrolidone and the like are preferably used, and a mixed solvent thereof may be used.

The solvent (d) used for dispersing the soluble conductive polymer (a) is a solvent capable of dissolving the heat-crosslinkable or ultraviolet- or electron-beam crosslinkable compound (b) and / or the crosslinkable compound (c). If it is not particularly limited, benzene, toluene, ethylbenzene, propylbenzene, tert-butylbenzene, o-xylene,
aromatic hydrocarbon solvents such as m-xylene, p-xylene, tetralin, decalin, methanol, ethanol, n-
Propanol, iso-propanol, n-butanol, iso-butanol, n-hexanol, n-octanol, iso-octanol, alcohol solvents such as 2-ethylhexanol, propylene glycol methyl ether, propylene glycol dimethyl ether,
Propylene glycol ethyl ether, propylene glycol diethyl ether, propylene glycol-n-
Propyl ether, propylene glycol-iso-propyl ether, propylene glycol di-n-propyl ether, propylene glycol di-iso-propyl ether, propylene glycol-n-butyl ether, propylene glycol-iso-butyl ether,
Propylene glycol alkyl ether solvents such as propylene glycol di-n-butyl ether and propylene glycol di-iso-butyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and cyclohexanone; methyl acetate, ethyl acetate, and acetic acid Ester solvents such as butyl and amyl acetate, methyl cellosolve, ethyl cellosolve, i
cellosolve solvents such as so-propyl cellosolve, n-butyl cellosolve, phenyl cellosolve, benzyl cellosolve, methyl carbitol, ethyl carbitol, n
Carbitol solvents such as -propyl carbitol, iso-propyl carbitol, n-butyl carbitol, iso-butyl carbitol, iso-amyl carbitol, phenyl carbitol, benzyl carbitol,
Hydroxyester solvents such as ethyl lactate and methyl lactate are preferably used.

The composition ratio of components (a), (b), (c) and (d) of the anticorrosion composition containing solvent (d) is such that (a) + (B),
(A) + (c) or (a) + (b) + (c) is preferably 0.01 to 500 parts by weight, more preferably 0.1 to 500 parts by weight.
It is 200 parts by weight, more preferably 0.5 to 100 parts by weight.

Various additives can be further added to the anticorrosion composition of the present invention to reduce the dispersibility and surface tension of the composition. As additives, surfactants,
And a blocking agent.

The surfactant is not particularly limited as long as it does not hinder the dissolution or dispersion of the anticorrosion composition of the present invention, and anionic, cationic and nonionic surfactants are used. , Anionic and nonionic are used.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; and polyoxyalkylenes such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Alkyl phenyl ethers;
Sorbitan aliphatic esters such as sorbitan monolaurate, sorbitan monostearate and sorbitan trioleate; polyoxyalkylene sorbitan aliphatic esters such as polyoxyethylene sorbitan monolaurate; polyoxyethylene monolaurate and polyoxyethylene mono Polyoxyalkylene fatty acid esters such as stearate; glycerin fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride; polyoxyethylene / polyoxypropylene / block copolymer; and the like.

Examples of the anionic surfactant include fatty acid salts such as sodium stearate, sodium oleate and sodium laurate; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate; alkyl sulfate salts such as sodium lauryl sulfate. Alkyl sulfosuccinates such as sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof; polyoxyalkylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate; poly Polyoxyalkylene alkylaryl ether sulfates such as sodium oxyethylene nonylphenyl ether sulfate; and the like. It is possible.

Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate; quaternary ammonium salts such as lauryltrimethylammonium chloride and alkylbenzyldimethylammonium chloride; and polyoxyethylalkylamine. .

When a surfactant is used, its preferred amount is from 0 to 5 based on the whole anticorrosive composition of the present invention.
% By weight, preferably 0 to 3%. If the amount exceeds 3% by weight, the water resistance and strength of the obtained thin film may decrease.

