CN117178078A - Aqueous chromium-free surface treatment agent, surface treatment metal and surface treatment method - Google Patents
Aqueous chromium-free surface treatment agent, surface treatment metal and surface treatment method Download PDFInfo
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- CN117178078A CN117178078A CN202280024767.0A CN202280024767A CN117178078A CN 117178078 A CN117178078 A CN 117178078A CN 202280024767 A CN202280024767 A CN 202280024767A CN 117178078 A CN117178078 A CN 117178078A
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- Prior art keywords
- surface treatment
- treatment agent
- aqueous chromium
- silane compound
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- MBIWXZXQMMLFAB-UHFFFAOYSA-N trimethoxy(9-trimethoxysilylnonyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCCCC[Si](OC)(OC)OC MBIWXZXQMMLFAB-UHFFFAOYSA-N 0.000 description 1
- DJYGUVIGOGFJOF-UHFFFAOYSA-N trimethoxy(trimethoxysilylmethyl)silane Chemical compound CO[Si](OC)(OC)C[Si](OC)(OC)OC DJYGUVIGOGFJOF-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- HFMRLLVZHLGNAO-UHFFFAOYSA-N trimethylsilyloxysilicon Chemical compound C[Si](C)(C)O[Si] HFMRLLVZHLGNAO-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
- C23F11/122—Alcohols; Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The present invention provides an aqueous chromium-free metal surface treatment agent capable of forming a coating film on a metal substrate, which coating film can withstand high strength and workability. An aqueous chromium-free surface treatment agent comprising a bifunctional silane compound (A), a monofunctional silane compound (B) and an acetylenic diol-based surfactant (C). The concentration of the bifunctional silane compound (A) is preferably in the range of 1 to 100g/L, the concentration of the monofunctional silane compound (B) is preferably in the range of 1 to 100g/L, and the concentration ratio (A/B) of the bifunctional silane compound (A) to the monofunctional silane compound (B) is preferably in the range of 0.1 to 5.
Description
Technical Field
The present invention relates to an aqueous chromium-free surface treatment agent, a surface-treated metal, and a surface treatment method.
Background
Conventionally, as a surface treatment agent for imparting corrosion resistance to a metal substrate, a chromium-based metal surface treatment agent such as a chromate treatment agent or a phosphate chromate treatment agent has been known, and has been widely used at present. However, according to recent environmental restrictions, there is a possibility that the use of chromium-based metal surface treatment agents will be restricted due to toxicity, particularly carcinogenicity, of chromium.
Accordingly, various chromium-free metal surface treatments have been developed which exhibit corrosion resistance equivalent to that of chromium-based metal surface treatments. For example, patent document 1 discloses a composition for metal surface treatment, which contains a condensation reactant of a titanium compound and/or a zirconium compound, an aminosilane, and a polysilicated functional group silane.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2011-068930
Disclosure of Invention
Problems to be solved by the invention
When a film is formed on a metal substrate using a chromium-free metal surface treatment agent, for example, when the metal substrate is used for precoating metal applications, the formed film is required to have coating adhesion that can withstand high-strength workability in addition to corrosion resistance. However, the conventional chromium-free metal surface treatment agent cannot sufficiently achieve coating adhesion in high-strength processing of the surface-treated metal substrate, and there is room for improvement. For example, in the case where a metal substrate as a coating object has a smooth surface, the treating agent containing a silane coupling agent as a main component described in patent document 1 causes shrinkage cracking of the coating material during coating, and thus a uniform film cannot be formed on the metal surface, and coating adhesion is also insufficient.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an aqueous chromium-free metal surface treatment agent capable of forming a coating film on a metal substrate, which coating film can withstand high-strength workability.
Means for solving the problems
(1) The present invention relates to an aqueous chromium-free surface treatment agent comprising a bifunctional silane compound (A), a monofunctional silane compound (B) and an acetylenic diol surfactant (C).
(2) The aqueous chromium-free surface treatment agent according to (1), wherein the concentration of the bifunctional silane compound (A) is in the range of 1 to 100g/L, the concentration of the monofunctional silane compound (B) is in the range of 1 to 100g/L, and the concentration ratio (A/B) of the bifunctional silane compound (A) to the monofunctional silane compound (B) is in the range of 0.1 to 5.
(3) The aqueous chromium-free surface treatment agent according to (1) or (2), wherein the concentration of the acetylenic diol surfactant (C) is in the range of 0.05 to 1 g/L.
(4) The aqueous chromium-free surface treatment agent according to any one of (1) to (3), wherein a contact angle on the surface of the mirror-finished aluminum plate is 25 degrees or less.
(5) The aqueous chromium-free surface treatment agent according to any one of (1) to (4), further comprising water-dispersible metal oxide particles (D), wherein the average particle diameter of the water-dispersible metal oxide particles (D) is 150nm or less, and the concentration of the water-dispersible metal oxide particles (D) is in the range of 1 to 20 g/L.
