CN107502140A - A kind of low prepared surface stainless steel substrate anticorrosive paint and preparation method thereof - Google Patents
A kind of low prepared surface stainless steel substrate anticorrosive paint and preparation method thereof Download PDFInfo
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- CN107502140A CN107502140A CN201710822616.0A CN201710822616A CN107502140A CN 107502140 A CN107502140 A CN 107502140A CN 201710822616 A CN201710822616 A CN 201710822616A CN 107502140 A CN107502140 A CN 107502140A
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- stainless steel
- low
- epoxy
- epoxy resin
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- 239000003973 paint Substances 0.000 title claims abstract description 50
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 50
- 239000010935 stainless steel Substances 0.000 title claims abstract description 50
- 239000000758 substrate Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000004593 Epoxy Substances 0.000 claims abstract description 59
- 239000003822 epoxy resin Substances 0.000 claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 53
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 35
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims abstract description 16
- 229910000165 zinc phosphate Inorganic materials 0.000 claims abstract description 16
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 14
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 13
- 239000002689 soil Substances 0.000 claims abstract description 13
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 29
- 239000008096 xylene Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229920000459 Nitrile rubber Polymers 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 14
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 14
- 229920006122 polyamide resin Polymers 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 9
- 239000005060 rubber Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 4
- 238000005488 sandblasting Methods 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 abstract 2
- 239000004952 Polyamide Substances 0.000 abstract 1
- 150000002118 epoxides Chemical class 0.000 abstract 1
- ZTFZSHLWORMEHO-UHFFFAOYSA-A pentaaluminum;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ZTFZSHLWORMEHO-UHFFFAOYSA-A 0.000 abstract 1
- 238000007747 plating Methods 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 21
- 230000007797 corrosion Effects 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 239000002585 base Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000005070 sampling Methods 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 5
- 229910001039 duplex stainless steel Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000005028 tinplate Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000003487 anti-permeability effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960001631 carbomer Drugs 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of low prepared surface stainless steel substrate anticorrosive paint and preparation method thereof, belong to anticorrosive paint technology field.Low prepared surface stainless steel substrate is included with anticorrosive paint：The weight ratio of component A and B component, component A and B component is 100：(15~25)；Wherein, component A includes：Low epoxide number epoxy resin, amino silane, high epoxy value epoxy resin, aluminium triphosphate, composite zinc phosphate, blanc fixe, organic soil paste, polyacrylate and the first solvent；Wherein, the first solvent includes：Dimethylbenzene, n-butanol and methyl iso-butyl ketone (MIBK)；B component includes：Polyamide, nbr carboxyl terminal and the second solvent by weight percentage；Wherein, the second solvent includes：Dimethylbenzene and n-butanol.The present invention is easy to use, it is not necessary to the pretreatment such as sandblasting, plating, phosphatization is carried out to stainless steel products, construction technology is simple, is adapted to all size and the stainless steel products or component of shape.
Description
Technical Field
The invention relates to the technical field of anticorrosive coatings, in particular to an anticorrosive coating for a low-surface-treated stainless steel substrate and a preparation method thereof.
Background
Chinese economy has been developed into outward economy highly dependent on the ocean, the development capability of ocean resources is improved, ocean economy is developed, the ocean ecological environment is protected, and important practical significance and strategic significance are achieved in building ocean strong countries. Stainless steel is increasingly used in coastal marine engineering, marine systems, etc. because of its particular mechanical and chemical properties that are favored by designers. The stainless steel is perforated and broken due to pitting corrosion, intergranular corrosion, stress corrosion and the like caused by the fact that the marine environment contains a large amount of chloride. Therefore, a protective layer must be designed for the stainless steel to prevent the corrosive action of chloride ions on the stainless steel. At present, the corrosion resistance of stainless steel is improved by adopting an anodic oxidation method, an electrochemical method and a medium treatment, which have advantages respectively, but have the common defects of not simple and high cost.
