TWI321582B - Fluororesin coating film - Google Patents

Description

[Technical Field] The present invention relates to a fluororesin coating film and a product containing the same, and more particularly to improved permeability resistance while maintaining excellent wear resistance. The fluororesin coating film is also a product containing the coating film. [Prior Art] In general, when a metal substrate such as aluminum is coated with a fluororesin, a primer is applied onto the substrate, and then a fluororesin is separately placed on the top thereof to form two Layer coating. However, when the fluororesin coating is in contact with a material having a hardness toward the fluororesin, the coatings are abraded. To prevent this phenomenon, a filler such as mica is usually included in the top coat to improve wear resistance. In order to improve the rubbing property of the fluororesin coating, it is proposed in the examined patent publication No. HEI 3 [1991]-14194 to add a new inorganic powder having a Mohs hardness of 8 to the fluororesin, and the transcript is not reviewed. A method of imparting sufficient hardness to a fluororesin film by dispersing ultrafine diamond particles into the top coat layer is proposed in Patent Publication No. HEI 7 [1995] _ φ 67784. However, in these applications, since the filler is included in the fluororesin, heat and money permeation are liable to occur, resulting in substrate rot, and between the substrate and the primer layer or the primer layer and the top coat layer. Or the problem of layer separation inside the primer layer. Therefore, the present invention provides a resin coating film having improved resistance to (four) properties while maintaining excellent abrasion resistance. The present invention provides a more desirable method for containing a fat-coated film product having excellent curability and improved penetration resistance. SUMMARY OF THE INVENTION 110595.doc U21582 Briefly described in accordance with an aspect of the present invention, the present invention provides a fluororesin coating film comprising a substrate on which at least two layers are formed, the layers being at least one containing a new Mohs hardness The 7 or higher filler is comprised of a melt processible fluorine-containing polymeric layer and a melt processable gas-containing polymer layer directly beneath the layer. According to another aspect of the present invention, the present invention provides a fluororesin coating film comprising a substrate on which at least two layers are formed and wherein the layers are at least _containing: a filler having a new Mohs hardness of 7 or higher A layer of tetrafluoroethylene-perfluoro-ethylidene-based copolymer, and a layer of a tetra-ethylene-perfluoro(alkylene vinyl ether) copolymer directly under the above layer. According to another aspect of the present invention, the present invention provides the gas resin coating film of the above paragraph, wherein the filler having a new Mohs hardness of 7 or higher and at least one selected from the group consisting of diamond powder, corundum powder, Quartz powder, synthetic diamond powder, boron nitride, carbonized carbon, carbonized stone, molten oxide, vermiculite powder and mica powder. According to another aspect of the present invention, the present invention provides a product having the above-mentioned main resin film, wherein one of the products is a cooking utensil. [Embodiment] The fluoropolymer used in the present invention is a meltable h fluoropolymer. Examples of such melt processible fluoropolymers include (iv) copolymers, and at least a sufficient amount of vaporized copolymerizable monomer (comonomer) is present in the rhodium polymer to reduce the redness of the copolymer. To substantially lower than the melting point of tfe homopolymer, polytetrafluoroethylene (PTFE), for example, to no more than 315. 〇之料田声. Preferred TFE comonomers include fully gasified monomers such as fully olefins having 3-6::110595.doc 1321582 and perfluoroalkyl wherein the alkyl group contains 1 to 5 carbon atoms, especially 1 to 3 carbon atoms ( Particularly preferred copolymers of alkyl vinyl ether) (PAVE) include hexa-propylene (HFP), perfluoro(ethyl vinyl ether) (PEve), perfluoro(propyl vinyl ether) (PPVE) and perfluoro (Mercapto vinyl ether) (PMVE). Preferred TFE copolymers include FEP (TFE/HFP copolymer), pFA (TFE/PAVE copolymer), TFE/HFP/PAVE 'where PAVE is PEVE and / or PPVE, and

