WO1992018574A1 - Article recouvert de resine fluoree - Google Patents

Article recouvert de resine fluoree Download PDF

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Publication number
WO1992018574A1
WO1992018574A1 PCT/JP1992/000059 JP9200059W WO9218574A1 WO 1992018574 A1 WO1992018574 A1 WO 1992018574A1 JP 9200059 W JP9200059 W JP 9200059W WO 9218574 A1 WO9218574 A1 WO 9218574A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluororesin
heat
coating
meltable
tetrafluoroethylene
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP1992/000059
Other languages
English (en)
Japanese (ja)
Inventor
Katsuya Yamada
Masahiro Morita
Nobutaka Matsushita
Yoshichika Nishimura
Fumio Matsuyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Electric Industries Ltd
Original Assignee
Sumitomo Electric Industries 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
Priority claimed from JP3189611A external-priority patent/JP2942389B2/ja
Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to KR1019920703280A priority Critical patent/KR930701295A/ko
Publication of WO1992018574A1 publication Critical patent/WO1992018574A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to a fluororesin covering, in particular, at least PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene).
  • PTFE polytetrafluoroethylene
  • PFA tetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • a metal such as a sand blast, a grid blast, or the like.
  • a fluorine-containing adhesive such as PAI (Polyamide Imid) or PES (Polyether Sulfone) is applied.
  • PAI Polyamide Imid
  • PES Polyether Sulfone
  • a binder such as PAI or PES is added to a fluorine resin composition together with a pigment together with a pigment, and the breaking elongation of the coating film is remarkably lost. It is mixed within the range that is not possible, coated on a substrate having fine concaves and convexes, and further, a facial pigment, a binder, etc. are practically provided on the outermost layer.
  • the press molding process can be performed after coating, and the surface can be modified by the adhesive mixture.
  • a coating with improved non-adhesiveness was obtained.However, even with the above method, the combination of PAI, PES, etc., could reduce the breaking elongation of the coating film. Low or pinhole Because of the tendency to increase, under severe press working conditions, it is not possible to obtain a coating with high corrosion resistance and force.
  • a fluorine resin coating such as PTFE, which has a high corrosion resistance
  • the number of pinholes can be reduced significantly by the method that has been implemented, but when the number of layers increases, the Since the resin part where the aging was performed was repeatedly heated to a temperature higher than the sintering temperature, there was a problem that the deterioration gradually progressed, and the economy became economical. Particularly, it was disadvantageous because the amount of resin and the process were increased.
  • PAI Polyamide Imide
  • PES Polyyester Sulfone
  • a method of laminating a fluororesin primer having an adhesive on it and laminating a fluororesin on the primer has been carried out.
  • the problem is that the mar layer is extremely likely to have a coating film defect such as a pinhole and is extremely likely to occur.
  • the rupture elongation of the coating film is small, after coating, the kettle, fly, etc. In the shape of a button.
  • the first invention and the second inventions of the present application preventing a decrease adhesion strength between I that the substrate surface to pigment (No. 2 ⁇ Invention), or with or without pigments, to further improve the adhesive strength (1st invention), and in any case, use ordinary adhesives such as PAI, PES, etc.
  • Discoloration such as browning like a chemical agent, decrease in elongation at break of a coating film and decrease in non-adhesiveness 0 No decrease in physical properties, strong adhesion to a substrate, few pinholes Low corrosion resistance It is intended to obtain a fluororesin coating that has been coated. Also, the third invention of the present application seeks to obtain a fluorine resin covering which has a higher corrosion resistance by reducing pinholes.
  • the third invention may be used in combination with the second invention, or may be used alone in the third invention.
  • a fluorine resin composition is layered on a fine concave-convex substrate, and the fluorine resin is made of a heat-fusible fluorine resin. 2% by weight or more 1 2% by weight or less Fluorine resin coating characterized by the fact that it is made of a mixture of PTFE and heat-soluble fluororesin that are present. is there .
  • the fluororesin coating of the first invention wherein the heat-meltable fluororesin is PFA.
  • the heat-fusible fluororesin is F-type- The fluororesin coating of the invention.
  • the substrate is made of aluminum or an aluminum alloy plate having fine concaves and convexes formed by chemical or electrochemical etching. There is the fluororesin coating of the first invention.
  • the second invention of the present application provides a method for manufacturing an image recording apparatus, comprising the steps of: forming an inorganic pigment on a substrate having fine concaves and convexes;
  • a fluororesin composition which is blended in an amount of 5% by weight or less and substantially does not contain a heat-resistant polymer is laminated, and the fluororesin is melted by heat.
  • the fluororesin is contained in an amount of 2% by weight or more and 12% by weight or less.
  • the fluororesin coating is characterized by being made of a mixture of PTFE (polytetrafluoroethylene) and hot-melt fluororesin.
  • the second fusible resin is PFA.
  • the fluororesin coating of the second invention which is a nickel alloy plate.
  • the inorganic pigment is any one of mica, pigment-coated mica, titanium oxyfluoride, graphite, graphite, and carbon; No. 2 above, which is a mixture of them.
  • the surface of the fluororesin covering is provided with a surface layer consisting essentially of fluororesin without any paint or adhesion aid on the surface.
  • the fluorine resin coating of the second invention is provided with a surface layer consisting essentially of fluororesin without any paint or adhesion aid on the surface.
  • the third invention of the present application relates to a method of covering a fluorine resin covering material.
