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WO1999046342A1 - Composition de traitement de surface pour materiau metallique et procede de traitement - Google Patents

Composition de traitement de surface pour materiau metallique et procede de traitement Download PDF

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Publication number
WO1999046342A1
WO1999046342A1 PCT/JP1999/001184 JP9901184W WO9946342A1 WO 1999046342 A1 WO1999046342 A1 WO 1999046342A1 JP 9901184 W JP9901184 W JP 9901184W WO 9946342 A1 WO9946342 A1 WO 9946342A1
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WO
WIPO (PCT)
Prior art keywords
group
silane coupling
surface treatment
coupling agent
water
Prior art date
Application number
PCT/JP1999/001184
Other languages
English (en)
Japanese (ja)
Inventor
Yasuhiko Nagashima
Hirokatsu Bannai
Original Assignee
Nihon Parkerizing Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nihon Parkerizing Co., Ltd. filed Critical Nihon Parkerizing Co., Ltd.
Priority to AU27476/99A priority Critical patent/AU2747699A/en
Priority to KR1020007010087A priority patent/KR20010041809A/ko
Publication of WO1999046342A1 publication Critical patent/WO1999046342A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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

Definitions

  • the present invention relates to a surface treatment composition and a treatment method capable of imparting excellent corrosion resistance and coatability to the surface of a metal material.
  • metal materials such as copper plates and aluminum plates with zinc-containing metal are used in a wide range of fields such as automobiles, building materials and home appliances.
  • zinc and aluminum have the drawback that they corrode in the air and produce corrosion products (so-called white), which degrade the appearance of metallic materials and adversely affect paint adhesion. I have.
  • chromate treatment is generally performed on the surface of the metal material with a treatment liquid mainly containing chromic acid, dichromic acid or salts thereof.
  • hexavalent chromium in the chromate treatment solution used to treat metal material surfaces has a direct adverse effect on the human body. Chromate processing is often avoided. Also, wastewater containing hexavalent chromium needs to be treated specially as stipulated in the Water Pollution Control Law, which will increase the cost of kana as a whole. In addition, chromate-treated metal materials have the major drawback that they cannot be recycled as chromium-containing industrial waste, which has become a major social problem.
  • a surface treatment agent using tannic acid containing polyvalent phenolcarbonic acid is well known.
  • the protective film formed by the reaction between the tannic acid and the metal material is barrier-free against the intrusion of corrosive substances, so that the corrosion resistance of the metal material is considered to be improved. its dependent c
  • a film using tannic acid alone or in combination with an inorganic component has insufficient corrosion resistance and cannot be practically used at present.
  • JP-A-53-2012 discloses a method of applying an aqueous solution comprising water-dispersible silica, an alkyd resin and a trialkoxysilane compound to a metal surface.
  • a hydroxypyrone compound--a water-soluble resin composed of a conductor--a surface treatment method for imparting corrosion resistance to a metal material and a water-soluble or water-dispersible polymer of a hydroxystyrene compound.
  • Methods for imparting corrosion resistance to metal materials are disclosed in Japanese Patent Application Laid-Open Nos. 57-4751 and 1-177380, and the like.
  • An object of the present invention is to solve the problems of the prior art and to provide a surface treatment agent for non-chromium-based metal materials which is excellent in hardness, corrosion resistance, and coatability.
  • the present inventors have conducted intensive studies to solve these problems of the prior art, and as a result, dispersed a silane coupling agent component, a water-soluble polymer component having a specific chemical structure in a colloidal state.
  • a surface treatment agent that contains the treated inorganic compound, the corrosion resistance and paintability, especially the slip resistance when applying a forming process such as bending after painting (coin)
  • the present inventors have newly found that a film having excellent scratch resistance can be formed, and have completed the present invention. Ie
  • the surface treatment composition for a metal material of the present invention comprises an aqueous medium, and the following components dissolved in the aqueous medium:
  • a silane coupling agent component comprising at least one silane coupling compound having at least one reactive functional group selected from methacryloxy groups and
  • X bonded to the benzene ring is a hydrogen atom, a hydroxy group, a C1-C5 alkyl group, a C1-C5 hydroxyalkyl group.
