CN1201872C - Fluorine resin enclose material and making method thereof - Google Patents
Fluorine resin enclose material and making method thereof Download PDFInfo
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- CN1201872C CN1201872C CNB001023470A CN00102347A CN1201872C CN 1201872 C CN1201872 C CN 1201872C CN B001023470 A CNB001023470 A CN B001023470A CN 00102347 A CN00102347 A CN 00102347A CN 1201872 C CN1201872 C CN 1201872C
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- 239000011347 resin Substances 0.000 title claims abstract description 104
- 229920005989 resin Polymers 0.000 title claims abstract description 104
- 239000000463 material Substances 0.000 title claims description 110
- 239000011737 fluorine Substances 0.000 title claims description 105
- 229910052731 fluorine Inorganic materials 0.000 title claims description 105
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 101
- 238000000034 method Methods 0.000 title claims description 31
- 238000000576 coating method Methods 0.000 claims abstract description 64
- 239000011248 coating agent Substances 0.000 claims abstract description 62
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 76
- 239000000654 additive Substances 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000009499 grossing Methods 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 12
- 239000003125 aqueous solvent Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011342 resin composition Substances 0.000 claims description 6
- 238000006056 electrooxidation reaction Methods 0.000 claims description 5
- 230000037452 priming Effects 0.000 claims description 5
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- 239000001023 inorganic pigment Substances 0.000 claims description 4
- 239000012766 organic filler Substances 0.000 claims description 4
- 239000012860 organic pigment Substances 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 93
- 235000013339 cereals Nutrition 0.000 description 27
- 230000007797 corrosion Effects 0.000 description 26
- 238000005260 corrosion Methods 0.000 description 26
- 238000010411 cooking Methods 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 15
- 239000004411 aluminium Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000003973 paint Substances 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000007547 defect Effects 0.000 description 10
- 238000005555 metalworking Methods 0.000 description 10
- 230000000472 traumatic effect Effects 0.000 description 10
- 239000000945 filler Substances 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003746 surface roughness Effects 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 230000003254 anti-foaming effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002221 fluorine Chemical class 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 150000001398 aluminium Chemical class 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 235000008429 bread Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000002421 finishing Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229960002668 sodium chloride Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- CZIRZNRQHFVCDZ-UHFFFAOYSA-L titan yellow Chemical compound [Na+].[Na+].C1=C(C)C(S([O-])(=O)=O)=C2SC(C3=CC=C(C=C3)/N=N/NC3=CC=C(C=C3)C3=NC4=CC=C(C(=C4S3)S([O-])(=O)=O)C)=NC2=C1 CZIRZNRQHFVCDZ-UHFFFAOYSA-L 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N5/00—Radiation therapy
- A61N5/06—Radiation therapy using light
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47C—CHAIRS; SOFAS; BEDS
- A47C21/00—Attachments for beds, e.g. sheet holders, bed-cover holders; Ventilating, cooling or heating means in connection with bedsteads or mattresses
- A47C21/04—Devices for ventilating, cooling or heating
- A47C21/048—Devices for ventilating, cooling or heating for heating
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47C—CHAIRS; SOFAS; BEDS
- A47C27/00—Spring, stuffed or fluid mattresses or cushions specially adapted for chairs, beds or sofas
- A47C27/14—Spring, stuffed or fluid mattresses or cushions specially adapted for chairs, beds or sofas with foamed material inlays
- A47C27/15—Spring, stuffed or fluid mattresses or cushions specially adapted for chairs, beds or sofas with foamed material inlays consisting of two or more layers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N5/00—Radiation therapy
- A61N5/06—Radiation therapy using light
- A61N2005/0658—Radiation therapy using light characterised by the wavelength of light used
- A61N2005/0659—Radiation therapy using light characterised by the wavelength of light used infrared
- A61N2005/066—Radiation therapy using light characterised by the wavelength of light used infrared far infrared
Abstract
The invention provides a fluorine-resin coating having the good properties of all wear-resistance, damage-resistance, corrosion-resistance and blister-resistance and the preparation thereof. A fluorine-resin coating and the preparation thereof, characterized in that a fluorine-resin coating comprising of coating one or two fluorine-resin layer on substrate, the most outer layer consisting of tetrafluoroethylene/perfluoroalkylvinylether (PFA) copolymer having melt flow-rate of 0.2 to 10 g/10min regulated in accordance with ASTM-D-3307, said PFA is in the amount of 20 to 100 weight % by the weight of total PFA layer, and having the thickness of 10 to 90 mum.
