CN104233243B - Aqueous metal surface treatment agent - Google Patents
Aqueous metal surface treatment agent Download PDFInfo
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- CN104233243B CN104233243B CN201410251078.0A CN201410251078A CN104233243B CN 104233243 B CN104233243 B CN 104233243B CN 201410251078 A CN201410251078 A CN 201410251078A CN 104233243 B CN104233243 B CN 104233243B
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Abstract
The present invention provides an aqueous metal surface treatment composition that is provided with a fur membrane with excellent processing, corrosion resistance, does not contain a chromium compound. An aqueous metal surface treatment agent is characterized, according to solids content, by comprising 100 parts by quality of at least one aqueous organic resin (A) among urethane resin, epoxy resin, acrylic resin and polyolefin resin, 100 parts by quality of a resin solid based on the aqueous organic resin (A), 0.1 to 40 parts by quality of a hydrolyzing condensation compound comprising silane coupling agent containing an epoxy group (a) and alkoxysilane compound (b) such as trialkyl alkoxysilane, and 5.0 to 50 parts by quality of colloidal silicon dioxide (C).
Description
Technical field
The present invention relates to a kind of aqueous metal surface treatment compositions, use the aqueous metal surface treatment compositions
Metal surface treating method and the surface-treated metal plate of the surface treating composition is used, the aqueous metal surface is processed
Compositionss are the aqueous metal surface treatment compositions of the nuisanceless type not comprising chromium, alternative conventional chromic acid salt treatment and
It is parkerized, excellent epithelium and the excellent storage stabilities such as processability, corrosion resistance, upper painting film adhesion can be obtained.
Background technology
In the past, in order to improve the corrosion resistance of metal surface, chromic acid salt treatment and phosphate treated are typically carried out.But it is near
Nian Lai, the toxicity of chromium become social problem.There are using the surface treatment method of chromate：Chromate cigarette in treatment process
The problem of dispersing of dirt, need to expend very big expense and because chromic acid is molten from Passivation Treatment epithelium in terms of sewage treatment equipment
Go out and caused problem etc..
In addition, in terms of phosphate treated, generally carrying out zinc phosphate class, the surface treatment of iron phosphate class, but being in order at tax
Corrosion proof purpose is given, after phosphate treated, chromic acid is generally utilized and is carried out cleaning treatment, thus there are asking for chromium process
Topic, and in order to carry out the etching of metal surface, thus there are and react with fluorine compounds being mixed in phosphate treated agent etc.
The wastewater treatment of accelerator and/or metal ion etc. and by metal ion from the caused sludge of the dissolution of metal to be treated
The problems such as process.
Processing method in addition to as processing except chromic acid salt treatment and/or zinc phosphate, it is proposed that following method etc.：
(1) processed by the aqueous solution containing aluminium dihydrogen phosphate, the surface that then temperature at 150～550 DEG C is heated
Processing method (referring for example to patent documentation 1 etc.).
(2) with the method processed containing tannin aqueous acid (referring for example to patent documentation 2 etc.).
But, in the method for (1), thereon in the case of coating process, the adhesion of coating is insufficient, in (2)
In method, the problem of corrosion resistance difference is there are.
In addition, for example in patent documentation 3, as the surface treatment overlay film with the film like that thickness is less than several μm
A kind of zinc class plated steel sheet, it is known to cationic electrodeposition coating Rustproof Steel Plate, which passes through with zinc class plated steel sheet as base material,
Chromate overlay film is formed on, organic composite silicate overlay film is further formed on and is obtained as the superiors, the sun
Cationic electrodeposition application Rustproof Steel Plate has the performance of processability and corrosion resistance excellent.But, as the Rustproof Steel Plate has
There is a chromate overlay film, thus with aforementioned similarly, the presence of having by chromate ion and caused safety and sanitation problem.In addition, from this
Rustproof Steel Plate removes the corrosion resistance of steel plate obtained from chromate overlay film and can be greatly reduced.
Patent Document 4 discloses a kind of surface treated steel plate, its by using comprising cationic polyurethane resin,
The surface treatment liquid of specific phenolic resin, silane coupler, titanium compound and specific sour or its salt, to zinc class plating
Steel plate or aluminum class plated steel sheet are surface-treated and are obtained.But, the planar portions corrosion resistance of the surface treated steel plate, processing department
The performance balance of the characteristics such as corrosion resistance, anti-finger printing, application adhesion, processability, resistance to water is not necessarily good.
The water-based coating agent of following one-pack type is Patent Document 5 discloses, wherein, using by aqueous dispersion tree
In fat, compounding silica granule and the water-based coating agent of steel plate obtained from organo titanate compounds, anti-corrosion so as to obtain
The water-based coating agent of the excellent one-pack type of property, solvent resistance, alkali resistance, application adhesion, epithelium adhesion, bath stability.
In addition, a kind of non-chromium class surface treated steel plate is Patent Document 6 discloses, wherein, by using with ormal weight
Containing specific resin compound (A), with the cationic sense selected from primary amino radical～tertiary amino and quaternary ammonium salt base
The cationic polyurethane resin (B) of group, the silane coupler with specific reactive group (C), specific oxygen compound
(E) surface conditioning agent, and obtain corrosion resistance excellent and excellent non-of anti-finger printing, resistance to blackening and application adhesion
Chromium class surface treated steel plate.
But, with regard to the technology described in patent documentation 5 or 6, which there are the surface if resin is anionic species
The alkali resistance that processes epithelium is weak, if cationic is then surface-treated the weak such shortcoming of acid resistance of epithelium, and purposes
It is restricted.
Patent Document 7 discloses following technologies：Using by containing organic resin, silane in lithium silicate aqueous solution
Treatment fluid obtained from coupling agent, kollag, is processed to metal sheet surface.But as inorganic constituentss easily form hard
Macromolecule, thus the corrosion resistance of the processing department of Bending Processing etc. becomes insufficient.Further, since containing more alkali metal,
Thus in the case of forming painting film on the surface treated steel plate, the upper secondary adhesion for applying film is inferior.
So cannot all be obtained using any one method and can replace surface conditioning agent as chromate epithelium, this is existing
Shape, people are urgently expected to develop the surface conditioning agent and surface treatment method that can replace chromate epithelium.