  • C6-C1 2 an aryl group, a benzyl group, a benzal group, an unsaturated hydrid carbon group condensed with the benzene ring to form a naphthalene ring, or a group represented by the following formula (II):
  • R 1 and R 2 in the formula (II) represent a hydrogen atom, a hydroxyl group, a C1-C5 alkyl group, or a C1-C10 hydroxyalkyl group, respectively.
  • Y 1 and Y 2 bonded to the benzene ring are each independently a Z group represented by the following formula (III) or (IV): CH 2
  • R 3, R 4, R 5, R 6 and R 7 in the above formulas (III) and (IV) each independently represent a hydrogen atom, a C 1 -C 10 alkyl group or a C 1- Represents a C 10 hydroxyalkyl group, and the average value of the number of substitutions of the Z group in each benzene ring in the polymer molecule is 0.2 to 1.0.
  • the silane coupling agent component is silane coupling agent component
  • Weight ratio of (A) to water-soluble polymer component (B) (A) / (B) Force 1: 10-: L 0: 1; (A) + (B) of inorganic compound (C) It is preferred that the weight ratio (C) / [(A) + (B)] to the weight ratio be 1: 5 to 5: 1.
  • the silane coupling agent component (A) may comprise (a) a silane coupling agent comprising one or more silane coupling compounds having one or more active hydrogen-containing amino groups. And (b) a silane coupling agent comprising one or more silane coupling compounds having one or more epoxysilane groups.
  • the equivalent ratio of the active hydrogen-containing amino group contained in the silane coupling agent (a) to the epoxy group contained in the silane coupling agent (b) is 3: 1 to 1: 1. : 3 to be preferable.
  • the weight ratio of the total amount of the silane coupling agent (a) and the silane coupling agent (b) to the water-soluble polymer component (B) [(a) + (b)] / (B) is preferably 1: 5 to 5: 1.
  • the surface treatment method for a metal material of the present invention comprises the step of preparing an aqueous surface treatment solution containing the above-mentioned surface treatment chemical composition for a metal material of the present invention and adjusted to a pH value of 2.0 to 6.5. deposited on the material, dried, is 0.0 to 2. which is characterized in that to form a coating having a dry weight of O g / m 2.
  • the surface of the metal material is previously subjected to a phosphate treatment or a chemical plating treatment before the aqueous surface treatment solution is attached to the metal material.
  • the surface treating agent composition for a metal material of the present invention comprises a silane coupling agent component (A) comprising at least one silane coupling compound having a specific reactive functional group, and a silane coupling agent component containing a special amino group.
  • A silane coupling agent component
  • B water-soluble polymerization component
  • B water-soluble polymerization component
  • C inorganic compound
  • the silane coupling compound contained in the silane coupling agent component (A) used in the present invention is a compound having a reactive functional group in one molecule comprising an active hydrogen-containing amino group, an epoxy group, a butyl group, a mercapto group and a methacryloxy group.
  • the structure is not particularly limited as long as it contains at least one selected member, but specific examples include those having the following compositions (1) to (4).
  • silane coupling agent component (A) used in the present invention comprises one or more silane coupling agents having one or more active hydrogen-containing amino groups. It is preferable that the silane coupling agent comprises a silane coupling agent (a) composed of a compound and a silane coupling agent (b) composed of one or more silane coupling compounds having one or more epoxy groups.
  • the silane coupling agent component (A) in the surface treatment agent composition according to the present invention is a silane coupling agent (a) comprising a silane coupling compound having an active hydrogen-containing amino group, and an epoxy group-containing silane coupling agent.
  • the equivalent ratio of the active hydrogen-containing amino groups contained in the silane coupling agent to the epoxy groups is preferably in the range of 3: 1 to 1: 3. If the equivalent ratio of the active hydrogen-containing amino group to the epoxy group exceeds 3: 1, the resulting film has poor film-forming properties, resulting in insufficient corrosion resistance and paintability. If it is less than 1: 3, the corrosion resistance and paintability of the treated film may be saturated.
  • the water-soluble polymer component (B) used in the present invention is an oligomer or a polymer containing the polymerized unit represented by the formula (I), and the average polymerization degree of the polymerized unit of the formula (I) is 2 ⁇ 50.
