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
  • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
  • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
• • 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
• • 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
  • C09D5/16—Antifouling paints; Underwater paints

Definitions

• the present invention relates to a metal material that can impart excellent corrosion resistance, paintability and fingerprint resistance to the surface of a metal material, and is used for home appliances and building material products.
• 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 corrode in the air and produce corrosion products (so-called white), which degrade the appearance of metallic materials and adversely affect paintability. It has the disadvantage that fingerprints and other stains can easily adhere to the product during the manufacture of the product, which can significantly reduce the commercial value.
• the surface of the metal material was subjected to chromate treatment using a treatment solution mainly containing chromic acid, dichromic acid or salts thereof.
• the upper layer is coated with a polyolefin resin having a carboxyl group containing colloidal silica, and a metal material is generally used.
• hexavalent chromium in the chromate treatment solution used to treat metal material surfaces has a direct adverse effect on the human body. Chromating is often avoided.
• wastewater containing hexavalent chromium needs to be treated specially as specified in the Water Pollution Control Law, which leads to an increase in the cost of kana as a whole.
• chromate-treated metal materials have the major disadvantage that they cannot be recycled as chromium-containing industrial waste, which has become a major social problem.
• a surface treatment method other than chromate 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 invasion of corrosive substances, so that the corrosion resistance of the metal material is considered to be improved. ing.
• the coating itself has been required to have high corrosion resistance. Therefore, a coating using tannic acid alone or in combination with an inorganic component has insufficient corrosion resistance, and practical application at present is not feasible. It is possible.
• Japanese Patent Application Laid-Open No. 53-121034 discloses an aqueous solution comprising water-dispersible silica, an alkyd resin, and a trioxy silane compound applied to the metal surface. A method for doing so is disclosed.
• a surface treatment method for imparting corrosion resistance to a metal material using a water-soluble resin composed of a hydroxypyrone compound derivative and a metal treatment using a water-soluble or water-dispersible polymer of a hydroxystyrene compound.
• a method for imparting corrosion resistance to a material is disclosed in Japanese Patent Application Laid-Open No. 57-444751, and
• An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a non-chromium-based organic composite coated metal material excellent in heat resistance, corrosion resistance, paintability and fingerprint resistance. is there.
• the present inventors have conducted intensive studies to solve these problems of the conventional technology, and as a result, a silane coupling agent component as a first layer on a metal material surface and a polymer component having a specific chemical structure have been developed.
• a silane coupling agent component as a first layer on a metal material surface and a polymer component having a specific chemical structure
• the upper layer of the first layer is coated with a resin composition containing a silicide force
• the present inventors have found an organic composite-coated metal material excellent in corrosion resistance, paintability, and fingerprint resistance, and a method for producing the same, and have completed the present invention. That is, the organic composite-coated metal material of the present invention has the following composition as a first layer on the surface of the metal material:
• Silane coupling comprising one or more silane coupling compounds having at least one reactive functional group selected from active hydrogen-containing amino, epoxy, butyl, mercapto and methacryloxy groups Agent components and
• X bonded to the benzene ring is a hydrogen atom, a hydroxy group, a C1-C5 alkyl group, a C1-C5 hydroxyalkyl group, a C6-C1 2, an aryl group, a benzyl group, a benzal group, an unsaturated hydrocarbon group condensed to the benzene ring to form a naphthalene ring, or a group of the following formula (II):
• R 1 and R 2 in the formula (II) each represent a hydrogen atom, a hydroxyl group, a C 1 to C 5 alkyl group, or a C 1 to C 10 hydroxyalkyl group
• Y 1 and Y 2 bonded to the benzene ring are each independently a hydrogen atom or a Z group represented by the following formulas (III) and (IV). :
• R 3, R 4, R 5, R 6 and R 7 in the above formulas (III) and (IV) are each independently a hydrogen atom, a C 1 -C 10 alkyl group or C 1 X represents a hydroxyalkyl group of ⁇ 10, and each of X, Y1 and Y2 bonded to each benzene ring in the polymer molecule is X, bonded to another benzene ring.