Description
The present invention relates to fluorine resin enclose material and manufacture method thereof.In detail, the present invention relates to all good fluorine resin enclose material and manufacture methods thereof such as its wearability, traumatic resistance, corrosion resistance, anti-foaming characteristic.The invention still further relates to the fluorine resin coating that the fluorine resin enclose material of making above-mentioned all characteristic goods is suited again.
Always because the fluorine resin enclose material that has coated fluororesin on base materials such as metal has non-cohesive surface, so in pot, steamer, frying pan, cooker cooking appliance such as pot; Electric hot plate, roaster, automatic bread maker, smash household electrical appliances cooking appliances such as rice cake device; Use in the wide spectrum of oil vessel etc. (spy opens clear 60-234618 communique, special fair 7-55182 communique).As fluororesin, generally use the polytetrafluoroethylene (PTFE) of excellent heat resistance and tetrafluoroethylene/perfluoro alkyl vinyl ether copolymer (PFA) etc.
Fluorine resin enclose material is usually by fluororesin-coated coating on base material, and roasting forms fluororesin coating film and makes.When fluorine resin enclose material being shaped in pot, steamer, frying pan, the cooker container shapes of pot etc., use metal material to make fluorine resin enclose material as base material, as required, desired shape is processed in moulding through its stamping-out being become behind the reservation shape such as circular plate type punch process etc.The metal base that use strikes out reservation shapes such as predetermined circular plate type also can be made into fluorine resin enclose material.Fluororesin layer forms one deck or more than two layers.Fluorine resin enclose material has the surface of non-cohesive, hear resistance, corrosion resistance, owing to do not adhere to the food of the cooking, so be specially adapted to the cooking appliance field.
Yet the wearability and the traumatic resistance of fluorine resin enclose material always are insufficient, in use repeatedly, have and are easy to wear away or injured problem.Its reason is the mechanical strength and the proof stress breaking property deficiency of fluororesin overlay film.Always, it seems from the processability viewpoint of filming, is coating processing by using the higher PTFE subparticle dispersion liquid of molecular weight as fluororesin; Or the dry type static powder coating of the greater particle size of the PFA system of use lower molecular weight.Think that in order to improve the molecular weight that mechanical strength and proof stress breaking property etc. can further improve employed fluororesin still, the PTFE of super high molecular weight and the PFA of HMW are by even and level and smooth the filming of the extremely difficult formation of coating.
The purpose of this invention is to provide all good fluorine resin enclose material and manufacture methods thereof such as a kind of wearability, traumatic resistance, corrosion resistance, anti-foaming characteristic.
Another purpose of the present invention provides a kind of fluorine resin coating that forms all good fluororesin coating film of this each characteristic.
The inventor etc. have carried out making great efforts research for the problem that overcomes above-mentioned technology always, found that, even if use the tetrafluoroethylene/perfluoro alkyl vinyl ether co-polymer (PFA) of the little HMW of its melt flow (MFR), also to make its average grain diameter be the PFA particle of 5～40 μ m (big particle diameter) and PFA groups of grains that average grain diameter is 0.1～0.5 μ m (small particle diameter) altogether, just can be easy to form good the filming of practicality, therefore, can form mechanical strength and all good the filming of proof stress breaking property.The two all can use the PFA particle of HMW as the PFA particle of the PFA particle of big particle diameter and small particle diameter, but also can use the particle of the big low-molecular-weight PFA of always MFR as small particle diameter PFA particle.When adopting the powder body coating method and selecting average grain diameter,, also may be formed with filming of practicality even use the PFA of HMW separately again.
As the fluorine resin coating that is used to form fluororesin coating film, also can use the powder of forming by the PFA particle of big particle diameter, but make big particle diameter PFA particle and small particle diameter PFA particle be scattered in the fluorine resin coating that forms dispersing morphology in the liquid medium, because it is superior as the stability of coating and the formability of filming, simultaneously, have only this coating just to have the effect of smoothing.So satisfactory especially, such PFA filmed on base material directly introduce or form outermost layer by one deck fluororesin layer at least, then can obtain the significantly improvement of wearability and traumatic resistance, corrosion resistance and the also good fluorine resin enclose material of anti-foaming characteristic.
Again, on base material, form at least three layers of fluororesin layer,, can improve wearability and traumatic resistance because configuration contains fluororesin layer by additives such as the pigment of special ratios and fillers in the intermediate layer.Owing to make the intermediate layer form decorative pattern, scale, literal figures, can make fluorine resin enclose material have pattern and deixis again again.The present invention is accomplished with regard to being based on these knowledge.
