WO2002064857A1 - Agent de traitement pour surface metallique, procede de traitement de la surface metallique et materiau metallique traite en surface - Google Patents

Agent de traitement pour surface metallique, procede de traitement de la surface metallique et materiau metallique traite en surface Download PDF

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Publication number
WO2002064857A1
WO2002064857A1 PCT/JP2002/001215 JP0201215W WO02064857A1 WO 2002064857 A1 WO2002064857 A1 WO 2002064857A1 JP 0201215 W JP0201215 W JP 0201215W WO 02064857 A1 WO02064857 A1 WO 02064857A1
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WIPO (PCT)
Prior art keywords
resin
metal surface
aqueous
aqueous dispersion
surface treatment
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Application number
PCT/JP2002/001215
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English (en)
Japanese (ja)
Inventor
Motohiro Sasaki
Koichi Saito
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Nippon Paint Co., Ltd.
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Filing date
Publication date
Application filed by Nippon Paint Co., Ltd. filed Critical Nippon Paint Co., Ltd.
Publication of WO2002064857A1 publication Critical patent/WO2002064857A1/fr

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    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process

Definitions

  • Metal surface treatment agent Metal surface treatment agent, metal surface treatment method and surface treated metal material
  • the present invention relates to a metal surface treatment agent, a metal surface treatment method, and a surface treatment metal material, and more particularly to a metal surface treatment agent containing an ionomer resin-based aqueous dispersion.
  • Organic composite coated steel sheets widely used for home appliances, office equipment, building materials, automobiles, etc. have excellent corrosion resistance.
  • the organic composite coated steel sheet has been widely put into practical use as a high-performance steel sheet provided with paint adhesion, fingerprint resistance, lubricity, etc., depending on the application.
  • the organic composite coated steel sheet refers to a steel sheet having a surface subjected to chromate treatment and further having a thin organic resin skin formed on the surface.
  • This ionomer resin has good adhesion to various base materials, especially metals, and the formed film is tough and resistant to scratches, and is resistant to organic solvents such as ethanol and methyl ethyl ketone. Is an excellent material.
  • the ionomer resin or the ionomer resin based on A film formed with the composition described above has insufficient conductivity when the film thickness is large, and when coating with a top coat, it is not always possible to obtain good coating adhesion.
  • the present invention has been made in view of the above problems, and has excellent conductivity of a film when used as a surface treatment agent, and excellent coating adhesion when a topcoat film is formed on the film.
  • An object of the present invention is to provide a metal surface treatment agent, a metal surface treatment method, and a surface treated metal material.
  • a metal surface treating agent comprising a composite aqueous dispersion resin obtained by radical polymerization of an unsaturated monomer in the presence of the above aqueous dispersion resin.
  • a metal surface treatment agent comprising a mixture of the above aqueous dispersion resin or composite aqueous dispersion resin with at least one aqueous resin selected from the group consisting of an aqueous polyurethane resin, an aqueous polyester resin, and an aqueous acryl 'resin. .
  • a metal surface treatment agent comprising a resin mixture.
  • a metal surface treatment method which comprises applying the metal surface treatment agent to a metal surface to form a film.
  • the metal surface treating agent of the present invention has an unsaturated carboxylic acid of 10 to 30 mass. /.
  • Aqueous dispersion obtained by neutralizing 30% or more of the carboxyl 'groups of the contained ethylene-unsaturated carboxylic acid copolymer with force rimion, and reacting the ionomer resin water-dispersed with the epoxy compound. Including resin.
  • Examples of the unsaturated carboxylic acid of the present invention include atrialic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid and the like, and acrylic acid and methacrylic acid are particularly preferable.
  • the ionomer resin of the present invention uses potassium as an ion source.
  • the ion source is another monovalent ion, for example, sodium
  • the formed film has insufficient conductivity.
  • the ion source is a divalent ion, for example, zinc or magnesium, the conductivity is not sufficient.
  • the ionomer resin of the present invention has a neutrality of carboxyl groups due to potassium ions of 30% or more.
  • the degree of neutralization is less than 30%, the conductivity is not sufficient, and when the degree of neutralization is extremely low, the solvent resistance decreases.
  • the upper limit of the degree of neutralization is not particularly limited, but is preferably 100% or less from the viewpoint of corrosion resistance.
  • the aqueous dispersion of the ionomer resin is reacted with an epoxy compound to form an aqueous dispersion resin, and a metal surface treating agent containing the aqueous dispersion resin is obtained.
  • the epoxy compound refers to a compound having at least one epoxy group in one molecule, and includes glycidyl ethers and glycidyl esters.
  • Glycidyl ethers include, for example, phenyl glycidyl ether, resole / syndiglycidyl ether, bisphenol / diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether One tel and the like.
  • Examples of the glycidyl esters include diglycidyl adipate and diglycidyl phthalate.
  • the reaction between the ionomer resin and the epoxy compound is carried out at a temperature in the range of 30 ° C. to the boiling point, more preferably at a temperature in the range of 60 to 95 ° C. When the temperature is lower than 30 ° C, the reaction does not proceed sufficiently.
  • the reaction time is 0.5 to 10 hours.
  • the above metal surface treatment agent has excellent conductivity of a film when used as a surface treatment agent, and also has excellent coating adhesion when a top coat is formed on the film.