• Y 1 and Y 2 may be the same or different from each other, and the average number of substitutions of the Z group in each benzene ring in the polymer molecule is 0.2 to 1.0. is there.
• the second layer is coated on the first layer with a resin composition containing silica in an amount of 5 to 70 parts by weight based on 100 parts by weight of the resin. Things.
• the weight ratio (A) / (B) of the silane coupling agent component (A) to the polymer component (B) used in the organic composite coated metal material of the present invention 1:10 to 10; Preferably, there is.
• silane adhesive used in the organic composite coated metal material of the present invention PT / JP99 / 01437
• the pulling agent component (A) is a substance having the pulling agent component (A)
• silane coupling agent comprising one or more silane coupling compounds having one or more active hydrogen-containing amino groups, and (b) one or more silane coupling compounds having one or more epoxysilane groups. It is preferable to include a silane coupling agent.
• 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) used in the organic composite coated metal material of the present invention is 3: It is preferably from 1 to 13.
• the weight ratio of the total amount of the silane coupling agent (a) and the silane coupling agent (b) used in the organic composite coated metal material of the present invention to the polymer component (B) [(a) + (b)] / (B) is preferably from 1: 5 to 5: 1.
• the first layer film used in the organic composite coated metal material of the present invention includes a silane coupling agent component (A) composed of at least one silane coupling compound having a specific reactive functional group, It is a polymerization component (B) comprising one or more phenolic resin-based polymers containing an amino group.
• 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 includes at least one selected member, but specific examples include those having the following compositions (1) to (4).
• the silane coupling agent component (A) used in the present invention comprises one or more silane groups having one or more active hydrogen-containing amino groups.
• the silane coupling agent preferably comprises a silane coupling agent (a) comprising a coupling compound and a silane coupling agent (b) comprising one or more silane coupling compounds having one or more epoxy groups.
• the silane coupling agent component (A) used in the present invention is a silane coupling agent (a) composed of a silane coupling compound having an active hydrogen-containing amino group, and an epoxy group-containing silane coupling agent (b).
• the equivalent ratio of the active hydrogen-containing amino group contained in the silane coupling agent to the epoxy group 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 will have poor film formability, and will have 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 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 polymerized unit of the formula (I) has an average polymerization degree of 2 to 5 It is 0.
• X bonded to the benzene ring is a hydroxyl group, a C1-5 alkyl group such as a methyl, ethyl, propyl group, etc., and a C1-5 hydroxyalkyl group such as a hydroxy group.
• C6 to C12 aryl groups such as hydroxymethyl, hydroxyethyl, 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; And a hydroxyalkyl group of 0, for example, hydroxymethyl, hydroxyshethyl, hydroxypropyl group and the like.
• Y 1 and Y 2 bonded to the benzene ring are each independently a hydrogen atom or Z represented by the formula (III) or (IV). Having a group.
• 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.
• C1 to C5 hydroxyalkyl groups for example, hydroxymethyl, hydroxyshethyl, hydroxypropyl 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 number of substitutions of the Z group in each benzene ring in the polymer molecule is from 0.2 to 1.0.
• the average value of the number of substitutions of the Z group is an average value of the number of the Z groups introduced into each benzene ring in the polymer molecule.
• Each of R 3 to R 7 in the Z group represented by the formulas (III) and (IV) is a C 1 to C 10 alkyl group or a C 1 to C 10 hydroxyalkyl group. Represents 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.
• the coating of the second layer used in the present invention preferably contains silica in an amount of 5 to 70 parts by weight based on 100 parts by weight of the resin. Preferably, it is 10 to 50 parts by weight. If the proportion is less than 5 parts by weight, the effect of improving the corrosion resistance and fingerprint resistance of the upper layer coating is lost, and the corrosion resistance and fingerprint resistance are reduced. On the other hand, if it exceeds 70 parts by weight, the coating of the upper layer becomes hard, and the corrosion resistance after processing decreases.
• colloidal silica, organosilica sol, gas-phase silica, silica powder, etc. can be used for the compounded silica. Snowtex 0, C, OS, N of Nissan Chemical Co., Ltd., Nippon Aerosil Co., Ltd. Aerosil 100, 200, 300, etc. The particle size is not particularly limited.
• the resin used for coating the second layer is preferably a resin having a hydroxyl group and / or a carboxyl group.