Patent documentation 1：Japanese Patent Publication 53-28857 publication
Patent documentation 2：Japanese Unexamined Patent Application 51-71233 publication
Patent documentation 3：Japanese Unexamined Patent Application 60-50180 publication
Patent documentation 4：Japanese Unexamined Patent Publication 2003-105562 publications
Patent documentation 5：Japanese Unexamined Patent Publication 2001-353750 publications
Patent documentation 6：Japanese Unexamined Patent Publication 2003-105562 publications
Patent documentation 7：Japanese Unexamined Patent Publication 11-58599 publication
The content of the invention
The problem for solving is wanted in invention
It is an object of the invention to provide a kind of aqueous metal surface treatment compositions, having used the surface treating composition
Metal surface treating method and obtained from the surface treating composition is surface-treated surface-treated metal
Plate, the aqueous metal surface treatment compositions do not contain chromium compound, you can solve problems of the prior art, and storage is steady
It is qualitative excellent, and can form that corrosion resistance, molding processibility, coating adhesion are excellent in metal material surface, and have resistance to
Acid, the surface treatment epithelium of alkali resistance.
For solution to problem
The present inventor etc. are had made intensive studies to solve above-mentioned problem, as a result find the following fact, so that can be real
Existing above-mentioned purpose, completes the present invention：Using by containing epoxy radicals with ormal weight compounding respectively in specific aqueouss organic resin
Silane coupler and alkoxy silane (condensation substance) hydrolysis cocondensation and colloidal silica and the aqueouss that formed are golden
Metal surface treatment compositions, so that the excellent storage stability of surface treating composition, and cause to be surface-treated group by this
The various performances such as the corrosion resistance of epithelium that compound is formed, molding processibility are extremely excellent.
So, the present invention provides a kind of water-based metal-surface-treating agent, it is characterised in which is according to solid content
And contain that (A) is selected from the group being made up of polyurethane resin, epoxy resin, acrylic resin and vistanex to
A kind of few 100 mass parts of aqueouss organic resin and
Based on 100 mass parts of resin solid content of the aqueouss organic resin (A), contain according to solid content：
(B) silane coupler (a) containing epoxy radicals and at least one alkoxysilane compound containing trialkylsilyl group in molecular structure shown in following formula [1]
And/or 0.1～40 mass parts of hydrolytic condensate of the condensation substance (b) of the alkoxysilane compound containing trialkylsilyl group in molecular structure
(R)4-n-Si-(X)n [1]
(in formula, R represents the alkyl of the carbon number 1～18 that can be replaced by the substituent group without reactivity, and X represents alkane
Epoxide, n represent 1～3 integer), and 5.0～50 mass parts of (C) colloidal silica.
In addition, the present invention provides a kind of metal surface treating method, it is characterised in that by the process of above-mentioned aqueous metal surface
Compositionss coat metal coated article, and are dried.
Further, the present invention provides a kind of surface-treated metal plate, and which is by using above-mentioned aqueous metal surface treatment group
Compound carries out surface treatment to the surface of metal coated article and forms.
The effect of invention
The aqueous metal surface treatment compositions of the present invention are free from the surface treating composition of chromium compound, and can be
It is excellent that metal material surface forms molding processibility, the coating adhesions such as the corrosion resistance of planar portions and/or processing department, deep-draw processability
It is different, and with acid resistance, alkali resistance, the balancing good of all performances surface treatment epithelium, and be excellent storage stability
Compositionss.
The surface-treated metal plate of the present invention is to metal quilt by using above-mentioned aqueous metal surface treatment compositions
The surface of coat be surface-treated obtained from surface-treated metal plate, be the excellent surface treatment of above-mentioned various performance balances
Metallic plate.The surface-treated metal plate of the present invention can be used in the state of no application coating, or also can be by applying
Fill coating and use.
In addition, the aqueous metal surface treatment compositions of the present invention, being surface-treated using the treatment compositions and being obtained
The surface-treated metal plate for arriving does not contain chromium compound, so as to overcome problem environmentally.
Specific embodiment
The present invention aqueous metal surface treatment compositions as must composition and contain (A) aqueouss organic resin, (B) and contain
The hydrolytic condensate of the condensation substance of the silane coupler and alkoxysilane compound containing trialkylsilyl group in molecular structure or the alkoxysilane compound containing trialkylsilyl group in molecular structure of epoxy radicals,
And (C) colloidal silica.
Each composition in the metal surface treating composition of the following narration present invention.
Aqueouss organic resin (A)
As the aqueouss organic resin of (A) composition of metal surface treating composition of the present invention, preferably from by polyurethane
At least one aqueouss organic resin selected in the group of resin, epoxy resin, acrylic resin and vistanex composition, it is excellent
Elect the aqueouss organic resin for being dissolved in or being scattered in water as, generally provided with the form of aqueous solution or aqueous dispersions.
As above-mentioned polyurethane resin, the polyhydric alcohol such as polyether polyol, PEPA, polycarbonate polyol are included
With the condensation polymer of aliphatic, ester ring type or aromatic polyisocyanate etc..
Method as being stably dispersed or dissolved in polyurethane resin in water, such as using following methods.Row
Enumerate：(1) hydroxyl, amino, carboxyl isoiony group are imported by the side chain to polyether polyols or end, so as to give
Hydrophilic and by self emulsifying and be dispersed or dissolved in the method in water；(2) by using emulsifying agent and mechanical shearing
Power, the polymer that reaction is terminated or by with end-capping reagents such as oxime, alcohol, phenol, mercaptan, amine, sodium sulfitees by terminal isocyanate
Perester radical blocked obtained from polymer, the method being forcibly dispersed in water；(3) will be with terminal isocyanate group
Carbamate prepolymer mixed with water, emulsifying agent and elongation agent, using mechanical shear stress while being disperseed
Change and the method for producing high-molecular；(4) using water-soluble polyol as Polyethylene Glycol as many of polyurethane primary raw material
First alcohol, makes water-soluble polyurethane so as to method for being dispersed or dissolved in water etc..In addition, the molecular weight of polyurethane resin
It is not particularly limited.10,000～1,000,000, preferably 50,000～500,000 is preferably according to weight average molecular weight.
As the commercially available product of above-mentioned polyurethane resin, can for example enumerate Hydran HW-330, Hydran HW-340,
Hydran HW-350 (are Dainippon Ink and Chemicals Inc. systems), Superflex100,
Superflex130, Superflex150, Superflex170 (being the first industrial pharmaceutical company system), Adeka
Bontighter HUX-206、Adeka Bontighter HUX-232、Adeka Bontighter HUX-360、Adeka
Bontighter HUX-540 (being ADEKA company systems) etc..
