CN1172996C - Water surface treatment agent for metal material and furface treated metal plate - Google Patents
Water surface treatment agent for metal material and furface treated metal plate Download PDFInfo
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- CN1172996C CN1172996C CNB001031155A CN00103115A CN1172996C CN 1172996 C CN1172996 C CN 1172996C CN B001031155 A CNB001031155 A CN B001031155A CN 00103115 A CN00103115 A CN 00103115A CN 1172996 C CN1172996 C CN 1172996C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
Abstract
The present invention relates to an aqueous surface-treating agent for metal materials to confer excellent corrosion protection on scared area in addition to good alkali-resistance and adhesivity, and also to the surface-treated metal plates. The aqueous metal surface treating agents are composed of water and (A) polyaminoester and/or polyacrylic resins, (B) a firming agent, (C) silica particles, (D) polyethylene with average praticle size of 0.01-0.2 muM, (E) a dispersant represented by the following formula (I), in which R1 and R4 is alkyl, alkenyl, R2 is (CH2CH2-O)m-(CH2CH2CHO)n and R3 is H or sulfonate group.
Description
The present invention for relevant on the surface of metallic substance for forming the planar portions solidity to corrosion, have the metallic substance use surface treatment agent of the superior resin coating usefulness of the solidity to corrosion of pars affecta and coating tack, and the surface-treated metal plate that relevant resin coating is formed.
For a long time, zinc system or zinc-based metal plated steel sheet are for being widely used in aspects such as family's electrification goods or building materials.These sheetmetals are maintaining the original state down, because solidity to corrosion or coating tack (on be coated with coating) deficiency, apply chromic salt chemistry method surface treatment or the surface treatment of phosphate chemical method through giving, Hou is more with the formation processing that applies mold pressing processing or warpage processing etc. or coating etc., according to employed purposes difference, the situation that plants the use that maintains the original state is quite a few not being coated with.
In the situation that is not coated with and adopts, can often be suitable for the surface treatment agent steel plate that is known as chromic salt chemistry method surface treated steel plate, but adhering to of the fingerprint when being shaped processing or combination, has the problem of the dispersiveness etc. of the tone that the difference of chromic salt tunicle amount causes.Therefore, for solving these problem points, can be used in and make the anti-finger print steel plate that forms organic envelope on the chromic salt tunicle.This anti-finger print steel plate is preventing that adhering to of fingerprint from being purpose, makes zinc-plated and forms organic resin layer about 1 μ m for chromate treating Hou on the surface of steel plate.This anti-finger print steel plate except that anti-fingerprint characteristic, also requires to have solidity to corrosion, solvent resistance, coating tack, anti-ly has the various by film properties of scar etc.
Among these performances, in recent years the anti-requirement that has scar is improved, anti-ly have the reason that scar is required and cause for the vibration of in the goods that transport the processing Hou that is shaped, being given birth to, the shaping thing is mutual or accommodating the container (Corrugated Box etc.) of molding and the friction between the shaping thing, can produce due to the damage on the surface of molding.This has the part of scar, because general organic coating steel is more inferior aspect solidity to corrosion, quality can reduce unavoidably.
Therefore, with except that solidity to corrosion, coating tack, consider that also anti-existing some relevant of the technology of surface treatment agent steel plate that has scar just is being suggested application.These technology have Japanese kokai publication hei 3-17189 communique, special fair 6-104799 communique, spy to open the method that flat 6-292859 communique is put down in writing.
In Japanese kokai publication hei 3-17189 communique, be combined with the relevant method of resin coating of fluorine carbon resin beads and silicon dioxide granule in announcement and the urethane upgrading polyolefin resin.Being characterized as of this method is to need to use fluorine carbon resin beads with boundary belt the pars affecta part to be arranged; for making homodisperse fluorine carbon resin beads in the aqueous solution; the use of tensio-active agent is essential and integral; owing to use this kind tensio-active agent; corrosion proof level is lower on the whole, fails to obtain satiable solidity to corrosion.
In the special fair 6-104799 communique of Japan, the relevant method of tunicle of announcement and the polyethylene-based wax that contains polyester based resin and linking agent and molecular-weight average 2000～8000.In this method, use vibrin in the base resin internal cause, it is not enough that tunicle itself anti-adds water decomposition, fails to obtain gratifying solidity to corrosion.
In Japanese kokai publication hei 6-292859 communique, announcement has the urethane resin that has an active hydrogen in intramolecularly to contain in the resin of cold cross-linking type Resins, epoxy, the relevant method of tunicle that the resin formation that contains cold cross-linking type Resins, epoxy is made contain spherical polyethylene wax particle and chain colloid silica.Colloid silica for adhering to solid surface and having the character that is known as the increasing property that improves frictional coefficient, uses the situation of the chain colloid silica of this method, because the constructivity of colloid silica itself can make the anti-scar reduction that has.Therefore, for cooperating spherical polyethylene wax, but drying temperature is low than 100 ℃ in this method, so polyethylene wax can bury in resin coating, oilness becomes deficiency, fails to obtain the satiable anti-solidity to corrosion that has the scar part.
Therefore, it is superior to fail to make the coating tack at present, and the solidity to corrosion surface of good that has the scar part is handled steel plate.
And, make urethane resin and/or Resins, epoxy, the silicon-dioxide that uses under the purpose that forms resin coating or (water-based) lubricious coatings of the wax that contains polyethylene wax in containing on cold-rolled steel sheet, zinc-based metal plated steel sheet or the aluminum-based metal plate, known to Japanese kokai publication hei 5-118550 communique, No. the 2617838th, No. the 2719571st, patent or patent put down in writing, but aspect other the constitutive requirements and the effect of invention, the present invention of the following stated is different with these inventions.
The present invention carries out for the problem points that solves above-mentioned known techniques, its objective is provides a kind of solidity to corrosion, coating tack, especially for adopting for metallic substance use surface treatment agent that is formed on the superior organic resin tunicle usefulness of the solidity to corrosion that has scar portion and the surface-treated metal plate that adopts this to get to provide.
The inventor, for solving the problem of above-mentioned known techniques, through self-criticism meticulously, found that by the polyethylene wax that adopts urethane resin and/or acrylic ester resin, solidifying agent, silicon dioxide granule, specified particle diameter, and as the aqueous surface-treating agent of the compound of the particular configuration of dispersion agent, can solve foregoing problems, so that finish the present invention.