The invention provides fluorine resin enclose material, it is characterized in that, coat on base material in the fluorine resin enclose material of one or more layers fluororesin layer, its outermost layer is that thickness is that melt flow that the PFA layer of 10～90 μ m is wherein measured among the ASTM-D-3307 is 0.2～10g/10 minute tetrafluoroethylene/perfluoro alkyl vinyl ether co-polymer (PFA), accounts for 20～100 weight % of PFA total amount.
Again, the manufacture method of fluorine resin enclose material provided by the invention, it is characterized in that, on base material, coat in the manufacture method of fluorine resin enclose material of one or more layers fluororesin layer, on base material, directly introduce or by one deck fluororesin layer at least, the melt flow that fluorine resin coating, this fluororesin contain among the ASTM-D-3307 to be measured is that 0.2-10g/ minute PFA amount is 20～100 weight % of PFA total amount; Forming thickness after the roasting is the outermost layer of the PFA layer of 10～90 μ m.
Moreover the invention provides fluorine resin coating and be by its average grain diameter is that melt flow 5～40 μ m, that measured among the ASTM-D-3307 is that 0.2～10g/10 minute PFA particle and average grain diameter are that melt flow 0.1～0.5 μ m, that measured among the ASTM-D-3307 is that 0.2-40g/10 minute PFA particle is to be dispersed in the liquid flux in 20: 80～80: 20 to make with weight ratio.
Moreover the present invention also provides a kind of fluorine resin enclose material, it is characterized in that, on base material, coat in the fluorine resin enclose material of fluororesin layer,
(1) the fluororesin clad is by the priming coat that joins with base material; At least the fluororesin layer more than three layers formed of intermediate layer of one deck and outermost layer forms; And,
(2) intermediate layer of one deck is that the fluorin resin composition that is selected from least a additive in organic pigment, inorganic pigment, organic filler and the inorganic filler that contains the ratio of 0.5～10 weight % forms at least.
Fluorine resin enclose material of the present invention is the fluorine resin enclose material that coats one or more layers fluororesin layer on base material.Can use the aluminium of aluminium and aluminium alloy etc. as base material is base material, magnetic or various metal bases such as composite base material such as nonmagnetic stainless steel substrate or aluminium-SUS.Also can use ceramic base material and glass baseplate etc. as base material again.In these base materials, when the cooking appliance, because that aluminium is the thermal conductivity and the processing and forming of base material is good, so be that base material is satisfactory with aluminium.
In fluorine resin enclose material of the present invention, when outermost layer is when containing the PFA by 0.2～10g/10 minute of defined MFR among the ASTM-D-3307 that accounts for PFA total amount 20～100 weight % and constituted, also can in PFA, add pigment and filler, but it seems from viewpoints such as wearability, traumatic resistance and formation property of filming, only to be advisable with PFA itself.Employed its MFR is that 0.2～10g/10 minute PFA is the PFA of HMW among the present invention.As less than 0.2g/10 minute, then be coated with poor in processability as MFR, be difficult to form even and level and smooth filming; As MFR greater than 10g/10 minute, then wearability and traumatic resistance to improve effect little, than always the employee is very different, therefore can not obtain sufficient durability.MFR preferably 0.5～5g/10 minute is more preferably 1～4g/10 minute.
Yet, used PFA in the fluorine resin enclose material technical field always, its MFR be surpass 10g/10 minute, the molecular weight that is lower than 40g/10 minute is lower.For example, the MFR of the PFA (commodity are called MP102) that fluorine chemistry company of Mitsui Du Pont is made is 13g/10 minute, and melt viscosity is 4 * 10 under 380 ℃
4Pool infers that its molecular weight is about 500,000.Again, the MFR of the PFA (commodity are called MP10) that fluorine chemistry company of Mitsui Du Pont is made is 16, and melt viscosity is identical with MP 102, is 4 * 10 under being 380 ℃
4Pool infers that its molecular weight is about 500,000.The PFA of peer-level molecular weight also can be from being with gold (ダ イ キ Application) industry and company of Asahi Glass to buy and providing the present technique field to use.These PFA are with spherical or be ground into difform powder and dispersion supply.In dispersion, estimate that its molecular weight is about 200,000 PFA and can buys from band metal working industry company, its MFR is 16～35, dissolve viscosity is 1.5 * 10 under 380 ℃
4Pool.Yet, use these PFA after, though its coating processability good, the wearability deficiency of the fluorine resin enclose material of gained.