MFA (TFE/PMVE/PAVE, wherein the alkyl group of the PAVE has at least two carbon atoms). The molecular weight of the melt-processable tetrafluoroethylene copolymer is not sufficient because the molecular weight of the melt-processable tetrafluoroethylene copolymer is sufficient to form a film and can be maintained in a molded shape so that the coating of the undercoat layer is uniform. It is generally measured according to ASTM DU% at 3 72C and may have a melt viscosity of at least x x 2 2 Pa * s and may be in the range of up to about 60 - ΙΟΟχ 1 〇 3 pa. S2. The present invention provides a fluororesin coating film having at least two layers formed on a substrate, wherein the layers are filled with at least one filler having a new Mohs hardness of 7 or higher and Perfluorination (Yuanji County, Copolymer

The layer 'and the tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymer layer directly under the layer just described. The embodiment of the present invention is a gas resin f film in which the filler has a new Mohs hardness of 7 or higher, and #includes at least one selected from the group consisting of diamond powder, corundum powder, stone powder, synthetic diamond, and ancient jade. Asphalt, boron nitride, boron carbide, carbonized crushed, melted and oxidized | Lu, Shi Xishi powder plate Emperor I _ 士 & -, the filler of the group of mother powder. A resin coating film formed on the 兮I, _^(iv) U substrate by applying a primer layer is a preferred embodiment of the present invention. The present invention is exemplified by the application of a primer layer to form a coating of a rat tree such as a coating film, and the primer layer Ϊ I0595.doc 1321582 contains a fluororesin. Further, the present invention provides a product or other tool containing the above-mentioned I resin coating film. An example of the product of the present invention having the resin coated film is a hoisting tool. The fluororesin coating films of the present invention have improved penetration resistance while maintaining excellent abrasion resistance. According to the present invention, a film which is resistant to foaming and which is resistant to peeling of the coating film, and which has a filler uniformly dispersed on the surface of the coating film, is obtained. Accordingly, the present invention provides a film having improved hardness and resistance to penetration and abrasion resistance. As described above, the fluororesin coating films of the present invention have improved impermeability while maintaining excellent abrasion resistance. Therefore, the products having the fluororesin coating films provided by the present invention have excellent durability. The present invention provides a fluororesin coating film in which at least two layers are formed on a substrate, wherein the layers include at least a filling having a new Mohs hardness of 7 or higher and a tetrathene-total gas ( A layer of the copolymer, and a layer of a tetrafluoroethylene (Chos-based vinyl bond) copolymer directly under the layer. The present invention also provides a film containing the fluororesin and is produced. The resin (4) of the present invention contains at least two layers, at least a filler having a new Mohs hardness of 7 or higher and a copolymer of dimegrin (hereinafter referred to as pF_匕^王 both) PFA resin is also used in the scope of the present invention and it is smothered. Filled with excellent wear resistance, accompanied by fπ + s ^ not W (four) (four) intrinsic non-pointing 'is therefore suitable for fluorine I10595.doc 1321582 resin top coat. The new Mohs hardness of 7 or higher is better filler Examples include diamond powder, corundum powder, quartz stone 2 cases of boron carbide powder, lanthanum carbide boron nitride powder, m feldspar roll, mica powder and gold jade, yellow,: pillar stone, stone stone, quartz, stone The weight stone, the molten oxidized sulphate, the stone anaesthesia, the oxidized sulphur, and the anaerobic 'reverse tungsten strontium powder. Among these fillers, the corundum powder, the corundum powder, the Yingjin fossil 帛 帛 ^ ^ ^ 'carburide Carbon = oxidized Ming 1 stone powder and # mother powder are better, and diamond powder is the best. γI^ 4 1 # ; Use of the article. 'The use of the combination alone or two or more types of mixing, although the new Mohs hardness of 7 or higher fillers (4) limit "but to achieve the present invention Such as the desired features, they have: the largest particles below 200 (four) straight through the filler is preferred, and they are better than _ μπι. The preferred composition for the intermediate layer is the melt viscosity is ΐχΐ〇7 a blend of a non-melt-processed fluoropolymer having a melt viscosity of from 1 x 3 〇 3 to 1 x 10 〇 5 Pa.sr & and a melt-processable polymer containing a polymer in the range of 〇 〇 Μ Μ. In the coating film, a layer containing a PFA resin is directly under the mixed layer of the PFA resin and a filler having a new Mohs hardness of 7 or higher. When the PFA layer is used as an intermediate coating, the relatively soft intermediate layer Used as a cushion to relieve external pressure and wear #, and to make the surface of the coating wear. Therefore, the wear resistance is further improved. Generally, for a coating containing a filler in a fluororesin, steam or the like is passed between the resin and the filler. The interface penetrates, causing corrosion of the substrate, reacting with the primer, 11059 5.doc -10· 1321582 In the long-term use, bubbles are formed in the coating film, the coating film is peeled off, etc., and the service life of the coating film is shortened. The fluororesin coating film of the invention exhibits excellent steam penetration resistance, etc., resulting in excellent waterproofness of the film. Because of these advantages, the fluororesin coating film of the present invention has a long service life. The PFA resin intermediate layer may also contain a tetrafluoroethylene copolymer (pTFE) and/or modified PTFE, wherein the modified pTFE A modifier containing less than 1 by weight of ruthenium, wherein a modifier such as hexafluoropropylene (HFP), fluoroalkoxytrifluoroethylene, fluoroalkylethylene, chlorotrifluoroethylene, etc. It is generally known that the increase in crystallinity of the coating film is improved. Therefore, when the intermediate coating layer contains PTFE and/or modified PTFE, the average spherule diameter of the intermediate coating layer is decreased to increase the crystallinity, and thus the intermediate coating layer has the fluororesin coating film of the present invention. Its resistance to permeability has a great contribution. Accordingly, the inclusion of PTFE and/or modified ptfe in the intermediate coating is a preferred embodiment of the invention.