The coating protection has the advantages of simplicity and low cost, but the stainless steel substrate is difficult to be adhered by the coating because of the lower surface energy of the stainless steel substrate. The alkyd system and the polyurethane system coating have certain adhesive force to the stainless steel base material, but the alkyd system has poor acid-base resistance and salt water resistance, and the polyurethane system has poor matching property as a front coating and is not suitable for being used as the stainless steel base material anticorrosive coating. At present, the anticorrosive paint for the stainless steel substrate is generally pretreated by adopting sand blasting, electroplating and phosphorization modes to increase the surface roughness and the adhesive capacity of the substrate, but the methods not only increase the process flow and the process cost, but also limit the size and the shape of a product, and finally limit the use of the stainless steel.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the anticorrosive coating for the low-surface-treated stainless steel base material, which is convenient to use, does not need pretreatment such as sand blasting, electroplating, phosphorization and the like on a stainless steel product, has a simple construction process, and is suitable for stainless steel products or components with various sizes and shapes.
The technical scheme for solving the technical problems is as follows:
an anticorrosive paint for a low-surface-treated stainless steel substrate, comprising: the weight ratio of the component A to the component B is 100: (15-25); wherein,
the component A comprises: 15-28% of low epoxy value epoxy resin, 1-5% of aminosilane, 5-8% of high epoxy value epoxy resin, 20-30% of aluminum tripolyphosphate, 15-25% of composite zinc phosphate, 8-12% of precipitated barium sulfate, 1-2% of organic soil slurry, 0.1-0.3% of polyacrylate and 10-15% of first solvent in percentage by weight; wherein the first solvent comprises: xylene, n-butanol and methyl isobutyl ketone, in weight ratio, xylene: n-butanol: methyl isobutyl ketone ═ (45-55): (25-35): (15-25);
the component B comprises: 70-80% of polyamide resin, 10-20% of carboxyl-terminated nitrile rubber and 8-15% of second solvent in percentage by weight; wherein the second solvent comprises: xylene and n-butanol, in weight ratio, xylene: n-butanol (65-75): (25-35).
The low epoxy value epoxy resin and the high epoxy value epoxy resin are used as film forming resins, wherein the low epoxy value epoxy resin has polyhydroxy and polyether bonds and is used as a main film forming substance to provide substrate wettability so that a coating has basic adhesive force to a stainless steel substrate; the epoxy resin with high epoxy value can improve the crosslinking degree, and as a secondary film forming material, the epoxy resin with low and high epoxy values is used in a matching way, so that the coating has excellent wetting capacity, and meanwhile, the defect of weak corrosion resistance caused by insufficient crosslinking degree is avoided, and the comprehensive performance of the paint film is excellent. Meanwhile, the invention also utilizes aminosilane to carry out graft modification on epoxy resin (high epoxy resin and low epoxy resin), so that the anticorrosive coating has excellent adhesion performance and can be tightly combined with a base material. The aluminum tripolyphosphate, the composite zinc phosphate and the precipitated barium sulfate are selected as corrosion-resistant materials, and are mutually synergistic, so that the corrosion resistance of the coating is effectively improved. Wherein, the aluminum tripolyphosphate can release antirust group (P) with strong coordination capability3O10 5-) The ion has very good activity, strong integration force and coordination capacity, has extremely strong inhibiting effect on corrosion of metal objects such as steel and the like, and has excellent antirust capacity; the zinc phosphate complex has the antirust effect and is based on the principle that zinc phosphate is hydrate and has the capability of forming basic complex, which is mixed with metal surface and Fe2+Form a firmly adhering complex Fe [ Zn ]3(PO4)3]A precipitate layerThe anode reaction is inhibited, and simultaneously the water-soluble organic silicon compound can coordinate with hydroxyl and carboxyl in the paint to generate a stable cross-linking coordination compound, so that chemical combination is formed between the pigment-paint-base material, and the adhesive force and the anti-permeability performance of a paint film are enhanced; then, the barium sulfate is precipitated by matching with a skeleton filler with strong chemical inertia to form a physical shielding effect, so that the corrosion resistance of the coating is comprehensively improved. The invention also introduces carboxyl-terminated butadiene-acrylonitrile rubber (CTBN), increases the flexibility of the coating and reduces the crack propagation and the impact resistance.