(6) The aqueous chromium-free surface treatment agent according to any one of (1) to (5), further comprising a urethane resin (E), wherein the urethane resin (E) is at least one of a urethane water-dispersible resin and a urethane water-soluble resin, and the concentration of the urethane resin (E) is in the range of 1 to 20 g/L.
(7) The aqueous chromium-free surface treatment agent according to any one of (1) to (6), further comprising a blocked isocyanate resin (F), wherein the concentration of the blocked isocyanate resin (F) is in the range of 1 to 20 g/L.
(8) The aqueous chromium-free surface treatment agent according to any one of (1) to (7), wherein the pH thereof is in the range of 5 to 7.
(9) A surface-treated metal obtained by forming a surface-treated film on a surface by using the aqueous chromium-free surface-treating agent according to any one of (1) to (8).
(10) A surface treatment method comprising a surface treatment film forming step of forming a surface treatment film by treating the surface of a coating object with the aqueous chromium-free surface treatment agent according to any one of (1) to (8).
Effects of the invention
According to the present invention, an aqueous chromium-free metal surface treatment agent capable of forming a coating film with high strength and workability on a metal substrate can be provided.
Detailed Description
The aqueous chromium-free surface treatment agent, the surface treatment metal, and the surface treatment method according to the embodiment of the present invention will be described below. The present invention is not limited to the description of the following embodiments.
Aqueous chromium-free surface treatment agent
The aqueous chromium-free surface treatment agent of the present embodiment contains a difunctional silane compound (a), a monofunctional silane compound (B), and an acetylenic diol surfactant (C). Further, it is preferable that the composition further contains at least one of water-dispersible metal oxide particles (D), a polyurethane resin (E) and a blocked isocyanate resin (F).
(bifunctional silane Compound (A))
The bifunctional silane compound (a) is a compound having 2 silanol groups in 1 molecule or a silyl group capable of generating silanol groups by hydrolysis. Examples of the bifunctional silane compound (a) include compounds represented by the following formula (I).
[ chemical 1]
(X 1 ) 3-a-b (R 1 ) a (R 2 ) b Si-Y-Si(R 3 ) c (R 4 ) d (X 2 ) 3-c-d …(I)
In the above formula (I), R 1 、R 2 、R 3 R is R 4 Each independently represents a hydrogen atom or a carbon atom number of 1 to 30A 1-valent organic group. Examples of the 1-valent organic group include hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, and aryl groups, hydrocarbon groups having functional groups such as hydroxyl groups, epoxy groups, and amino groups, and the like. The 1-valent organic group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group.
In the above formula (I), Y represents a 2-valent organic group or an amine. Examples of the 2-valent organic group include an alkylene group, an alkyleneoxy group, an alkylenethio group, and a group containing the above 2-valent organic group as a partial structure. As the above-mentioned 2-valent organic group, an alkylene group is preferable. The number of carbon atoms of the 2-valent organic group is preferably 2 to 30, more preferably 2 to 12.
In the above formula (I), X 1 And X 2 Each independently represents a hydrolyzable group. Examples of the hydrolyzable group include a hydroxyl group and an alkoxy group having 1 to 4 carbon atoms. X is X 1 And X 2 Preferably a hydroxyl group. At X 1 And X 2 In the case of an alkoxy group, the alkoxy group is preferably a methoxy group or an ethoxy group.
In the above formula (I), a and b each independently represent an integer of 0 to 2, and 0.ltoreq.a+b.ltoreq.2. In addition, c and d each independently represent an integer of 0 to 2, and 0.ltoreq.c+d.ltoreq.2. a+b and c+d are each preferably 0 or 1.
Specific examples of the bifunctional silane compound (A) represented by the above formula (I) include bis (trimethoxysilyl) methane, 1, 2-bis (trimethoxysilyl) ethane, 1, 2-bis (triethoxysilyl) ethane, 1, 6-bis (trimethoxysilyl) hexane, 1, 6-bis (triethoxysilyl) hexane, 1, 8-bis (trimethoxysilyl) octane, 1, 8-bis (triethoxysilyl) octane, 1, 9-bis (trimethoxysilyl) nonane, 1, 9-bis (triethoxysilyl) nonane, bis (trimethoxysilyl) amine, bis (triethoxysilyl) amine, bis (trimethoxysilylmethyl) amine, bis (triethoxysilylmethyl) amine, bis (trimethoxysilylpropyl) amine, and bis (triethoxysilylpropyl) amine. Among them, 1, 2-bis (triethoxysilyl) ethane is preferable from the viewpoints of safety in handling, corrosion resistance and adhesion of the obtained film.
The bifunctional silane compound (A) may be used alone or in combination of 1 or more than 2. The bifunctional silane compound (a) may be partially hydrolyzed or may be condensed by hydrolysis.
The concentration of the bifunctional silane compound (A) in the aqueous chromium-free metal surface treating agent is preferably in the range of 1 to 100 g/L.