The PTFE and/or the modified pTFE included in the intermediate coating can be obtained, for example, by radiochemical or thermal decomposition of a PTFE plastic powder, fine powder or the like, or by polymerization of TFE in the presence of a chain transfer agent. PTFE and/or modified pTFE powder having an average particle diameter of less than 20 μηι can also be purchased. The PTFE and/or modified PTFE may be included in an amount of wt%, preferably 〇1 wt%, based on the combined weight of the PFA in the intercoat. Since PTFE and/or modified; pTFE is a fluororesin which is sufficiently contiguous with the pFA resin, it is difficult for Luoqi and the like to penetrate through the inside of the resin. The PTFE and/or modified PTFE inclusions are typically 0.001% by weight or greater, and more preferably 10,000 by weight, 110595.doc 1321582 or higher, relative to their combined weight with pFA.豸 Especially, when one of the resin coatings of the present invention is required to have a non-stick property, the filler having a new Mohs hardness of 7 or higher included in the top coat layer and the fluororesin may be microcapsule-sealed. The filler is prevented from being exposed to the surface of the coating film to obtain a fluororesin coating film which is to maintain the non-stick property. The microcapsule-sealed diamond powder is especially useful for this purpose. In order to improve the adhesion of the resin coating film to the substrate, a primer is usually applied to the substrate as an undercoat layer. The primers used in (iv) fluororesin can be used. * When a primer containing a fluororesin, especially a PFA resin, is used, it has a high adhesion to the pFA layer of the medium coating. This is an example of a preferred embodiment of the present invention. The preferred embodiment of the present invention is to apply a coating agent as an undercoat layer to enhance adhesion between the resin coating material and the substrate. As a coating of the coating, the coating resin coating material is baked to form the intermediate coating 'coating a top coating powder coating material and bake again. The material I resin coating of the present invention is formed on the surface of various products. The fluororesin coating films of the present invention have improved resistance to permeation while maintaining excellent grindability, and therefore the products having the gas-resin coating films of the present invention are excellent in economics. Especially when used to cook spare parts, they are characterized. The inclusion of the present invention is an example of a good application of the present invention. The fluororesin coating film of the present invention exhibits the cooking utensils of the fluororesin coating film 110595.doc: When the fluororesin coating film of the present invention is used for heating cooking utensils, the chefs boil 35, roast Steel isochronous' can form a top coat surface with a hardness higher than that of a conventional cookware and excellent wear resistance. Since A ’ does not peel off or scratches even when metal is used, it does not cause food after a long time: live # does not cause bubbles or coating peeling due to water content or the like. Therefore, cooking utensils have a long service life. EXAMPLES The invention is illustrated by further details of the following examples. However, the invention is not limited to the examples. Preferred fluoropolymer materials are powders. An example of such a powder (for example, a manufacturing method and a feature) is described in the following documents: Japanese Examined Patent Publication No. S52-44576 (JP 77044576 B), Japanese Examined Patent Publication S53 11296 (10) 78〇11296 B), Japanese Unexamined Patent Open H6 346〇i take 6346017 A). The [\41>-1〇2 with 10_2〇 μηι particle size, 890-1150 g/Ι bulk density, and 9.7_u.7 g/1 minute mfr are described in these examples. The method for measuring the properties of the present invention is as follows. (1) New Mohs hardness The new Mohs hardness of each material is determined according to the material list known in the art and the MSDS specification of each filler. (2) Average particle diameter Each filler was measured by a wet laser diffraction scattering method (wet method) using a Micr〇track MT3000 (manufactured by Nikkiso Co., Ltd.), and 50% of the diameter value given As the average particle is straight. (3) Maximum particle diameter Each filler is used by the wet laser diffraction scattering method (wet method) using U0595.doc 1321582