In contrast, in the present invention, use with special ratios, MFR is 0.2～10g/10 minute HMW PFA.Commercially available prod as such HMW PFA can be fit to use.For example having as the commercially available prod, E.I.Du Pont Company makes commercially available PFA (commodity are called MP 103).Melt viscosity is high to being about 2 owing to its MFR is little for this MP 103, and is high to 380 ℃ following 3 * 10
5Therefore pool, is difficult to processing.Be difficult to use when for this reason, the PFA of such HMW is used to be coated with kitchens such as the interior pot of cooker and pot, steamer, frying pan utensil for cooking.On the other hand, the molecular weight of this PFA is about more than 900,000, and mechanical strength and proof stress breaking property are good, therefore, if can make it be applicable to the fluorine resin enclose material field, then is expected to obtain wearing away all good filming such as durability and traumatic resistance.The inventor uses this HMW PFA, and when test film was made in its compression moulding, affirmation can obtain being the abrasion durability of the product of PFA moulding always more than 2 times.
Yet the dispersion coating no matter PFA of the HMW that this MFR is little is scattered in the liquid flux as its particle carries out application; Still with powder body coating, all be difficult to form densification and the thickness that do not have a paint film defect is filmed uniformly.Can consider that as the method for sort this problem out the average grain diameter that for example increases HMW PFA carries out with the powder body coating method.Study once more through the inventor, found that, to use average grain diameter be that 5～40 μ m, MFR are that 0.2～10g/10 minute PFA particle and average grain diameter is that 0.1～0.5 μ m, MFR are the fluorine resin coating of 0.2～40g/10 minute PFA particle owing to forming with 20: 80～80: 20 ratios, can form processability and well not have filming of paint film defect, and, make this smoothing of filming easily.As average grain diameter is the small particle diameter PFA particle of 0.1～0.5 μ m, also can use MFR to be 0.2-10g/10 minute HMW PFA particle, but preferably uses MFR for greater than the 10g/10 minute low-molecular-weight PFA particle less than 40g/10 minute.Here, be that the proportion scale of big particle diameter PFA particle of 5～40 μ m is too small as average grain diameter, formation property of then filming is poor; If excessive, during then as wet type coating (dispersion), its stability decreases.The proportion scale of big particle diameter PFA particle and small particle diameter PFA particle is preferably 50: 50～and 80: 20.
The fluorine resin coating that contains employed PFA particle among the present invention is powder coating preferably, but above-mentioned two kinds of PFA particles are scattered in the dispersion (wet type coating) in the aqueous solvent and when using, be coated with the membrane granule gap and be easy to compacting, also smoothing easily, therefore satisfactory.Again, big particle diameter PFA particle and small particle diameter PFA particle all use HMW PFA particle also can, but as the PFA particle of big particle diameter, as use little and the PFA particle that molecular weight is high of its MFR, then excellent processability is easy to suppress the generation of paint film defect, therefore, satisfactory.The PFA particle of the HMW that MFR is little shared ratio in total PFA amount is 20～100 weight %, but for making processability and each rerum natura balance, and then 20～80 weight % preferably are more preferably 50～80 weight %.This ratio is decided to be more than the 20 weight %, can obviously improves the wearability of filming.
The fluorine resin coating of the above-mentioned PFA of containing particle can be by for example powder electrostatic application, dispersion liquid spraying, transfer printing, flow coat, the printing gimmick except that the web plate coating, spin coating, roller coating etc. carry out application.In these finishings, the spraying process of dispersion liquid obtain easily filming zero defect and be easy to filming of smoothing.
When film with PFA (PFA layer) formed outermost layer, the thickness of its film must be in 10～90 mu m ranges.Require fluorine resin enclose material except that possessing wearability (abrasion durability), also will possess the characteristic that goes up necessity as practical: corrosion resistance and anti-foaming characteristic (foaming durability).Corrosion resistance is when cooking food etc., because of the durability of substrate metal corrosion due to the salt of invading from the tiny flaw of filming and the organic matter.The foaming durability is: cooking repeatedly in the use, not can because of be coated with intermembranous and film and base material between the bubble performance of peeling off of causing and bubbling of what is called.Can guess, film inside and film between and film and base material between the moisture that accumulates when the heating rapidly of the cooking etc. produces gas, surpassed bonding force and will film and up push away, therefore produce and bubble.From result of the test as can be known, if when the average thickness of outermost PFA layer surpasses 90 μ m, the frequency that takes place of bubbling is just high.For improving wearability, the thickness of PFA layer is thick more good more, but it seems from foaming durability viewpoint, is advisable with a thin side.If the thickness of PFA layer is thin excessively, then be easy to run through the paint film defects such as pinprick of filming, so corrosion resistance descends.Therefore, be balance foaming durability and corrosion resistance, outermost thickness is decided to be 10～90 μ m, preferred 15～60 μ m.