  • X bonded to the benzene ring is a hydroxyl group, a C1-5 alkyl group, for example, a methyl, ethyl, propyl group, etc., a C1-5 hydroxyalkyl group, for example, C6-12 aryl groups such as hydroxymethyl, hydroxyxethyl, hydroxypropyl, etc.
  • Benzyl group, benzal group, etc. an unsaturated hydrocarbon group condensed to the benzene ring to form a naphthalene ring
  • R 1 and R 2 in the formula (II) each independently represent a hydrogen atom, a hydroxyl group, a C 1 -C 10 alkyl group, for example, a methyl, ethyl, propyl group or the like; Examples include a hydroxyalkyl group, for example, hydroxymethyl, hydroxyshethyl, hydroxypropyl group and the like.
  • Y 1 and Y 2 bonded to the benzene ring each independently have a Z group represented by the formula (III) or (IV).
  • R 3, R 4, R 5, R 6 and R 7 in the formulas (III) and (IV) each independently represent a C 1 -C 10 alkyl group such as methyl, ethyl, propyl, etc.
  • C 1 to C 5 hydroxyalkyl groups for example, hydroxymethyl, hydroxyxethyl, hydroxypropyl group and the like.
  • X and Y 1 in Formula (I) and Y 2 in Formula (II) each bonded to each benzene ring in the polymer molecule are X bonded to other benzene rings.
  • Y 1 and Y 2 may be the same or different from each other.
  • the average value of the number of substitution of the ⁇ ⁇ group in each benzene ring in the polymer molecule is from 0.2 to 1.0.
  • ⁇ in the formula (I) represents an average degree of polymerization of 2 to 50. When ⁇ is less than 2, the molecular weight of the obtained polymer is too small, the corrosion resistance of the obtained film is insufficient, and when it exceeds 50, the obtained surface treating agent composition and The stability of the aqueous treatment solution containing the compound is poor, causing practical inconvenience.
  • the average value of the number of substituted ⁇ groups is the average value of the number of ⁇ groups introduced into each benzene ring in the polymer molecule.
  • the resulting polymer will have insufficient water solubility, and the stability of the surface treatment composition will be poor.
  • the force exceeds 1.0, the water solubility of the obtained polymer becomes excessive, and the effect of improving the corrosion resistance and coating property of the obtained film becomes insufficient.
  • Each of R 3 to R 7 in the Z group represented by the formulas (III) and (IV) represents a C 1 to C 10 alkyl group and a C 1 to C 10 hydroxyalkyl group. Represent. When the number of carbon atoms is 11 or more, the film forming property of the formed film is reduced, so that the corrosion resistance and the paintability become insufficient.
  • At least one inorganic compound (C) selected from the group consisting of silica, a silicate, a metal salt compound and a mixture thereof used in the present invention is uniformly dispersed in a colloidal state in the aqueous medium. It must be a liquid. Therefore, use of fine particles is preferred.
  • the weight ratio (A) / (B) to the silane coupling agent component (A) and the water-soluble polymer component (B) is from 1:10 to 10: 1. And preferably 1: 5 to 5: 1. If the weight ratio is less than 1:10, that is, if the ratio of the silane coupling agent component (A) is low, the adhesion to the substrate surface is reduced, and the corrosion resistance and coating properties are insufficient. On the other hand, if it exceeds 10: 1, that is, if the silane coupling agent component (A) ratio is high, the film-forming properties of the film will be reduced, and the resulting film will have insufficient corrosion resistance and paintability. .
  • the weight ratio of the inorganic compound component (C) to the total amount of the silane coupling agent component (A) and the water-soluble polymer component (B) (C) / [( A) + (B)] is 1: 5 to 5: 1, preferably-.
  • the polymerization ratio is less than 1: 5, that is, when the ratio of the inorganic compound component (C) is small, the physical strength of the obtained film becomes insufficient, Paintability, especially coin scratching, is insufficient.
  • it exceeds 5: 1 that is, if the content of the inorganic compound component (C) is too large, the film-forming properties of the obtained surface treatment composition will decrease, so that the corrosion resistance of the resulting film. In particular, the adhesion becomes insufficient.