• resins include commercially available epoxy resins, alkyd resins, acrylic resins, urethane resins, acryl-modified polyester resins, phenol-modified alkyd resins, polybutylbutyral resins, phenol resins, melamine resins, and ethylene acrylic resins.
• Can be The structure and molecular weight of these resins are not particularly limited, but they must be within a range in which silicic acid can be uniformly dispersed and contained.
• coating adhesion amount of the second layer 0. 1 to 5.
• O g Zm 2 is preferred.
• the upper layer coating is less than 0.1 g / m 2 , the corrosion resistance and the fingerprint resistance become insufficient.
• it exceeds 5.0 g / m 2 the paintability, especially the adhesion, becomes insufficient.
• a wax can be contained in the coating of the second layer, and lubricity can also be imparted.
• an ordinary protective pigment for example, a molybdate-based pigment, a phosphate-based pigment, or a protective agent (for example, tannic acid, gallic acid) Phenolic carboxylic acids, etc.) may synergistically improve the corrosion resistance.
• the weight ratio (A) Z (B) to the silane coupling agent component (A) and the water-soluble polymer component (B) is 1:10.
• ⁇ : L 0: 1 is preferred, and preferably 1: 5 to 5: 1.
• this 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 become insufficient.
• it exceeds 10: 1 that is, if the silane coupling agent component (A) ratio is high, the film-forming properties of the film decrease, and the corrosion resistance and paintability of the resulting film become insufficient.
• an aqueous surface treatment solution containing the surface treatment agent composition as the first layer and having a pH adjusted to a range of 2.0 to 6.5 is adhered to the surface of the metal material.
• the deposition amount after drying was dry 10 ⁇ 500mgZ m 2, preferably to be 5 0 ⁇ 50 OnigZni 2.
• the aqueous treatment liquid is brought into contact with the surface of the metal material at a temperature of 10 to 60 ° C. for 0.1 to 30 seconds and dried by heating.
• the pH of the first layer aqueous surface treatment solution is adjusted to the range of 2.0 to 6.5 using phosphoric acid, acidic phosphate, fluoride, complex fluoride, sulfuric acid, nitric acid, and organic acid. You.
• the preferred PH value is between 3.0 and 5.0. If the pH is less than 2.0, the reactivity between the composition in the obtained processing solution and the substrate surface becomes excessively high, so that a film defect occurs and the obtained film has insufficient corrosion resistance and paintability. . If the pH exceeds 6.5, the water-soluble polymer component (B) itself tends to precipitate out of the aqueous aqueous surface treating solution, so that the life of the aqueous treating 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, an immersion method, a spray 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 from 10 to 60 ° C, and the processing time is preferably from 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. 7
• the metal ion eluted and mixed from the metal material and the water-soluble polymer component (B) form a complex.
• precipitation may occur.
• a sequestering agent may be added to the surface treatment composition.
• the sequestering agent include EDTA, Cy-DTA, triethanolamine, dalconic acid, heptgluconic acid, oxalic acid, tartaric acid, and malic acid.
• the treatment method is carried out at a temperature of 10 to 60 ° C for 0.1 to 10 seconds, followed by heating and drying. Is preferred.
• the metal material used in the present invention can be selected from iron plates, zinc-plated copper plates, aluminum plates, aluminum alloy plates, stainless copper plates, and the like.
• Electro-galvanized steel sheet (EG material)
• the surface of the above metal material is treated with a medium alkali degreasing agent (registered trademark: Fine Talina 4336, manufactured by Nippon Parkerizing Co., Ltd.). Chemical concentration: 20 gZ 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 alkali degreasing agent registered trademark: Fine Talina 4336, manufactured by Nippon Parkerizing Co., Ltd.
• Treatment liquid A at 25 ° C is roll-coated on a hot-dip galvanized steel sheet (GI) that has been previously cleaned by the method described in (2.) to a dry weight of 0.3 g / m 2. And dried at an ultimate plate temperature of 80 ° C.
• An aqueous resin composition containing silica powder manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL 200
• the coating was applied at a dry weight of 2 g / m 2 and dried at an ultimate plate temperature of 100 ° C.
• the treatment liquid B at 15 ° C was applied to the aluminum plate (AL) previously cleaned by the method described in (2.) by a roll coating method so as to have a dry weight of 0.1 gm 2 . Drying was performed so that the reached plate temperature was 150 ° C.
• An aqueous resin composition containing silica powder (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil 300) in a ratio of 70 parts by weight to 100 parts by weight of the phenol-modified alkyd resin was dried by a roll coating method. 1 gZm 2 and dried at an ultimate plate temperature of 150 ° C.
• the treatment liquid B at 30 ° C is applied to a copper plate (GI) coated with hot-dip zinc that has been cleaned in advance as described in (2.) by a roll coating method to a dry weight of 0.05 g / m 2. And dried so that the plate temperature reached 100 ° C.