Fluorine resin enclose material of the present invention by on base material directly or by one deck fluororesin layer at least, with average grain diameter be 5～40 μ m, its MFR be 0.2～10g/10 minute PFA particle and average grain diameter be 0.1～0.5 μ m, its MFR is that PFA particle sintering after the fluorine resin coating coating of forming in 20: 80～80: 20 of 0.2～40g/10 minute prepares.In this manufacture method, form by contain account for the PFA total amount be 20～100 weight %, its MFR is 0.2～10g/10 minute film (PFA layer) that PFA constituted.The thickness of outermost PFA layer is in 10～90 mu m ranges.Suitably determine as formation methods of can filming by common PFA such as roasting conditions.
Can carry out smoothing to fluorine resin enclose material of the present invention as required handles.Be coated with the wet type coating that contains big particle diameter PFA particle and small particle diameter PFA particle and also can carry out smoothing and handle, also can carry out with heating pressurization described later, they can carry out separately, combine to carry out better.Because fluorine resin enclose material outermost layer of the present invention is to be formed by above-mentioned specific PFA layer, so be easy to carry out the smoothing processing on surface.It is by behind the outermost layer that is made of the PFA layer that this smoothing is handled, and heats under the temperature less than PFA crystalline melt point temperature, pressurizes on the right angle orientation of outermost surface simultaneously and carries out.Pressure method has: when heating under the above temperature of room temperature, from the method for passing through between the roller of crimping such as pinch roll or leveller; The method that is used for the bonding pressure sintering of different metal etc., in heating, the method for on direction that application face is met at right angles, pressurizeing.When carrying out smoothing with pressure sintering and handle, usually 150 °～300 ℃, preferably under 220～280 ℃ heating, in inert gas atmospheres such as nitrogen, argon gas, be reduced under the normal pressure or in the atmosphere below 1.5 air pressure, usually with 200～1000kgf/cm
2, preferably with 300～800kgf/cm
2Exert pressure 5～60 minutes, preferred 10～30 minutes.
The flatness on fluorine resin enclose material of the present invention surface depends on application condition and smoothing treatment conditions, but surface roughness Ra can be worked in about 0.1 μ m～about 5 mu m ranges.By the selection to all conditions, surface roughness can reach and be suitable for 0.2～3 mu m range that pot and cooking appliance are used in the cooker.
Primer coating in advance on the base material of metal base etc., can improve and fluororesin coating film between cohesive.Under the situation of metal base, should pass through chemistry or electrochemical corrosion treatment, on the surface of metal base, form fine male and fomale(M﹠F), thus the cohesive between raising and the fluororesin coating film.When the metal base of corrosion treatment is carried out in use, after forming fluororesin coating film on the sheet material, can be processed into shape arbitrarily, the smoothing processing that also is easy to carry out the wet type paint spraying and pressurizes and done.The bonding agent mode that the priming paint that is combined with the low concentration adhesive is coated with on corrosion treatment face and also be suitable for by the hybrid mode that the physics bonding way of corrosion treatment gained combines.Prime treatment and corrosion treatment can be undertaken by conventional process.
Fluorine resin enclose material of the present invention as requested, also can form one deck or above fluororesin layer between base material and outermost layer.This fluororesin layer can by each fluororesin in polytetrafluoroethylene (PTFE), PFA, the tetrafluoroethylene/hexafluoropropylene fluororesin such as (FEP) individually or two kinds or above combination be coated with and form.The kind and the conditions such as coating, sintering of the employed fluorine resin coating of lower floor can be selected from conventional process.The also available and outermost layer PFA of the same race as the employed PFA of lower floor; The big low-molecular-weight PFA of also available always used MFR.Owing to make two layers or above fluororesin layer, the paint film defect of pinprick etc. is eliminated, thereby be can further improve wearability.Also can carry out paintedly to lower floor's fluororesin layer, form decorative pattern etc., therefore can have the function of pattern etc.When lower floor's fluororesin layer was set, there is no particular restriction to its number of plies, and normally about 1～3 layer, its gross thickness is generally 5～100 μ m, preferred 10～60 μ m.