  • the aqueous surface treating solution containing the surface treating agent composition described above, having a pH adjusted to a range of 2.0 to 6.5, is adhered to the surface of the metal material, and dried to obtain a solution.
  • 0 to 2.0 g / ni 2 preferably 0.05 to:
  • a film having a dry weight of L.O g / m 2 is formed.
  • the aqueous treatment liquid in contact from 0.1 to 30 seconds at a temperature of 1 0 ⁇ 6 0 ° C to the metal surface, the surface treatment method that is preferable c
  • the present invention for heating drying, an aqueous surface treatment liquid
  • the surface treatment agent is adjusted by diluting or undiluted the composition with an aqueous medium, for example, water.
  • the PH value is, for example, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, complex acid, etc. It is adjusted to a range of 2.0 to 6.5 using fluoride and organic acid.
  • Phosphoric acid, acidic phosphate, fluoride, and complex fluoride are preferably used for adjusting the pH value of the aqueous surface treatment solution used in the present invention.
  • the preferred PH value is 3.0-5.0. If the pH is less than 2.0, the reactivity between the composition in the obtained treatment liquid and the surface of the substrate becomes excessively high, resulting in poor coating, resulting in insufficient corrosion resistance and coating properties of the obtained coating. become. If the pH exceeds 6.5, the water-soluble polymer component (B) itself tends to precipitate out of the aqueous surface treatment solution, so that the life of the aqueous treatment solution is shortened.
  • the method of treating the surface of a metal material using the surface treating agent is not particularly limited, and for example, a dipping method, a spraying method, a roll coating method, and the like can be applied.
  • the processing temperature and the processing time are not particularly limited, but generally, the processing temperature is preferably 10 to 60 ° C, and the processing time is preferably 0.1 to 20 seconds. Further, it is preferable to heat and dry the treated metal material.
  • the heating temperature is preferably from 50 to 280 ° C.
  • the metal ion eluted and mixed from the metal material and the water-soluble polymer component (B) are complexed. May form body and precipitate.
  • a sequestering agent may be added to the surface treatment composition.
  • EDTA EDTA
  • Cy-DTA triethanolamine
  • dalconic acid heptgluconic acid
  • oxalic acid tartaric acid
  • lingic acid organic phosphonic acid
  • a surfactant for improving coatability may be added to the aqueous surface treatment solution used in the surface treatment method of the present invention.
  • the surfactant include commercially available anionic surfactants such as a carboxylate type, a sulfate type, a sulfonate type, and a phosphate type, a polyethylene glycol type nonionic surfactant, and a polyhydric alcohol type.
  • anionic surfactants such as a carboxylate type, a sulfate type, a sulfonate type, and a phosphate type, a polyethylene glycol type nonionic surfactant, and a polyhydric alcohol type.
  • examples include an ionic surfactant and an amine-based cationic surfactant.
  • the metal material used in the present invention can be selected from an iron plate, a zinc-plated copper plate, an aluminum plate, an aluminum alloy plate, a stainless steel plate and the like.
  • the steel sheet may be selected from steel sheets which have been subjected to a phosphate treatment or a chemical plating treatment. In this case, the corrosion resistance and the paintability are improved.
  • the chemical plating treatment includes, for example, substitution plating of metals such as cobalt, nickel, copper, iron, silver, and gold.
  • the inventors consider as follows. First, the metal surface is etched by phosphoric acid, acid phosphate, fluoride and complex fluoride in the surface treatment composition. As a result, the pH at the interface increases, and a reaction between the eluted metal ions and the water-soluble polymer component forms a poorly soluble film at the interface. It is thought that the corrosion resistance is improved because this hardly soluble film exerts a barrier effect.
  • the functional group (—OR group) in the hydrolyzed silane coupling agent can be brought into contact with the metal material surface by using the silane coupling agent component in combination. Oxane bond, and the other reactive functional group in the silane coupling agent reacts with the water-soluble polymer component, presumably improving the adhesion between the metal material and the water-soluble polymer component. Is done.
  • the inorganic compound component dispersed in a colloidal state forms fine irregularities on the surface of the metal material, and the irregularities exert an anchoring effect on the paint applied on the metallic material. It is presumed that they exhibit workability after painting such as inscratching property.