Further, in a preferred embodiment of the present invention, the epoxy equivalent of the low epoxy resin is 1500 to 2200 g/eq.
The epoxy resin with high hydroxyl and ether bond contents in the equivalent range ensures that the coating has excellent wetting capacity on the stainless steel substrate and provides basic adhesive force.
Further, in a preferred embodiment of the present invention, the epoxy equivalent of the high epoxy resin is 150 to 200 g/eq.
The epoxy resin in the equivalent range has high epoxy group content, so that the coating has high crosslinking density, and the corrosion resistance of the coating is improved.
Further, in a preferred embodiment of the present invention, the aminosilane is γ -aminopropyltrialkoxysilane.
Further, in a preferred embodiment of the present invention, the precipitated barium sulfate is obtained by sieving with a 900-mesh sieve of 700-.
The particle size of the precipitated barium sulfate is controlled within the range of 700-900-mesh sieve, the particle size is moderate, and the insufficient shielding effect of the coating caused by the undersize particle size of the precipitated barium sulfate can be avoided; and the paint film defects are increased and the corrosion resistance effect is reduced due to the overlarge particle size.
A preparation method of an anticorrosive paint for a low-surface-treated stainless steel substrate comprises the following steps:
1) preparing a component A:
(11) according to the proportion, sequentially adding a first solvent and the low epoxy value epoxy resin into a reaction kettle for stirring, adding the high epoxy value epoxy resin and aminosilane after the low epoxy value epoxy resin is completely dissolved, heating the reaction kettle to 50-65 ℃, and preserving heat for 3-4 hours;
(12) after the reaction is finished, adding aluminum tripolyphosphate, composite zinc phosphate and precipitated barium sulfate, and continuously stirring in the feeding process;
(13) dispersing the materials after feeding, then grinding the dispersed materials, heating the temperature of the reaction kettle to 115-125 ℃, refluxing at constant temperature for 2-3 hours, and driving the materials into a paint mixing cylinder after bonding;
(14) sequentially adding organic soil slurry and polyacrylate into a paint mixing cylinder, then performing dispersion treatment on the materials, and filtering to obtain a component A;
2) preparing a component B:
adding a second mixed solvent, polyamide resin and carboxyl-terminated butadiene-acrylonitrile rubber into the reaction kettle in sequence according to the proportion, dispersing and filtering to obtain a component B;
3) and mixing the component A and the component B according to the weight ratio to prepare the anticorrosive paint.
In the preparation process of the component A, after the matrix resin and the filler are put into the reactor, the mixture is refluxed for 2 to 3 hours at a constant temperature of 115 to 125 ℃, and the filler and the matrix resin are changed from the physical bonding of a secondary valence bond into the chemical bonding by utilizing the mechanochemical action principle, so that the density of the coating is increased, and the long-acting corrosion resistance of the paint film is ensured.
Further, in the preferred embodiment of the present invention, in the step (12), the stirring is performed at a rotation speed of 500 to 800 r/min.
Further, in the preferred embodiment of the present invention, in the step (13), the material is dispersed at a rotation speed of 1200-1300 r/min for 25-35 min.
Further, in the preferred embodiment of the present invention, in the step (14), the material is dispersed for 8-15 min at a rotation speed of 1200-1300 r/min.
Further, in the preferred embodiment of the present invention, in the step (2), the material is dispersed at a rotation speed of 500-800 r/min for 25-35 min.
The invention has the following beneficial effects:
(1) the low-surface-treatment stainless steel base material anticorrosive coating has excellent adhesion performance. According to the invention, macromolecular epoxy resin with a low epoxy value is selected from film forming materials, so that the contents of hydroxyl and ether bonds in the resin are increased, and the wetting capacity of the coating on a stainless steel substrate is improved; the gamma-aminopropyltrialkoxysilane is used for carrying out graft modification on the epoxy resin, so that the stainless steel substrate has excellent adhesive strength without pretreatment such as sand blasting, electroplating, phosphating and the like, and the adhesive force can reach more than 12 MPa.