As above-mentioned epoxy resin, for example, can enumerate：The epoxy obtained by the reaction of polyphenolic substance and epichlorohydrin
Compound, by amine addition in the cationic epoxy resin of the epoxide, by polyprotic acid addition in the epoxy compound
Thing and import acidic group obtained from anionic species epoxy resin, to these epoxides and/or cationic or the moon from
Subclass epoxy resin carries out modified epoxy etc. obtained from acrylic acid modified, urethane-modified etc. being modified.
Used as above-mentioned epoxide, number-average molecular weight is preferably 400～4000, particularly preferably 800～2000, epoxy
Equivalent is preferably 190～2000, particularly preferably 400～1000.As above-mentioned polyphenolic substance, for example, include double (4- hydroxyls
Base phenyl) -2,2- propane, 4,4- dihydroxy benaophenonels, double (4- hydroxy phenyls) -1,1- ethane, double (4- hydroxy phenyls) -1,
1- iso-butanes, double (4- hydroxy-tert-butyl phenyl) -2,2- propane, double (2 hydroxy naphthalene base) methane, 1,5- dihydroxy naphthlenes, it is double (2,
4- dihydroxy phenyls) methane, four (4- hydroxy phenyls) -1,1,2,2- ethane, 4,4- dihydroxy-diphenyl sulfones, phenol novolacs
Resin, cresol novolac resin etc..
As aforesaid propylene acid resin, for example, include：(methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (first
Base) butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid shrink it is sweet
The acrylate such as grease, (methyl) acrylate, the homopolymer of methacrylate, copolymer and, they with can be total to
Poly- monomer for example styrene, acrylonitrile, acrylic acid, methacrylic acid, maleic acid, acrylamide, N hydroxymethyl acrylamide,
The copolymer of diallylamine etc..Acrylic resin can be：By anionic property group, the ammonia such as acidic group are imported in resin
The cationic groups such as base, these groups are neutralized and acrylic resin obtained from being dispersed or dissolved in water.Separately
Can also be outward：The water serial emulsion that emulsion polymerization carried out by using surfactant, reactive emulsifier etc. and is obtained, Jiang Shui
The soluble macromolecular soap-free emulsion for being emulsifying agent.
As said polyolefins resin, include：Using ammonia and/or amine by ethylene and acrylic acid or methacrylic acid
Copolymer carries out vistanex obtained from moisture dissipates, forces the copolymer of ethylene and vinyl alcohol with surfactant
Vistanex obtained from emulsifying etc..
Hydrolytic condensate (B)
As the hydrolytic condensate of (B) composition of metal surface treating composition of the present invention it is：Silane idol containing epoxy radicals
The condensation of connection agent (a) and at least one alkoxysilane compound containing trialkylsilyl group in molecular structure and/or the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in following formula [1]
The hydrolytic condensate of thing (b) (below, abbreviation is " alkoxy silane (condensation substance) is (b) " sometimes)
(R)4-n-Si-(X)n [1]
(in formula, R represents the alkyl of the carbon number 1～18 that can be replaced by the substituent group without reactivity, and X represents alkane
Epoxide, n represent 1～3 integer).
With regard to the above-mentioned silane coupler (a) containing epoxy radicals, as long as there is in 1 molecule at least one epoxy radicals and water
The silane coupler of solution property group, is just not particularly limited.With regard to above-mentioned hydrolization group, it is not particularly limited, but conduct
It is preferred that person, can enumerate the alkoxysilyl for being bonded directly to element silicon.
As the specific example of the above-mentioned silane coupler (a) containing epoxy radicals, γ-glycidoxypropyl group front three is included
TMOS, γ-glycidoxypropyl dimethoxysilane, γ-glycidoxypropyl group triethoxysilane etc., its
In preferably use γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxysilane.
As above-mentioned alkoxy silane (condensation substance) (b) in the alkoxysilane compound containing trialkylsilyl group in molecular structure represented by formula [1], Ke Yishi
Trialkoxy silane inclusion, dialkoxysilane compounds, monoalkoxysilane compound, it is contemplated that in aqueous medium
In deliquescent viewpoint etc., preferably trialkoxy silane compound.
As above-mentioned trialkoxy silane compound, for example, can enumerate MTMS, methyltriethoxy silane
Alkane, methyl tripropoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl group three
Ethoxysilane, butyl trimethoxy silane, amyltrimethoxysilane, hexyl trimethoxy silane, octyl group trimethoxy silicon
Alkane, methyl three (methoxy ethoxy) silane, ethyl three (methoxy ethoxy) silane, 3,3,3- trifluoro propyl trimethoxy silicon
Alkane, vinyltrimethoxy silane, VTES, vinyl three (methoxy ethoxy) silane, phenyl front three
TMOS, phenyl triethoxysilane etc..Among them, particularly preferably MTMS, methyl triethoxy
Silane, methyl tripropoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl group
Triethoxysilane, butyl trimethoxy silane, methyl three (methoxy ethoxy) silane, ethyl three (methoxy ethoxy) silicon
Alkane.
As above-mentioned list or dialkoxysilane compounds, for example, can enumerate trimethylmethoxysilane, trimethyl second
The monoalkoxysilanes such as TMOS, trimethyl npropoxysilane, triethyl group methoxy silane, triethyl-ethoxy-silicane alkane, two
Methyl dimethoxysilane, dimethyldiethoxysilane, dimethyl dipropoxy silane, diethyldimethoxysilane, two
Ethyl diethoxy silane, Methylethyl dimethoxysilane, Methylethyl diethoxy silane, dipropyl trimethoxy silane
Deng dialkoxy silicane etc..
As the condensation substance of above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure, can be 1.5～10, be preferably 1.5 using average degree of polymerization
～5 condensation substance.
With regard to hydrolytic condensate (B), can be by by the above-mentioned silane coupler (a) containing epoxy radicals and above-mentioned alkoxy silane
(condensation substance) compounding ratio (b) according to the former/ratio of the element silicon amount of the latter is preferably set in the range of 3/1～1/3, enters one
Step is preferably set to 2/1～1/2, and Hydrolysis condensation reaction is so as to obtaining.
With regard to above-mentioned hydrolysis-condensation reaction, preferably by the silane coupler (a) containing epoxy radicals (is contracted with alkoxy silane
Compound) (b) both, as desired comprising acid catalyst aqueous medium, react 0.5 at such as 20～100 DEG C
～20 hours, react 1～10 hour or so preferably at 40～90 DEG C.The silane coupler containing epoxy radicals of aqueous medium
A (b) both are added up in the range of 3～40 mass % for () and alkoxy silane (condensation substance), preferably 5～30 mass %
In the range of.The weight average molecular weight of hydrolytic condensate (B) is preferably 500～12000 scope in the range of 400～20000
It is interior.