Promptly, the present invention is to contain (A) urethane resin and/or acrylic ester resin, (B) solidifying agent, (C) silicon dioxide granule, (D) polyethylene wax of averaged particles 0.01～0.2 μ m, (E) as the compound and the water with following formula (I) expression of dispersion agent, composition (A) reaches and (B) is dispersed or dissolved in water for each order, composition (C) reaches and (D) is scattered in water, composition (E) is dissolved in water, whole shape branches admittedly to composition (A)～(E), (A)+(B) ratio that solid shape is divided is 50～95 weight %, (C) ratio that solid shape is divided is 3～40 weight %, (D)+(E) ratio that solid shape is divided is 2～20 weight %, and (A)/(B) solid shape divides weight ratio to be the metallic substance use surface treatment agent of feature 4/1～49/1;
(in the formula, R
1The alkyl of expression carbon number 1～20 or the thiazolinyl of carbon number 2～20, R
2Expression (EO)
m-(PO)
n(in the formula, E represents that vinyl, P represent that propenyl, m represent 5～20 integer, and n represents 0 or 1～10 integer), R
3Expression hydrogen atom or SO
3M (in the formula, M represents hydrogen atom, alkali metals ion or ammonium ion), R
4Expression hydrogen atom, the alkyl of carbon number 1～4 or the thiazolinyl of carbon number 2～4).
(E) solid shape divides ratio that the solid shape to (D)+(E) divides to be advisable at 10～40 weight %, the second-order transition temperature of composition (A) is to be advisable-40～0 ℃ scope, composition (B) is advisable with Resins, epoxy, and composition (B) is suitable especially with the Resins, epoxy that has the epoxy group(ing) more than three in a part.
The present invention relates to again has the first layer in the chromium metal 3～100mg/m that converts on the surface of metallic substance
2Chromic salt by rete, above-mentioned metallic substance use surface treatment agent, drying of the coating second layer also given the about 0.3～3.0g/m of formation
2The resin coating layer be the surface-treated metal plate of feature.
Below describe technology contents of the present invention in detail.
First feature of the present invention is for cooperating the resin of suitable kind as base resin with certain weight ratio.As for resin, necessity of making the isostatic structure of taking solidity to corrosion, wear resistant, resistance to chemical reagents is arranged.Therefore, for using (A) urethane resin and/or acrylic ester resin, this resin is for being dissolved or dispersed in this metal material with in the property surface treatment agent in the present invention.
Urethane resin used in the present invention is made by the raw material with polyhydroxy reactant, polymeric polyisocyanate composition, carboxylic acid composition and active hydrogen compound structure side more than three for adopting.
As for polyhydroxy reactant, can list by ethylene glycol, Diethylene Glycol, triethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, six methylene glycol, Hydrogenated Bisphenol A, dihydroxyphenyl propane, TriMethylolPropane(TMP), the oxyethane of low-molecular-weight polyvalent alcohol such as glycerine and/or propylene oxide adduct, polyoxyethylene glycol, polypropylene glycol, the polyethylene/polypropylene glycol, polycaprolactone polyol, polyolefin polyhydric alcohol, the polyether glycol of polybutadiene polyol etc., these polyvalent alcohols and succsinic acid, the amido pentanedioic acid, hexanodioic acid, sebacic acid, xylyl alcohol, m-phthalic acid, terephthalic acid, reaction between many alkali base acid of first bridge tetrahydrochysene phthalic acid etc. and getting, terminal has the many glycol of polyester of hydroxyl etc.
As for the polymeric polyisocyanate composition, can enumerate: aliphatics, ester ring type and aromatic poly-isocyanate, also can enumerate: four methylene vulcabond, six methylene vulcabond, rely the amino acid vulcabond, hydrogenation dimethylbenzene two isocyanic acids, 1, the 4-ring is stretched hexyl diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, 2,4 '-dicyclohexyl methane diisocyanate, different Buddhist is ketone two isocyanide esters, 3,3 '-dimethoxy-4 ', 4 '-biphenyl diisocyanate, 1, the 5-vulcabond, 1,5-tetrahydrochysene vulcabond, 2,4-first phenylene vulcabond, 2,6-first phenylene vulcabond, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, stretch phenyl diisocyanate, stretch the xylyl vulcabond, tetramethyl-is stretched xylyl vulcabond etc.Wherein adopting four methylene vulcabond, six methylene vulcabond, relying amino acid vulcabond, hydrogenation to stretch Xylene Diisocyanate, 1, the 4-ring is stretched hexyl vulcabond, 4,4 '-dicyclohexyl methane diisocyanate, 2,4 '-dicyclohexyl methane diisocyanate, different Buddhist are the situation of the polymeric polyisocyanate of the fat of ketone two isocyanide esters etc. or ester ring type, especially can get solidity to corrosion, tunicle that resistance to chemical reagents is superior.
As for the carboxylic acid composition, can enumerate: 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, 2,2-dihydroxymethyl valeric acid etc.
As for the compound bearing active hydrogen that has more than three, can list: trimeric cyanamide, diethylenetriamine, TriMethylolPropane(TMP), season the eleventh of the twelve Earthly Branches tetrol, glycerol, and these oxyethane and/or propylene oxide adduct etc.
When making urethane resin, look in case of necessity can add usually used two compound bearing active hydrogen (chain lengthening agent) that have again again.As for this chain lengthening agent, can list: ethylene glycol, propylene glycol, neopentyl glycol, 1, the polyalcohols of 6-hexylene glycol or these ethylene oxide adduct and/or propylene oxide adduct etc., ethylene glycol, propylene glycol, six methylene diamines, stretch the phenyl diamines, stretch diphenyl diamine, two amido ditans, two amido dicyclohexyl methyl hydrides, hexahydro-pyrazine, 2-methyl hexahydro-pyrazine, different Buddhist are amine of ketone diamines, succsinic acid two acyl callositys, hexanodioic acid two acyl callositys, phthalic acid two acyl callositys etc. etc.
The usage quantity of urethane resin raw material used in the present invention, to urethane resin 100 weight parts, be polyhydroxy reactant 30～70 weight parts, be preferably 35～65 weight parts, polymeric polyisocyanate composition 20～50 weight parts, be preferably 25～40 weight parts, carboxylic acid composition's 0.5～1.0 weight part, be preferably 1～8 weight part, contain compound 0.1～5 weight part of active hydrogen more than three, be preferably 0.2～3 weight part.The usage quantity of the chain lengthening agent when using again to urethane resin 100 weight parts, is 1～15 weight part, is preferably 3～10 weight parts.