(monofunctional silane Compound (B))
The monofunctional silane compound (B) is a compound having 1 silanol group in 1 molecule or a silyl group which can generate a silanol group by hydrolysis. Examples of the monofunctional silane compound (B) include an amino silane such as 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-2- (aminoethyl) -3-aminopropyl trimethoxysilane, an epoxy-containing silane such as N-2- (aminoethyl) -3-aminopropyl methyldimethoxy silane, 3-aminopropyl methyldiethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl triethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, an epoxy-containing silane such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldimethoxy silane, 3-glycidoxypropyl methyldiethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, a monosilanol compound such as trimethylsilanol, a monosilane such as triethylsilanol, a monostearyl silane, a trimethylsiloxy silane, and the like. Among them, aminosilanes are preferable, and 3-aminopropyl triethoxysilane is more preferable.
The monofunctional silane compound (B) may be used alone or in combination of 1 or more than 2. The monofunctional silane compound (B) may be partially hydrolyzed or may be condensed by hydrolysis.
The concentration of the monofunctional silane compound (B) in the aqueous chromium-free metal surface treatment agent is preferably in the range of 1 to 100 g/L.
The concentration ratio (a/B), which is the ratio of the concentration of the bifunctional silane compound (a) to the concentration of the monofunctional silane compound (B), is preferably in the range of 0.1 to 5, more preferably in the range of 0.25 to 2.5. When the concentration ratio (a/B) exceeds 5, the number of hydrogen bonds at the interface between the film and the coating film decreases, and the strength decreases, thereby decreasing the adhesion with the coating film. When the concentration ratio (a/B) is less than 0.1, the film becomes highly hydrophilic, which tends to cause moisture permeation, and corrosion resistance after coating and film adhesion are reduced.
(Alkynediol based surfactant (C))
The acetylenic diol surfactant (C) is a nonionic surfactant having an acetylene group. The acetylenic diol surfactant (C) is contained in the aqueous chromium-free metal surface treatment agent together with the bifunctional silane compound (a) and the monofunctional silane compound (B), whereby the wettability of the aqueous chromium-free metal surface treatment agent to a metal substrate as a coating object can be improved. For example, the contact angle with respect to the metal substrate can be adjusted to 25 degrees or less. This enables to form a uniform coating film on the metal substrate. Examples of the acetylenic diol surfactant (C) include compounds represented by the following formula (II).
[ chemical 2]
In the above formula (II), R 5 And R is 6 Each independently represents a hydrogen atom or a methyl group. In the above formula (II), R 7 And R is 8 Each independently represents a hydrogen atom or an alkylene group. Examples of the alkylene group include an ethylene group and a propylene group. That is, the acetylenic diol surfactant (C) may be an alkylene oxide addition type or a non-alkylene oxide addition type.
In the above formula (II), n and m each independently represent an integer of 1 to 10.
As the acetylenic diol surfactant (C) represented by the above formula (II), commercially available ones can be used. Examples of commercial Products include Surfynol (Surfynol 104, surfynol465, etc.) manufactured by the japanese letter chemical industry co, and OLFINE series manufactured by Air Products. The acetylenic diol surfactant (C) may be used alone or in combination of 1 or more than 2.
The concentration of the acetylenic diol surfactant (C) in the aqueous chromium-free metal surface treatment agent is preferably in the range of 0.05 to 1g/L, more preferably in the range of 0 to 0.5 g.
(Water-dispersible metal oxide particles (D))
The water-dispersible metal oxide particles (D) are water-dispersible metal oxide particles such as Zr oxide, ti oxide, si oxide, al oxide, ce oxide, nb oxide, nd oxide, sn oxide, nd oxide, and La oxide. By adding the water-dispersible metal oxide particles (D) to the aqueous chromium-free metal surface treatment agent, brittle fracture of the formed coating film can be suppressed, and coating adhesion that can withstand high-strength processing can be further improved. As the water-dispersible metal oxide particles (D), zr oxide is preferable. The water-dispersible metal oxide particles (D) may be used alone or in combination of at least 2 kinds.
The concentration of the water-dispersible metal oxide particles (D) in the aqueous chromium-free metal surface treatment agent is preferably in the range of 1 to 20g/L, more preferably in the range of 2 to 15 g.
The average particle diameter (median diameter D50 measured by a dynamic light scattering method) of the water-dispersible metal oxide particles (D) is preferably 150nm or less, more preferably 10nm to 120nm.
(polyurethane resin (E))
The polyurethane resin (E) is at least one of a polyurethane water-dispersible resin and a polyurethane water-soluble resin. That is, the polyurethane resin (E) has either water-soluble or water-dispersible properties. By adding the urethane resin (E) to the aqueous chromium-free metal surface treatment agent, brittle fracture of the formed film can be suppressed, and the coating adhesion that can withstand high-strength processing can be further improved. The polyurethane resin (E) is not particularly limited, and can be obtained by polymerizing a polyol compound and a polyisocyanate compound by a conventionally known method. The polyurethane resin (E) may be used alone or in combination of at least 2 kinds.
