Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • C09D5/002—Priming paints
• • 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
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene

Definitions

• Aqueous dispersion composition for primer for primer
• the present invention relates to an aqueous dispersion composition for a primer, particularly an aqueous dispersion composition for a primer having a topcoat layer containing a fluorine resin, and has excellent interlayer adhesion with the topcoat layer, and the coating film as a whole.
• the present invention relates to an aqueous dispersion composition capable of forming a primer layer capable of improving the hardness and abrasion resistance of the composition.
• Fluorine resin has been widely used as a coating material for metal substrates of cooking appliances and home appliances, utilizing the excellent non-adhesiveness, antifouling properties, and heat resistance of fluorine resin.
• a primer layer having excellent adhesion to a metal substrate is used as an undercoat layer for the top coat of fluorine resin.
• an organic solvent-soluble thermosetting heat-resistant binder is used to increase the coating film hardness, and one of them is a water-soluble and thermosetting binder polymer.
• Polyamideimide or polyimide may be used.
• a primer obtained using a water-soluble binder polymer contains a sufficient amount of ceramic spherical particles to improve the film hardness in a water-soluble binder polymer whose film hardness is difficult to increase. .
• a sufficient amount of ceramic spherical particles is added to improve the coating film hardness, the interlaminar adhesion between the primer layer and the top coat layer thereon is lowered.
• PTFE particles or modified PTFE particles to be added that have a specific melt viscosity, a primer layer and a fluororesin coating layer (without using FEP or PFA) ( It has been proposed to improve the interlayer adhesion with the top coat (Japanese Patent Publication No. 2001-519830).
• the tetrafluoroethylene (TFE) homopolymer PTFE particles used have a melt creep viscosity of 3 X 10 8 to 3 X 10 9 Pa's and a standard specific gravity (a factor that is a measure of molecular weight).
• PTFE particles with a standard specific gravity (molecular weight) of this level are still insufficient, and there is sufficient molecular weight between the primer and the top coat. It is difficult to obtain interlayer adhesion.
• modified PTFE particles (PTFE copolymerized with a small amount of a modifying monomer) particles have a standard specific gravity of 2.165 or more and are swept toward the high molecular weight side, but the melt creep viscosity is 1 X 10 7 ⁇ It is insufficient in terms of peel strength in a high temperature environment as low as 1 X 10 9 Pa's. Disclosure of the invention
• the present invention provides an aqueous dispersion assembly capable of forming a primer layer that is excellent in interlayer adhesion with a topcoat layer containing fluorine resin and that can improve the hardness and wear resistance of the entire coating film.
• the purpose is to provide a composition.
• the present invention relates to (A) a water-soluble and curable polyamideimide-based and Z- or polyimide-based binder polymer, (B) ceramic spherical particles, (C) modified polytetrafluoroethylene particles and ( D) In the aqueous dispersion composition for a primer of the fluororesin coating layer containing an aqueous medium, the modified polytetrafluoroethylene particles (C) have a melt creep viscosity at 380 ° C.
• the present invention relates to an aqueous dispersion composition for a primer characterized in that it is a modified polytetrafluoroethylene particle having a standard specific gravity of 2.170 or less in the range of X 10 u Pa's.
• the present invention provides a layer structure comprising a primer layer obtained by applying this aqueous dispersion composition for a primer to a substrate, and a fluorine resin top coat layer provided immediately above the primer layer. Further, the present invention relates to a coating film structure to be included, and also to a coated article having this coating film structure on the surface.
• the aqueous dispersion composition for a primer of the present invention comprises (A) a water-soluble and curable polyamideimide-based and Z- or polyimide-based binder polymer, (B) ceramic spherical particles, and (C) a modified polytetrafluorocarbon.
• A a water-soluble and curable polyamideimide-based and Z- or polyimide-based binder polymer
• ceramic spherical particles ceramic spherical particles
• C a modified polytetrafluorocarbon.
• specific modified PTFE particles (C) are used as the modified polytetrafluoroethylene particles (C).