Manufacture method as for urethane resin used in the present invention is not given special restriction, can adopt known method, but is fabricated to suitable with widely used prepolymer method on technical scale.At prepolymer method, when reaction inertia and with the bigger organic solvent of the avidity of water in use polyvalent alcohol, polymeric polyisocyanate composition, carboxylic acid composition and have the active oxygen more than three the compound reaction and polymkeric substance, be scattered in the aqueous solution that contains neutralizing agent and chain extension agent, produce urethane resin.
As for above-mentioned organic solvent, can enumerate two acetone, methylethylketone, diox, tetra oxygen furyl, N-N-methyl-2-2-pyrrolidone N-, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), vinyl acetic monomer etc.As for neutralizing agent, can enumerate: inorganic alkali such as the organic amine of Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, N methyldiethanol amine, trolamine etc., sodium hydroxide, potassium hydroxide, ammonia again.
Molecular weight as for the urethane resin of gained does not give special restriction, but to be advisable more than 5,000.
Secondly, acrylic ester resin used in the present invention makes (methyl) vinylformic acid for meaning, with this (methyl) vinylformic acid have the two key bonds of different ethene monomer and multipolymer.
As for relevant monomer; can list: maleic acid; MALEIC ANHYDRIDE; Ba Dousuan; Yi Kang acid; along or methylmaleic acid; TRANSCINNAMIC ACID; vinylformic acid 2-hydroxyethyl (methyl) ester; (methyl) vinylformic acid-2 hydroxypropyl ester; (methyl) vinylformic acid 3-hydroxypropyl ester; (methyl) vinylformic acid 2-hydroxyl butyl ester; (methyl) vinylformic acid 3-hydroxyl butyl ester; (methyl) vinylformic acid 4-hydroxyl butyl ester; 2-hydroxyethyl (methyl) allyl ether; 3-hydroxypropyl (methyl) allyl ether; 4-hydroxybutyl (methyl) allyl ether; vinyl carbinol; glycidyl methacrylate; vinylformic acid 2-(1-azacycloalkyl) ethyl ester; vinyltrimethoxy silane; the vinyltriethoxysilane allyl glycidyl ether; the methacrylic acid imidohydrine; acryloyl morpholine; N-methylol (methyl) acrylamide; N-methoxymethyl (methyl) acrylamide; N-ethoxyl methyl (methyl) acrylamide; N-butoxymethyl (methyl) acrylamide; (methyl) acrylamide; N-methyl (methyl) acrylamide; N, N-dimethyl (methyl) acrylamide; N-dimethyl amido propyl group (methyl) acrylamide; vinyl formate; vinyl-acetic ester; vinyl butyrate; vinyl acrylate; vinylbenzene; alpha-methyl styrene; tributyl vinylbenzene; Vinyl toluene; (methyl) propylene; the TRANSCINNAMIC ACID nitrile; (methyl) propenyloxy group ethyl phosphonic acid ester; two (methyl) propenyloxy group ethyl phosphonic acid ester; (methyl) propenyloxy group ethylphenyl acid phosphoric acid ester etc.
(methyl) acrylic acid usage quantity to acrylic ester resin 100 weight parts used in the present invention, is preferably 1～20 weight part, with 2～15 weight parts for more suitable.
Manufacture method as for acrylic ester resin used in the present invention is not given special restriction, but make the tensio-active agent that is known as emulsifying agent and monomer is dispersed in the water and make monomer become the emulsion polymerization method that emulsified state Hou is carried out polyreaction, monomer is scattered in fully or hardly in the solvent of dissolved monomer (for example water) and adopt and be insoluble in solvent and dissolve in monomeric polymerization starter the method for using on the industrial foundation of the suspension polymerization that carries out polyreaction in the monomeric water droplet that has suspended etc. is advisable.
Again, the molecular weight of acrylic ester resin used in the present invention does not give special qualification, but with the situation that gel infiltration form and aspect chromatography is measured, is advisable with about 10,000～1,000,000.
(A) used in the present invention resin is advisable at-40～0 ℃ with second-order transition temperature, with-40～-5 ℃ for more suitable.Second-order transition temperature is-40 ℃ of low situations, and the anti-folded viscosity (antiblocking) of the tunicle of gained is inferior, so improper.Again, the tunicle rerum natura of resin is that to have with the second-order transition temperature be the tendency that boundary has bigger variation.Usually, though the temperature that the goods of the processing Hou that is shaped can give processing is 10～50 ℃ scope, yet the situation that second-order transition temperature is arranged in this temperature range, because the temperature difference, the tunicle rerum natura of resin can cause variation, and it is higher that tunicle anti-has the inferior possibility of scar.Moreover second-order transition temperature surpasses 50 ℃ situation and since tunicle make the film reduction, so necessity of the drying temperature of raising treatment agent is arranged.Form waste economically.Therefore, the second-order transition temperature of resin is advisable to be located in-40～0 ℃ the scope.
Secondly, the measuring method of the second-order transition temperature of resin is described, when measuring second-order transition temperature, adopt determinator: the smart mechanism of (thigh) Japan is made the Rheographsolid S-1 of manufacturing, test piece: adopt film at 30 minutes thickness of 100 ℃ of dryings, 100 μ m, width 8mm, length 30mm, 100Hz measures in frequency, is asked for by the weight break point of elastic loss rate.
In the present invention, for bringing into play the characteristic of (A) resin, and cooperate (B) solidifying agent.As for (B) used in the present invention solidifying agent, with isocyanate compound, azepine propane compounds, epoxy tree oxygen is advisable, with Resins, epoxy that the epoxy group(ing) more than three is arranged in a part for more suitable.Because resin used in the present invention is owing to have carboxyl, thus the reaction between the functional group of carboxyl and solidifying agent (isocyanate group, ethylenimine base, epoxy group(ing) etc.) and the structure of resin can form three-dimensional mesh structure, be significantly by film properties and improve.As for relevant Resins, epoxy, can enumerate phenolic resin varnish type epoxy resin, by the compound with the H base more than three and the reaction between Epicholorohydrin and Resins, epoxy etc.Again, the molecular weight of above-mentioned Resins, epoxy used in the present invention does not give special restriction, but the situation of measuring with gel infiltration form and aspect chromatography, to be advisable below 3,000.