In this manual, the value that the weight average molecular weight of hydrolytic condensate (B) is in the following way and obtains, i.e. profit
With the retention time (reserve capacity) of polystyrene standard known to the molecular weight for determining under the same conditions, will be using gel
Permeation chromatograph (GPC) and the retention time (reserve capacity) that determines are scaled the molecular weight of polystyrene so as to obtain
Value." HLC-8120GPC " (trade name, Tosoh Corporation systems) can be used as chromatograph of gel permeation device, used
One " TSKgel GMHHR-L " (trade name, Tosoh Corporation systems) as chromatographic column, using differential refractometer as
Detector, can be in mobile phase：Dimethylformamide (including 0.5 mass % of triethanolamine), temperature of the measurement：25 DEG C, flow velocity：1mL/
It is measured under conditions of min.
With regard to the amount of hydrolytic condensate (B), based on 100 mass parts of resin solid content of aqueouss organic resin (A), with solid
Thing content is calculated as the scope of 0.1～40 mass parts, the preferably scope of 5～20 mass parts.
Colloidal silica (C)
With regard to the colloidal silica of (C) composition as metal surface treating composition of the present invention, preferably use by sodium,
Ammonium is by silicon dioxide (SiO2) ultramicro powder carry out colloidal silica obtained from stabilisation.Silicon dioxide (SiO2) it is super
Microparticle to be preferably and carry out molecular weight using siloxanes key and can have the spherical titanium dioxide of hydroxyl in its surface
Silicon.In addition, the microgranule is preferably dimensioned to be the scope of 1～50nm, the particularly preferably scope of 5～20nm.
The colloidal silica that can be used as (C) composition can be obtained in the way of commercially available product, for example, include Snowtex
N, Snowtex S, Snowtex NXS, Snowtex C (being Nissan Chemical Ind Ltd's system, trade name), Adelite
AT-20A, Adelite AT-2045 (Adeka Corporation systems, trade name) etc..
In addition, colloidal silica (C) can above-mentioned colloidal silica be processed using silane coupler and
The colloidal silica for obtaining, in the case where being processed using silane coupler, can consolidating relative to colloidal silica
100 mass parts of shape thing content, add 1～50 mass parts of silane coupler, are preferably added to 3～30 mass parts, further preferably add
Enter 5～20 mass parts, reacted so as to obtain.
As above-mentioned silane coupler, can for example enumerate vinyltrimethoxy silane, VTES, β-
(3,4- epoxycyclohexyls) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy
Propyl-triethoxysilicane, gamma-amino propyl trimethoxy silicane, N- β (amino-ethyl) gamma-amino propyl trimethoxy silicon
Alkane, γ-methacryloxypropyl trimethoxy silane etc..
By being compounded colloidal silica (C) in the compositions of the present invention, so as to obtained process epithelium pair can be improved
The adhesion of base material, and the corrosion resistance of epithelium can be improved, but when being excessively compounded, then reduce the processability of epithelium, make
Adhesion deterioration, and damage the barrier of surface treatment epithelium, it is impossible to suppress the transmission of the corrosion factor in corrosive environment,
It is easily reduced corrosion resistance.
With regard to the compounding amount of colloidal silica (C), the resin solid content based on aforementioned aqueouss organic resin dispersion liquid (A)
100 mass parts, are 5.0～50 mass parts, and in the range of preferably 10～30 mass parts, this considers it is suitable from above-mentioned viewpoint
's.
Water-based metal-surface-treating agent
The water-based metal-surface-treating agent of the present invention contains the aforementioned aqueouss organic resin (A) of ormal weight, hydrolytic condensate
(B) organic phosphoric acid compound (D), antirust can further be contained as desired and colloidal silica is used as required composition,
Metallic compound (E), wax (F) etc..In the water-based metal-surface-treating agent of the present invention, preferably make above-mentioned each stable components ground molten
Solution in or be scattered in water.Hereinafter above-mentioned (D)～(F) compositions are illustrated.
Organic phosphoric acid compound (D)
In the water-based metal-surface-treating agent of the present invention, for improving, surface treatment epithelium is close to the epithelium of metal surface
The purposes such as connecing property, can contain organic phosphoric acid compound (D) as desired.Organic phosphoric acid compound (D) can be with colloidal silica
Silicon further improves rust-preventing characteristic together, in addition, can also contribute to improve the storage-stable of metal conditioner.
As organic phosphoric acid compound (D), such as 1- hydroxy methane -1 is included as preferred person, 1- di 2 ethylhexyl phosphonic acids, 1-
The organic phosphorous acid of the hydroxyls such as hydroxyl ethane -1,1- di 2 ethylhexyl phosphonic acids, 1- hydroxy propane -1,1- di 2 ethylhexyl phosphonic acids, 2- hydroxy phosphinylidyne base second
The carboxylic organic phosphorous acids such as acid, 2- phosphinylidyne butane -1,2,4- tricarboxylic acids, and their salt etc..It is wherein particularly preferred
1- hydroxyl ethane -1,1- di 2 ethylhexyl phosphonic acids.
In the case of organic phosphate cpd (D) is compounded in the water-based metal-surface-treating agent of the present invention, add with regard to which
Dosage, based on 100 mass parts of resin solid content of aqueouss organic resin (A), is calculated as 0.1～5.0 mass parts with solid content
Scope, the preferably scope of 0.5～3.0 mass parts.
Anti-rust metal compound (E)
In the water-based metal-surface-treating agent of the present invention, for purposes such as the rust-preventing characteristics for improving surface treatment epithelium, can
Contain anti-rust metal compound (E) as desired.
As anti-rust metal compound (E), can enumerate with titanium, zirconium, hafnium, vanadium, magnesium, manganese, zinc, tungsten, molybdenum, aluminum, nickel, cobalt,
The metallic compound of the metallic elements such as calcium.
As anti-rust metal compound (E), for example, include：Above-mentioned metallic element and fluoric acid, phosphoric acid, carbonic acid, nitric acid with
And the mineral acid such as sulphuric acid or formic acid, acetic acid, butanoic acid, ethanedioic acid, succinic acid, lactic acid, L-AA, tartaric acid, citric acid,
The salt of the organic acid such as DL-malic acid, malonic acid, maleic acid, phthalic acid；The oxide of these metallic elements；The metal
Complex salts such as alkoxide, alkyl pyruvate, two oleate of alkane, lactate, ammonium salt and stearate etc..These metallic compounds can
Be anhydride can also be hydrate.