  • the present invention will be specifically described with reference to the following examples, but the scope of the present invention is not limited to these examples.
  • Electro-galvanized steel sheet (EG material)
  • the surface of the above metal material is treated with a medium alkaline degreasing agent (registered trademark: Fine Cleaner 4336, manufactured by Nippon Parkerizing Co., Ltd.). Chemical concentration: 20 g / liter, treatment temperature: 60 ° C, treatment time: 20 seconds Spray treatment was performed under the following conditions to remove dust and oil adhering to the surface. Next, the alkali remaining on the surface was washed with tap water to clean the surface of the test material.
  • a medium alkaline degreasing agent registered trademark: Fine Cleaner 4336, manufactured by Nippon Parkerizing Co., Ltd.
  • X — CH 2 — C 6 H 4 — OH
  • average number of Z group substitutions 0.75
  • a hot-dip galvanized steel sheet that had been cleaned in advance by the method described in (2) and then subjected to a Ueckel surface conditioner (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Preparen 4015; 2 OmgZm 2 as a Ueckel) GI) was applied with a treatment liquid E at 20 ° C by a roll coating method so as to have a dry weight of 1.5 g / m 2, and was dried so as to have an ultimate plate temperature of 15 (TC).
  • (GI) was coated with a treatment liquid C at 20 ° C by a roll coating method so as to have a dry weight of 0.1 lg / m 2, and was dried so that the reached plate temperature was 100 ° C.
  • Preliminary cleaning was performed by the method described in (2.), and treatment with zinc phosphate (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Palbond-1 L3300; coating weight 2 gZm 2 ) was performed by a known method.
  • zinc phosphate manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Palbond-1 L3300; coating weight 2 gZm 2
  • GI hot-dip galvanized steel sheet
  • the treatment liquid E at 20 ° C was applied by a roll coating method so as to have a dry weight of 0.3 g / m 2, and was dried so that the reached plate temperature was 100 ° C.
  • the treatment liquid G at 30 ° C was applied by a roll coating method so as to have a dry weight of 0.3 g nom 2, and was dried so that the reached plate temperature was 200 ° C.
  • the treatment liquid H at 20 ° C was applied by a roll coating method so as to have a dry weight of 0.3 gZm 2, and was dried so that the ultimate plate temperature became 80 ° C.
  • Fused zinc which had been cleaned in advance by the method described in (2.) and then treated with a nickel surface conditioner (manufactured by Nippon Parkerizing Co., Ltd .: (trademark) Preparen 410; 20 mg zm 2 as Etkel)
  • Treatment solution I at 20 ° C is applied to a coated steel sheet (GI) by a roll coating method to a dry weight of 0.3 g / m 2 so that the ultimate sheet temperature reaches 150 ° C Was dried.
  • a hot-dip galvanized steel which had been cleaned in advance by the method described in (2.) and then treated with an Eckel surface conditioner (manufactured by Nippon Parkerizing Co., Ltd .: (registered trademark) Preparen 410; 2 Om gZm 2 as nickel).
  • the treatment solution J was applied to a coated steel sheet (GI) by a roll coating method so as to have a chromium content of 4 OmgZm 2, and was dried so that the ultimate sheet temperature reached 80 ° C.
  • a commercially available undercoat recoat (V-nit # 200, manufactured by Dainippon Co., Ltd.) was applied to each of the treated plates prepared in Examples and Comparative Examples (film thickness 5.5 ⁇ ) 200 ° C After baking, a top coat repaint (V-nit # 500, manufactured by Dai Nippon Paint Co., Ltd.) was applied (film thickness: 17 // m) 22 (TC baking to make a test plate.
  • a scratch reaching the copper plate base was cut into the coating film with a cutter, and a salt spray test specified in JIS Z 237 1 was performed for 480 hours. As a criterion, the width from the cut part (wake) was measured.
  • ⁇ 3 mm or more to less than 5 mm
  • ⁇ 5 mm or more to less than 10 mm
  • test plate After the test plate was immersed in boiling water for 2 hours, it was allowed to stand for one day, and the test was performed in the same manner as the primary bending adhesion test.
