CN1043240C - Self-abrasion anti-foul paint compound - Google Patents
Self-abrasion anti-foul paint compound Download PDFInfo
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- CN1043240C CN1043240C CN91105581A CN91105581A CN1043240C CN 1043240 C CN1043240 C CN 1043240C CN 91105581 A CN91105581 A CN 91105581A CN 91105581 A CN91105581 A CN 91105581A CN 1043240 C CN1043240 C CN 1043240C
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- antifouling paint
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Abstract
The present invention relates to a self-abrasion type antifouling paint compound comprising a metal soap resin. A metal compound containing at least bivalent metals, and an unsaturated fatty acid, or a mixture containing an unsaturated fatty acid, or a mixture containing an unsaturated fatty acid and other saturated organic acids react with each other to obtain the metal soap resin.
Description
The present invention relates to a kind of antifouling paint compositions, relate to a kind of self-abrasion anti-foul paint compound particularly, particularly a kind of antifouling paint compositions that comprises polymerisable fatty acid metal soap, and the method for utilizing described composition protection hull.
Antifouling marine paint mainly is divided into two types, autogenous grinding type and insoluble matrix type.Autogenous grinding type antifouling varnish can be by seawater hydrolysis gradually, polish, and causes level and smooth, fresh surface and reduces friction between ship surface and the water, reduces running resistance by this.Unsalted surface includes the antifouling toxin of coating, till they are used up.
Autogenous grinding type coating comprises a kind of resin that contains the hydrolyzable base usually, for example organic acidic group.This hydrolysis rate trembled of being coated with is according to organic acidic group and cationic type force, and acidic group in resin per-cent and decide.
Self-abrasion anti-foul paint can be to contain toxin type or do not have toxin type.The toxic agent coating that for example contains organotin is the polyacrylic ester that tin replaces, and this coating is owing to having superior didirtresistance and self-grinding, so generally be used.Yet therefore this coating Nitrosamines is subjected to the restriction of law.Copper bearing antifouling paint toxicity is less, can be in conjunction with adding toxic agent when needing.
The antifouling paint compositions that the purpose of this invention is to provide a kind of hydrolyzable or autogenous grinding type, composition can form a kind of film, can form low viscosity and need not use expensive tin metal compound just to have antifouling unsaturated acid metallic soap of advising effect, because its viscosity is low, so can carry a large amount of toxic agent easily, reach the good antifouling effect.
From highly hydrophobic saturated species (for example fatty acid, acids) and polyvalent metal (for example Co, Mn, Zn, Cu, Ca etc.) compound making soap class is that the system paint industry is known, for example siccative and catalyzer.These soap classes are water insoluble, but slowly hydrolysis.The speed of hydrolysis is according to the kind of acid and soap class institute's cation and decide.This expression: can adjust the speed of hydrolysis through changing acids and positively charged ion.These metallic soap classes can not be as the tackiness agent of coating composition.But according to the present invention, the metallic soap of making from unsaturated fatty acids (for example linolenic acid) coexists and is exposed to the air with siccative when normal room temperature and just can form film.
The present invention relates to a kind of being used on the surface of ship through crosslinked and form the hydrolyzable antifouling paint compositions of antifouling coating, this antifouling coating is immersed in the seawater and hydrolysis and form smooth and new surface continuously gradually in seawater, and described composition comprises:
(1) have the metallic soap binder for film formation of following general formula:
R1-A1-M-A2-R2
Wherein, R1 is from unsaturated fatty acids or the pure alkenyl of deriving and obtaining, M is a kind of metal of divalence at least that has, A1 and A2 are the functional group of carboxylic acid, sulfonic acid or phosphoric acid respectively independently, R2 is a kind of aliphatics, aromatic series, alicyclic unit price organic acid, or the unsaturated or saturated residue of acrylic acid oligomer; With
(2) stain control agent that prevents to be immersed in the hull surface knot dirt in the seawater of significant quantity;
Wherein, described metallic soap binder for film formation is to comprise the metallic compound and the product that comprises the reaction constituent interreaction of unsaturated fatty acids of the above metal of divalence, and
Described metallic soap binder for film formation is as the binder for film formation of described stain control agent.
According to hydrolyzable antifouling paint compositions of the present invention, wherein said reaction constituent further comprises carboxylic acid.