• the ceramic spherical particles (B) and PTFE particles (C) can be uniformly dispersed as a solid-liquid dispersion.
• polyamideimide polymer examples include HPC-1000-28 (acid value 42mgKOH / g) manufactured by Hitachi Chemical Co., Ltd., JP 7-506514, JP 2001 2001— Those described in Japanese Patent No. 519830.
• Polyamideimide binder The acid value of the polymer is preferably in the range of 40 to 90 mgKOHZg, and more preferably 42 to 8 OmgKOHZg.
• polyamideimide-based polymer strength is particularly preferable.
• Ceramic spherical particles can be used.
• examples of such particles include high-hardness ceramic spherical particles described in JP 7-506514 A, JP 2001-519830 A, and the like, such as calcium metasilicate and potassium titanate. Of these, it is cheap and easy to obtain despite its high hardness, food When used for containers and the like, particularly preferred are aluminum oxide particles, ultramarine particles, glass particles, and titanium oxide particles, which have good safety.
• the hardness of the ceramic spherical particles is preferably 6 or more, particularly 8 or more in terms of Mohs hardness.
• a spherical shape is adopted because the shape close to a sphere can be uniformly dispersed. Therefore, fibrous materials are not suitable.
• the average particle size is not particularly limited, but those exceeding 10 m are preferable because the coating surface becomes rough.
• the present invention relates to PTFE particles having (i) a melt creep viscosity at 380 ° C. in the range of 2 ⁇ 10 9 to 1 ⁇ 10 1 ipa's and (ii) a standard specific gravity of 2.170 or less. It is characterized by the use of PTFE particles.
• melt creep viscosity (i) is within this range, the modified PTFE particles have a low melt creep viscosity instead of a high molecular weight, and thus the adhesion of the modified PTFE particles is improved, so that the interlayer adhesion is improved.
• Preferred melt creep viscosities are 5 ⁇ 10 9 Pa ′s or more and 8 ⁇ 10 9 Pa ′s or more.
• the melt creep viscosity is low, the surface of the topcoat layer tends to be scratched.
• the melt creep viscosity is high, the melt adhesion is lowered and the interlayer adhesion between the topcoat layer and the primer layer is reduced, particularly at high temperatures. Works in a direction that impairs interlayer adhesion.
• the preferred upper limit is 5. ⁇ ⁇ 1 ⁇ 10 ⁇ a 's, or even 1. OX lC ⁇ Pa' s.
• the standard specific gravity of the modified PTFE particles (C) must be 2.170 or less! /.
• the molecular weight of PTFE is difficult to measure directly because the melt viscosity of PTFE is extremely high, and the standard specific gravity is used as one means of evaluating the molecular weight.
• the relationship between the standard specific gravity and the molecular weight is a linear correlation in which the molecular weight decreases as the standard specific gravity increases.
• the lower limit of the standard specific gravity (the upper limit of the molecular weight) is usually about 2.146, but it is 2.146, preferably 2.165, due to the balance between fusion and durability.
• the modified PTFE particles (C) may be modified PTFE in which PTFE is modified with another monomer V. It is difficult to obtain a balance between melt creep viscosity and standard specific gravity with PTFE particles, which are homopolymers of TFE, but it is easy to adjust the balance between melt creep viscosity (i) and standard specific gravity (ii) by modification. Become.
• Monomers used for modification include, for example, black trifluoroethylene (CTFE), hexafluoropropylene (HFP), and perfluoro (alkyl butyl ether) having 1 to 3 carbon atoms in the alkyl group ( PAVE) and the like, and HFP and PAVE are also particularly preferred for their excellent heat resistance.
• the amount of modification may be appropriately selected according to the target melt creep viscosity and standard specific gravity according to the monomer used for modification, and is usually 0.01% by mass or more, preferably 0.10% by mass or more. Adjust it. The upper limit same viewpoint force even 0.22% by mass, preferably 0.20 mass 0/0.