At above-mentioned Resins, epoxy in aqueous surface-treating agent of the present invention, to be dissolved or dispersed in the water.
(A) urethane resin used in the present invention and/or acrylate be resin and (B) the solid shape branch anharmonic ratio (A)/(B) between solidifying agent be advisable with 4/1～49/1, with 10/1～10/1 for more suitable.(A)/(B) ratio is less than 4/1 o'clock, (A) to fail performance special for resin, and again, unreacted solidifying agent is residual, and for reaching plastic role, solidity to corrosion can reduce, and improper.The ratio of (A)/(B) surpasses at 49/1 o'clock on the other hand, the fiting effect shortcoming of solidifying agent, and failing to obtain can gratifying solidity to corrosion.
The solid shape of the composition of aqueous surface-treating agent of the present invention (A)+(B) is divided the ratio of the solid shape branch (to call full shape branch admittedly in the following text) to (A)+(B) (C)+(D)+(E), need be 50～95 weight %, is advisable with 60～85 weight %.This ratio is during less than 50 weight %, and the water tolerance of tunicle itself can reduce, so and unsuitable.On the other hand, if this ratio is when surpassing 95 weight %, and the solidity to corrosion that has the scar part can reduce, so not good.
(C) used in the present invention silicon dioxide granule does not give special restriction in particle diameter, shape, kind, but relevantly with particle diameter is advisable with the scope at 3～30nm.Silicon dioxide granule is for to be scattered in the water in aqueous surface-treating agent of the present invention.Silicon dioxide granule is required to be 3～40 weight %, to be advisable at 10～30 weight % to the ratio that full shape is admittedly divided.This ratio is less than 3 weight % the time, and corrosion proof raising effect lacks, and when surpassing 40 weight % on the other hand, the binding agent effect of resinous principle (A) diminishes, and solidity to corrosion reduces, so and unsuitable.
(D) used in the present invention polyethylene wax gives cooperation for the anti-level that has scar is improved, and its median size 0.01～0.2 μ m is advisable with 0.05～0.18 μ m.Generally speaking, as the frictional coefficient of oilness index, the tendency of step-down when having the wax particle diameter to become big.Yet this frictional coefficient and the anti-scar that has might not be consistent, and the relation between slip number of times (or sliding distance) and frictional coefficient is more important.The inventor etc. find to become 0.01～0.2 μ m by the median size of setting wax through examining the median size of wax and the result of the relation between the slip number of times meticulously, can get the superior anti-scar that has.The median size of wax is for the melt viscosity that makes wax can disperse, so the performance of the machinery that is used influences.Therefore, the median size of wax is used the machinery of superior performance during less than 0.01 μ m because of needs, also uneconomical on cost, on the other hand, when surpassing 0.2 μ m, become easily when sliding by the outstanding wax in tunicle surface and to take off, the continuous sliding of result can reduce, and improper.
And, in the present invention, to the molecular weight of (D) polyethylene wax, fusing point do not give not Xian Zhi, but acid number is advisable with 5～50 scope, the scope with 10～30 is preferable.Acid number was less than 5 o'clock, and wax and resin mix hardly, so when forming tunicle, wax can be oriented on the tunicle surface fully, causes the anti-reduction that has scar and coating tack, and improper.On the other hand, acid number surpasses at 50 o'clock, the wetting ability grow of wax, so the oilness of the institute of wax tool own reduces, the anti-scar that has can reduce, so and improper.
(E) used in the present invention dispersion agent is the compound with aforementioned formula (I) expression.
R in above-mentioned
1For the alkyl of carbon number 5～20 or the thiazolinyl of carbon number 2～5 are advisable, m is that 8～20 integer is advisable, and n is that 0 or 1～5 integer is advisable R
3Be hydrogen atom or SO
3NH
4Be advisable.R
4For the thiazolinyl of hydrogen atom or carbon number 2～4 is advisable.
(D) used in the present invention polyethylene wax is generally the water dispersion that makes as adopting (E) dispersion agent and giving preparation.Dispersing method to polyethylene wax does not give special restriction, if get final product according to industrial used method.
And the median size of aforesaid (D) polyethylene wax is the value in this water dispersion.
(E) it is that 5～40 weight % are advisable that solid shape is divided the ratio to the solid shape branch (that is solid shape branch (D)+(E)) of above-mentioned water dispersion, with 5～30 weight % for more suitable.Aforementioned proportion is less than 10 weight % the time, and the water tolerance of the tunicle of the aqueous surface-treating agent gained of employing gained can reduce, and unsuitable.
Above-mentioned water dispersion is to the full ratio of shape branch (being the solid shape branch of composition (A)+(B)+(C)+(D)+(E)) admittedly of aqueous surface-treating agent of the present invention, the proportional meter that divides with the solid shape of (D)+(E), be required to be 2～20 weight %, be advisable with 3～15 weight %, with 3～10 weight % for more suitable.This ratio is during less than 2 weight %, and the anti-effect of improving that has scar lacks, when surpassing 20 weight % on the other hand, on be coated with coating and can reduce, and unsuitable.
In aqueous surface-treating agent of the present invention, make and contain and to form uniform tunicle and the tensio-active agent that is known as wet moistening property rising agent of usefulness in coated surface, or improve weldability and the conductive material of usefulness, improve appearance design and the tinting pigment of usefulness, improve and make film and the solvent of usefulness etc. also can as composition arbitrarily.
Mentioned component (A), (B), (C) and water dispersion (i.e. (D)+(E)), and, can get metallic substance use surface treatment agent of the present invention by above-mentioned any composition being mixed in water and making dissolving, dispersion.The interpolation order of composition is not given special qualification, for example can adopt propeller-type mixer etc. but mix, and it is more suitable to be undertaken by stirring.
The aqueous surface-treating agent of the present invention of gained, in the scope of 5～50 weight %, being advisable with solid shape branch concentration, with in the scope of 5～40 weight % for more suitable.Gu when shape was divided concentration less than 5 weight %, time of drying can be elongated, and improper.On the other hand, Gu when shape branch concentration surpassed 50 weight %, the viscosity height of treatment agent itself caused the misgivings of obstacle in the processing.