  • a 10-yen coin was placed at an angle of 45 ° with respect to each test plate, and the coating film was rubbed at a load of 3 kg at a constant speed, and the damage of the coating film was determined.
  • the scratch resistance of the coating film was evaluated according to the following criteria. 5 points: substrate exposure is 0% (only primer is exposed)
  • Base exposure is 50% or more to less than 80%
  • Base exposure is 80% or more
  • Examples 1 to 8 using the surface treatment composition of the present invention showed good corrosion resistance and coating properties, and Comparative Example 5 which was a general-purpose coating type chromate treatment. It has almost the same performance as.
  • Comparative Example 1 containing no silane coupling agent and Comparative Examples 3 and 4 using a composition outside the scope of the present invention exhibited inferior corrosion resistance and paintability (particularly, bending adhesion). I have.
  • Comparative Example 2 containing no inorganic compound component the slip resistance (coin scratch resistance) was poor.
  • the surface treatment agent of the present invention can provide excellent corrosion resistance and coating performance without using chromate, so it is suitable for the industry where solvent-based cleaning and water-based cleaning must be performed in accordance with future solvent regulations. It becomes possible. Furthermore, since there is no selectivity for a metal material, it is possible to improve the heat resistance and the paintability while utilizing the characteristics of the material.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
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  • Polymers & Plastics (AREA)
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  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention porte sur une composition de traitement de surface permettant de conférer une excellente résistance à la corrosion et aptitude à l'enduction, à la surface d'un matériau métallique, ainsi que sur un procédé de traitement de surface. Ladite composition comprend (A) un agent de couplage au silane, possédant un groupe fonctionnel réactif, tel qu'un groupe amino contenant de l'hydrogène actif ou un groupe époxy, (B) au moins un polymère hydrosoluble comprenant un polymère hydrosoluble représenté par la formule (I), présentant un degré de polymérisation moyen de 2 à 50, et (C) une dispersion colloïdale d'un composé organique choisi parmi silice, silicates, chlorures métalliques, etc. Ledit procédé consiste à appliquer un liquide de traitement de surface aqueux contenant la composition et ayant un pH de 2,0 à 6,5, de sorte qu'un film soit formé, à raison de 0,01 à 2,0 g/m2 sur sec.
PCT/JP1999/001184 1998-03-12 1999-03-11 Composition de traitement de surface pour materiau metallique et procede de traitement WO1999046342A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU27476/99A AU2747699A (en) 1998-03-12 1999-03-11 Surface treatment composition for metallic material and method of treatment
KR1020007010087A KR20010041809A (ko) 1998-03-12 1999-03-11 금속재료용 표면처리제 조성물 및 표면처리 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/60773 1998-03-12
JP10060773A JPH11256096A (ja) 1998-03-12 1998-03-12 金属材料用表面処理剤組成物および処理方法

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WO1999046342A1 true WO1999046342A1 (fr) 1999-09-16

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JP (1) JPH11256096A (fr)
KR (1) KR20010041809A (fr)
CN (1) CN1299401A (fr)
AU (1) AU2747699A (fr)
WO (1) WO1999046342A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1002889A3 (fr) * 1998-11-18 2000-09-13 Nippon Paint Co., Ltd. Compositions et procédés de revêtement anticorrosif pour métaux
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CN114381148A (zh) * 2021-12-03 2022-04-22 广东红日星实业有限公司 一种处理剂及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
EP1002889A3 (fr) * 1998-11-18 2000-09-13 Nippon Paint Co., Ltd. Compositions et procédés de revêtement anticorrosif pour métaux
EP1108755A1 (fr) * 1999-12-13 2001-06-20 Nippon Paint Co., Ltd. Procédé pour la fabrication d'une composition de résine à base d'eau pour revêtement antirouille
US6447589B2 (en) 1999-12-13 2002-09-10 Nippon Paint Co., Ltd. Method of producing a water-base resin composition for rust-preventive coating
CN114381148A (zh) * 2021-12-03 2022-04-22 广东红日星实业有限公司 一种处理剂及其制备方法和应用

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JPH11256096A (ja) 1999-09-21
KR20010041809A (ko) 2001-05-25
CN1299401A (zh) 2001-06-13
AU2747699A (en) 1999-09-27

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