Examples of the blocking agent include liquid paraffin having 16 or more carbon atoms, microcrystalline wax, natural paraffin, synthetic paraffin, polyolefin wax and aliphatic hydrocarbon blocking agents such as partial oxides, fluorides and chlorides thereof. Higher aliphatic alcohols / higher fatty acids such as higher aliphatic alcohols having 16 or more carbon atoms / higher fatty acid-based blocking agents, metal soap-based blocking agents such as metal salts of fatty acids having 10 or more carbon atoms, fatty acid ester-based blocking agents, fatty acid amides And a fluorine-based blocking agent.

The ratio of the soluble conductive polymer (a) and the crosslinkable compound (b) and / or (c) is (b) /
(A), (c) / (a) or [(b) + (c)] /
(A) is 0.01 / 100 to 99900/100, preferably 0.1 / 100 to 9900/100, more preferably 1/100 to 900/100. The ratio of (b), (c) or (b) + (c) to (a) is 9990
If it exceeds 0/100, practical corrosion protection cannot be obtained, and
If it is less than 01/100, crosslinking will be insufficient and solvent resistance and water resistance will be poor.

The anticorrosion composition of the present invention may be added to a conventionally known corrosion inhibitor (for example, a corrosion inhibitor or metal oxide pigment such as a phosphate or borate-containing pigment, or another organic or inorganic corrosion inhibitor). For example, nitroisophthalic acid salts, phosphorus-containing esters, industrial amines, substituted benzotriazoles, etc.).

The anticorrosion composition of the present invention is applied to the surface of a substrate and then dried by heating to form a film. As the coating method, the conductor can be formed by a simple method such as a spray coating method, a dip coating method, a roll coating method, a gravure coating method, a reverse coating method, an air knife coating method, and a curtain coating method. The base material is not particularly limited as long as it is a metal.Steel, such as steel plate, zinc steel plate, aluminum, copper, zinc, nickel, silver, cobalt, lead, chromium, titanium, and substantially all metals such as stainless steel Metal alloys are mentioned. The heating temperature is
It is usually at least 50 ° C, preferably from 60 to 500 ° C, more preferably from 80 to 400 ° C. The thickness of the anticorrosion film is usually 0.001 to 1000 μm, preferably 0.01 to 1000 μm.
05-500 μm, more preferably 0.01-100 μm
m.

After forming a film by the above method, the anticorrosion composition is insolubilized in water or a solvent by heating, irradiation with ionizing radiation, or a combination thereof. The temperature for crosslinking is preferably 80 ° C. or higher, more preferably 100 ° C.
To 500 ° C, more preferably 120 to 400 ° C. As the ionizing radiation used for crosslinking, ultraviolet (UV), far ultraviolet, electron beam (EB), proton beam and the like are preferably used. It is more effective to use them in combination.

The temperature at which the crosslinkable compound (b) crosslinks with the soluble conductive polymer (a) depends on the type of the crosslinkable compound (b) and is shown in Table 1 below.

[Table 1] 1) Methyl methacrylate-hydroxyethyl methacrylate

The anticorrosion composition of the present invention containing the soluble conductive polymer (a) and the crosslinkable compound (b) and / or (c) is obtained by dissolving (a) in (b) and / or (c). Alternatively, it may be a dispersed system, and (a) and (b) and / or
Alternatively, a system in which (c) is dissolved in the solvent (d) may be used, or a system in which (b) and / or (c) is dispersed in a system consisting of (a) and the solvent (d). When a cross-linkable compound (b) and / or (c) is used in a dispersed state in a system, for example, when a coating film is formed, a part of the particles of (b) and / or (c) is converted into (a). Since it becomes a form to cover and only a part of the particle surface layer becomes a cross-linked form, it is insolubilized as a whole layer, but the cross-linking reaction does not proceed to the inside of the particle,
It is very preferable because the deterioration of the anticorrosive property is extremely small.

[0076]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[Measurement Method] The molecular weight distribution and the molecular weight were measured by GPC measurement (in terms of polyethylene oxide) using a GPC column for an aqueous solvent. As the column, three types of columns for water were used in combination. In addition, a 0.2 mol / l phosphate buffer solution was used as an eluent. Conductivity is measured by a four-terminal method for measuring conductivity, and 2 for measuring surface resistance.
The terminal method was used.