Microtrack ΜΤ 3000 (manufactured by Nikkiso Co.) measures the size of the wheel and 100% of the value falls within the distribution table. Application Examples 1 and 2 1. Powder Coating Material The powder coating material used for the intermediate coating layer was PFA powder coating material MP-1 02 (manufactured by Mitsui Dupont Fluorochemicals Co.). The powder coating material used for the top coat layer is a PFA powder coating material, which is composed of MP_102 as a main component and with a diamond micron of 3 μm (UF-44, manufactured by Diamond Innovation) as 99. : 1 weight ratio, '日人<丨0 q 〇2. Preparation of test board

The test panels were prepared using the powder coating materials by the process given below. U The surface of the pure aluminum plate (A-11 〇〇) as the substrate is subjected to detachment by isopropanol, and the surface is sufficiently coarsened by sandblasting, and the surface dust is removed by blowing air, and the PFA resin is used. Anti-corrosive water-based primer PR-915AL (manufactured by Di• Mitsui-DUp〇nt Fluorochemicals c〇) is applied to the watch! Give the dry thickness. The coating was dried by hot air at about 12 (TC) for 1 minute and applied to the post-pick thickness given by y via a powder coating material used as an intermediate coating to form an intermediate coating. It is given in 1 at 400 ° C. The powder coating material is coated on the top of the intermediate coating and baked for 20 minutes to obtain a top coating. The thickness of the top coating is shown in Table 3. The corrosion resistance and wear resistance were measured by the following method. The corrosion resistance was evaluated. The results are given in Table 1. 4 · Test method Corrosion resistance First, the test board was placed on 170. (: Lower, 0.7 MPa steam for 50 h, gradually cool it to room temperature' and then immersed it at 90 ° C in 2 〇g Japanese hodgepodge essence (made by SB Foods) In a solution prepared by dissolving in 1 L of water, the bubbles, corrosion, etc. of the coating were observed every other week and evaluated using the following criteria: 5: After 4 weeks, 'visual observation, no bubbles, no corrosion, good appearance. 4 After 4 weeks, visually observe '<2 mm bubbles, less than 3. 3. 4 weeks later' Observe 'formation> 2 mm of bubbles. 2. After 3 weeks 'visual observation, bubbles, corrosion. 1 : 2 weeks of 'visual observation, bubbles, corrosion. Wear resistance by thrust type friction and wear test method (JIS) K-7218) was evaluated. The measuring instrument used was EFM-III-EN manufactured by 〇rientech c〇. The counter fitting was an external diameter of 25 6 φ, an internal diameter of 2 〇〇φ, and a cross-sectional area. It is a 2 cm2 iron drum. The wear test block is connected to the counter fitting barrel and rotated at room temperature for 5 minutes under no-load conditions at a speed of 5 〇〇m/sec, followed by a load of 1 〇kgf. It was rotated for 10 minutes, and the loss due to abrasion was measured. Application Examples 3 and 4 A test sheet having a thickness as shown in Table 110595.doc 1321582 was prepared similarly to the method used in Application Example 1, and the powder coating material was applied. As the top coat layer, a PFA powder coating material MP102 was mixed with a glass flake having a new Mohs hardness of 7 in a weight ratio of 99: 1. The obtained test sheet was also subjected to evaluation as in the case of Application Example 1. It is given in Table 1. Application Example 5 Preparation Example 1 was repeated application of a layer thickness of the test panel shown in Table 1, which is used by the PFA powder coating material MP-102 (of Mitsui-Dupont