The polyol compound is not particularly limited, and conventionally known synthetic materials can be used. Examples thereof include polyester polyols, polyester amide polyols, polyether polyols, polythioether polyols, polycarbonate polyols, polyacetal polyols, polyolefin polyols, and polysiloxane polyols.
The polyisocyanate compound is not particularly limited, and conventionally known synthetic materials can be used. Examples thereof include aliphatic isocyanates, alicyclic diisocyanates, aromatic diisocyanates, and aromatic aliphatic diisocyanates.
The concentration of the polyurethane resin (E) in the aqueous chromium-free metal surface treatment agent is preferably in the range of 1 to 20g/L, more preferably in the range of 5 to 15g, in terms of the resin solid content.
(blocked isocyanate resin (F))
The blocked isocyanate resin (F) is a water-soluble resin which reacts with the polyurethane resin (E) to form a crosslinked structure. The blocked isocyanate resin (F) is a polycondensate of a compound (monomer) having at least 1 blocked isocyanate group in 1 molecule blocked with a blocking agent such as a phenol-based, alcohol-based, oxime-based, active methylene-based, amide-based, carbamate-based, sulfite-based, or the like.
The blocked isocyanate resin (F) is obtained by adding a blocking agent to a compound having at least 1 isocyanate group in 1 molecule. Examples of the compound having at least 1 isocyanate group in 1 molecule include aliphatic diisocyanates such as hexamethylene diisocyanate (including 3-mer), tetramethylene diisocyanate and trimethylhexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and 4,4 '-methylenebis (cyclohexyl isocyanate), and aromatic diisocyanates such as 4,4' -diphenylmethane diisocyanate, toluene diisocyanate and xylylene diisocyanate. The blocked isocyanate resin (F) may be used alone or in combination of 1 or more than 2.
The concentration of the aqueous chromium-free metal surface treatment agent of the blocked isocyanate resin (F) is preferably in the range of 1 to 20g/L, more preferably in the range of 5 to 15g in terms of the resin solid content.
(other Compounds)
In addition to the above-described components, the aqueous chromium-free metal surface treatment agent of the present embodiment may contain other components. Examples of the other components include a crosslinking agent other than those described above for accelerating the curing of the resin, a surface conditioner for leveling purposes, an antifoaming agent for foam suppression purposes, and the like.
(pH of aqueous chromium-free Metal surface treatment agent)
The aqueous chromium-free metal surface treatment agent of the present embodiment preferably has a pH in the range of 5 to 7. The storage stability is further improved by setting the pH of the aqueous chromium-free metal surface treatment agent to 7 or less.
(contact angle of aqueous chromium-free Metal surface treatment agent)
The aqueous chromium-free metal surface treatment agent of the present embodiment has a contact angle of 25 degrees or less on the surface of the mirror-finished aluminum plate. Therefore, the coating film has good wettability to the metal substrate as the coating object, and can be uniformly formed. As a result, the coating adhesion can be improved. The aluminum sheet subjected to mirror finishing may be polished by using an ultrafine polishing material to a surface roughness Rz of 0.05 to 0.2 μm, and the surface may be washed with a degreasing agent (for example, surfcleaner 155 manufactured by NIPPON PAINT SURF CHEMICALS company) and water. The contact angle may be a value of a static contact angle measured with a contact angle meter (for example, DSA20E manufactured by KRUSS corporation) in a constant temperature chamber set at 20 ℃.
Surface treatment method
The surface treatment method of the present embodiment includes a surface treatment film forming step of forming a surface treatment film by treating a metal substrate as a coating object with the aqueous chromium-free metal surface treatment agent of the present embodiment. The surface treatment film forming step includes, for example, a coating step of coating an aqueous chromium-free metal surface treatment agent on the surface of a metal substrate as a coating object, and a drying step of drying the metal substrate coated with the aqueous chromium-free metal surface treatment agent to form a film.
(coating step)
In the coating step, the method of applying the aqueous chromium-free metal surface treatment agent to the metal substrate is not particularly limited, and examples thereof include roll coater coating, brush coating, roll coating, bar coater coating, flow coating, and the like.
(drying step)
The drying method in the drying step is not particularly limited, and a known method can be used. The drying temperature in the drying step is preferably 60 to 90 ℃ for example, based on the reaching temperature of the surface of the metal substrate, i.e., the peak metal temperature.
The coating process and the drying process may be performed simultaneously in parallel. For example, the aqueous chromium-free metal surface treatment agent may be applied to a preheated metal substrate and dried by waste heat.
Regarding the amount of the aqueous chromium-free metal surface treatment agent in the surface treatment film forming step, the amount of the film after drying is preferably 0.1 to 500mg/m 2 More preferably in the range of 1 to 250mg/m 2 Within a range of (2).
The surface treatment method of the present embodiment may further perform primer coating or top coating on the metal substrate on which the film is formed in the surface treatment film forming step.