As for the metallic substance (starting material) of coating aqueous surface-treating agent of the present invention, can enumerate: cold-rolled steel sheet, zinc-based metal plated steel sheet, to aluminize be metal sheets such as steel plate, aluminium sheet.
Aqueous surface-treating agent of the present invention, also can directly coat relevant metallic substance, but for enabling to give full play to effect of the present invention, at first utilize the chromate treating that is undertaken by common method, form the chromic salt tunicle, be coated with aqueous surface-treating agent of the present invention thereon and form resin coating and get final product.
As for chromate treating, the favourable electrolytic chromate that forms the chromic salt tunicle with electrolysis, reaction between utilization and starting material makes the formation tunicle, the response type chromic acid salt of the treatment solution that its Hou flush away is unnecessary, treatment solution is coated on the object being treated the dry application type chromic salt that forms tunicle that makes under will not washing, and the present invention also can adopt any treatment process.
In utilizing on the formed substrate tunicle of above-mentioned chromate treating, at 10～50 ℃ of coating aqueous surface-treating agents of the present invention, give drying by making for 60～200 ℃ at the arrival plate, can form resin coating, as for coating process, can adopt well-established law, for example running roller spreader method, pickling process, electrostatic applications method etc.
Utilize the relevant two-stage to handle and surface-treated metal plate of the present invention because on the surface of metallic substance, have in convert 3～100mg/m of the 1st layer of chromium metal
2Chromic salt by rete, be coated with metallic substance use surface treatment agent of the present invention and the dry 0.3～3.0g/m that makes formation
2The resin coating layer be the surface-treated metal plate of feature as the 2nd layer.Chromic salt by the weight of rete in the chromium metal 3～50mg/m that converts
2Be advisable, with 5～40mg/m
2For more suitable.
The chromium adhesion amount is less than 3mg/m
2The time, lack corrosion proof raising, surpass 100mg/m on the other hand
2The time, corrosion proof raising effect is saturated, and uneconomical.Again, dry resin tunicle amount is less than 0.3g/m
2The time, solidity to corrosion improves effect and not enough, surpasses 3.0g/m
2The time, solidity to corrosion improves effect can be saturated and uneconomical.
Be coated with aqueous surface-treating agent of the present invention and give dry formed resin coating, then surface-treated metal plate, anti-corrosion in planar portions, have scar portion solidity to corrosion and the coating tack is superior.To the coating of coating on the resin coating, do not give special restriction, for example can enumerate: Air drying type trimeric cyanamide alkyd is that coating, baking-type trimeric cyanamide alkyd are that coating, acrylate resin are that coating, ultraviolet curing resin are coating etc.
Embodiment
Below adopt Production Example, embodiment and comparative example, specific description the present invention, this case embodiment says that for supplying the present invention record person is not in order to limit the present inventor.
The making of test plate (panel)
(1) for the examination material
Use the commercially available starting material that show down as supplying the examination material.
. electrogalvanizing steel plate (EG)
Thickness of slab 0.8mm, weight per unit area=20/20 (g/m
2)
. contain the steel plate galvanized (GF) of 5% aluminium
Thickness of slab 0.8mm, weight per unit area=90/90 (g/m
2)
. aluminium sheet (AL)
Thickness of slab 1.0mm, 5182 is
(2) skimming treatment
Carry out skimming treatment with above-mentioned each for Fine cleaner4336 of examination material silicon phosphate-gallate series alkali grease-removing agent (registered trademark: Japanese Parkerizing limited-liability company makes).And handle 2 minutes Hous at concentration 20g/L, 60 ℃ of sprays of temperature cloth, clean with tap water.
(3) substrate treatment
(3-1) response type chromic acid salt chemical surface control (starting material: EG, GF)
Adopt Zinchrome 357 (registered trademark: Japanese Parkerizing limited-liability company makes), carry out spraying for 5 seconds cloth 50 ℃ of liquid temperature and handle, it is air-dry to clean Hou with tap water, the making test plate (panel).
(3-2) application type chromic salt chemistry method surface treatment (starting material: EG, GF)
Adopt Zinchrome 1300AN (registered trademark: Japanese Parkerizing limited-liability company makes),, will not wash down immediately under 200 ℃ air themperature dry 10 seconds and make test plate (panel) with the coating of running roller spreader method.And the arrival temperature of this moment is 100 ℃.
(3-3) response type chromic acid salt is handled (starting material: AL)
Adopt Alchrome713 (registered trademark: Japanese Parkerizing limited-liability company makes), spray cloth 50 ℃ of liquid temperature and handled for 5 seconds, it is air-dry to clean Hou with tap water, the making test plate (panel).
(preparation of aqueous surface-treating agent)
In room temperature, adopting propeller stirrer to stir the resin of table 1 in regular turn, the solidifying agent of table 2, the silicon dioxide granule of table 3, the wax water dispersion of table 4 also gives mixing, add the solid shape of distilled water and adjustment and divide concentration, the aqueous surface-treating agent of the embodiment shown in the preparation table 5 and the aqueous surface-treating agent of the comparative example shown in the table 6.And the wax water dispersion, for the wax shown in the table 4, compound (I) and water full dose are put into autoclave, are heated to 130～140 ℃ of temperature and give stirring and prepared.
(aqueous surface-treating agent is to the coating process of test plate (panel))
Adopt the coating rod spreader,, coat on above-mentioned each test plate (panel), 240 ℃ 10 seconds of air themperature drying each aqueous surface-treating agent of above-mentioned preparation.It is 100 ℃ that this agent arrives plate temperature.And the solid shape concentration that is adjusted into suitable this constituent of change of adhesion amount and the kind of coating rod spreader are given inferior carrying out.
(coated panel performance test)
(1) planarity solidity to corrosion
The situation of EG plate was carried out 240 hours, and the situation of GF plate was carried out 480 hours, and the situation of AL material is carried out 600 hours the salt spray testing of utilizing the JIS-Z2371 regulation, observed white rust erosion situation occurred, assessed according to following benchmark.