  • the surface is provided with a surface layer that is substantially free of paint and adhesives, and the surface layer is formed of a heat-meltable fluorine resin and PTFE (polyethylene). (Fluorofluoroethylene), and the composition of the heat-soluble fluororesin is not less than 2% by weight and less than 12% by weight.
  • PTFE polyethylene
  • the composition of the heat-soluble fluororesin is not less than 2% by weight and less than 12% by weight.
  • the irregularities such as I 0 are not concave and convex due to physical roughening of a metal surface or the like which is usually performed such as sand blast and grind blast. May be used in combination, but the concave and convex O due to etching mainly performed chemically or electrochemically, or a combination of these. It means this.
  • the treatment method is limited to chemical or electrochemical etching, but it is not o: If the concave and convex surface is combined with a coating made of PTFE only, this rough surface can provide a separation strength of about 2 kg / cm. It can be applied to the first and second inventions.
  • Such concavities and convexities can be obtained by electrochemically etching aluminum or aluminum alloy. For this reason, such materials and methods are particularly advantageously used.
  • the fluorine resin composition used in the first and second inventions may be in any form such as aqueous dispersion or powdery powder. Preferably, it is a water-based dispersion.
  • the heat-fusible fluororesin is PFA (tetrafluoroethylene resin-no. 1 fluoroacrylic vinylizoleate copolymer), FEP (tetrafluoroethylene-hexafluoropropylene copolymer), ETFE (tetrafluoroethylene-ethylene copolymer) Polymer), Polymers and copolymers such as CTFE (Polycro-trifluoroethylene) are used.
  • PFA tetrafluoroethylene resin-no. 1 fluoroacrylic vinylizoleate copolymer
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • ETFE tetrafluoroethylene-ethylene copolymer
  • CTFE Polymers and copolymers such as CTFE (Polycro-trifluoroethylene) are used.
  • PTFE is 3 4 0 to have you in the 'C ⁇ 3 8 0' C 1 0 1 ' ⁇ 1 0 1 3 against to Oh Ru in general have it non-melting in the poise and high viscosity, to Re this mixing heat-meltable fluorine resins you are, PFA (3 8 0 have you to hand 1 0 4 ⁇ 1 0 5) .
  • FEP have you to 3 8 0 4 X 1 -0 4 ⁇ 1 0 5) .
  • ETFE (3 0 0 ⁇ 3 3 0 have you in hand 1 0 4 ⁇ 1 0 5) .
  • CTFE and the melt viscosity Te because the pole (2 3 0 1 0 7 have you in hand) there is and this has low It is a point and is not limited to these as long as it is a heat-meltable fluororesin. .
  • the second invention is especially so-called post-processing in which after coating on a flat plate, it is pressed into a shape such as a hook. It has an effect on the coating to be coated, and therefore, the breaking elongation of the coating film is an important factor.
  • the material itself has a rupture elongation of only about tens of percent even in the ideal state, so that it is directly mounted on the base material as a primer 5 —
  • cracking will occur even if press processing is performed at a relatively low elongation, and a small amount will be used as an adhesive aid. Even in such cases, cracks and the like are likely to be generated by ordinary deep drawing of a pot, etc., and even if no cracks or the like are confirmed, the binhole can be used.
  • the heat-fusible fluorine resin is almost the same as PTFE.
  • the resin itself is colorless and has no coloring due to baking or the like.
  • the elongation at break is extremely small in the range exceeding the above range, which is inappropriate for the first and second studies. Specifically, less than 12 wt%, which has a breaking elongation of 80% or more, is preferred, and particularly severe shearing (for example, aluminum sheet thickness reduction rate ⁇ 0%) you have a Cristianos Ru and 1 0 0% or more of elongation at break a case cormorant line for more than 1 0 w - Les% or less of the formulation is by 'Ri have the good or e
  • the adhesives such as PAI and PES are as described above.
  • FEP also excels in heat resistance, and in particular it excels in dispersing especially with PTFE. It is difficult to form spots etc. on the coating surface, and as a result, it is easy to form a coating film which has excellent physical properties and non-adhesiveness. ('' It is.
  • PFA is added to issue No. 63-'33'11. It shows a fluororesin coating composition that is contained in a specific ratio of ⁇ 50%, and is difficult to recrystallize after sintering. It is known that the resistance to scratching of the surface is enhanced by taking advantage of the fact that the elasticity of the coating film increases due to the increase in the number of surface parts.
  • the present application differs from this in technical idea, and utilizes low melt viscosity.
  • the fusible hydrogen resin is added by 2 wt% or more. w With less than 1% of the compound, it can penetrate into concaves and convexes and increase the adhesive force mainly by the drawing effect.
  • the base plate is a necessary condition, and will be described in more detail in the description of the second invention.However, the effect of the present invention is particularly effective when combining the facial material. It is done.
  • the pigment used is titanium white, carbon, graphite, fluoride fluoride, and ultramarine.
  • Typical inorganic pigments such as lime, red iron oxide, etc., and pigments in the form of scales, such as mica, paint-coated mycelium, scale-like iron oxide, scale-metals, etc. are typically used. Yes.
  • titanium white or fluorinated graphite is used for the second invention of the present application, it is possible to obtain a pure white color coating.
  • the oxidized titanium is covered, and the iris color strength and the rainbow color strength are obtained by the interference of light. Power, and the combination of these with a general face will result in paler, more vivid colors and colors. Wide color tones such as these metallic colorings can be obtained without discoloration.
  • a beautiful color tone with a colored My power covered with titanium oxide and iron oxide can of course be obtained without discoloration.
  • Pigments that are particularly preferably used include mica (synonymous with mica), pigment-coated mica (synonymous with pigment-coated mica), titanium oxide, and fluorinated graphite. Items, graphites, carbon, etc. are used, and they can be used alone or in combination. When these amounts are used alone, the my power and the pigment coated my power are more preferably i15% by weight in the solid content. Or 110% by weight. More preferably, the content of titanium oxide or oxidized darafite is 125% by weight.