According to hydrolyzable antifouling paint compositions of the present invention, wherein said reaction constituent further comprises a kind of low-molecular-weight polymeric acid that is selected from a group that is made up of polyacrylic acid and polyester.
According to hydrolyzable antifouling paint compositions of the present invention, wherein said composition further comprises the polymkeric substance that has hydrophilic group of a kind of and described undersaturated metallic soap binder for film formation blending.
According to hydrolyzable antifouling paint compositions of the present invention, wherein said metal is to be subordinated in the metal of periodictable I b, II b, III a, III b, IV a, IV b, V a, V b, VI a and VII family to select.
According to hydrolyzable antifouling paint compositions of the present invention, wherein said unsaturated organic acid is a kind of unsaturated fatty acids, wherein selects from be made up of oleic acid, linolic acid, linolenic acid, oil-stearic acid, galactosonic acid, ricinolic acid, erucic acid one group.
According to hydrolyzable antifouling paint compositions of the present invention, wherein said unsaturated organic acid is a kind of unsaturated fatty acids, described unsaturated fatty acids obtains from a kind of oil, and described oil is to select from be made up of Viscotrol C, soybean oil, oil of maize, oleum gossypii seminis, Semen Lini oil, oiticica oil, perilla oil, poppyseed oil, rape seed oil, safflower oil, Trisun Oil R 80, pine tar, walnut oil, pilchardine, big menhaden fish oil and sardine oil one group.
According to hydrolyzable antifouling paint compositions of the present invention, wherein said unsaturated organic acid be from by acetate, propionic acid, butyric acid, defend one group that acid, caproic acid, sad, capric acid, laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid, phenylformic acid, phthalandione, toluic acid, O-hydroxybenzoic acid, nitre phenylformic acid, toluenesulphonic acids, naphthenic acid, sylvic acid and natural acid form and select.
According to hydrolyzable antifouling paint compositions of the present invention, wherein said unsaturated organic acid is the polymeric acid that comprises polyradical, described polyradical be from by acrylic copolymer, vinylformic acid-Sipacril 2739OF, comprise the ethylene copolymer of vinylbenzene acid iodide and form by the polyester that multi-group alcohol and polyfunctional group acid are made one group and select.
According to hydrolyzable antifouling paint compositions of the present invention, the wherein said polymkeric substance that has hydrophilic group is from by rosin, polyacrylamide, polyacrylic acid, polyester with have one group that the polyurethane of hydrophilic group forms and select.
According to hydrolyzable antifouling paint compositions of the present invention, wherein said stain control agent is CuO.
The invention still further relates to a kind of method of protecting hull, comprising:
Apply a kind of hydrolyzable antifouling paint compositions forming a kind of protectiveness film at described hull surface, this film life can be in seawater hydrolysis and form smooth and new surface continuously gradually, described composition comprises:
(1) a kind of metallic soap binder for film formation;
(2) stain control agent of significant quantity;
Described metallic soap binder for film formation has following general formula:
R1-A1-M-A2-R2
Wherein, R1 is from unsaturated fatty acids or the pure alkenyl of deriving and obtaining, M is a kind of metal of divalence at least that has, A1 and A2 are the functional group of carboxylic acid, sulfonic acid or phosphoric acid respectively independently, R2 is a kind of aliphatics, aromatic series, alicyclic unit price organic acid, or the unsaturated or saturated residue of acrylic acid oligomer; And
Wherein, described metallic soap binder for film formation is to comprise the metallic compound and the product that comprises the reaction constituent interreaction of unsaturated organic acid of the above metal of divalence, and
Described metallic soap binder for film formation is as the binder for film formation of described stain control agent.
According to the present invention, the metallic soap of unsaturated fatty acids or oil has direct structure, just can harden into crosslinked film through being exposed to the oxygen that exists in the air under coexisting with siccative.Because the unsatuated metal soap has low-down viscosity, therefore can add a large amount of stain control agents, for example CuO.For not using the antifouling paint of any costliness and highly toxic toxic agent (for example tin compound), in order to reach the permanent anti-fouling effect that continues, the toxic agent that loads high quantity easily is important.
Through the quantity and the pattern that change unsaturated fatty acids, can adjust cross-linking density according to the formed film of the present invention.Can reduce cross-linking density and influence the character of film in conjunction with a kind of saturated fatty acid.In order, the speed of the property effect hydrolysis of cross-linking density and film.