Reference Example 1 Synthesis of poly (2-sulfo-5-methoxy-1,4-iminophenylene) (I) 100 mmol of 2-aminoanisole-4-sulfonic acid
Was dissolved in a 4 mol / l aqueous ammonia solution at 25 ° C. with stirring, and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed, and dried to obtain 15 g of a polymer powder. The volume resistivity of this polymer is 9.0 Ωcm
Met.

Reference Example 2 Poly (2-sulfo-1,4-iminophenylene) (II)
Synthesis of poly (2-sulfo-1,4-iminophenylene) (II)
By a known method [J. Am. Chem. Soc. , 11
3, 2665-2666 (1991)]. The content of the obtained sulfonic acid group is 5 to the aromatic ring.
2%. The volume resistance value of the polymer (II) is 50 Ωcm
Met.

Reference Example 3 Synthesis of poly (N-sulfopropyl-1,4-iminophenylene) (III) Poly (N-sulfopropyl-1,4-iminophenylene) (III) was synthesized by a known method [J. Chem. Soc. ,
Chem. Commun. , 1990, 180].

Reference Example 4 Synthesis of poly (sulfopropyl-2,5-thienylene) (IV) Poly (sulfopropyl-2,5-thienylene) (IV) was synthesized by a known method [Preprints of the 39th Annual Meeting of the Society of Polymer Science, 1990,5
61].

Reference Example 5 Poly (2-carbonyl-1,4-iminophenylene)
Synthesis of (V) 2-aminoanisole-4-carboxylic acid 100 mmol
Was dissolved in a 4 mol / l aqueous ammonia solution at 25 ° C. with stirring, and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was separated by filtration, washed, and dried to obtain 10 g of a polymer powder.

Examples 1-33 The soluble conductive polymer (a) synthesized in Reference Examples 1 to 5 and the crosslinkable compound (b) and / or (c) were mixed with a solvent (d).
To prepare a composition for anticorrosion. Examples 1 to 10
Is an example of preparing a homogeneous composition in which a soluble conductive polymer (a) and a crosslinkable compound (c) are both dissolved in a solvent (d). This is an example of preparing a heterogeneous composition in which the soluble conductive polymer (a) is dissolved but the crosslinkable compound (c) is suspended. Examples 18 to 23 show the soluble conductive polymer (a)
This is an example of preparing a homogeneous composition in which the and the crosslinkable compound (b) are both dissolved in the solvent (d), or a heterogeneous composition in which the crosslinkable compound (b) is suspended. Example 2
Examples 4 to 28 are examples of preparing a composition in which a soluble conductive polymer is dispersed in a system in which a crosslinkable compound (b) is dissolved in a solvent (d). In Examples 29 to 33, the soluble conductive polymer (a) and the homogeneous composition in which the crosslinkable compounds (b) and (c) are both dissolved in the solvent (d), or the crosslinkable compound (b) 2) is an example of preparing a heterogeneous composition in which the composition is suspended in the solvent (d).

The anticorrosion composition thus obtained was applied to a galvanized steel sheet (50 mm × 100 mm × 1 mm) by a roll coating method or a spin coating method, and treated under the crosslinking conditions shown in the table. A film having a predetermined thickness was formed. Both ends were cut at a distance of 5 mm from the long side of these test steel plates, and after salt water spraying (based on JIS-K-5400 method) at 35 ° C., the corrosion length from the terminal was measured.

Comparative Examples 1-4 Coatings were formed on the same galvanized steel sheets as in the examples using the compositions shown in the table as the anticorrosion compositions, and the same anticorrosion tests as in the examples were performed.