Fluorochemicals Co.) and PTFE TLP-6 (by Mitsui-Dupont

Fluorochemicals Co., an intermediate coating powder coating material having a weight ratio of 99:1, and a PFA powder coating material ΜΡ-1〇2 (manufactured by Mitsui-Dupont Fluorochemicals Co.) and an average particle diameter of 3 A diamond micron powder (manufactured by Diamond Innovation Co., UF-445) of μιη was used as a top coat powder coating material in a weight ratio of 99:1. The resulting test panels were also subjected to a property evaluation similar to that of Application Example 1. The results are given in Table 1. Application Example 6 A test plate having a layer thickness as shown in Table 1 was prepared by repeating Application Example 1, using a PFA powder coating material MP_1〇2 (manufactured by Mitsui_Dup〇nt Fluorochemicals Co.) and a ptFE additive TLp 6 (by Mitsui). -Dupont Fluorochemicals Co.) an intermediate coating powder coating material having a weight ratio of 99:1, and a weight of 99" of a glass flake containing a PFA powder coating material MP-102 and a new Mohs hardness of 7. A top coat powder coating material that is more than mixed. 110595.doc • 16-1321582 The resulting test panels were subjected to a property evaluation similar to that of Application Example 1. The results are given in Table I. Comparative Example 1 A test plate having a layer thickness as shown in Table 1 was prepared by repeating Application Example 1, in which a PFA powder coating material MIM02 (manufactured by Mitsui-Dupont Fluorochemicals Co.) was used as a coating layer without an intermediate coating. The resulting test panels were subjected to a property evaluation similar to that of Application Example 1. The results are given in Table 1. Comparative Example 2 A test plate having a layer thickness as shown in Table 1 was prepared by repeating Application Example 1, in which a PFA powder-containing coating material MP-1 02 (manufactured by Mitsui-Dupont Fluorochemicals Co.) was used with an average particle diameter of 3 _ The diamond was mixed with a top coat powder coating material from a rice powder (UF-445 'manufactured by Diamond Innovation Co.) in a weight ratio of 99:1, and a pFA powder coating material MP-102 was used alone as a top coat. The resulting test panels were subjected to a property evaluation similar to that of Application Example 1. The results are given in Table 1. Comparative Example 3 A test plate having a layer thickness as shown in Table 1 was prepared by repeating Application Example 1, in which a PFA powder-containing coating material Mp_1〇2 (manufactured by Mitsui-Dupont Fluorochemicals Co.) and an average particle diameter of 4 〇μηι were used. The mica flakes (Iridion 153, manufactured by Merck Co.) were mixed with the intermediate coating powder coating material in a weight ratio of 99:1, and the PFA powder coating material MP-102 alone was used as the top coat. 110595.doc 17 1321582

The resulting test panels were subjected to a property evaluation similar to that of Application Example 1. The results are given in Table 1. Comparative Example 4 A test plate having a layer thickness as shown in Table 1 was prepared by repeating Application Example 1, in which the PFA powder coating material ΜΡ·102 (manufactured by Mitsui-Dupont Fluorochemicals Co.) was used with an average particle diameter of 40 μm. The mica flakes (Iridion 153' manufactured by Merck Co.) are mixed with an intermediate coating powder coating material in a weight ratio of 99:1, and a PFA powder coating material MP-102 and a diamond micron having an average particle diameter of 3 μm. Powder (UF-445, by

Diamond Innovation Co.) Top coat powder coating material mixed in a weight ratio of 99:1. The resulting test panels were subjected to a property evaluation similar to that of Application Example 1. The results are given in Table 1. Comparative Example 5 A test plate having a layer thickness as shown in Table 1 was prepared by repeating Application Example 1, in which a shai PFA powder coating material MP-102 (manufactured by Mitsui-Dupont Fluorochemicals Co.) was used with a new Mohs hardness of The glass flakes of 7 were mixed as a coating layer in a weight ratio of 99:1 without an intermediate coating. The resulting test panels were subjected to a property evaluation similar to that of Application Example 1. The results are given in Table 1. 110595.doc .18- 1321582