Through the mixture that makes metallic compound and unsaturated fatty acids, unsaturated fatty acids or comprise the mixture reaction of one or more unsaturated fatty acidss and unsaturated organic acid, can be made into above-mentioned metallic soap resin.In addition, other polymkeric substance can with the metallic soap resinous blending, with the character of improvement metallic soap resin.
Available unsaturated fatty acids of the present invention has oleic acid, linolic acid, linolenic acid, oil-stearic acid, galactosonic acid, ricinolic acid, erucic acid.Other available lipid acid is to obtain from Viscotrol C, soybean oil, oil of maize, oleum gossypii seminis, Semen Lini oil, oiticica oil, perilla oil, poppyseed oil, rape seed oil, safflower oil, Trisun Oil R 80, pine tar, tung oil, walnut oil, pilchardine, big menhaden fish oil and sardine oil; Also can utilize the unsaturated organic acid class in addition, above-mentioned unsaturated acids can be transformed into a kind of Fatty Alcohol(C12-C14 and C12-C18), in order, can be used to make a kind of phosphoric acid or sulfonic acid that comprises the unsaturated aliphatic base.
Metallic compound can be oxide compound, oxyhydroxide or the muriate of metal.Containing at least in periodictable, most of metal of divalence can be used for the present invention.They are the metals that belong to I b, II a, II b, III a, III b, IV a, IV b, V a, V b, VI a and VII class.The metal that is used for making metallic soap can influence the speed of hydrolysis.Alkali-metal soap class can be water-soluble immediately.The soap class of alkaline-earth metal is water-fast, but can hydrolysis in water.Different alkaline-earth metal can cause the different hydrolysis rate of soap class.The alkaline-earth metal (for example barium) that for example has higher molecular weight has slower hydrolysis rate than other alkaline-earth metal with lower molecular weight (for example magnesium).When using III and IV metalloid and transition metal (for example Al, Co, Zn, Mn, Ca etc.), hydrolysis rate also can change to some extent.
Available unsaturated organic acid class of the present invention comprises-COOH ,-OSO
3H or-O-PO
3H
3Acids.These acids can adopt aliphatics, aromatic series, alicyclic unit price organic acid or natural acids, and the natural acid of indication can be selected from acetate, propionic acid, butyric acid, valeric acid, caproic acid, sad, capric acid, laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid, phenylformic acid, phthalandione, toluic acid, O-hydroxybenzoic acid, nitre phenylformic acid, chloro-benzoic acid, toluenesulphonic acids, naphthenic acid, sylvic acid and various natural fat acids here.
Other saturated species of available of the present invention are the polymkeric substance with acids, for example acrylic copolymer, vinylformic acid-Sipacril 2739OF, have-COOH ,-OSO
3H-or-O-PO
3H
3Poly-acids.The example of acrylic copolymer from vinylformic acid and (or) methacrylic acid, styrene sulfonic acid and (or) vinyl monomer makes.The example of polyester is made from polyfunctional group alcohols and polyfunctional group acids.The effect of the functional group of polymkeric substance is not to form film, but therefore the self-grinding of improvement cross linking membrane can adopt oligopolymer or low-molecular weight polymer.
The polymkeric substance that can be metallic soap resinous blending of the present invention is water soluble (for example Gum Rosin and acrylamide) and comprises hydrophilic group (for example hydroxyl) and polyacrylamide.Other available polymkeric substance comprises polyacrylic, polyester and the polyamine esters of carboxylic acid group, sulfonic group, phosphate, amido or amide group.
Below by embodiment the present invention is described in further detail:
Embodiment 1
In the reactor of one four neck, mix 280 gram Semen Lini oil lipid acid, 50 gram Cu (OH)
2With 200 gram dimethylbenzene, slowly be heated to 140 ℃ and holding temperature at 140 ℃ and continue heating two hours, reaction is finished to obtain a kind of clear solution with 60% solids content.
Embodiment 2
In the reactor of one four neck, mix 150 gram tung oil lipid acid, 120 gram stearic acid, 50 gram Cu (OH)
2, 200 gram dimethylbenzene, slowly be heated to 140 ℃ and holding temperature at 140 ℃ and continue heating two hours, reaction is finished.Obtain a kind of clear solution with 57% solids content.