(2) The low-surface-treatment stainless steel base material anticorrosive coating has excellent corrosion resistance. The invention not only selects macromolecular epoxy resin (namely low epoxy value epoxy resin) providing polyhydroxy in the film forming material, but also uses micromolecular high epoxy value epoxy resin for improving crosslinking density; meanwhile, the selection and preparation process of the corrosion-resistant pigment are improved, the film-forming resin and the corrosion-resistant filler are chemically bonded by utilizing a chemical bonding principle, the compactness and the corrosion inhibition capability of the coating are improved, the paint film does not foam and fall off after a 3000-hour manual accelerated neutral salt spray test, and the paint film has very excellent permeation resistance and corrosion resistance.
(3) The low-surface-treatment stainless steel base material anticorrosive coating has excellent impact resistance. According to the invention, carboxyl-terminated butadiene-acrylonitrile rubber (CTBN) is introduced while the epoxy value of the film-forming resin is matched, so that the flexibility of the coating is increased, the crack expansibility is reduced, the coating has high crosslinking density and impact resistance, and the measured paint film does not crack and fall off under the rapid impact of 80 kg-cm.
(4) The low-surface-treatment stainless steel base material anticorrosive paint has the advantages of environmental protection and low toxicity. The solid content of the low-surface-treatment stainless steel base material anti-corrosive paint is 85 percent, the VOC content is low, and all the organic solvents used by the low-surface-treatment stainless steel base material anti-corrosive paint are low in toxicity or non-toxic, so that the requirement on ventilation volume is lowered, the pollution caused by organic matter volatilization and the damage to constructors are reduced, and the low-surface-treatment stainless steel base material anti-corrosive paint meets the requirement of low-VOC environment-friendly products through inspection.
(5) The technical product can be applied to various stainless steel products such as austenitic stainless steel, martensitic stainless steel, duplex stainless steel and the like, shows good matching property, and can be randomly matched with epoxy paint, alkyd paint, polyurethane paint and fluorocarbon paint for use.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention. The raw material products according to the embodiments of the present invention can be purchased directly, wherein the raw materials of the specific product types are given for illustration only and are not intended to limit the raw materials.
It should be noted that the low epoxy resin and the high epoxy resin of the embodiment of the present invention are defined by defining their epoxy equivalent, and since the epoxy equivalent of the resin is a range value in the actual production and the epoxy equivalent ranges of the resins produced by different manufacturers are different, when applying the present invention, a person skilled in the art can select the corresponding range of the resin according to the epoxy equivalent range defined by the present invention.
Example 1
The anticorrosive paint for the low-surface-treated stainless steel substrate of the embodiment comprises: the weight ratio of the component A to the component B is 100: 20.
1) the component A comprises the following substances in percentage by weight:
28 percent of low epoxy value epoxy resin is NPES 907 in south Asia, and the epoxy equivalent is 1800 g/eq;
4% of gamma-aminopropyltrialkoxysilane;
6 percent of high epoxy value epoxy resin is NPEL 127 of south Asia, and the epoxy equivalent is 176-184 g/eq;
25% of aluminum tripolyphosphate;
16% of composite zinc phosphate;
8.8 percent of precipitated barium sulfate and is sieved by a 700-mesh sieve;
2% of organic soil slurry;
0.2% of polyacrylate and KM-115;
10% of a first solvent, wherein the ratio of xylene: n-butanol: methyl isobutyl ketone ═ 45:35: 20.
2) The component B comprises the following substances in percentage by weight:
75% of polyamide resin;
15% of carboxyl-terminated butadiene-acrylonitrile rubber;
10% of a second solvent, wherein the ratio of xylene: and 35 parts of n-butyl alcohol.