< surface treatment Metal >)
The surface-treated metal of the present embodiment is formed by forming a surface-treated film on the surface of a metal substrate as a coating object using the aqueous chromium-free surface-treating agent of the present embodiment. The metal substrate is not particularly limited, and examples thereof include zinc-plated steel sheets such as aluminum sheets, stainless steel sheets, zinc-plated steel sheets, zinc alloy-plated steel sheets, and hot-dip zinc-plated steel sheets. The metal substrate may be subjected to a lamination process by a laminate film after a surface treatment film is formed thereon.
Examples of the aluminum sheet include aluminum-plated steel sheets such as 3000 aluminum alloy, 4000 aluminum alloy, 5000 aluminum alloy, 6000 aluminum alloy, and aluminum-plated, melt-plated, and vapor-deposited aluminum.
Examples of the stainless steel plate include SUS 300-series stainless steel and SUS 400-series stainless steel.
Examples of the zinc-based steel sheet include zinc-aluminum steel sheets such as zinc-nickel steel sheets, zinc-iron steel sheets, zinc-chromium steel sheets, and zinc-55 wt% aluminum alloy steel sheets, zinc-titanium steel sheets, zinc-magnesium steel sheets, and zinc-based plating such as zinc-manganese steel sheets, and zinc-or zinc-based alloy steel sheets such as hot-dip plating and vapor deposition steel sheets.
As the laminate film, for example, a resin film is used. As the resin film, for example, thermoplastic resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polycarbonate (PC), triacetyl cellulose (TAC), polyvinyl chloride (PVC), polyester, polyolefin, polyphenylene Sulfide (PPs), and acrylic are used. The lamination method for laminating the laminated film is not particularly limited, and a dry lamination method and an extrusion lamination method can be exemplified.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Preparation of aqueous chromium-free surface treatment agent
Example 1
The aqueous chromium-free surface treatment agent of example 1 was obtained by mixing and stirring the components (a), (B) and (C) in ion-exchanged water at the concentrations shown in table 1. As the bifunctional silane (A), 1, 2-bis-triethoxysilylethane (KBE-3026, manufactured by Xinyue chemical Co., ltd.) was hydrolyzed in advance, as the monofunctional silane (B), 3-aminopropylethoxysilane (KBE-903, manufactured by Xinyue chemical Co., ltd.) was used, and as the activator (C), surfynol104 (acetylenic diol surfactant, ethylene oxide addition type) manufactured by Air Products was used.
Examples 2 to 21 and comparative examples 1 to 5
In example 19, as the bifunctional silane (A), bis (triethoxysilyl) amine (Dynasylan 1124, manufactured by EVONIC Co., ltd.) was used. In example 20, 3-glycidoxyltriethoxysilane (KBE-403, made by Xinyue chemical Co., ltd.) was used as the monofunctional silane (B). In example 21, surfynol465 (an acetylenic diol surfactant, ethylene oxide non-additive) manufactured by Air Products was used as the active agent (C). In comparative example 4, newcol 1000 (alkyl ether surfactant) manufactured by japan emulsifier corporation was used as the active agent (C). In comparative example 5, a 6-valent chromium-containing treating agent (Surfcoat NRC 300 manufactured by NIPPON PAINT SURF CHEMICALS corporation) was used instead of the aqueous chromium-free surface treating agent. The procedure was the same as in example 1 except for the above.
< manufacture of test plate >)
Surface treatments were carried out on 3000-series and 5000-series aluminum plates (manufactured by Testpanel corporation, japan, plate thickness: 0.35 mm) as metal substrates shown in Table 1 using the surface treatment agents of examples 1 to 21 and comparative examples 1 to 5, respectively. The surface treatment was performed in the following order. Aluminum plates were spray degreased with surfclean 155 (manufactured by NIPPON PAINT SURF CHEMICALS company) as an alkali degreaser at 60 ℃ for 10sec, then spray water washed to dry, and then a surface treatment agent was applied to the aluminum plates with a bar coater #3, followed by drying at PMT (peak metal temperature) 80 ℃. In comparative example 5, the chromium deposit amount after degreasing, washing with water and drying was 30mg/m 2 Is coated by a bar coater and dried at PMT 60 ℃. The aluminum plate surface-treated by the above method was coated with a thermosetting acrylic varnish (super-block) D1F R-37Gold extinction (modified) AP, manufactured by Nippon Paint Industrial Coatings, so that the dry film thickness became 5 μm, and then sintered and dried at PMT 250 ℃ for 50sec to obtain test plates of examples 1 to 21 and comparative examples 1 to 5.
< evaluation >
[ 1-fold adhesion ]
The test plate was subjected to 180 ° bending (0 TT) without sandwiching a spacer between the test plates or two 0.35mm aluminum plates as spacers between the test plates, 180 ° bending (2 TT) was performed, the tape of the bending portion was peeled 3 times, and the degree of peeling was observed with a 20-fold magnifying glass, and evaluated according to the following criteria. The results are shown in table 1, assuming that 4 or more were acceptable.
5: no peeling; 4.5: stripping 1-10%; 4: stripping 11-20%; 3.5: stripping 21-30%; 3: stripping 31-40%; 2.5: stripping 41-50%; 2: 51-60% stripping; 1.5: stripping 61-70%; 1: 71-80% stripping; 0.5: stripping 81-90%; 0: 91-100% peeling.