Embodiment 3
In the reactor of one four neck, make 60 gram methyl methacrylates, 80 gram butyl acrylates, 60 restrain vinylformic acid, 3 gram butyl sulfhydryl, 50 gram propyl carbinols and 200 gram dimethylbenzene, reacted three hours down at 120 ℃, and form a kind of polymkeric substance.In this polymkeric substance, add 50 gram Semen Lini oil lipid acid and 50 gram Ca (OH) then
2, and be heated to 140 ℃.Reactor maintains 140 ℃ and continues two hours, so that reaction is finished.
Embodiment 4
According to the identical program of embodiment 1, from soya fatty acid and Cu (OH)
2Make resin.Make acrylic copolymer through using 80 gram methyl methacrylates, 50 gram butyl acrylates, 70 gram vinylformic acid, 3 gram azobis isobutyronitriles and 200 gram dimethylbenzene.With 50 gram acrylic copolymer and the above-mentioned resinous blending of 50 grams.
Embodiment 5 to 8
Adopt the resin of embodiment 1 to 4 preparation, make antifouling varnish according to following prescription:
Composition quantity (gram)
Resin 25
CuO 40
Wilkinite #34 1.5
Talcum 10
CaCO
3 5
Dimethylbenzene 20
The physical properties of antifouling varnish and antifouling character are summarized in the table 1.Contrast 1 is made by a kind of chlorine rubber rosin, and contrasts 2 by a kind of autogenous grinding type organotin resin making.Table 1 embodiment 5678 contrasts 1 contrast 2 hardness H H H HB H H viscosity, (ku) but 70 65 85 93 85 93 shock resistance cocoas are good good good, (* 50 centimetres of 500 grams) are antifouling, (%) 1 month 00000 03 months 15 10 10 5 30 26 months 45 40 40 30 70 209 months 90 90 70 70 100 60
Annotate: the enforcement of antifouling test be that test film is immersed in the seawater, and antifouling ability is to represent with the geographic per-cent of dirt.
Claims (11)
1, a kind of being used on the surface of ship through crosslinked and form the hydrolyzable antifouling paint compositions of antifouling coating, described composition comprises:
(1) have the metallic soap binder for film formation of following general formula:
R1-A1-M-A2-R2
Wherein, R1 is the alkenyl of deriving and obtaining from unsaturated fatty acids, and M is a kind of metal of divalence at least that has, and A1 and A2 are the functional group of carboxylic acid respectively independently, R2 is a kind of aliphatics, aromatic series, alicyclic unit price organic acid, or the unsaturated or saturated residue of acrylic acid oligomer; With
(2) stain control agent that prevents to be immersed in the hull surface knot dirt in the seawater of significant quantity;
Wherein, described metallic soap binder for film formation is to comprise the metallic compound and the product that comprises the interreaction of unsaturated fatty acids acid-respons constituent of the above metal of divalence, and
Described metallic soap binder for film formation is as the binder for film formation of described stain control agent.
2, according to the described hydrolyzable antifouling paint compositions of claim 1, it is characterized in that: described reaction constituent further comprises unsaturated organic acid.
3, according to the described hydrolyzable antifouling paint compositions of claim 1, it is characterized in that: described reaction constituent further comprises a kind of low-molecular-weight polymeric acid that is selected from a group that is made up of polyacrylic acid and polyester.
4, according to the described hydrolyzable antifouling paint compositions of claim 1, it is characterized in that: said composition further comprises the polymkeric substance that has hydrophilic group of a kind of and described undersaturated metallic soap binder for film formation blending, and the described polymkeric substance that has hydrophilic group is from by rosin, polyacrylamide, polyacrylic acid, polyester with have one group that the polyurethane of hydrophilic group forms and select.
5, according to the described hydrolyzable antifouling paint compositions of claim 1, it is characterized in that: described metal is to be subordinated in the metal of periodictable I b, II b, III a, III b, IV a, IV b, V a, V b, VI a and VII family to select.
6, according to the described hydrolyzable antifouling paint compositions of claim 1, it is characterized in that: described, unsaturated fatty acids is to select from be made up of oleic acid, linolic acid, linolenic acid, oil-stearic acid, galactosonic acid, ricinolic acid, erucic acid one group.
7, according to the described hydrolyzable antifouling paint compositions of claim 1, it is characterized in that: described unsaturated fatty acids obtains from a kind of oil, and described oil is to select from be made up of Viscotrol C, soybean oil, oil of maize, oleum gossypii seminis, Semen Lini oil, oiticica oil, perilla oil, poppyseed oil, rape seed oil, safflower oil, Trisun Oil R 80, pine tar, walnut oil, pilchardine, big menhaden fish oil and sardine oil one group.