  • More preferably 1525% by weight of carbon or graphite is 1.10 weight% ; more preferred and even more preferred.
  • the pinhole can be used according to the second invention. Even if the reduction of the tool is measured, it may still have a large number of pinholes, and it may be non-adhesive and may be reduced.
  • the outermost layer is essentially facial material
  • fluorine resin that does not impede the use, it is possible to reduce the pinhole and improve the non-stickiness to the extent that there is no practical problem.
  • the fluororesin used here is not particularly limited (except for the fact that the paint is not practically used).
  • the third invention is not limited to being used only in combination with the second invention, and the third invention alone may be used as a conventional technology (general technology). Combined with,. It is effective enough even when used.
  • thermofusible fluororesin Such effects are manifested by the incorporation of 2 wt% or more of the thermofusible fluororesin, and are remarkable in the range exceeding 4 wt%. .
  • spots and the like are generated on the coating film, and the effect of the coating film formation is reduced, and the effect is reduced. I don't like it ⁇ 5 .
  • the composition ratio of the heat-fusible fluorine resin (PFA in this example) is Above 12 wt%, the elongation at break decreases remarkably, causing defects when the coating film is stretched in press processing. Not good Especially when strict deep drawing is performed (for example, when reducing the thickness of the substrate is 10% or more), it has a breaking elongation of 100% or more. % Or less is more preferable.
  • the fluororesin composition used is the same as that used in the first and second inventions of the present application. Although it may be in any form such as a portion and a powder, it is particularly preferable to use an aqueous disperser.
  • the hot-melt fluororesin to be mixed with the PTFE the same ones as those of the first and second inventions are used.
  • the thickness of the surface layer is 10 or more.
  • the upper 20 or lower is preferred. If it is less than 0, it is a pinho figure.
  • Fig. 1 shows the addition of PFA in the fluorine resin in the present invention.
  • Fig. 2 shows the relationship between the amount of FEAP added in the fluorine resin and the separation strength in the present invention.
  • Example 18 and Comparative Example 15 As the aluminum material, a 2.5 mm-thick (ASB material made by Kobe Seisakusho) was used.
  • electrochemical and etching treatments are performed with an amount of electricity of 25 clones / cm 2 in an aqueous solution of ammonium chloride to form fine irregularities on the surface.
  • an amount of electricity of 25 clones / cm 2 in an aqueous solution of ammonium chloride to form fine irregularities on the surface.
  • the first layer was coated with the resin composition shown in Tables 1 and 2 as a first layer and baked. Then, as a second layer, a PTFE device (D-1K, manufactured by Daikin Industries, Ltd.), which is not filled with a filler, is used as a core. After drying and drying the water, it was baked at 400 for 10 minutes. The resin thickness was adjusted such that the total resin thickness of the first layer and the second layer was 15 (a total of 30) (however, Comparative Example 3 and Example 7 were the second layer). The eyes are not stacked. The coating plate thus obtained was deep-drawn by press molding to obtain a rice cooker.
  • a PTFE device D-1K, manufactured by Daikin Industries, Ltd.
  • the percentage of the remaining resin in the first resin is defined as the welding rate (%) (both bottom and side surfaces were evaluated).
  • a tape made of fluororesin is heat-sealed on the coating surface, peeled off in the direction of 180 °, and a force of 1 cm in width is applied.
  • Pinhole strength (m A) which is the peeling strength of the force required
  • the base plate in this embodiment, the aluminum alloy
  • the amount of electricity transmitted is large and the degree of power is large.
  • Corrosion resistance is low-.
  • Example 9 and Comparative Example 67 The aluminum plate (without pigment) of 2.5 mm thick aluminum plate (ASB material manufactured by Kobe Steel) was used as the positive electrode. Electrochemical, 5-etching treatment with 25 Coulombs / cm 2 of electricity in an aqueous solution of salinated ammonium salt forms fine irregularities on the surface. I let you. After coating the resin composition shown in Table 3 on this surface and drying the water, it was baked at 400 and 30 minutes. The resin thickness was adjusted to 25.
  • An aluminum plate with a thickness of 2.5 mm (ASB material manufactured by Kobe Seisakusho) is used as the anode, and an electrical current of 25 cm 2 in ammonium chloride aqueous solution is obtained. Electrochemical and etching treatments were performed by the amount described above to form fine irregularities on the surface.
  • the resin composition shown in Table 4 above was coated as a second layer, and after drying the water, it was baked at s400 ° C for 10 minutes. I got it.
  • the resin thickness of the second layer was set to 15 (however, Comparative Example 18 laminated the second layer).
  • a mixture of PTFE and a thermofusible fluororesin is used for the surface layer of the fluororesin coating.
  • the third invention of the present application has a remarkable effect in combination with the second invention.
  • the third invention alone can be used in combination with a conventional technology (general technology). Can also obtain a sufficient effect.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention se rapporte à un article recouvert de résine fluorée comprenant une matière de base ayant de minuscules inégalités, ainsi qu'une composition de résine fluorée spécifiée, déposée en strates sur la matière de base. L'article contient un petit nombre de trous d'épingle, et possède une excellente résistance à la corrosion. La composition de résine fluorée contient du PTFE et une résine fluorée thermofusible, la teneur en résine fluorée étant comprise entre 2 % en poids et moins de 12 % en poids.
PCT/JP1992/000059 1991-04-19 1992-01-20 Article recouvert de resine fluoree Ceased WO1992018574A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019920703280A KR930701295A (ko) 1991-04-19 1992-01-20 플루오르 수지 피복물