＜assessment benchmark 〉
◎: area occupation ratio takes place less than 3% of gross area in the white rust erosion
Zero: white rust erosion take place area occupation ratio gross area more than 3% less than 10%
△: white rust erosion take place area occupation ratio gross area more than 10% less than 30%
*: area occupation ratio takes place at more than 30% of gross area in the white rust erosion
(2) have the solidity to corrosion of scar portion
Test piece is cut into the yardstick of 30mm * 300mm, the pearl that falls test (drop bead test, bead front end 1mmR, bead height 4mm, dice shape dice shoulder 1mmR, pressing 30 ℃ of load 500kg, temperature).As for the slipper of this test piece, the situation of EG material to be carried out 120 hours, the situation of GF material was carried out 240 hours, the situation of AL material was carried out 360 hours, utilize the salt spray testing of JIS-Z2371 regulation, observe white rust erosion situation occurred, assess according to following benchmark.
＜assessment benchmark 〉
◎: area occupation ratio takes place less than 3% of gross area in the white rust erosion
Zero: white rust erosion take place area occupation ratio gross area more than 3% less than 10%
△: white rust erosion take place area occupation ratio gross area more than 10% less than 30%
*: area occupation ratio takes place at more than 30% of gross area in the white rust erosion
(3) coating tack
With melamine alkyd be coating be applied to the baking dry Hou thickness become 25 μ m, 125 the baking 20 minutes.Baking Hou is adopted the test piece through 24 hours, describes 100 Hous of 1mm checker according to the JIS-Z5400 regulation, utilizes the imitative tape stripping of match Lopa Nationality to film, and assesses according to following benchmark.
＜assessment benchmark 〉
◎: peel off, film 100 of remaining numbers that not having films
Zero: few part is filmed and is peeled off 100 of the remaining numbers of filming
△: 95～99 of the remaining numbers of filming
*: film remaining number below 94
Test-results is shown in table 7 and table 8.Adopting the embodiment 1～21 of aqueous surface-treating agent of the present invention, in the planar portions solidity to corrosion, any one that has scar portion solidity to corrosion and a coating tack is well.On the other hand, adopting the comparative example 1～9 of extraneous aqueous surface-treating agent of the present invention, planar portions solidity to corrosion, at least two performances that have scar portion solidity to corrosion and a coating tack are inferior.
Table 1
Embodiment and more used resin
| Resin | The name of an article | The name of manufacturer | Resin system | Glass transition temp | Gu shape is divided concentration | The request scope | Reason |
| A1 | Super flex 107M | The first industrial pharmacy (strain) | Urethane | -40℃ | 25％ | ○ | |
| A2 | Adecarbontighter HUX-580 | Rising sun electrochemical industry (strain) | Urethane | -14℃ | 62％ | ○ | |
| A3 | Primal K-3 | ROHM&HAAS | Acrylate | -27℃ | 46％ | ○ | |
| A4 | Primal NW-1715 | ROHM&HAAS | Acrylate | -6℃ | 44％ | ○ | |
| A5 | VironalMD-1930 | Japan's weaving (strain) | Ester | -10℃ | 30％ | × | The resin system difference |
Table 2
Embodiment and more used stiffening agent
| Stiffening agent | The name of an article | The name of manufacturer | The functional group | Gu shape is divided concentration |
| B1 | Dinacore EX-512 | Negas (long rapids) changes into (strain) | Epoxy | 100％ |
| B2 | Elastron BN-69 | The first industrial pharmacy (strain) | Isocyanic ester | 40％ |
Table 3
Embodiment and more used silicon-dioxide
| Silicon-dioxide | The name of an article | The name of manufacturer | Gu shape is divided concentration |
| C1 | Snowtex-N | Daily output chemical industry (strain) | 20％ |
| C2 | Snowtex-O | Daily output chemical industry (strain) | 20％ |
Table 4
Embodiment and more used wax water dispersion (Gu shape is divided concentration 20%)
| Wax | Compound (I) | Median size μ m | The request scope | |||||||
| Kind *1 | Use level *2 | R1 | R2 | R3 | R4 | Use level *2 | ||||
| M | n | |||||||||
| W1 | Mitsui Chemicals (strain) system Hiwax 4202E acid number 17 | 75 | C 2H 19- | 12 | 0 | -H | -CH＝ CHCH 3 | 25 | 0.08 | ○ |
| W2 | Mitsui Chemicals (strain) system Hiwax 42203A acid number 30 | 95 | C 18H 37- | 20 | 0 | -SO 3NH 4 | -H | 5 | 0.12 | ○ |
| W3 | Mitsui Chemicals (strain) system Hiwax 4202E acid number 17 | 90 | C 8H 17- | 10 | 5 | -H | -H | 10 | 0.15 | ○ |
| W4 | Mitsui Chemicals (strain) system Hiwax 4051E acid number 12 | 80 | CH 2＝ CHCH 2- | 10 | 5 | -H | -H | 20 | 0.15 | ○ |
| W5 | Mitsui Chemicals (strain) system Hiwax 4202E acid number 17 | 85 | C 9H 19- | 12 | 0 | -H | -H | 15 | 0.45 | × *3 |
| W6 | Mitsui Chemicals (strain) system Hiwax NP055 acid number 0 | 90 | C 18H 37- | 20 | 0 | -SO 3NH 4 | -H | 10 | 0.10 | × *4 |
*1:W1～W5 is a polyethylene wax, and W6 is a Poly Propylene Wax.
*2: the numerical value of use level divides weight % for the solid shape that the full shape admittedly to the wax water dispersion is divided.
*3: the kind of grain is outside scope.
*4: the kind of wax is outside scope.