8, according to the described hydrolyzable antifouling paint compositions of claim 2, it is characterized in that: described unsaturated organic acid be from by acetate, propionic acid, butyric acid, defend one group that acid, caproic acid, sad, capric acid, laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid, phenylformic acid, phthalandione, toluic acid, O-hydroxybenzoic acid, nitre phenylformic acid, toluenesulphonic acids, naphthenic acid, sylvic acid and natural acid form and select.
9, according to the described hydrolyzable antifouling paint compositions of claim 2, it is characterized in that: described unsaturated organic acid is the polymeric acid that comprises polyradical, described polyradical be from by acrylic copolymer, vinylformic acid-Sipacril 2739OF, comprise the ethylene copolymer of vinylbenzene acid iodide and form by the polyester that multi-group alcohol and polyfunctional group acid are made one group and select.
10, according to the described hydrolyzable antifouling paint compositions of claim 1, it is characterized in that: described stain control agent is CuO.
11, a kind of method of protecting hull comprises:
Apply a kind of hydrolyzable antifouling paint compositions to form a kind of protectiveness film at described hull surface, described composition comprises:
(1) a kind of metallic soap binder for film formation;
(2) stain control agent of significant quantity;
Described metallic soap binder for film formation has following general formula:
R1-A1-M-A2-R2
Wherein, R1 is the alkenyl of deriving and obtaining from unsaturated fatty acids, and M is a kind of metal of divalence at least that has, and A1 and A2 are the functional group of carboxylic acid respectively independently, R2 is a kind of aliphatics, aromatic series, alicyclic unit price organic acid, or the unsaturated or saturated residue of acrylic acid oligomer; And
Wherein, described metallic soap binder for film formation is to comprise the metallic compound and the product that comprises the reaction constituent interreaction of unsaturated fatty acids of the above metal of divalence, and
Described metallic soap binder for film formation is as the binder for film formation of described stain control agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91105581A CN1043240C (en) | 1991-08-15 | 1991-08-15 | Self-abrasion anti-foul paint compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91105581A CN1043240C (en) | 1991-08-15 | 1991-08-15 | Self-abrasion anti-foul paint compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1069505A CN1069505A (en) | 1993-03-03 |
| CN1043240C true CN1043240C (en) | 1999-05-05 |
Family
ID=4907247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91105581A Expired - Fee Related CN1043240C (en) | 1991-08-15 | 1991-08-15 | Self-abrasion anti-foul paint compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1043240C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013108880A1 (en) * | 2012-01-18 | 2013-07-25 | 三菱レイヨン株式会社 | Method for producing vinyl polymer and resin composition for water-based antifouling paint containing vinyl polymer |
| CN103254708A (en) * | 2013-05-22 | 2013-08-21 | 江苏紫石化工科技有限公司 | Compound paint |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0204456A1 (en) * | 1985-05-17 | 1986-12-10 | Nippon Paint Co., Ltd. | A hydrolyzable resin composition and an antifouling coating composition containing the same |
| EP0342276A1 (en) * | 1986-11-17 | 1989-11-23 | Nippon Paint Co., Ltd. | A process for preparing a metal containing resin composition and the use of the composition thus prepared as a resinous vehicle in antifouling paint |
| CN1055940A (en) * | 1990-04-10 | 1991-11-06 | 库尔脱活兹涂料有限公司 | Antifouling paint compositions |
-
1991
- 1991-08-15 CN CN91105581A patent/CN1043240C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0204456A1 (en) * | 1985-05-17 | 1986-12-10 | Nippon Paint Co., Ltd. | A hydrolyzable resin composition and an antifouling coating composition containing the same |
| EP0342276A1 (en) * | 1986-11-17 | 1989-11-23 | Nippon Paint Co., Ltd. | A process for preparing a metal containing resin composition and the use of the composition thus prepared as a resinous vehicle in antifouling paint |
| CN1055940A (en) * | 1990-04-10 | 1991-11-06 | 库尔脱活兹涂料有限公司 | Antifouling paint compositions |
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| Publication number | Publication date |
|---|---|
| CN1069505A (en) | 1993-03-03 |
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Granted publication date: 19990505 Termination date: 20100815 |