• the average particle size of the modified PTFE particles (C) is 0.20 ⁇ m or more, and the point power with good film-forming property, adhesion to the substrate and melt adhesion with the top coat is also preferred. Furthermore, the thing of 0.25 micrometer or more is preferable.
• the upper limit is preferably 10 m from the viewpoint of not roughening the coating surface. Modified PTFE particles having such a particle size can be obtained in the form of a dispersion by emulsion polymerization of TFE and a modifying monomer.
• Water is sufficient and preferred.
• a surfactant described later may be added to this aqueous medium, and a water-soluble organic solvent may be used in combination as necessary.
• the mass ratio (C) / (A) of water-soluble and curable polyamideimide-based and Z- or polyimide-based noinder polymer (A) to modified PTFE particles (C) is in the range of 60Z40-80Z20. It is also preferable to have a point force that provides good adhesion to the substrate and adhesion to the topcoat layer. Furthermore, (C) Z (A) is preferably 70-30 to 80-20, particularly 70 30 to 7525.
• ceramic spherical particles (beta) is ceramic spherical particles of the type and hardness such as by the amount force can be adjusted normally used in 30-250 capacitance range 0/0 of Noin Zehnder polymer (Alpha) However, a point force capable of maintaining high hardness is also preferable. Especially for acid-aluminum particles In this case, when it is within this range, cracks are not generated in the DuPont impact test, and the corrosion resistance is also good. A particularly preferred range from 50 to 200 volume 0/0, even at 100-175% by volume.
• the aqueous medium (D) is added in an arbitrary amount in consideration of coatability.
• the amount that makes the viscosity of the aqueous dispersion composition for primer in the range of 100 to 350 Pa ⁇ s is preferable.
• the primer-based aqueous dispersion composition of the present invention may contain other components as needed. These representative examples will be described below.
• surfactants such as cationic surfactants, cationic surfactants and amphoteric surfactants are difficult to thermally decompose, and when metal ions are contained, they tend to lower the corrosion resistance.
• nonionic surfactants are, for example, those that do not contain or release the alkyl phenol units that are environmentally friendly. Specific examples include nonionic surfactants described in International Publication No. 03 Z106556 pamphlet and the like, and among these, they are particularly susceptible to thermal decomposition! Agents, and even polyoxyethylene isotridecyl ether, are preferred.
• the addition amount varies depending on the addition amount of the modified PTFE particles, etc. Usually in the range of 5.0 to 7.0 parts by weight, particularly 5.5 to 6.5 parts by weight with respect to 100 parts by weight of the modified PTFE particles. It is preferable to select.
• modified PTFE particles C
• other fluororesin particles or TFE homopolymer (PTFE) particles may be added for the purpose of improving corrosion resistance.
• Examples of other fluorinated resin particles include PFA particles, FEP particles, or one or more of PTFE particles other than the modified PTFE particles (C).
• the average particle size of the other fluorinated resin particles (F) is in the range of 0.15 to 0.60 m.
• Strength The film forming property is not lowered and the processed coating surface is not roughened. Further, it is preferable to have a force of 0.16 to 0.55 m.
• the amount of the applied force may be selected within the range that achieves the purpose of the above-mentioned additive, but if the amount is too large, the interlayer adhesion is impaired.
• Particles (C) It is preferably 0 to 30 parts by mass, more preferably 20 parts by mass or less, per 100 parts by mass.
• Ordinary inorganic pigments such as carbon black, titanium oxide, and bengara, and inorganic pigments such as My strength coated with titanium oxide and bengara may be added.
• the aqueous dispersion composition for a primer of the present invention can be produced by mixing each component by a usual method. However, it is preferable that the binder polymer (A) is preliminarily dissolved in the aqueous medium (D) to form an aqueous solution, and a solid component is appropriately added to this and stirred and mixed in order to obtain a uniform dispersed state. ⁇ .
• the primer-based aqueous dispersion composition of the present invention is applied to a substrate by a usual method and dried and cured to form a primer layer.
• the coating method is not particularly limited, and a roll coating method, a spray method, a spin coating method and the like are employed. Drying and curing conditions are infrared drying, hot air drying, etc.