The results of Examples 1 to 33 are shown in Tables 2 to 6.
Table 7 shows the results of Comparative Examples 1 to 4. However, the abbreviations in the table are as follows. PVA; polyvinyl alcohol PEG-OP; polyethylene glycol octyl phenyl ether IPA; isopropanol HMMM; hexamethoxymethylol melamine 1,4-CHDO; 1,4-cyclohexanediol 1,4-CHDM; 1,4-cyclohexanedimethanol DEG; diethylene glycol DMF; N, N-dimethylformamide UV; UV rays PEG-NP; Polyethylene glycol nonyl phenyl ether MMA; Methyl methacrylate HEMA; Hydroxyethyl methacrylate HEA; Hydroxyethyl acrylate BA; n-Butyl acrylate MAA; Acrylamide EA; ethyl acrylate DAA; diacetone acrylamide NMP; -2-pyrrolidone

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

[Table 4]

[0090]

[Table 5]

[0091]

[Table 6]

[0092]

[Table 7]

[0093]

The anticorrosion composition of the present invention exhibits a very excellent anticorrosion effect as compared with conventional corrosion inhibitors and can easily form a film on a metal surface. That is: 1) It is soluble in both water and organic solvents, and has very good coatability and coatability on metals. 2) Since it has an extremely excellent anticorrosion effect, it can exhibit sufficient anticorrosion performance even with an extremely thin film.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 201/02 C09D 201/02 C23F 11/00 C23F 11/00 D (72) Inventor Naoki Suga Ogurocho, Tsurumi-ku, Yokohama-shi, Kanagawa Prefecture No. 10-1 Nitto Chemical Industry Co., Ltd.

Claims (20)