As the typical example of above-mentioned metallic compound (E), include：Alkaline carbonic acid zirconium (ZrCO4·ZrO2·8H2O), carbon
Sour zirconium ammonium, nickel sulfate, zirconium nitrate, vanadium oxysulfate, Disulfatozirconic acid., aluminum nitrate, nickel acetate, zirconium acetate, vanadium oxide, ammonium metavanadate, five
Vanadium oxide (V2O5), phosphovanadomolybdic acid, hexafluorotitanic acid (H2TiF6), hexafluoro zirconate (H2ZrF6), hexafluoro hafnium acid (H2HfF6), hexafluoro aluminum
Acid (H3AlF6) etc. fluoric acid, the salt (for example, sodium salt, potassium salt, lithium salts, ammonium salt, amine salt, zinc salt etc.) of these fluoric acids etc..Above-mentioned gold
Among category compound, the especially preferably metallic compound of vanadium, zirconium.As anti-rust metal compound (E), can be by metallic compound
It is used alone or combines two or more and use.
, it can be said that anti-rust metal compound (E) is with following effect：By ion, control corrosion rate ring are produced in water
The corrosion potential of the metal surface in border and control redox reaction, using film forming from very thin films epithelium to metal surface
And with epithelium composition in functional group cross-linking reaction and improve epithelium density etc., so as to improve corrosion resistance.
In the case of anti-rust metal compound (E) is compounded in the water-based metal-surface-treating agent of the present invention, add with regard to which
Dosage, based on 100 mass parts of resin solid content of aqueouss organic resin (A), is calculated as 0.1～30 mass parts with solid content
Scope, the preferably scope of 1.0～20 mass parts.
Wax (F)
In the water-based metal-surface-treating agent of the present invention, for purposes such as the lubricities for improving surface treatment epithelium, can
Contain wax (F) as desired.
As wax (F), as long as the wax of the lubricity of surface treatment epithelium can be improved, just it is not particularly limited, can enumerates
The pertroleum waxes such as paraffin, microwax, polyethylene and polypropylene and fluorinated organic compound etc., can by they be used alone or
It is applied in combination.As above-mentioned fluorinated organic compound, for example include by fluorine atom by the repetitives of polyethylene (PE)-
(CH2-CH2)-hydrogen atom replace obtained from polymer, i.e. polyvinyl fluoride (PVF), polyvinylidene fluoride (PVdF), poly- trifluoro
Copolymer or their modifier of ethylene (PTrFE), politef (PTFE) and these polymer and olefines etc.
Various macromolecule fluorinated organic compounds.
As wax (F), wherein it is 50 that softening point specified in JIS K2351 is preferably from the viewpoint of improving from lubricity
～160 DEG C of wax.In addition, with regard to the particle diameter of wax, little (less than 1 μm) particle diameter is excellent in terms of the stability of surface conditioning agent,
From from the aspect of lubricity raising, big (several μm～10 several μm) particle diameter is excellent, thus it is preferred that suitably being selected according to application target
Select one or more.
As the species of wax (F), wherein preferably using Tissuemat E, polypropylene wax.
In the case of wax (F) is compounded in the water-based metal-surface-treating agent of the present invention, with regard to its addition, based on aqueouss
100 mass parts of resin solid content of organic resin (A), are calculated as 0.5～50 mass parts with solid content, and preferably 1.0～20
The scope of mass parts.
The water-based metal-surface-treating agent of the present invention is comprising building bath compositionss (concentrated solution) and operation compositionss are (dilute
Release liquid) both.The total solid matter concentration built in bath compositionss is preferably 10～40 mass %, more preferably 15～30 matter
Amount %.Total solid matter concentration in operation compositionss is preferably 1～40 mass %, more preferably 5～30 mass %.
With regard to the present invention surface conditioning agent, at 20 DEG C of temperature of the measurement, using Type B rotating cylinder viscometer 60rpm bar
It is below 2.5mPas that the viscosity for obtaining is determined under part, and this is preferred from the aspect of coating from surface conditioning agent.
In the water-based metal-surface-treating agent of the present invention, in addition to aforesaid ingredients, also further can fit as desired
When containing pH regulators (acid or alkali), filler, coloring agent, surfactant, defoamer, levelling agent, antibacterial etc..
Using the present invention water-based metal-surface-treating agent as the pH in the case of operation compositionss be preferably 5.0～
10.0 scope, more preferably 6.0～9.0 scope.Now, as pH regulators, surface treatment compositionss are being improved
In the case of pH, can be using alkali metal carbonic acid such as the alkali metal hydroxides such as ammonia, aminated compoundss, sodium hydroxide, sodium carbonate
Salt etc., in the case where pH is reduced, preferably by organic carboxyl acids such as formic acid, acetic acid, propanoic acid, lactic acid, ATMP,
The acid composition such as organic phospho acids such as 1- hydroxyl ethane -1,1- di 2 ethylhexyl phosphonic acids is adjusted.
As above-mentioned filler, the micropowder of silicon dioxide, Talcum, Barium monoxide, Calcium Carbonate, Muscovitum etc. can be enumerated, can example
Filler as extender pigment is shown.As above-mentioned coloring agent, coloring pigment, dyestuff etc. can be enumerated.
Metal surface treating method
The metal surface treating method of the present invention is characterised by, the aqueous metal surface of the invention described above is processed and is combined
Thing coats metal coated article, and is dried, and which is existed using the aqueous metal surface treatment compositions of the present invention
Metal coated article surface forms the method for processing epithelium.
In the present invention, " process epithelium " not only processes epithelium comprising continuous, also includes：Due to process adhesion amount it is few because
And cannot become continuous and process epithelium, and become discontinuous processed material.
With regard to above-mentioned metal coated article, if raw material metal is then unrestricted, for example enumerate tap a blast furnace, copper,
Aluminum, stannum, zinc and the alloy comprising these metals and be based on plated steel sheet obtained from these metals or evaporation product
Deng.Wherein, preferably using metallic plate.
As the metallic plate as above-mentioned coated article, such as cold-rolled steel sheet, hot-dip galvanized steel sheet, electrolytic zinc-coated steel sheet can be enumerated
Plate, galvanized alloy (alloy such as zinc-ferrum, zinc-aluminum, zinc-nickel) steel plate, aludip, stainless-steel sheet, copper plated steel, tin-coated steel
Plate, aluminium sheet, copper coin etc..Wherein preferably using galvanized steel plain sheet (comprising hot-dip galvanized steel sheet, any one in plated steel sheet),
Galvanized alloy steel plate.