• a primer layer with the required hardness is usually obtained at 80 to 200 ° C for 3 to 20 hours.
• the substrate is not particularly limited.
• various metals, enamel, glass, and various ceramics can be used, and the surface is preferably roughened by a sandblasting method in order to improve adhesion.
• various metals can be sprayed onto the substrate surface.
• the fluororesin containing fluorephine as a structural unit has good non-adhesiveness. Is preferable.
• Fluoroolefins such as tetrafluoroethylene (TFE), perfluoro (alkyl ether) (PAVE), hexafluoropropylene (HFP), black trifluoroethylene (CTFE), etc.
• Perhaloolefins vinylidene fluoride (VdF) and the like.
• Perhaloolefins, particularly perfluoroolefin homopolymers or copolymers, are particularly preferred because of their excellent non-adhesiveness. Better ,.
• modified PTFE examples include modified PTFE, PFA, and FEP. Of these, high molecular weight Low melt creep viscosity, point power modified PTFE is preferred because melt creep viscosity is relatively low V, PFA is also preferred!
• the modified PTFE for the topcoat may be the same as or different from the modified PTFE for the primer in terms of properties, modification monomer, and modification amount.
• the comonomers for modification can be those described for the modified PTFE particles (C), and the modification amount is usually in the range of 0.18 to 0.22 mass%.
• modified PTFE particles to be blended in the primer composition of the present invention may be added to the topcoat layer.
• the presence of the modified PTFE particles also in the topcoat layer further improves the interlayer adhesion with the primer layer.
• the amount to be blended is preferably 50% by mass or more of the total amount of the top coat layer.
• the entire topcoat layer may be composed of modified PTFE. If necessary, PFA may be mixed and used.
• a two-layer coating film structure of the primer layer of the present invention and a topcoat layer containing fluorine resin can be formed.
• a multi-layer structure of three or more layers may be used.
• a primer layer + an intermediate layer + a top coat layer (fluorine resin) can be exemplified.
• the intermediate layer is coated with a normal colored top coat and the pigment is added to the finish. It is desirable to provide it when there is a request for a specific application or use environment, such as when applying a tally layer or metallic layer.
• the intermediate layer may be formed of, for example, a composition obtained by arbitrarily mixing the primer composition and the topcoat composition or a colored topcoat composition.
• the thickness of the primer layer is preferably 5 to 15 m, and the thickness of the topcoat layer is preferably 20 to 30 ⁇ m.
• the thickness of the primer layer is preferably 5 to 15 m
• the thickness of the intermediate layer is 5 to 15 m
• the other layers are articles for forming a coating film.
• the primer layer of the present invention has high hardness and high adhesiveness to fluorine resin. Therefore, even if the coating film has a two-layer structure as described above, the excellent effect that the balance of hardness and adhesion can be obtained to the same extent as the three-layer structure can be exhibited. In addition, the wear resistance of the coating film as a whole is improved regardless of the material of the topcoat layer.
• This is a primer layer and fluorine resin top coat It is considered that wear due to delamination (abrasion delamination) is reduced by improving interlayer adhesion with the layer.
• the topcoat has good wear resistance as well as excellent interlayer adhesion. Heat resistance can be further improved.
• when used together with low chemical permeability fluorine resin eg FEP and PFA
• delamination and discoloration due to chemical (solvent) penetration can be further suppressed.
• the coating film structure of the present invention having the above properties and effects is advantageous, for example, for coating metal utensils, particularly frying pans.
• This composition is suitable for coating other articles that require corrosion resistance.
• Other articles include, for example, bearings, valves, electric wires, metal foil, boilers, pipes, ship bottoms, oven linings, iron bottom plates, baking molds, rice cookers, grill pans, electric pots, various rolls of OA equipment, ice trays, Snow shovels, plows, chutes, conveyors, rolls, dies, various tools (dies, saws, files, drills, etc.), knives, scissors, hoppers, other industrial containers (especially for the semiconductor industry) and vertical molds It is done.