The preparation method of the anticorrosive paint for the low-surface-treated stainless steel substrate comprises the following steps:
1) preparing a component A:
firstly, putting a first solvent (solvent anhydrous n-butyl alcohol with the purity of more than 99.9 percent, methyl isobutyl ketone and xylene) and low-epoxy-value epoxy resin south Asia NPES 907 into a reaction kettle, and stirring; adding high epoxy value epoxy resin south Asia NPEL 127 and gamma-aminopropyl trialkoxy silane when the low epoxy value epoxy resin is completely dissolved, heating to 50 ℃, and keeping for 3.5 hours; secondly, sampling and measuring an amino value, and adding aluminum tripolyphosphate, composite zinc phosphate and barium sulfate if the reaction is finished, and stirring at a rotating speed of 500r/min in the feeding process; dispersing at high speed: continuously dispersing at high speed of 1200r/min for 30min after the feeding is finished; grinding the mixture in a sand mill, heating the mixture to 125 ℃, refluxing the mixture for 2 hours at constant temperature, and driving the mixture into a paint mixing cylinder after bonding; sequentially adding organic soil slurry and polyacrylate carbomer KM-115, and dispersing at a high speed of 1200r/min for 10 min; sixthly, sampling, inspecting, filtering by a 180-mesh filter screen after the product is qualified, and filling; the technical process has the following index requirements: grinding fineness: 20um, viscosity: 120 s/coat-4 (25 ℃), color and appearance: smooth and bubble-free.
2) Preparing a component B:
sequentially adding a second solvent (anhydrous n-butanol and xylene with purity of more than 99.9%), polyamide resin and carboxyl-terminated butadiene-acrylonitrile rubber (CTBN), starting a stirrer, stirring and dispersing at the rotating speed of 800r/min for about 25min to fully dissolve and mix, filtering, packaging, sealing and storing.
When in use, the component A and the component B are mixed according to the weight ratio and then sprayed to obtain the paint.
Example 2
The anticorrosive paint for the low-surface-treated stainless steel substrate of the embodiment comprises: the weight ratio of the component A to the component B is 100: 25.
1) the component A comprises the following substances in percentage by weight:
25 percent of low epoxy value epoxy resin is Mitsui R307, and the epoxy equivalent is 1750-2100 g/eq;
5% of gamma-aminopropyltrialkoxysilane;
8 percent of high epoxy value epoxy resin is Mitsui R139, and the epoxy equivalent is 190 g/eq;
20% of aluminum tripolyphosphate;
20% of composite zinc phosphate;
7.8 percent of precipitated barium sulfate and 800-mesh sieve;
2% of organic soil slurry;
0.2% of polyacrylate and 0190% of Junjiang D0190;
12% of a first solvent, wherein the ratio of xylene: n-butanol: methyl isobutyl ketone 50:30: 20;
2) the component B comprises the following substances in percentage by weight:
80% of polyamide resin;
12% of carboxyl-terminated nitrile butadiene rubber (CTBN);
8% of a second solvent, wherein the ratio of xylene: and (4) n-butyl alcohol is 70: 30.
The preparation method of the anticorrosive paint for the low-surface-treated stainless steel substrate comprises the following steps:
1) preparing a component A:
firstly, putting a first solvent (solvent anhydrous n-butyl alcohol with the purity of more than 99.9 percent, methyl isobutyl ketone and xylene) and a low-epoxy-value epoxy resin three-well R307 into a reaction kettle, and stirring; when the low epoxy value epoxy resin is completely dissolved, adding the high epoxy value epoxy resin three-well R139 and gamma-aminopropyl trialkoxysilane, heating to 60 ℃, and keeping for 4 hours; secondly, sampling and measuring an amino value, and adding aluminum tripolyphosphate, composite zinc phosphate and barium sulfate if the reaction is finished, and stirring at a rotating speed of 600r/min in the feeding process; dispersing at high speed: continuously dispersing at a high speed of 1250r/min for 25min after the feeding is finished; grinding the mixture in a sand mill, heating the mixture to 115 ℃, refluxing the mixture for 3 hours at constant temperature, and driving the mixture into a paint mixing cylinder after bonding is finished; sequentially adding organic soil slurry and polyacrylate Junjiang D0190, and dispersing at a rotating speed of 1300r/min for 8 min; sixthly, sampling, inspecting, filtering by a 180-mesh filter screen after the product is qualified, and filling; the technical process has the following index requirements: grinding fineness: 25um, viscosity: 115 s/coat-4 (25 ℃), color and appearance: smooth and bubble-free.