Before the aqueous metal surface treatment compositions of the present invention are coated with above-mentioned metal coated article, using de-
More than one or two in fat, pickling, hot water wash, lotion washing etc. surface adjustment is carried out to metal coated article, it is in office
In the case of one kind, all preferably sufficiently washed finally.In addition, the aqueous metal surface treatment group of present invention during coating
The liquid temperature of compound can be room temperature, but cools down also dependent on hope or heat.
On above-mentioned metal coated article, using rolling method, injection finishing, spread coating, electrostatic coating processes, immersion method,
The aqueous metal surface treatment compositions of the known method applications such as electrodeposition coating method, curtain finishing, the roller finishing present invention,
And be dried, so as to process epithelium can be formed.In addition, with regard to the formation of above-mentioned surface treatment epithelium, can only in metal
The one side of coated article processed is formed, it is also possible to formed on two sides.
The epithelium amount that epithelium is processed obtained from aqueous metal surface treatment compositions based on the present invention is not especially limited
It is fixed, but 0.4～4.0g/m is generally from from the viewpoint of corrosion resistance, processability2, preferably 0.7～3.0g/m2Scope.
The drying condition for processing epithelium suitably sets, but is obtaining to carrying out application by coil rubbing method etc.
Painting object continuously toast in the case of, generally raw material reach maximum temperature be 80～200 DEG C, be preferably 90～120 DEG C
Under conditions of heat 5～60 seconds, so as to be dried.In the case where being toasted with batch-type, for example also can be by environment temperature
Heat 1～30 minute at 100～180 DEG C of degree, so as to be dried.
Surface-treated metal plate
The present invention surface-treated metal plate be：Using the aqueous metal surface treatment compositions of the present invention to metal quilt
The surface of coat carries out the surface-treated metal plate being surface-treated.The metal system of the surface-treated metal plate of the present invention is applied
Thing is plate-like shape, and the surface-treated metal plate can be obtained using the metal surface treating method of the invention described above.
Aqueouss with regard to the surface-treated metal plate of the present invention, from from the viewpoint of corrosion resistance, processability, based on the present invention
The epithelium amount that epithelium is processed obtained from metal surface treating composition is 0.4～4.0g/m2Scope, preferably 0.7～
3.0g/m2Scope.
The present invention surface-treated metal plate process epithelium on, also can further for improve makeups, durability,
The purposes such as other features, form the upper layer films such as coloring film, transparent coating.With regard to the formation of the upper layer film, also can be to this
The surface-treated metal plate of invention is carried out before carrying out processing and forming, it is preferred that carrying out after processing and forming.
Hereinafter, the present invention is more particularly described by including Production Example, embodiment and comparative example.But the present invention is unrestricted
In this.
Embodiment
Then embodiment and comparative example are included and the present invention is illustrated, the present invention is not only restricted to these embodiments,
In each example, " part " and " % " is namely based on quality criteria as long as no especially record, in addition, processing the epithelium amount of epithelium
It is based on being dried epithelium amount.
The manufacture of hydrolytic condensate (B)
Production Example 1
To in blender, reflux condenser, the four-hole boiling flask of thermometer, 1000 parts of deionized water of compounding, methanol
1000 parts, 10 parts of acetic acid, heat up and are maintained at 40 DEG C.1 hour is spent using the 3- rings as the silane coupler (a) containing epoxy radicals
101 parts of oxygen propoxypropyl trimethoxy silane and 58 parts of the MTMS as alkoxysilane compound containing trialkylsilyl group in molecular structure (b)
159 parts of Deca of mixture in above-mentioned flask.After completion of dropwise addition, further stir 1 hour, then reduced pressure at 60 DEG C
Distillation, the methanol distillation generated by the methanol being compounded and by hydrolysis are removed.While according to solid concentration is kept
Mode below 10% suitably puts into deionized water, proceeds vacuum distillation until the first determined by gas chromatography
Determining alcohol reaches less than 1%.The mode for becoming 10% according to final solid content is adjusted, and produces hydrolytic condensation thing liquid.
In the hydrolytic condensate manufacture, the use of the element silicon ratio of (a)/(b) of raw material is 1/1.
Production Example 2～6
In addition to the species of (a) composition and (b) composition and amount are set shown in table 1 as be described hereinafter, grasp in the same manner as Production Example 1
Make, so as to produce the hydrolytic condensate of Production Example 2～6.
Production Example 7
To in blender, reflux condenser, the four-hole boiling flask of thermometer, 58 parts of MTMS of loading,
10 parts of methanol, 1 part of acetic acid, 7 parts of water, stir 1 hour at 40 DEG C, carry out under reduced pressure distilling up to no volatile matter, so as to
Become the MTMS oligomer of (b) composition.The 3- glycidoxies third as (a) composition are put into thereto
101 parts of base trimethoxy silane, so as to prepare silane mixture liquid.
To in blender, reflux condenser, another four-hole boiling flask of thermometer, 1000 parts of deionized water of compounding, first
1000 parts of alcohol, 9 parts of acetic acid, heat up and are maintained at 40 DEG C.The silane mixture drop of above-mentioned preparation is added on flask in 1 hour by cost
It is interior.Further stir 1 hour, then vacuum distillation is carried out at 60 DEG C, generated by the methanol being compounded and by hydrolysis
Methanol distillation remove.While deionized water is suitably put into according to solid concentration is maintained at 10% in the following manner,
Proceed vacuum distillation until the methanol concentration determined by gas chromatography reaches less than 1%.According to final solid content into
Mode for 10% is adjusted, and produces the hydrolytic condensation thing liquid of Production Example 7.In the hydrolytic condensate manufacture, using original
The element silicon ratio of (a)/(b) of material is 1/1.
By above-mentioned Production Example 1～7 manufacture hydrolytic condensate by GPC determine obtained from weight average molecular weight all 500
In the range of～12000.
Table 1
The manufacture of metal surface treating composition
Embodiment 1～21 and comparative example 1～8
It is compounded according to the compounding ratio shown in aftermentioned table 2, the mode for becoming 25 mass % according to solid concentration is added
Deionized water and be adjusted, be fully stirred and obtain each metal surface treating composition.In addition, the formula of table 2 is with solid
Shape amount of substance is represented.
The storage-stable of each surface treating composition with regard to being obtained, evaluates according to following test methods.By institute
The result of the test of acquisition is shown in aftermentioned table 2.
Storage-stable：Each surface conditioning agent 500g is put into in the glass container of inner capacitiess 1L and is sealed, at 40 DEG C
Preserve 14 days in thermostatic chamber.Thereafter, room temperature is returned to, the state observed among container by visual observation, by following benchmark evaluation：
◎：It was found that significant thickening, soft junction block and/or separation, well.