[Claims] 1. An anticorrosion composition comprising a soluble conductive polymer, which comprises a self-doping soluble conductive polymer (a) having an acidic group. 2. Self-doping type soluble conductive polymer (a)
Is a soluble conductive polymer having a sulfonic acid group and / or a carboxylic acid group. The anticorrosive composition comprising the soluble conductive polymer according to claim 1. 3. The soluble conductive polymer (a) has a general formula
(1)(Where R₁, R_TwoAre each independently H, -SO_Three ^-, -SO
_ThreeH, -R₂₀SO_Three ^-, -R₂₀SO_ThreeH, -OCH_Three, −
CH_Three, -C_TwoH_Five, -F, -Cl, -Br, -I,-
N (R₁₉)_Two, -NHCOR₁₉, -OH, -O^-, -S
R₁₉, -OR₁₉, -OCOR₁₉, -NO_Two, -COO
H, -R₂₀COOH, -COOR₁₉, -COR₁₉,
Selected from the group consisting of -CHO and -CN, wherein:
R₁₉Is an alkyl, aryl or ara having 1 to 24 carbon atoms
Alkyl group, R₂₀Is alkylene having 1 to 24 carbon atoms, aryl
A ren or aralkylene group;₁And R_TwoHorse
At least one is -SO_Three ^-, -SO_ThreeH, -R₂₀SO_Three
^-, -R₂₀SO_ThreeH, -COOH and -R₂₀CO
It is a group selected from the group consisting of OH. Rings containing acidic groups
Is 20 to 100%. ), General formula (2)(Where R_Three, R_FourAre each independently H, -SO_Three ^-, -SO
_ThreeH, -R₂₀SO_Three ^-, -R₂₀SO_ThreeH, -OCH_Three, −
CH_Three, -C_TwoH_Five, -F, -Cl, -Br, -I,-
N (R₁₉)_Two, -NHCOR₁₉, -OH, -O^-, -S
R₁₉, -OR₁₉, -OCOR₁₉, -NO_Two, -COO
H, -R₂₀COOH, -COOR₁₉, -COR₁₉,
Selected from the group consisting of -CHO and -CN, wherein:
R₁₉Is an alkyl, aryl or ara having 1 to 24 carbon atoms
Alkyl group, R₂₀Is alkylene having 1 to 24 carbon atoms, aryl
A ren or aralkylene group;_ThreeAnd R_FourHorse
At least one is -SO_Three ^-, -SO_ThreeH, -R₂₀SO_Three
^-, -R₂₀SO_ThreeH, -COOH and -R₂₀COOH
A group selected from the group consisting of Splitting of rings containing acidic groups
In the case, it is 20 to 100%. ), General formula (3)(Where R_Five~ R₈Are each independently H, -SO_Three ^-, -SO
_ThreeH, -R₂₀SO_Three ^- , -R₂₀SO_ThreeH, -OCH_Three, −
CH_Three, -C_TwoH_Five, -F, -Cl, -Br, -I,-
N (R₁₉)_Two, -NHCOR₁₉, -OH, -O^-, -S
R₁₉, -OR₁₉, -OCOR₁₉, -NO_Two, -COO
H, -R₂₀COOH, -COOR₁₉, -COR₁₉,
Selected from the group consisting of -CHO and -CN, wherein:
R₁₉Is an alkyl, aryl or ara having 1 to 24 carbon atoms
Alkyl group, R₂₀Is alkylene having 1 to 24 carbon atoms, aryl
A ren or aralkylene group;_Five~ R₈Of which
At least one is -SO_Three ^-, -SO_ThreeH, -R₂₀SO_Three ^-,
-R₂₀SO_ThreeH, -COOH and -R₂₀From COOH
It is a group selected from the group consisting of The proportion of rings containing acidic groups is
20 to 100%. ), General formula (4)(Where R₉~ R₁₃Are each independently H, -SO_Three ^-, -SO
_ThreeH, -R₂₀SO_Three ^-, -R₂₀SO_ThreeH, -OCH_Three, −
CH_Three, -C_TwoH_Five, -F, -Cl, -Br, -I,-
N (R₁₉)_Two, -NHCOR₁₉, -OH, -O^-, -S
R₁₉, -OR₁₉, -OCOR₁₉, -NO_Two, -COO
H, -R₂₀COOH, -COOR₁₉, -COR₁₉,
Selected from the group consisting of -CHO and -CN, wherein:
R₁₉Is an alkyl, aryl or ara having 1 to 24 carbon atoms
Alkyl group, R₂₀Is alkylene having 1 to 24 carbon atoms, aryl
A ren or aralkylene group;₉~ R₁₃Of which
At least one is -SO_Three ^-, -SO_ThreeH, -R₂₀SO_Three ^-,
-R₂₀SO_ThreeH, -COOH and -R₂₀From COOH
It is a group selected from the group consisting of The proportion of rings containing acidic groups is
20 to 100%. ), And the general formula (5)(Where R₁₄Is -SO_Three ^-, -SO_ThreeH, -R₂₀SO_Three ^-,
 -R₂₀SO_ThreeH, -COOH and -R₂₀Selected from the group consisting of COOH
Where R₂₀Is an alkylene having 1 to 24 carbon atoms,
Or an aralkylene group. A group consisting of
At least one selected repeating unit, and
A water-soluble conductive polymer having a molecular weight of 2,000 or more.
Anticorrosion composition comprising the soluble conductive polymer according to claim 1.
Stuff. 4. The soluble conductive polymer (a) is represented by the following general formula (6): (Where 0 ≦ y ≦ 1 and R _{1 to} R ₁₈ are each independently
^{_{H, -SO 3 -, -SO 3}} H, -R 20 SO 3 -, -R 20 SO
_{3 H, -OCH 3, -CH 3} , -C 2 H 5, -F, -C
l, -Br, -I, -N ( R 19) 2, -NHCOR 19,
_{^{-OH, -O -, -SR 19,}} -OR 19, -OCO
_{R 19, -NO 2, -COOH,} -R 20 COOH, -COOR 19, -COR 19, -CHO
And -CN, wherein R ₁₉ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, R ₂₀ is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and R ₁ to At least one of R ₁₆ is —SO ₃ ⁻ , —SO ₃ H, —R ₂₀ SO ₃ ⁻ , —R ₂₀ SO ₃ H, —COOH, and —R
It is a group selected from the group consisting of ₂₀ COOH. The ratio of the ring containing an acidic group is 20 to 100%. 2. The anticorrosion composition comprising the soluble conductive polymer according to claim 1, which comprises a repeating unit represented by the formula: 5. The soluble conductive polymer (a) is represented by the general formula (7): Wherein A is one group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, an alkali metal salt thereof, an ammonium salt and a substituted ammonium salt, and B is a methyl group, an ethyl group, an n- Propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group, is