2) Preparing a component B:
sequentially adding a second solvent (anhydrous n-butanol and xylene with purity of more than 99.9%), polyamide resin and carboxyl-terminated butadiene-acrylonitrile rubber (CTBN), starting a stirrer, stirring and dispersing at a rotating speed of 500/min for 35min to fully dissolve and mix, filtering, packaging, sealing and storing.
When in use, the component A and the component B are mixed according to the weight ratio and then sprayed to obtain the paint.
Example 3
The anticorrosive paint for the low-surface-treated stainless steel substrate of the embodiment comprises: the weight ratio of the component A to the component B is 100: 15.
1) The component A comprises the following substances in percentage by weight:
15 percent of low epoxy value epoxy resin is NPES 907 in south Asia, and the epoxy equivalent is 1800 g/eq;
2% of gamma-aminopropyltrialkoxysilane;
5 percent of high epoxy value epoxy resin is Mitsui R139, and the epoxy equivalent is 190 g/eq;
29% of aluminum tripolyphosphate;
25% of composite zinc phosphate;
8% of precipitated barium sulfate and 800-mesh sieving;
1.5 percent of organic soil slurry;
polyacrylate 0.3%, Henscman 125-3;
14.2% of a first solvent, wherein the ratio of xylene: n-butanol: methyl isobutyl ketone 55:25: 20;
2) the component B comprises the following substances in percentage by weight:
70% of polyamide resin;
20% of carboxyl-terminated nitrile butadiene rubber (CTBN);
10% of a second solvent, wherein the ratio of xylene: and (5) n-butyl alcohol is 75: 25.
The preparation method of the anticorrosive paint for the low-surface-treated stainless steel substrate comprises the following steps:
1) preparing a component A:
firstly, putting a first solvent (solvent anhydrous n-butyl alcohol with the purity of more than 99.9 percent, methyl isobutyl ketone and xylene) and low-epoxy-value epoxy resin south Asia NPES 907 into a reaction kettle, and stirring; when the low epoxy value epoxy resin is completely dissolved, adding the high epoxy value epoxy resin three-well R139 and gamma-aminopropyl trialkoxysilane, heating to 65 ℃, and keeping for 3 hours; secondly, sampling and measuring an amino value, and adding aluminum tripolyphosphate, composite zinc phosphate and barium sulfate if the reaction is finished, and stirring at a rotating speed of 800r/min in the feeding process; dispersing at high speed: continuously dispersing at the high speed of 1300r/min for 35min after the feeding is finished; grinding the mixture in a sand mill, heating the mixture to 120 ℃, refluxing the mixture for 2.5 hours at constant temperature, and driving the mixture into a paint mixing cylinder after bonding is finished; sequentially adding the organic soil slurry and the polyacrylate Henscman 125-3, and dispersing at a rotating speed of 1250r/min for 15 min; sixthly, sampling, inspecting, filtering by a 180-mesh filter screen after the product is qualified, and filling; the technical process has the following index requirements: grinding fineness: 25um, viscosity: 115 s/coat-4 (25 ℃), color and appearance: smooth and bubble-free.
2) Preparing a component B:
sequentially adding a second solvent (anhydrous n-butanol and xylene with purity of more than 99.9%), polyamide resin and carboxyl-terminated butadiene-acrylonitrile rubber (CTBN), starting a stirrer, stirring and dispersing at a rotating speed of 600/min for 30min to fully dissolve and mix, filtering, packaging, sealing and storing.
When in use, the component A and the component B are mixed according to the weight ratio and then sprayed to obtain the paint.
Example 4
The anticorrosive paint for the low-surface-treated stainless steel substrate of the embodiment comprises: the weight ratio of the component A to the component B is 100: 22.