Table 5
The aqueous surface-treating agent that embodiment is used
| The solid shape of aqueous surface-treating agent is divided concentration *1 | (A)/(B) ratio | The solid shape of aqueous surface-treating agent is divided concentration | |||||
| Resin | Stiffening agent | Silicon dioxide granule | The wax water dispersion | ||||
| Aqueous surface-treating agent | 1 | A1(72) | B1(3) | C1(20) | W1(5) | 24.0 | 12.0％ |
| 2 | A2(72) | B1(3) | C1(20) | W1(5) | 24.0 | 12.0％ | |
| 3 | A3(72) | B1(3) | C1(20) | W1(5) | 24.0 | 12.0％ | |
| 4 | A4(72) | B1(3) | C1(20) | W1(5) | 24.0 | 12.0％ | |
| 5 | A1(72) | B2(3) | C1(20) | W1(5) | 24.0 | 12.0％ | |
| 6 | A1(72) | B1(3) | C2(20) | W1(5) | 24.0 | 12.0％ | |
| 7 | A1(82) | B1(3) | C1(10) | W1(5) | 27.3 | 12.0％ | |
| 8 | A1(63) | B1(2) | C1(30) | W1(5) | 31.5 | 12.0％ | |
| 9 | A1(61) | B1(4) | C1(20) | W1(5) | 15.3 | 12.0％ | |
| 10 | A1(80) | B1(2) | C1(10) | W1(8) | 40.0 | 12.0％ | |
| 11 | A1(70) | B1(7) | C1(20) | W1(3) | 10.0 | 12.0％ | |
| 12 | A1(72) | B1(3) | C1(20) | W2(5) | 24.0 | 12.0％ | |
| 13 | A1(72) | B1(3) | C1(20) | W3(5) | 24.0 | 12.0％ | |
| 14 | A1(72) | B1(3) | C1(20) | W4(5) | 24.0 | 12.0％ | |
| 15 | A1(72) | B1(3) | C1(20) | W1(5) | 24.0 | 40.0％ | |
| 16 | A1(72) | B1(3) | C1(20) | W1(5) | 24.0 | 5.0％ | |
*1:() Nei numerical value is the solid shape branch weight % to the full branch of shape admittedly of aqueous surface-treating agent
Table 6
The aqueous surface-treating agent that comparative example is used
| The solid shape of aqueous surface-treating agent is divided concentration *1 | (A)/(B) ratio | The solid shape of aqueous surface-treating agent is divided concentration | Reason | |||||
| Resin | Stiffening agent | Silicon dioxide granule | The wax water dispersion | |||||
| Aqueous surface-treating agent | 17 | A5(72) | B1(3) | C1(20) | W1(5) | 24.0 | 12.0％ | The kind difference of resin |
| 18 | A1(72) | B1(3) | C1(20) | W5(5) | 24.0 | 12.0％ | The particle diameter of wax is outside scope | |
| 19 | A1(72) | B1(3) | C1(20) | W6(5) | 24.0 | 12.0％ | The kind of wax is outside scope | |
| 20 | A1(74) | B1(3) | C1(20) | W1(5) | 74.0 | 12.0％ | (A)/(B) ratio is outside scope | |
| 21 | A1(50) | B2(25) | C1(20) | W1(5) | 2.0 | 12.0％ | (A)/(B) ratio is outside scope | |
| 22 | A1(80) | B1(3) | C2(2) | W1(15) | 26.7 | 12.0％ | Silica volume is less | |
| 23 | A1(48) | B1(32 | C1(45) | W1(5) | 24.0 | 12.0％ | Silica volume is more | |
| 24 | A1(76) | B1(3) | C1(20) | W1(1) | 25.3 | 12.0％ | The wax amount is less | |
| 25 | A1(50) | B1(5) | C1(20) | W1(25) | 10.0 | 12.0％ | The wax amount is more | |
*1:() Nei numerical value is the solid shape branch weight % to the full branch of shape admittedly of aqueous surface-treating agent
Table 7
Embodiment tests level and by film properties
| Starting material | The surface treatment of chromic salt chemistry method | Aqueous surface-treating agent | The coated panel performance | ||||||
| Kind | Adhesion amount *1 mg/m 2 | Kind | Adhesion amount *2 mg/m 2 | Solidity to corrosion | The coating tack | ||||
| Planar portions | Have scar portion | ||||||||
| Embodiment | 1 | EG | Response type | 20 | 1 | 1.0 | ◎ | ◎ | ◎ |
| 2 | EG | Response type | 20 | 2 | 1.0 | ◎ | ◎ | ◎ | |
| 3 | EG | Response type | 20 | 3 | 1.0 | ◎ | ◎ | ◎ | |
| 4 | EG | Response type | 20 | 4 | 1.0 | ◎ | ◎ | ◎ | |
| 5 | EG | Response type | 20 | 5 | 1.0 | ◎ | ◎ | ◎ | |
| 6 | EG | Response type | 20 | 6 | 1.0 | ◎ | ◎ | ◎ | |
| 7 | EG | Response type | 20 | 7 | 1.0 | ◎ | ◎ | ◎ | |
| 8 | EG | Response type | 20 | 8 | 1.0 | ◎ | ◎ | ◎ | |
| 9 | EG | Response type | 20 | 9 | 1.0 | ◎ | ◎ | ◎ | |
| 10 | EG | Response type | 20 | 10 | 1.0 | ◎ | ◎ | ◎ | |
| 11 | EG | Response type | 20 | 11 | 1.0 | ◎ | ◎ | ◎ | |
| 12 | EG | Response type | 20 | 12 | 1.0 | ◎ | ◎ | ◎ | |
| 13 | EG | Response type | 20 | 13 | 1.0 | ◎ | ◎ | ◎ | |
| 14 | EG | Response type | 20 | 14 | 1.0 | ◎ | ◎ | ◎ | |
| 15 | EG | Response type | 20 | 15 | 3.0 | ◎ | ◎ | ◎ | |
| 16 | EG | Response type | 20 | 16 | 0.3 | ○ | ○ | ◎ | |
| 17 | EG | Application type | 20 | 1 | 1.0 | ◎ | ◎ | ◎ | |
| 18 | EG | Response type | 10 | 1 | 1.0 | ◎ | ○ | ◎ | |
| 19 | EG | Response type | 50 | 1 | 1.0 | ◎ | ◎ | ◎ | |
| 20 | GF | Response type | 20 | 1 | 1.0 | ◎ | ◎ | ◎ | |
| 21 | AL | Response type | 20 | 1 | 1.0 | ◎ | ◎ | ◎ | |
*1: chromium metal conversion adhesion amount
*2: dry resin tunicle adhesion amount
Table 8
The test level of comparative example and by film properties
| Starting material | The chromic acid chemical surface control | Aqueous surface-treating agent | The coated panel performance | ||||||
| Kind | Adhesion amount *1 mg/m 2 | Kind | Adhesion amount *2 mg/m 2 | Solidity to corrosion | The coating tack | ||||
| Planar portions | Have the traumatic part | ||||||||
| Comparative example | 1 | EG | Response type | 20 | 17 | 1.0 | △ | × | △ |
| 2 | EG | Response type | 20 | 18 | 1.0 | △ | △ | △ | |
| 3 | EG | Response type | 20 | 19 | 1.0 | △ | △ | × | |
| 4 | EG | Response type | 20 | 20 | 1.0 | △ | △ | △ | |
| 5 | EG | Response type | 20 | 21 | 1.0 | △ | △ | △ | |
| 6 | EG | Response type | 20 | 22 | 1.0 | △ | × | △ | |
| 7 | EG | Response type | 20 | 23 | 1.0 | △ | × | △ | |
| 8 | EG | Response type | 20 | 24 | 1.0 | △ | × | △ | |
| 9 | EG | Response type | 20 | 25 | 1.0 | △ | △ | △ | |
As above-mentioned, coat with on the surface that imposes the chromate treating metal sheet and give drying by aqueous surface-treating agent of the present invention, can get the planar portions solidity to corrosion, have scar portion solidity to corrosion and the superior surface-treated metal plate of coating tack.