  • the metal surface treating agent thus obtained can be further compounded or blended with another resin in the aqueous dispersion resin.
  • a composite aqueous dispersion resin of an ionomer-based aqueous dispersion resin and an acryl resin can be obtained by subjecting an unsaturated monomer to radical polymerization using an initiator in the presence of the aqueous dispersion resin.
  • At least one water-based resin selected from water-based polyurethane resin, water-based polyester resin and water-based acrylic resin may be further added to the water-based dispersion resin or the composite water-based dispersion resin.
  • the unsaturated monomer is subjected to radical polymerization in a mixture of the above aqueous dispersion resin and at least one aqueous resin selected from an aqueous polyurethane resin, an aqueous polyester resin, and an aqueous acryl resin to form a composite aqueous dispersion resin mixture. Is also good.
  • alkyl (meth) acrylates styrene, (meth) acrylic acid, hydroxyalkyl (meth) acrylates and the like can be used.
  • persulfates such as potassium persulfate and ammonium persulfate
  • azo compounds such as azobiscyanovaleric acid and azobisisobutyronitrile
  • the aqueous polyurethane resin is prepared, for example, by reacting a diol with a diisocyanate compound such as hexamethylene diisocyanate, isophorone diisocyanate, or tolylene diisocyanate, and further elongating the chain with diamine or the like to disperse in water. Can be obtained.
  • a diisocyanate compound such as hexamethylene diisocyanate, isophorone diisocyanate, or tolylene diisocyanate
  • the aqueous polyester resin can be obtained by, for example, dehydrating and condensing a diol and a polybasic acid, neutralizing the resultant with an amine or the like, and making it water-soluble or water-dispersed.
  • the aqueous acrylic resin is prepared, for example, by radically polymerizing an unsaturated monomer containing an unsaturated carboxylic acid in an organic solvent, and then neutralizing the radical with an amine or the like to make it water-soluble or dispersed in water. Emulsion polymerization of unsaturated monomers Therefore, it can be obtained.
  • the above composite or other resin to be compounded is 50% by mass with respect to the aqueous dispersion resin before the composite or compound. / 0 or less, more preferably 30 mass. Use in the range of / 0 or less.
  • the metal surface treating agent obtained as described above can improve the corrosion resistance of a film when used as a surface treating agent.
  • the combined or compounded amount is 50 mass. If it exceeds / 0 , the effect of improving the conductivity of the obtained metal surface treating agent will be impaired.
  • the radical polymerization conditions for obtaining the composite aqueous dispersion are a reaction temperature of 40 to 90 ° C. and a reaction time of 0.5 to 10 hours.
  • the metal surface treating agent of the present invention is obtained by further mixing fine particles of silicic acid with the aqueous dispersion resin or the composite aqueous dispersion resin.
  • the silica fine particles are not particularly limited, but, for example, those having an average particle size of about 0.01 to 0.5 m are suitable, and are appropriately selected from colloidal silica, fumed silica, and the like. be able to. It is preferable that the silica fine particles be blended in an amount of 10 to 50% by mass based on the total amount of all the aqueous resins blended. By blending the fine particles, the corrosion resistance of the metal material surface-treated with the metal surface treating agent can be improved.
  • the above-mentioned metal surface treatment agent is applied to a metal surface to form a film.
  • the coating method is not particularly limited, and a normal coating method such as a roll coating method, a spraying method, and a dipping method can be used.
  • the film formed by the above metal surface treatment method has excellent conductivity and corrosion resistance, and also has excellent solvent resistance.
  • a top coat is applied on the above-mentioned film to form a coated film.
  • the coating method is not particularly limited, and a normal coating method such as a roll coating method, a spray method, and a dipping method can be used.
  • the surface-treated metal material obtained by the above-described metal surface treatment method has excellent coating adhesion of the topcoat.
  • BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be further described with reference to Examples and Comparative Examples. The present invention is not limited to the embodiments described below.
  • the metal surface treating agents of Examples and Comparative Examples were Primacol 59801 (Dow Chemical's atrialic acid content: 20% by mass) or ethylene-methacrylic acid as an ethylene-acrylic acid copolymer.
  • Primacol 59801 Low Chemical's atrialic acid content: 20% by mass
  • ethylene-methacrylic acid as an ethylene-acrylic acid copolymer.
  • 2 Utrell 206 Mitsubishi Chemical's DuPont Polychemical Co., Ltd., methacrylic acid content: 20% by mass
  • Potassium hydroxide was used as a potassium ion source in the examples.
  • sodium hydroxide was used as a monovalent sodium ion source
  • zinc oxide was used as a divalent zinc ion source.
  • ammonia which is a volatile neutralizer, was used in combination with a metal ion source or used instead of a metal ion source.
  • Epoxy compounds of the examples include denacol 313 (glycerin polyglycidyl-ter Nagase Kasei Kogyo), denacol 321 (trimethylolpropane polyglycidyl mono-ter Nagase Kasei Kogyo), or Epikote 828 (bisphene).
  • Denacol 313 glycerin polyglycidyl-ter Nagase Kasei Kogyo
  • denacol 321 trimethylolpropane polyglycidyl mono-ter Nagase Kasei Kogyo
  • Epikote 828 bisphene
  • Adekabon Titer HU X-320 manufactured by Asahi Denka Kogyo was used.
  • the unsaturated monomers used in forming the composite aqueous dispersion were those shown in Table 1.
  • KPS is potassium persulfate as a polymerization initiator.
  • the 1 0 to 2 0 nm colloidal silica particle size as a solid content 2 0 mass 0/0 containing Snowtex N (manufactured by Nissan Chemical Industries) Using.