[ adhesion after bending 2 times ]
After immersing the test board in boiling water for 2 hours, the test board was left in the room for 24 hours, and the test board was evaluated on the same basis under the conditions of 0TT and 2TT, respectively, in the same manner as the primary bending adhesion. The results are shown in Table 1, with the results being acceptable at 3.5 or more.
[ Silk rust Length ]
The test plate subjected to the transverse cutting was placed in a 2L beaker containing 50mL of concentrated hydrochloric acid, exposed to hydrochloric acid vapor for 10 minutes, placed in a constant temperature and humidity chamber at 40℃and at RT82%, and after 250 hours, the length of the filiform rust and the number of fragments (number of filiform rust) from the cut portion were measured to calculate the total length of the filiform rust. And the diameter of the glass is below 2mm, and the glass is qualified. The results are shown in Table 1.
[ SST (salt spray test) ]
The test plate subjected to the transverse cutting was put into a salt spray corrosion tester shown in JIS Z2317 for 1000hr, and the average blister width of one-side corrosion from the cut portion and the average blister width of corrosion from the end face (upper burr, lower burr) were measured. The results are shown in Table 1, assuming that the test pieces were 1mm or less.
[ CCT (composite cycle Corrosion test) ]
The test plate subjected to the transverse cutting was put into a composite cycle corrosion tester shown in JIS K5621 for 1000hr, and the average blister width of one-side corrosion from the cut portion and the average blister width of corrosion from the end face (upper burr, lower burr) were measured. The results are shown in Table 1, assuming that the test pieces were 1mm or less.
[ contact Angle measurement ]
The surface treatments of examples 1 to 21 and comparative examples 1 to 4 were set in an automatic contact angle meter (DSA 20E, KRUSS Co., ltd.) and the static contact angle of the treatment agent dropwise added to the aluminum plate was measured in a thermostatic chamber at 20 ℃. The aluminum plate used was polished by an ultrafine particle polisher to a surface roughness Rz of 0.05 to 0.2 μm, and then degreased with a degreasing agent (Surfcleaner 155, manufactured by NIPPON PAINT SURF CHEMICALS Co.) at 60℃for 30 seconds, followed by washing with water. The results are shown in table 1, assuming that the test pieces were acceptable at 25 degrees or less.
TABLE 1
Examples 22 to 38 and comparative examples 6 to 9
Further, metal oxide particles (D) of the kind and amount shown in Table 2 were added. In comparative example 9, a 6-valent chromium-containing treating agent (Surfcoat NRC 300 manufactured by NIPPON PAINT SURF CHEMICALS corporation) was used instead of the aqueous chromium-free surface treating agent. Preparation of the surface treatment agent was performed in the same manner as in example 1, except for the above. The average particle diameter (D50) of the metal oxide particles (D) shown in table 2 is as follows.
ZrO 2 ：80nm；TiO 2 ：10nm；SiO 2 ：9nm；CeO 2 ：15nm；Nb 2 O 5 ：4nm；SnO 2 ：2nm；Al 2 O 3 ：50nm。
< manufacture of test plate >)
Surface treatments were performed in the same manner as in example 1 and comparative example 5 except that a zinc-55 wt% aluminum alloy steel sheet (GL) (manufactured by Testpanel corporation, japan, plate thickness 0.35 mm) as a metal base material was subjected to surface treatments. The epoxy polyester PRIMER (NSC 5610NC PRIMER, manufactured by Nippon Paint Industrial Coatings) was applied to the GL steel sheet surface-treated by the above method so that the dry film thickness became 5. Mu.m, followed by firing and drying at the temperature of PMT 215. Mu.m, and then the polyester top coat (S/C460 HQ 1C4661, manufactured by Nippon Paint Industrial Coatings) was applied so that the dry film thickness became 15. Mu.m, followed by firing and drying at the temperature of PMT 230. Mu.m, whereby test plates of examples 22 to 38 and comparative examples 6 to 9 were obtained.
< evaluation >
[ 1-time adhesion after bending and 2-time adhesion after bending ]
Tests were carried out in the same manner as in examples 1 to 21 and comparative examples 1 to 5, and evaluation was carried out on the basis of the following criteria. The results are shown in Table 2, with the results of 4 or more being acceptable.
5: no crack; 4: cracking the whole surface of the processing part; 3: the stripping area is less than 20% of the processing part; 2: the peeling area is more than 20% and less than 80% of the processing part; 1: the peeling area is 80% or more of the processed portion.
[ SST (salt spray test), CCT (composite cycle Corrosion test) ]
Tests and evaluations were carried out in the same procedure as in examples 1 to 21 and comparative examples 1 to 5. SST further evaluates the corrosion resistance of the processed portion. For the corrosion resistance of the processed portion, the white rust area ratio (%) of the coated surface after the SST test (2 TT) was evaluated visually according to the following criteria.