1) The component A comprises the following substances in percentage by weight:
20 percent of low epoxy value epoxy resin is 7050 percent of Dielseng, and the epoxy equivalent is 1750-2100 g/eq;
1% of gamma-aminopropyltrialkoxysilane;
8 percent of high epoxy value epoxy resin is Dielsen 840s, and the epoxy equivalent is 180-one 195 g/eq;
30% of aluminum tripolyphosphate;
15% of composite zinc phosphate;
precipitating barium sulfate 12%, and sieving with 900 mesh sieve;
2% of organic soil slurry;
polyacrylate 0.1%, Ming Yu EU 8115;
11.9% of a first solvent, wherein the ratio of xylene: n-butanol: methyl isobutyl ketone 55:25: 20;
2) the component B comprises the following substances in percentage by weight:
70% of polyamide resin;
15% of carboxyl-terminated nitrile butadiene rubber (CTBN);
15% of a second solvent, wherein the ratio of xylene: and (5) n-butyl alcohol is 75: 25.
The preparation method of the anticorrosive paint for the low-surface-treated stainless steel substrate comprises the following steps:
1) preparing a component A:
firstly, putting a first solvent (solvent anhydrous n-butyl alcohol with the purity of more than 99.9 percent, methyl isobutyl ketone and dimethylbenzene) and low-epoxy-value epoxy resin Dielseng 7050 into a reaction kettle, and stirring; when the low epoxy value epoxy resin is completely dissolved, adding high epoxy value epoxy resin Dielsen 840s and gamma-aminopropyl trialkoxy silane, heating to 55 ℃, and keeping for 3.5 hours; secondly, sampling and measuring an amino value, and adding aluminum tripolyphosphate, composite zinc phosphate and barium sulfate if the reaction is finished, and stirring at a rotating speed of 600r/min in the feeding process; dispersing at high speed: continuously dispersing at a high speed of 1280r/min for 25min after the feeding is finished; grinding the mixture in a sand mill, heating the mixture to 125 ℃, refluxing the mixture for 2 hours at constant temperature, and driving the mixture into a paint mixing cylinder after bonding; sequentially adding organic soil slurry, polyacrylate Ming Yu EU8115 and xylene, and dispersing at a high speed of 1200r/min for 10 min; sixthly, sampling, inspecting, filtering by a 180-mesh filter screen after the product is qualified, and filling; the technical process has the following index requirements: grinding fineness: 25um, viscosity: 115 s/coat-4 (25 ℃), color and appearance: smooth and bubble-free.
2) Preparing a component B:
sequentially adding a second solvent (anhydrous n-butanol and xylene with purity of more than 99.9%), polyamide resin and carboxyl-terminated butadiene-acrylonitrile rubber (CTBN), starting a stirrer, stirring and dispersing at the rotating speed of 800/min for 25min to fully dissolve and mix, filtering, packaging, sealing and storing.
When in use, the component A and the component B are mixed according to the weight ratio and then sprayed to obtain the paint.
Test example 1
First, sample preparation
Sample 1: a martensitic stainless steel sheet having a size of 150X 70X 4 mm;
sample 2: an austenitic stainless steel plate having a size of 150X 70X 4 mm;
sample 3: a duplex stainless steel plate having a size of 150X 70X 4 mm;
sample 4: a tin plate with the size of 120 multiplied by 50 multiplied by 0.3 mm.
The surface of the martensitic stainless steel plate, the austenitic stainless steel plate, the duplex stainless steel plate and the tinplate is subjected to oil removal and dust removal treatment, and in addition, the tinplate is also required to be polished by sand paper to remove a tin layer.
Second, test method and test result
The above samples were sprayed at 23. + -. 2 ℃ with the coating compositions of examples 1-4, respectively. The dry film thickness of the coatings of the martensitic stainless steel plate, the austenitic stainless steel plate and the duplex stainless steel plate is 90-100 um, and the maintenance is carried out for 7 d. The thickness of the dry film of the coating of the tin plate is 23 +/-3 um, and the other items are maintained for 48 hours except the drying time.