o-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, heptoxy group, hexoxy group, octoxy group, dodecoxy group, tetracosoxy group, fluoro group, fluoro group, chloro group, and bromo group Represents one group selected from the group;
And n represents the degree of polymerization and is 3 or more. A composition for corrosion protection comprising the soluble conductive polymer according to claim 1). 6. The anticorrosion composition containing the soluble conductive polymer according to claim 1, wherein the content of the repeating unit containing a sulfonic acid group of the soluble conductive polymer (a) is 50% or more. 7. An anticorrosion composition comprising the soluble conductive polymer according to claim 1, wherein the substituent of the soluble conductive polymer (a) is an electron donating group. 8. The method according to claim 1, wherein the substituent of the soluble conductive polymer (a) is an electron donating group, and the content of the repeating unit containing a sulfonic acid group is 80% or more.
An anticorrosion composition comprising the soluble conductive polymer according to the above item. 9. The soluble polymer according to claim 1, wherein the substituent of the soluble conductive polymer (a) is an alkoxy group, and the content of the repeating unit containing a sulfonic acid group is 80% or more. An anticorrosion composition comprising a conductive polymer. 10. The soluble conductive polymer (a) has a weight average molecular weight in the range of 1,000 to 1,000,000.
An anticorrosion composition comprising the soluble conductive polymer according to any one of claims 9 to 10. 11. The soluble conductive polymer (a) according to any one of claims 1 to 10, further comprising a heat-crosslinkable or ultraviolet- or electron-beam-crosslinkable compound (b) and an acid group of the polymer (a). An anticorrosion composition comprising a soluble conductive polymer, comprising at least one compound (c) having at least two functional groups capable of reacting (hereinafter also referred to as a crosslinkable compound (c)). . 12. The crosslinking compound (b) may be an epoxy resin, oligoester acrylate, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, phenol resin, unsaturated polyester resin, furan resin, polyimide, poly (p -Hydroxybenzoic acid), a heat-crosslinkable compound selected from the group consisting of polyurethane, maleic resin, melamine resin and urea resin. 13. The crosslinkable compound (b) is a liquid polybutadiene compound, an unsaturated polyester compound, or a polyene compound.
An ultraviolet or electron beam cross-linking compound selected from the group consisting of polythiol compounds, cationically polymerizable compounds, aminoalkyd resins, urethane acrylates, epoxy acrylates, polyester acrylates, polyether acrylates, acrylate monomers, acrylic oligomers and aqueous acrylates. Item 11. An anticorrosion composition comprising the soluble conductive polymer according to item 11. 14. The anticorrosive composition containing a soluble conductive polymer according to claim 11, wherein the functional group of the crosslinkable compound (c) is selected from the group consisting of a hydroxyl group, a silanol group, a thiol group, an amino group, and an epoxy group. . 15. The anticorrosive composition comprising the soluble conductive polymer according to claim 11, wherein the crosslinkable compound (b) and the crosslinkable compound (c) are emulsions. 16. The anticorrosive composition comprising the soluble conductive polymer according to claim 11, wherein the crosslinkable compound (b) and the crosslinkable compound (c) are water-soluble resins. 17. An anticorrosion composition comprising the soluble conductive polymer according to any one of claims 1 to 16 on at least one surface of a substrate to be subjected to anticorrosion. Anticorrosion film. 18. An anticorrosion composition containing the soluble conductive polymer according to claim 1 on at least one surface of a substrate to be subjected to anticorrosion, to form a film. An anticorrosion method characterized by the following. 19. The anticorrosion method according to claim 18, wherein after forming the film, the anticorrosion composition is insolubilized by heating and / or irradiation with ionizing radiation. 20. The method according to claim 19, wherein the irradiation of the ionizing radiation is ultraviolet (UV).
The anticorrosion method according to claim 19, which is irradiation or electron beam (EB) irradiation.