• Polyamideimide with an acid value of 40-90mgKOHZg Used in the form of an aqueous dispersion.
• Cooking utensils such as frying pans, hot plates, grilled meat plates, range tables, baking molds, rice cookers and grill pans;
• Measuring device Laser diffraction scattering method
• Measurement method Measured according to JIS K5600. In the case of 200 ° C, install a heater in the device.
• Measuring device Pencil hardness tester with hot stage (Installed on Yasuda Seiki Seisakusho Co., Ltd. Pencil hardness tester with temperature adjustable stage)
• Evaluation method Indicates the pencil hardness used when the coating film peels from the substrate. High pencil hardness Indeed, the substrate adhesion is strong.
• Measuring method Same as base material peel test (6).
• Pencil hardness tester with heater Pencil hardness tester manufactured by Yasuda Seiki Seisakusho Co., Ltd. has a temperature adjustable stage
• Evaluation method Indicates the pencil hardness used when the top coat peels from the primer. The higher the pencil hardness, the stronger the substrate adhesion.
• Measurement method JIS K5600, load 0.5kg is dropped from the height of lm.
• Measuring device DuPont drop impact tester
• A1 Toluon AI-10 (acid value 80mgKOH / g) from Solvay, USA neutralized with ammine (10%)
• A2 HPC manufactured by Hitachi Chemical Co., Ltd. 1000-28 (acid value 42mgKOH / g, 28% aqueous solution)
• B1 Aluminum oxide particles (Admafine AO502 manufactured by Admatechs Co., Ltd. Mohs hardness 9, average particle size 0.4 ⁇ m
• B2 Aluminum oxide particles (. Co. Admatechs made ADMAFINE ⁇ 502 Mohs Hardness 9, the average particle diameter of 0. 4 i um) and ultramarine blue particles (first chromatography Kasei E Industry Co. ultramarine N O .2200 24776 (Mass ratio) with Mohs hardness of 5 and average particle size of 1.4 111)
• B4 Aluminum borate particles (Albolite PF03 manufactured by Shikoku Kasei Kogyo Co., Ltd. Mohs hardness 7, average particle size 2.5 m)
• PTFE particles CI Modified PTFE dispersion (average particle size 0.25 ⁇ m, melt creep viscosity 8.7 X 10 9 Pa 's, standard specific gravity 2. 165, 60 mass% dispersion)
• Fl FEP particles (average particle size 0.23 ⁇ m, 63% by weight dispersion)
• an aqueous dispersion composition for a primer was prepared as follows.
• ceramic spherical particles (B) were added to the polyamideimide aqueous dispersion (A) and dispersed by a sand mill to prepare a filler dispersion.
• an aqueous dispersion of modified PTFE particles (C), an aqueous dispersion of FEP particles (F), and a nonionic interface in a carbon mill base an aqueous dispersion in which carbon black is dispersed with a surfactant.
• primer-prepared aqueous dispersion compositions prepared in Examples 1 to 6 on a pure aluminum plate (described in JIS H4000 !, A1050) with a blasted surface have a dry film thickness of 10 m. Spray primer and dry at about 150 ° C for 15 minutes to form a primer layer
• an aqueous dispersion composition for topcoat of the following formulation was spray-coated to a dry film thickness of 20 m, dried at about 80 ° C for 15 minutes, and then 380 ° A topcoat layer was formed by baking at C for 20 minutes.
• the resulting two-layer coating film was subjected to a cross cut test, a substrate peeling test (room temperature, 200 ° C), an interlayer peeling test (room temperature, 200 ° C), and a DuPont impact test. .
• the results are shown in Table 1.
• a primer layer that is excellent in interlayer adhesion with a topcoat layer containing fluorine resin and can improve the hardness and wear resistance of the entire coating film, and has a high strength fluorine. Even a two-layer structure can be formed with a resin film structure.

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• 2006
  • 2006-03-30 JP JP2006094597A patent/JP4853081B2/ja active Active
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