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3189611A JP2942389B2 (ja) 1990-06-23 1991-04-19 弗素樹脂被覆物
JP3/189611 1991-04-19

Publications (1)

Publication Number Publication Date
WO1992018574A1 true WO1992018574A1 (fr) 1992-10-29

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PCT/JP1992/000059 Ceased WO1992018574A1 (fr) 1991-04-19 1992-01-20 Article recouvert de resine fluoree

Country Status (2)

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KR (1) KR930701295A (fr)
WO (1) WO1992018574A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117285786A (zh) * 2022-06-24 2023-12-26 霓佳斯株式会社 片材、印刷基板用基材、以及片材的制造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57137365A (en) * 1981-01-13 1982-08-24 Du Pont Fluoropolymer coated article
JPS6010793B2 (ja) * 1980-07-18 1985-03-20 三菱電機株式会社 樹脂被覆方法
JPS6333511B2 (fr) * 1978-10-31 1988-07-05 Ii Ai Deyuhon De Nimoasu Ando Co
JPS63200868A (ja) * 1987-02-16 1988-08-19 Nippon Paint Co Ltd フツ素樹脂塗膜の形成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6333511B2 (fr) * 1978-10-31 1988-07-05 Ii Ai Deyuhon De Nimoasu Ando Co
JPS6010793B2 (ja) * 1980-07-18 1985-03-20 三菱電機株式会社 樹脂被覆方法
JPS57137365A (en) * 1981-01-13 1982-08-24 Du Pont Fluoropolymer coated article
JPS63200868A (ja) * 1987-02-16 1988-08-19 Nippon Paint Co Ltd フツ素樹脂塗膜の形成方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117285786A (zh) * 2022-06-24 2023-12-26 霓佳斯株式会社 片材、印刷基板用基材、以及片材的制造方法

Also Published As

Publication number Publication date
KR930701295A (ko) 1993-06-11

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