Claims (5)
1. metallic substance use surface treatment agent, the polyethylene wax, (E) that it is characterized in that containing (A) urethane resin and/or acrylic ester resin, (B) solidifying agent, (C) silicon dioxide granule, (D) averaged particles 0.01～0.2 μ m as dispersion agent with following formula (I)
[R in the formula
1The alkyl of expression carbon number 1～20 or the thiazolinyl of carbon number 2～20, R
2Expression (EO) m-(PO) n (E represents that vinyl, P represent that propenyl, m represent that 5～20 integer, n represent 0 or 1～10 integer in the formula), R
3Expression hydrogen atom or SO
3M (in the formula M represent hydrogen atom, alkali metals from or ammonium ion), R
4The expression hydrogen atom, the thiazolinyl of the alkyl of carbon number 1～4 or carbon number 2～4] expression compound and water, composition (A) reaches (B) for being dispersed or dissolved in water separately, composition (C) reaches and (D) is scattered in water, composition (E) is dissolved in water, whole shape branches admittedly to composition (A)～(E), (A)+(B) ratio that solid shape is divided is 50～95 weight %, (C) ratio that solid shape is divided is 3～40 weight %, (D)+(E) ratio that solid shape is divided is 2～20 weight %, (A)/(B) solid shape divides weight ratio 4/1～49/1, wherein the particle diameter of (C) is 3～30nm, and second-order transition temperature (A) is in-40～0 ℃ scope.
2. metallic substance use surface treatment agent according to claim 1, wherein the solid shape branch of (E) is 5～40 weight % to the ratio of the solid shape branch of (D)+(E).
3. according to the metallic substance use surface treatment agent described in claim 1 or 2, wherein composition (B) is a Resins, epoxy.
4. metallic substance use surface treatment agent according to claim 3, wherein composition (B) be one minute in have the epoxy group(ing) more than three Resins, epoxy.
5. a surface-treated metal plate on the surface of metallic substance, has in chromium metal conversion 3～100mg/m
2Chromic salt by rete as the first layer, and on the first layer each described metallic substance use surface treatment agent and give drying and form and have 0.3～3.0mg/m in the coating claim 1～5
2The resin coating layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP070470/1999 | 1999-03-16 | ||
| JP07047099A JP3869577B2 (en) | 1999-03-16 | 1999-03-16 | Water-based surface treatment agent for metal material and surface-treated metal plate |
| JP070470/99 | 1999-03-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1266872A CN1266872A (en) | 2000-09-20 |
| CN1172996C true CN1172996C (en) | 2004-10-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001031155A Expired - Fee Related CN1172996C (en) | 1999-03-16 | 2000-03-16 | Water surface treatment agent for metal material and furface treated metal plate |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP3869577B2 (en) |
| KR (1) | KR20000062848A (en) |
| CN (1) | CN1172996C (en) |
| CA (1) | CA2366516A1 (en) |
| TW (1) | TW554019B (en) |
| WO (1) | WO2000058086A1 (en) |
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| EP1479950B1 (en) | 2002-02-27 | 2019-07-31 | Nsk Ltd. | Rolling bearing |
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| CN103360839B (en) * | 2012-03-31 | 2015-10-28 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of metal protection coating and uses thereof and hot-dip metal plated material |
| CN103360815B (en) * | 2012-03-31 | 2016-04-06 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of metal protection coating and uses thereof and hot-dip metal plated material |
| CN102757721B (en) * | 2012-07-12 | 2015-09-23 | 上海盖特建筑技术咨询有限公司 | A kind of protective material for the protection of corrosion art steel plate |
| CN105073921B (en) * | 2013-04-01 | 2018-04-06 | Dic株式会社 | Aqueous surface-treating agent and the article for having used the aqueous surface-treating agent |
| JP6302367B2 (en) | 2014-06-24 | 2018-03-28 | ニチアス株式会社 | Coating agent |
| CN110205008A (en) * | 2019-05-24 | 2019-09-06 | 上海丰野表面处理剂有限公司 | A kind of chromium-free fingerprint-resistant inorganic agent |
| CN112280452B (en) * | 2020-10-29 | 2021-11-02 | 蓝帆新材料技术(广州)有限公司 | Chromium-free fingerprint-resistant coating composition for galvanized steel sheet |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0104679B1 (en) * | 1982-09-01 | 1989-08-09 | Unilever N.V. | Abrasive agglomerates for use in scouring cleaning compositions |
| US5798136A (en) * | 1997-05-19 | 1998-08-25 | Eastman Kodak Company | Simultaneous coatings of wax dispersion containing lubricant layer and transparent magnetic recording layer for photographic element |
-
1999
- 1999-03-16 JP JP07047099A patent/JP3869577B2/en not_active Expired - Lifetime
-
2000
- 2000-02-25 TW TW089103302A patent/TW554019B/en not_active IP Right Cessation
- 2000-03-13 KR KR1020000012389A patent/KR20000062848A/en not_active Application Discontinuation
- 2000-03-16 CA CA002366516A patent/CA2366516A1/en not_active Abandoned
- 2000-03-16 CN CNB001031155A patent/CN1172996C/en not_active Expired - Fee Related
- 2000-03-16 WO PCT/US2000/006897 patent/WO2000058086A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| TW554019B (en) | 2003-09-21 |
| WO2000058086A8 (en) | 2001-05-25 |
| KR20000062848A (en) | 2000-10-25 |
| CN1266872A (en) | 2000-09-20 |
| CA2366516A1 (en) | 2000-10-05 |
| WO2000058086A1 (en) | 2000-10-05 |
| JP3869577B2 (en) | 2007-01-17 |
| JP2000265111A (en) | 2000-09-26 |
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