○：Confirmation has soft junction block and/or separation, but is changed into uniform by the stirring of less than 10 minutes,
△：Confirmation has soft junction block and/or separation, becomes equal by the stirring more than 10 minutes and less than 60 minutes
It is even.
×：Confirmation has scleroma block and/or separation, even if cannot also become uniform by the stirring more than 60 minutes.
Table 2
The species of the organic resin (A) in table 2 is for example following shown.
A1：Adeka Bontighter HUX-206 (Adeka Corporation systems, trade name, polyurethane resin moisture
Dispersion liquid, pH8, solid content 30%),
A2：Adeka Bontighter HUX-540 (Adeka Corporation systems, trade name, anionic property polyurethane
Aqueous resin dispersion liquid, pH8, resinous acid value 32mgKOH/g, 30 mass % of solid content),
A3：(DIC (strain) makes Watersol CD-550LAP, trade name, epoxy resin aqueous solution, pH9, solid concentration
40%),
A4：(Arakawa Chemical Industries, Ltd.'s system, trade name are epoxy resin aqueous solution, pH8.5, solid for Modepics302
Shape thing concentration 33%.)、
A5：(DIC (strain) makes Aquabrid CC234, trade name, acrylic resin aqueous solution, pH7, solid concentration
34%),
A6：Chemipearl S-100 (Mitsui Chemicals, Inc's system, trade name, the sodium salt of ethylene-acrylic acid copolymer
Aqueous dispersions, ionomer, pH10, solid concentration are 27%).
Colloidal silica (C), organic phosphoric acid compound (D), anti-rust metal compound (E) and wax (F) in table 2
Species is for example following shown.
C1：Snowtex NSX (make, colloidal silica aqueous dispersions, pH9.0～10.0, grain by Nissan Chemical Industries (strain)
Footpath 5nm),
C2：Snowtex N (make, colloidal silica aqueous dispersions, pH9.0～10.0, particle diameter by Nissan Chemical Industries (strain)
10～20nm),
D1：1- hydroxyl ethane -1,1- di 2 ethylhexyl phosphonic acids,
E1：Ammonium metavanadate,
E2：Zirconium carbonate ammonium,
E3：Lithium zirconium ammonium,
F1：LUVAX1151 (essence Inland Steel of Japan system, 107 DEG C of Tissuemat E, ring and ball softening point).
Hydrolytic condensate (B) in table 2 although X and Y described in this hurdle are not hydrolytic condensates, for side
Just it is documented in the hurdle, with following meanings.
X：γ-glycidoxypropyltrime,hoxysilane,
Y：MTMS.
Embodiment 22～48 and comparative example 9～16
Using aforementioned each surface treating composition, according to the mode shown in Table 3 below, surface-treated metal plate is obtained.
Metallic plate species in table 3 is for example following shown.
(metallic plate species)
EG：Plating adhesion amount is one side 20g/m2, thickness of slab 0.8mm two sides plated steel sheet,
GA：Plating adhesion amount is one side 45g/m2, thickness of slab 0.8mm two surface alloying Zn-Fe melting plated steel sheet,
GI：Plating adhesion amount is one side 60g/m2, thickness of slab 0.6mm two sides hot-dip galvanized steel sheet.
(treatment process)
In each case, for metallic plate (EG), using alkali cleaner " CC-561B " (the The Japan Cee- of concentration 2%
Bee Chemical Co., Ltd.s system, the suitable product of silicic acid 3) aqueous dispersions, injection defat in 60 seconds is carried out at 65 DEG C of liquid temperature,
Then hot water wash is carried out under conditions of 20 seconds in 50 DEG C of liquid temperature, injecting time.For the alkali degreasing metallic plate for being obtained, according to rear
State the combination shown in table 3 and be dried epithelium quality, the surface treatment group obtained by aforementioned each example is coated with using metering bar coater
Compound, the mode for becoming 110 DEG C according to the maximum temperature reached of metallic plate carry out 15 seconds heat dryings, so as to obtain at each surface
Reason metallic plate.
For the surface-treated metal plate of each example for being obtained, epithelium performance is processed according to following test method evaluations, will
The result for being obtained is shown in aftermentioned table 3.
Outward appearance after making；The outward appearance of obtained surface-treated metal plate is evaluated below.
◎：Without abnormal
○：The major diameter that less than 1～5 is produced in 30cm × 30cm squares is the speckle of 0.1～5mm
△：The major diameter that 5～19 are produced in 30cm × 30cm squares is the speckle of 0.1～5mm
×：The major diameter that more than 20 are produced in 30cm × 30cm squares is the speckle of 0.1～5mm.
Corrosion resistance：For the bread board for sealing the end face portion and back part of surface-treated metal plate, carry out
Salt spraytest specified in JIS Z2371 was processed the degree of the rust of face up to 360 hours by following benchmark evaluations.
◎：It was found that the generation of white rust.
○：Confirmation has the generation of white rust, but produces the 5% of the not enough process membrane area of degree.
△：The generation degree of white rust be process more than the 5% of membrane area, and less than 20%.
×：The generation degree of white rust is process membrane area more than 20%.
Anti-finger printing：The application face of bread board 1/2nd coating vaseline and to be positioned over 20 DEG C of thermostatic chamber 24 little
When, then vaseline is wiped away with gauze, determine the aberration in the painting face of the painting face after wiping vaseline away and uncoated vaseline, press
State benchmark to be evaluated.In addition, carrying out color difference measurement by using Minolta colour difference meters " CR-100 ".
○：Aberration (△ E) is less than 2
×：Aberration (△ E) is more than 2.
Deep-draw processability：For surface-treated metal plate, using the sheet metal cup-drawing test device of Erichsen company systems
142 types, have carried out cup-drawing test at 20 DEG C.The condition of processing experiment is sheet scaffold pressure 1500kg, drift footpath 50mm, blank
Mould footpath 110mm, drawing ratio：2.2nd, the drawing speed 10mm/ second, entered according to the apparent condition of machined object according to following metewands
Row is evaluated.
◎：No attachment on mould, does not find scratch on the surface of machined object.
○：Micro attachment is there are on mould, confirms there is small scratch on the surface of machined object.
△：Slightly many attachments are there are on mould, on the surface of machined object, although be not on whole face, but
Confirmation has many scratches.
×：Substantial amounts of attachment is there are on mould, confirms there is significant scratch in the whole face in the surface of machined object, or
Person cannot be processed.