  • the preparation method of the metal surface treating agent using each of the above-mentioned raw materials was based on the following method.
  • a predetermined amount of ethylene- (meth) acrylic acid copolymer set in each of the examples and comparative examples and a predetermined amount of A metal ion source, a predetermined amount of 25% by mass ammonia water for some examples and comparative examples, and a slightly different amount of deionized water for each example and comparative example were charged and stirred. It was kept at a temperature of ° C for 2 hours.
  • Example 2 an aqueous polyurethane resin was further added to the aqueous dispersion resin.
  • Example 3 an unsaturated monomer was polymerized in the presence of the aqueous dispersion resin.
  • Example 4 an unsaturated monomer was polymerized in a mixture of the aqueous dispersion resin and the aqueous polyurethane resin.
  • Polymerization of the unsaturated monomer was performed as follows. First, half of the value of the unsaturated monomer shown in Table 1 was poured into a flask containing an aqueous dispersion resin maintained at 80 ° C with stirring, and after 10 minutes, a 1% aqueous solution of potassium persulfate was added. The reaction was started by feeding 2 Z 3 of the numerical value shown in Table 1. After a further 10 minutes, the remaining unsaturated monomer was added, and then, after a further 10 minutes, the remaining 1% aqueous persulfuric acid aqueous solution was added, and then the temperature was maintained at 80 ° C for 2 hours. The reaction was completed.
  • aqueous dispersion resin or composite aqueous dispersion resin predetermined amounts of colloidal silica and deionized water set in each of Examples and Comparative Examples were added to uniformly adjust the solid content to 20% by mass.
  • a metal surface treatment agent was obtained.
  • Table 1 shows specific raw material mixing conditions of each of Examples 1 to 6 and Comparative Examples 1 to 5 for the metal surface treating agent.
  • EG Electro Galvanized Steel Sheet
  • GI Hot Dipped Galvanized Steel Sheet
  • GL Three types of steel sheets were used: molten zinc-aluminum alloy coated steel sheets. Note that the three types of steel plates used had dimensions of 7 Omm X 15 Omm X 0.8 mm manufactured by Japan Test Panel. . I
  • GI in the steel sheet type indicates a steel sheet coated with molten zinc.
  • GL in the steel sheet type indicates a steel sheet coated with a molten zinc aluminum alloy.
  • GI in the steel sheet type indicates a steel sheet coated with molten zinc.
  • r “GL” in the steel sheet type indicates a steel sheet coated with a molten zinc aluminum alloy.
  • Example Apply a point-to-point point metal surface treatment agent using a bar coater # 3 so that the film thickness after drying is 1 ⁇ m, and bake dry until the steel sheet reaches a temperature of 150 ° C. Then, a film was formed, and a test plate for evaluating conductivity, corrosion resistance, and solvent resistance described below was obtained. Further, a super coat 100 (Melamine alkyd paint manufactured by Nippon Paint) was further applied to the above test material using a bar coater # 32 as a top coat paint so that the film thickness after drying became 2; The coating was formed by baking and drying at 50 ° C for 20 minutes to obtain a test plate for evaluating the overcoat adhesion described later.
  • a super coat 100 Melamine alkyd paint manufactured by Nippon Paint
  • the evaluation method was based on the following methods.
  • the conductivity of the coating was evaluated by measuring the surface resistance (unit: ⁇ ) of the test material using Loresta (Mitsubishi Chemical surface resistance measuring device). Therefore, the smaller the value, the better the conductivity.
  • the numerical values in Tables 2 and 3 used the average of 10 measurements.
  • the corrosion resistance of the film was evaluated by spraying a 5% saline solution at 35 ° C while sealing the end face and the back face of the test material, and evaluating the white area generation area rate after 240 hours out of 10 points. The evaluation criteria are as follows.
  • Paint adhesion was evaluated by a secondary adhesion test.
  • test plate was immersed in boiling water for 30 minutes, and then the following three items were evaluated: grid, elixir, and grid + Eriksen.
  • the grid is formed in advance and then processed using an Erichsen tester so that the grid-formed part protrudes by 7 mm.
  • the same evaluation as the item of the eye was performed.
  • the evaluation criteria for all three items are as follows.
  • the coating film residual ratio is 90% or more
  • the metal surface treating agent used is an ethylene-unsaturated carboxylic acid containing 10 to 30% by mass of an unsaturated carboxylic acid. 30% or more of the carboxyl groups of the copolymer are neutralized with potassium ion, and the aqueous dispersion resin obtained by reacting the ionomer resin water-dispersed with the epoxy compound contains the conductive and corrosion-resistant coatings. In addition, it is possible to obtain an effect of excellent coating adhesion when a top coat is formed on the film.
  • the aqueous dispersion resin is further compounded or compounded with another resin, or further mixed with silica fine particles. Has better corrosion resistance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne un agent de traitement pour des surfaces métalliques qui procure un film de revêtement excellent en termes de conductivité, de résistance à la corrosion et d'adhérence à des films de revêtement supérieur à former en surface. Cet agent de traitement contient une dispersion aqueuse obtenue par réaction entre un composant époxy et une résine ionomère sous forme de dispersion aqueuse obtenue à partir d'un copolymère d'acide carboxylique éthylène/insaturé contenant 10 % à 30 % par poids d'unités d'acide carboxylique insaturé en neutralisant au moins 30 % des groupes carboxyles du copolymère par des ions potassium.
PCT/JP2002/001215 2001-02-14 2002-02-14 Agent de traitement pour surface metallique, procede de traitement de la surface metallique et materiau metallique traite en surface WO2002064857A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001037606A JP2002241670A (ja) 2001-02-14 2001-02-14 金属表面処理剤、金属表面処理方法および表面処理金属材料
JP2001-37606 2001-02-14