The performance of the cured sample and domestic similar products is detected, and the test results are shown in table 1. Wherein, when the salt tolerance test is carried out, the salt solution is NaCl solution with the concentration of 3 percent. In the alkali resistance test, the alkali solution used was a 0.5% NaOH solution. In the acid resistance test, the acid solution used was 0.5% H2SO4And (3) solution.
TABLE 1
As can be seen from Table 1, the anticorrosive coatings prepared in examples 1 to 4 of the present invention, no matter which stainless steel substrate the anticorrosive coatings are attached to, show superior performance, mechanical properties and corrosion resistance compared with similar products on the premise of satisfying the technical standards.
Test example 2
The anticorrosive coatings prepared in examples 1 to 4 were coated on a martensitic stainless steel plate, an austenitic stainless steel plate and a duplex stainless steel plate, respectively, and the adhesion thereof was measured, and the results of the measurements are shown in table 2.
TABLE 2
As can be seen from Table 2, the adhesion of the anticorrosive coating prepared by the embodiment of the invention on the base material is far greater than that of the like products.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. An anticorrosive paint for a low-surface-treated stainless steel substrate is characterized by comprising: the weight ratio of the component A to the component B is 100: (15-25); wherein,
the component A comprises: 15-28% of low epoxy value epoxy resin, 1-5% of aminosilane, 5-8% of high epoxy value epoxy resin, 20-30% of aluminum tripolyphosphate, 15-25% of composite zinc phosphate, 8-12% of precipitated barium sulfate, 1-2% of organic soil slurry, 0.1-0.3% of polyacrylate and 10-15% of first solvent in percentage by weight; wherein the first solvent comprises: xylene, n-butanol and methyl isobutyl ketone, in weight ratio, xylene: n-butanol: methyl isobutyl ketone ═ (45-55): (25-35): (15-25);
the component B comprises: 70-80% of polyamide resin, 10-20% of carboxyl-terminated nitrile rubber and 8-15% of second solvent in percentage by weight; wherein the second solvent comprises: xylene and n-butanol, in weight ratio, xylene: n-butanol (65-75): (25-35).
2. The anticorrosive paint for the low-surface-treated stainless steel substrate according to claim 1, wherein the epoxy equivalent of the low-epoxy-value epoxy resin is 1500 to 2200 g/eq.
3. The anticorrosive paint for low-surface-treated stainless steel substrates according to claim 1, wherein the epoxy equivalent of the high-epoxy-value epoxy resin is 150 to 200 g/eq.
4. The anticorrosive coating for low-surface-treated stainless steel substrates according to claim 1, wherein the aminosilane is γ -aminopropyltrialkoxysilane.
5. The anticorrosive paint for low-surface-treated stainless steel substrates as claimed in claim 1, wherein the precipitated barium sulfate is obtained by sieving with a 900-mesh sieve of 700-.
6. The process for producing an anticorrosive coating for a low-surface-treated stainless steel substrate according to any one of claims 1 to 5, comprising:
1) preparing a component A:
(11) according to the proportion, a first solvent and the low epoxy value epoxy resin are sequentially added into a reaction kettle for stirring, after the low epoxy value epoxy resin is completely dissolved, the high epoxy value epoxy resin and aminosilane are added, the temperature of the reaction kettle is raised to 50-65 ℃, and the temperature is kept for 3-4 hours;
(12) after the reaction is finished, adding aluminum tripolyphosphate, composite zinc phosphate and precipitated barium sulfate, and continuously stirring in the feeding process;
(13) dispersing the materials after feeding, then grinding the dispersed materials, heating the temperature of the reaction kettle to 115-125 ℃, refluxing at constant temperature for 2-3 hours, and driving the materials into a paint mixing cylinder after bonding;
(14) sequentially adding organic soil slurry and polyacrylate into the paint mixing cylinder, then dispersing the materials, and filtering to obtain the component A;
2) preparing a component B:
according to the proportion, a second solvent, polyamide resin and carboxyl-terminated butadiene-acrylonitrile rubber are sequentially added into a reaction kettle, dispersed and filtered to obtain the component B;
3) and mixing the component A and the component B according to the weight ratio to prepare the anticorrosive paint.
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