5: rust-free; 4.5: 0-10%; 4: 11-20%; 3.5: 21-30%; 3: 31-40%; 2.5: 41-50%; 2: 51-60%; 1.5: 61-70%; 1: 71-80%; 0.5: 81-90%; 0: 91-100%.
The standard for the SST and CCT tests shown in table 2 is as follows. SST (machined part corrosion resistance): 4 or more; SST (cutting portion): 1 or less; SST (end face up and down): 7 or less; CCT (cutting section): 0.7 or less; CCT (end face up and down): 3 or less.
TABLE 2
Examples 39 to 56 and comparative examples 10 to 13
Preparation of a surface treatment agent and production of test boards were performed in the same manner as in examples 22 to 38 and comparative examples 6 to 9, except that metal oxide particles (D), polyurethane resin (E) (superfex 650, manufactured by first industrial pharmaceutical company) and blocked isocyanate resin (F) (Lanxess Solutions Japan, inc. Manufactured by Aqua BI 220) were further added in the amounts and types shown in table 3.
TABLE 3
< evaluation >
Evaluation was performed under the same conditions as in examples 22 to 38 and comparative examples 6 to 9 except that the conditions for the SST test and CCT test were changed from 1000hr to 1500 hr. The results are shown in Table 4. The standard for the SST and CCT tests shown in table 4 is as follows. SST (machined part corrosion resistance): 3.5 or more; SST (cutting portion): 1.5 or less; SST (end face up and down): 6.1 or less; CCT (cutting section): 0.7 or less; CCT (end face up and down): 3.5 or less.
TABLE 4
Examples 57 to 74 and comparative examples 14 to 17
Further, metal oxide particles (D), polyurethane resin (E) and blocked isocyanate resin (F) were added in the amounts and types shown in Table 5, and Al having an average particle diameter (D50) of 100nm was used in example 65 2 O 3 The preparation of the surface treatment agent was carried out in the same manner as in examples 22 to 38 and comparative examples 6 to 9 except that the metal oxide particles (D) were used. The test panels were produced in the same manner as in examples 22 to 38 and comparative examples 6 to 9, except that the metal base material was a hot-dip galvanized steel sheet (GI) (manufactured by Testpanel Co., ltd., thickness: 0.35 mm), and the test panels were immersed in a nickel sulfate-based surface conditioner (NP adjuster 700, pH 3.0, 60 ℃ C.) for 5 seconds after spray water washing.
TABLE 5
< evaluation >
[ stability ]
The liquid stability of the surface treatment liquid after preparation was evaluated by visual observation in an incubator at 40℃for 3 months according to the following criteria. 1: no problem exists; 2: slightly cloudy.
Except for the above, the evaluation was performed under the same conditions as in examples 22 to 38 and comparative examples 6 to 9. The results are shown in Table 6. The standard for the SST and CCT tests shown in table 6 is as follows. SST (machined part corrosion resistance): 3.5 or more; SST (cutting portion): 6.0 or less; SST (end face up and down): 6.1 or less; CCT (cutting section): 0.7 or less; CCT (end face up and down): 3.5 or less.
TABLE 6
Examples 75 to 92 and comparative examples 18 to 21
Further, metal oxide particles (D), polyurethane resin (E) and blocked isocyanate resin (F) were added in the amounts and types shown in Table 7, and Al having an average particle diameter (D50) of 140nm was used in example 83 2 O 3 The preparation of the surface treatment agent and the test plate production were performed in the same manner as in examples 22 to 38 and comparative examples 6 to 9 except that the metal substrate was a stainless steel plate (SUS 304 and 430 shown in Table 7 are SUS 430) (plate thickness is 0.35mm, manufactured by Testpanel Co., ltd.).
TABLE 7
/>
< evaluation >
Evaluation was performed in the same manner as in examples 57 to 74 and comparative examples 14 to 17, except that SST and CCT were set to 1500 hr. The results are shown in Table 8. The standard for the SST and CCT tests shown in table 8 is as follows. SST (machined part corrosion resistance): 4.0 or more; SST (cutting portion): 1.0 or less; SST (end face up and down): 0.5 or less; CCT (cutting section): 0 or less; CCT (end face up and down): and 0.5 or less.
TABLE 8
Examples 93 to 112 and comparative examples 22 to 25
Preparation of surface treatment agents was carried out in the same manner as in examples 22 to 38 and comparative examples 6 to 9, except that the metal oxide particles (D), the polyurethane resin (E) and the blocked isocyanate resin (F) were further added in the amounts and types shown in table 9. In the production of the test plate, a GI plate or a GL plate (both manufactured by Testpanel, japan, and having a plate thickness of 0.35 mm) shown in table 9 was spray-degreased at 60 ℃ for 10 seconds, then spray-water washed, then immersed in a cobalt ion-containing alkaline surface conditioner (NP regulator 200, ph11, 60 ℃) for 5 seconds, water washed, then dried at PMT 80 ℃, and then a treatment agent containing the components described in bar coater #3 was applied to the GI plate or GL plate, and then dried at PMT (peak metal temperature) 80 ℃. After the surface treatment, a polyurethane-based adhesive was applied, and then an acrylic-based laminate film (polypropylene film having a thickness of 50 μm) was pressure-bonded by a roller, and heated and bonded at 230℃to obtain test boards of examples 93 to 112 and comparative examples 22 to 25.