• An aqueous resin composition containing 50 parts by weight of silica powder (trade name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) in 100 parts by weight of acryl resin as a dry weight by a roll coating method in an upper layer of the aqueous resin composition. g / m 2 was applied and dried at an ultimate plate temperature of 100 ° C.
• silica powder trade name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.
• a treatment liquid D at 20 ° C is applied to a hot-dip zinc-plated copper plate (GI) previously cleaned by the method described in (2.) by a roll coating method so as to have a dry weight of 0.1 lg / m 2. And dried so that the reached plate temperature was 80 ° C.
• An aqueous resin composition containing colloidal silica manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex N
• a treatment liquid E at 20 ° C by a roll coating method to a dry weight of 0.03 g nom 2 . And dried so that the reached plate temperature was 80 ° C.
• the upper layer is roll-coated with an aqueous resin composition containing colloidal silica (produced by Nissan Chemical Co., Ltd., trade name: SNOTETUS TAS O) in a ratio of 20 parts by weight to 100 parts by weight of ethylene acryl resin. and dried in a dry weight 1 gZ m 2 coating reached plate temperature 8 0 law.
• the treatment liquid D at 20 ° C was applied to a copper plate (EG) plated with electro-zinc which had been cleaned in advance according to (2. g / m 2 , and dried so that the reached plate temperature was 180 ° C.
• An aqueous resin composition containing silica powder (trade name: Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) in an upper layer at a ratio of 50 parts by weight to 100 parts by weight of ethylene acryl resin was subjected to a roll coating method. in the 0. 0 5 gZm 2 applied it was dried at peak metal temperature 1 00 ° C as dry weight.
• Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex N) was added to 100 parts by weight of ethylene acryl resin on an electro-zinc-plated copper plate (EG) previously cleaned by the method described in (2).
• the aqueous resin composition contained in a ratio of 1 part by weight was applied as a dry weight of 1 gZm 2 by a roll coating method, and dried at a temperature of 100 ° C. of the arrival plate.
• ⁇ Whiteness occurrence rate 10% or more, less than 50%
• test surface-treated metal material was coated under the following conditions, and a coating film adhesion test was performed.
• a scratch reaching the copper plate body was made in the coating film with an acryl cutter, and a salt spray test specified in JIS-2372 was carried out for 240 hours. After the operation, the cut portion was peeled off with an adhesive tape, and the peel width was evaluated. Judgment standard is cut part The peeling width (mm) of the coating film from was measured.
• Re j mm or more, less than 5 mm
• ⁇ 5 mm or more, less than 10 mm
• a finger was pressed against the test plate, and the trace state of the fingerprint was visually evaluated.
• the criteria are as follows.
• Examples 1 to 8 using the surface treating agent composition of the present invention show good corrosion resistance, coating properties, corrosion resistance after painting, and fingerprint resistance.
• Comparative Example 1 in which the upper layer coating treatment was not performed was inferior in corrosion resistance and fingerprint resistance.
• Comparative Example 2 in which no silica was contained in the upper layer resin was inferior in corrosion resistance and fingerprint resistance.
• Comparative Example 3, which contained silica outside the scope of the present invention exhibited a decrease in adhesion.
• Comparative Example 4 in which the amount of the upper layer film is out of the range of the present invention satisfactory corrosion resistance cannot be obtained.
• Comparative Example 5 in which the undercoating treatment was not performed the corrosion resistance and adhesion were extremely poor.
• the organic composite coated metal material formed using the manufacturing method of the present invention can provide high corrosion resistance, paint adhesion and fingerprint resistance without using chromate, unlike conventional products. Regulations make it possible to adapt to industries that are forced to go chrome-free. Furthermore, since there is no selectivity for the metal material, it is possible to improve the heat resistance and the paintability while utilizing the characteristics of the material.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Laminated Bodies (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=13798212

Family Applications (1)

Country Status (6)

Cited By (1)

Families Citing this family (7)

Citations (2)

• 1998
  • 1998-03-30 JP JP10083288A patent/JPH11276987A/ja active Pending
• 1999
  • 1999-03-23 WO PCT/JP1999/001437 patent/WO1999050366A1/ja not_active Application Discontinuation
  • 1999-03-23 CN CNB998068616A patent/CN1172987C/zh not_active Expired - Fee Related
  • 1999-03-23 KR KR1020007010870A patent/KR20010042321A/ko not_active Application Discontinuation
  • 1999-03-23 AU AU28549/99A patent/AU2854999A/en not_active Abandoned
  • 1999-03-26 TW TW088104858A patent/TW446737B/zh active

Patent Citations (2)

Also Published As

Similar Documents

Legal Events