Upper painting film adhesion：On the surface of surface-treated metal plate, according to the mode application that dry film thickness is 25 μm
" Magicron1000White " (Kansai Paint Co., Ltd.s system, acrylic resin-melmac class coating,
White), toast 20 minutes at 150 DEG C and obtain test coated plate.The test coated plate is immersed in 2 in about 98 DEG C of boiled water
Hour, then lift and place 2 hours in room temperature, in the coated surface of the test coated plate, go out to reach checker-wise using knife scribing
The scar of each in length and breadth 11 of the bottom of shape, has made the grid of 100 1mm square.Cellophane adhesive tape is close contact in into this
Gridiron pattern sub-portion, in moment stripping tape.According to the quantity of the checker-wise film peeled off from test coated plate in stripping tape,
According to following benchmark evaluation.
◎：It was found that the upper stripping for applying film.
○：Confirmation has the stripping of 1～20 checker-wise film, but in usage range.
△：Confirmation has the stripping of 20～50 checker-wise films.
×：Confirmation has the stripping of 5 more than one checker-wise films.
Table 3
Claims (8)
1. a kind of water-based metal-surface-treating agent, it is characterised in that
Contain (A) according to solid content from by polyurethane resin, epoxy resin, acrylic resin and vistanex
At least one 100 mass parts of aqueouss organic resin selected in the group of composition, and
Based on 100 mass parts of resin solid content of the aqueouss organic resin (A), contain according to solid content：
(B) silane coupler (a) containing epoxy radicals with shown in following formula [1] at least one alkoxysilane compound containing trialkylsilyl group in molecular structure and/or
0.1～40 mass parts of hydrolytic condensate of the condensation substance (b) of the alkoxysilane compound containing trialkylsilyl group in molecular structure
(R)4-n-Si-(X)n [1]
In formula, R represents the alkyl of the carbon number 1～18 that can be replaced by the substituent group without reactivity, and X represents alkoxyl, n
1～3 integer is represented, and
(C) 5.0～50 mass parts of colloidal silica.
2. water-based metal-surface-treating agent according to claim 1, it is characterised in that (B) in composition containing epoxy radicals
Silane coupler is from γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl dimethoxy silicon
At least one compound selected in alkane, γ-glycidoxypropyl group triethoxysilane, (B) alkoxy silane in composition
Compound is from MTMS, MTES, methyl tripropoxy silane, ethyl trimethoxy silicon
Alkane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, butyl trimethoxy silane, amyl group three
Methoxy silane, hexyl trimethoxy silane, octyl group trimethoxy silane, methyl three (methoxy ethoxy) silane, ethyl three
(methoxy ethoxy) silane, 3,3,3- trifluoro propyl trimethoxy silanes, vinyltrimethoxy silane, three ethoxy of vinyl
Select in base silane, vinyl three (methoxy ethoxy) silane, phenyltrimethoxysila,e, phenyl triethoxysilane to
A kind of few trialkoxy silane.
3. water-based metal-surface-treating agent according to claim 1 and 2, it is characterised in that (B) in composition containing epoxy radicals
Silane coupler (a) and alkoxysilane compound containing trialkylsilyl group in molecular structure and/or the alkoxysilane compound containing trialkylsilyl group in molecular structure condensation substance (b) mix ratio
Example, according to the former/ratio of the element silicon amount of the latter is in the range of 3/1～1/3.
4. water-based metal-surface-treating agent according to claim 1 and 2, wherein, the resin based on aqueouss organic resin (A)
100 mass parts of solid content, (D) organic phosphoric acid compound containing 0.1～5.0 mass parts further according to solid content.
5. water-based metal-surface-treating agent according to claim 1 and 2, wherein, the resin based on aqueouss organic resin (A)
100 mass parts of solid content, (E) anti-rust metal compound containing 0.1～30 mass parts further according to solid content.
6. water-based metal-surface-treating agent according to claim 1 and 2, wherein, the resin based on aqueouss organic resin (A)
100 mass parts of solid content, (F) wax containing 0.5～50 mass parts further according to solid content.
7. a kind of metal surface treating method, it is characterised in that by the Water based metal table any one of claim 1～6
Face inorganic agent coats metal coated article, and is dried.
8. a kind of surface-treated metal plate, which is processed by using the water-based metal-surface any one of claim 1～6
Agent carries out surface treatment to the surface of metal coated article and forms.
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| JP2016030777A (en) * | 2014-07-28 | 2016-03-07 | 奥野製薬工業株式会社 | Process liquid for siliceous film formation |
| JP2016175257A (en) * | 2015-03-19 | 2016-10-06 | 株式会社神戸製鋼所 | Resin coated metal plate |
| JP6946377B2 (en) * | 2015-03-19 | 2021-10-06 | 株式会社神戸製鋼所 | Resin coated metal plate |
| CN105440754A (en) * | 2015-12-07 | 2016-03-30 | 铜陵市明诚铸造有限责任公司 | Hydrophilic anti-rusting metal intermediate coating |
| EP3456862A4 (en) | 2016-05-10 | 2020-01-08 | Hoden Seimitsu Kako Kenkyusho Co., Ltd. | Aqueous anti-rust surface treatment composition and surface-coated metal member |
| KR102045881B1 (en) * | 2016-09-28 | 2019-11-19 | 주식회사 포스코 | Solution composition for surface treating of steel sheet, steel sheet using the same, and manufacturing method of the same |
| US11377568B2 (en) * | 2017-05-11 | 2022-07-05 | Nihon Parkerizing Co., Ltd. | Metal surface treatment agent, metal surface treatment method, and metal material |
| KR102178725B1 (en) * | 2018-12-19 | 2020-11-13 | 주식회사 포스코 | Two layeer composition for surface treating of steel sheet and steel sheet using the same |
| EP3845610B1 (en) * | 2019-12-31 | 2023-10-11 | Industrial Technology Research Institute | Water-based coating material and method for manufacturing the same |
| CN113122131A (en) * | 2019-12-31 | 2021-07-16 | 财团法人工业技术研究院 | Aqueous coating and method of forming the same |
| CN111455361A (en) * | 2020-03-11 | 2020-07-28 | 惠州市瑞翔丰科技有限公司 | Surface treatment agent and metal surface treatment method |
| CN113817391A (en) * | 2020-09-07 | 2021-12-21 | 帕珂表面处理技术(上海)有限公司 | Surface treatment agent for stainless steel material |
| CN117082793B (en) * | 2023-10-11 | 2024-03-12 | 荣耀终端有限公司 | Shell, manufacturing method thereof and electronic equipment |
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