ϊ< Comparative Example 5 1 1 t 1 1 Ο ο ο ο 00 - Comparative Example 4 〇\ 1 〇\ OS 1 1 ο ο 1 < ο ο f Ν (Ν Compare Example 3 〇1 1 ON 〇\ 1 1 ο ο ο ο CN (Ν 〇\Comparative example 2 〇1 1 ON OS 1 1 1 ο ο ο ο ο » - I inch 10.2 Comparative example 1 Ο ο w 1 4 1 1 1 1 1 1 ο ο to ο ο 12.5 Application Example 6 〇\ Os 1 σ\ Os r * 1 1 ο ο ο ο ψ > i cn Application Example 5 〇\ 〇\ 1 σ\ σ\ 1 1 ο ο ο ο 1-Η v〇cn Application Example 4 ON 晒 1 1 1 ο »Τϊ ο ΓΛ ΓΛ (Ν Application example 3 〇\ Os 1 ο r-Η 1 1 1 ο τ—Η ο ο ο 寸 (Ν Application example 2 Os Os 1 Ο 1 1 1 ο ν 〇ο inch On Ο Application example 1 Os a\ 1 Ο ψ "Η 1 1 1 ο ο ψ < ο ο inch οο Ο PFA Diamond (particle diameter 3 μηι) Glass flake PFA PTFE Diamond (particle diameter 3 μηι) Mica (Particle diameter 40 μηι) PR-915AL Top coat intermediate coat primer Viscosity rotability (mg) Composition wt% 1_ Composition. Weight % Primer thickness (μηι) Top coat intermediate coat -19-110595. The fluororesin coating film provided by the present invention has improved permeability resistance while maintaining excellent abrasion resistance. The fluororesin coating film provided by the present invention is resistant to foaming and peeling, and the filler is uniformly dispersed. On the surface of the coating film, the hardness of the coating film is improved, and the coating film has both permeability resistance and abrasion resistance. The fluororesin coating film of the invention has improved permeability resistance while maintaining excellent performance.

Only when it is formed on the surface of the device, it can provide a product with excellent durability. A product of the fluororesin coating film of the present invention has excellent durability and is suitable for use in utensils. Kangben Mingming provides a cooking utensil with excellent durability, which has a fluororesin coating film which is excellent in permeability resistance while maintaining wear resistance. Therefore, it is apparent that a resin coating film which completely satisfies the above objective is provided in accordance with the present invention. At the same time, the present invention is described in conjunction with its specific embodiments,

颂", ''Xu Xi's substitution, improvement and change are obvious to them. Therefore, 'the intention is to cover all the substitutions, improvements and changes in the spirit of the attached and the main spirits. .doc

Claims (1)

1321582 〇95lMl57 Patent Application Chinese Patent Application Scope Replacement (December 10, 1998, Patent Application Range: 1. A fluororesin coating film comprising a primer layer formed on a substrate; formed on the primer At least two layers on the agent layer, the layers being composed of at least one layer comprising a filler having a new Mohs hardness of 7 or higher and a melt processible fluoropolymer, and a melt processable fluorine directly below the layer The polymer layer composition 2. The gas resin coating film of the item i, wherein the smelting plastic fluoropolymer comprises 3 tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymer. 3. =: The fluororesin coating film of 2 is characterized in that the filler having a new Mohs hardness of 7 / / has at least - selected from the group consisting essentially of diamond at the end, corundum powder, quartz powder, and synthetic diamond at the end of the jewel a substance of boron, tantalum carbide, β, tert-butyl, boron nitride, carbon group. Siushi powder and mica powder composition 4. The fluororesin resin of claim 1. The coating film is characterized by the primer layer Containing fluorine 5. A product, coated film. It has the product of claim item i 6_, such as claim 5, wherein the fluororesin of any of items 2, 3 or 4 is a cooking utensil. 110595-9812I4.doc