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WO2002064857A1 true WO2002064857A1 (fr) 2002-08-22

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018040374A1 (fr) * 2016-08-29 2018-03-08 常熟市诺信达机械设备有限公司 Plieuse pour production industrielle
CN110066360A (zh) * 2019-04-04 2019-07-30 南京瑞固聚合物有限公司 一种抗回黏水性丙烯酸乳液及其制备方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006028469A (ja) * 2004-06-14 2006-02-02 Dainichiseika Color & Chem Mfg Co Ltd 帯電防止塗料、帯電防止シートおよびその製造方法
WO2007102554A1 (fr) * 2006-03-07 2007-09-13 Kobe Steel, Ltd. Composition de resine aqueuse
MX366519B (es) 2013-07-18 2019-07-11 Mitsui Chemicals Inc Estructura compuesta de metal-resina y miembro metalico.
CN103695904A (zh) * 2013-12-26 2014-04-02 常熟市美尔特金属制品有限公司 金属表面处理方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09173972A (ja) * 1995-12-27 1997-07-08 Kawasaki Steel Corp 溶接性、連続加工性、および加工部耐食性に優れた潤滑樹脂処理金属板

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09173972A (ja) * 1995-12-27 1997-07-08 Kawasaki Steel Corp 溶接性、連続加工性、および加工部耐食性に優れた潤滑樹脂処理金属板

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018040374A1 (fr) * 2016-08-29 2018-03-08 常熟市诺信达机械设备有限公司 Plieuse pour production industrielle
CN110066360A (zh) * 2019-04-04 2019-07-30 南京瑞固聚合物有限公司 一种抗回黏水性丙烯酸乳液及其制备方法和应用

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