TABLE 9
< evaluation >
[ 1-pass adhesion test (Elmendorf cup test) ]
The test plate was cut with a cutter to form a grid-like cut, and the test plate was subjected to tape peeling by an Elmendorf machine after extrusion processing to 8mm. Tape peel test according to JIS Z0237: 2009. The degree of tape peeling was evaluated based on the following criteria, and was rated as being 4 or more. The results are shown in Table 10.
5: no peeling; 4.5: stripping 1-10%; 4: stripping 11-20%; 3.5: stripping 21-30%; 3: stripping 31-40%; 2.5: stripping 41-50%; 2: 51-60% stripping; 1.5: stripping 61-70%; 1: 71-80% stripping; 0.5: stripping 81-90%; 0: 91-100% peeling
[ 2-pass adhesion test (Elmendorf cup test) ]
As a preliminary treatment, a test plate was cut with a cutter to form grid-like cuts, and after extrusion to 6mm with an Elmendorf machine, the plate was immersed in boiling water at 98℃for 1 hour, and then tape was peeled off at the extrusion part. The degree of tape peeling was evaluated in the same manner as in the 1-pass adhesion test. The results are shown in Table 10.
In addition to the above, the SST and CCT were set at 1000hr, and evaluation was performed. The results are shown in Table 10. The standard for the SST and CCT tests shown in table 10 is as follows. SST (cutting portion): 5.0 or less; SST (end face up and down): 6.0 or less; CCT (cutting section): 2 or less; CCT (end face up and down): 3.5 or less.
TABLE 10
From the results of the above examples and comparative examples, it was confirmed that the aqueous chromium-free metal surface treatment agent of the examples has superior coating adhesion to the surface treatment agent of the comparative examples, and can form a coating film on a metal substrate that can withstand high-strength workability.
Claims (10)
1. An aqueous chromium-free surface treatment agent comprising a bifunctional silane compound (A), a monofunctional silane compound (B) and an acetylenic diol-based surfactant (C).
2. The aqueous chromium-free surface treatment agent according to claim 1, wherein,
the concentration of the bifunctional silane compound (A) is in the range of 1 to 100g/L,
the concentration of the monofunctional silane compound (B) is in the range of 1 to 100g/L,
the concentration ratio (A/B) of the difunctional silane compound (A) to the monofunctional silane compound (B) is in the range of 0.1 to 5.
3. The aqueous chromium-free surface treatment agent according to claim 1 or 2, wherein,
the concentration of the acetylenic diol surfactant (C) is in the range of 0.05 to 1 g/L.
4. The aqueous chromium-free surface treatment agent according to any one of claim 1 to 3, wherein,
the contact angle on the surface of the mirror-finished aluminum plate is 25 degrees or less.
5. The aqueous chromium-free surface treatment agent according to any one of claims 1 to 4, wherein,
further comprising water-dispersible metal oxide particles (D) having an average particle diameter of 150nm or less, wherein the concentration of the water-dispersible metal oxide particles (D) is in the range of 1 to 20 g/L.
6. The aqueous chromium-free surface treatment agent according to any one of claims 1 to 5, wherein,
further comprises a polyurethane resin (E) which is at least one of a polyurethane water-dispersible resin and a polyurethane water-soluble resin, and the concentration of the polyurethane resin (E) is in the range of 1-20 g/L.
7. The aqueous chromium-free surface treatment agent according to any one of claims 1 to 6, wherein,
further comprises a blocked isocyanate resin (F), wherein the concentration of the blocked isocyanate resin (F) is in the range of 1-20 g/L.
8. The aqueous chromium-free surface treatment agent according to any one of claims 1 to 7, wherein,
the pH is in the range of 5 to 7.
9. A surface-treated metal obtained by forming a surface-treated coating film on a surface with the aqueous chromium-free surface-treating agent according to any one of claims 1 to 8.
10. A surface treatment method comprising a surface treatment film forming step of forming a surface treatment film by treating the surface of a coating object with the aqueous chromium-free surface treatment agent according to any one of claims 1 to 8.
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| JP2021054776A JP7194768B2 (en) | 2021-03-29 | 2021-03-29 | Aqueous chromium-free surface treatment agent, surface treated metal, and surface treatment method |
| PCT/JP2022/007523 WO2022209453A1 (en) | 2021-03-29 | 2022-02-24 | Aqueous chrome-free surface treatment agent, surface treatment metal, and surface treatment method |
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| JP2003138385A (en) | 2001-10-29 | 2003-05-14 | Nippon Steel Corp | Non-lubricating film removal type plated steel sheet having excellent adhesion of coating film, corrosion resistance in worked zone and reduced environmental load |
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