According to the present invention, be coated in the fluorine resin enclose material on the base material, the fluororesin clad is by the priming coat that engages with base material, at least three layers of being constituted of the intermediate layer of one deck and outermost layer or above fluororesin layer are formed at least, and, disposed by containing the fluororesin layer that 0.5～10 fluorin resin composition weight % ratio, that be selected from least a additive in organic pigment, inorganic pigment, organic filler and the inorganic filler forms as the intermediate layer of one deck at least, thereby can be obtained superior fluorine resin enclose materials such as wearability.In this case, outermost layer not necessarily by above-mentioned PFA film form.As the fluororesin that forms each layer PTFE, PFA, FEP etc. can be arranged.
The intermediate layer is one deck, two layers or above multilayer.Can utilize the intermediate layer to repair paint film defects such as pinprick.To the wearability reinforcement, make to have pattern and deixis.In order to repair paint film defect such as pinprick, then need not make it contain additive as only, but for strengthening wearability, making and have pattern and deixis then must be allocated additive into.At least a additive in organic pigment, inorganic pigment, organic filler and the inorganic filler of being selected from that in the one deck at least in intermediate layer, contains 0.5～10 weight % ratio.
For example can have as organic additive: polyamidoimide, polyimides, PEI, polyether sulfone, polysulfones, polybenzimidazoles, poly-p-phenylene sulfide, polyether-ether-ketone engineering plastics such as (Port リ エ-テ Le エ-テ Le Network ト Application).These organic additives are allocated into to tens of microns larger particles shape with the fine particle below the submicron usually.Have as inorganic additive: representative pigment such as titanium white, titan yellow, carbon black, iron oxide red, ultramarine; Representative flakey pigment class such as the mica that mica, pigment coat, lemel, glass fine powder, graphite, fluorocarbons; Glass particle, metallic particles, metal oxide particle, ceramic particle etc. strengthen with filler etc.But additive is not limited to above-mentioned, and all additives that may buy also are suitable for.Allocation ratio as additive is too small, then is difficult to obtain above-mentioned effect; As excessive, coating strength reduces or produces paint film defects such as interlayer bonding force and pinprick, so bad.The allocation ratio of additive can suitably be stipulated by purpose, but generally be advisable with 1～5 weight %.
The formation method in intermediate layer can be used rubbing method and print process arbitrarily such as serigraphy, die printing, ink jet printing, spraying, spin coating, roller coating.When the intermediate layer comprehensively and just partly is not coated with, then available serigraphy, printing processes such as die printing, ink jet printing are advisable.
When fluorine resin enclose material being used for electric hot plate, baking tray, automatic bread maker, smashing the household electrical appliances cooking appliance of rice cake device representative; During the interior pot of general cooking appliance such as pot, steamer, frying pan, cooker etc., can the cooking and wash Mi Shiyong be easy to friction or abrasion partly disposes the intermediate layer.Particularly be shaped in the fluorine resin enclose material of container shapes such as the interior pot of cooker and pot, steamer, frying pan, in the position of the bottom surface of container-like article shaped inboard or bottom surface and side Lower Half, should dispose the intermediate layer.Also the intermediate layer can be arranged in other parts, but near do not contain additive the strict middle part, side of processing, top, side, flange part intermediate layer is difficult to take place paint film defect mostly, also satisfactory aspect corrosion resistance.Configuration contains the position of intermediate layer part of additive and design should be by the usage of fluorine resin enclose material, purposes, function, decision such as attractive in appearance, but generally near the middle part of the side height when forming container-like article shaped the following intermediate layer that disposes up to the bottom surface be advisable.The high such performance of durability should be disposed the intermediate layer of containing filler with this point that the pattern impression shows.
By the decorative pattern that the intermediate layer forms that fluorin resin composition constituted that contains additive.As decorative pattern and without particular limitation, various decorative patterns, literal, scale etc. can be arranged.Pattern is that the mark, the sign except that enterprise, information of illustration, drawing, photography, painting and calligraphy or numeral design, the armory etc. of geometry style and personage, landscape, still life etc. etc. forms the decorative pattern shape as the intermediate layer.The formation of decorative pattern can be in office institute where, but to avoid the place of pattern distortion, on the bottom surface, form favourable to producing.Certainly, near side and flange, also can form style.At this moment, must pre-estimate because the distortion due to the back processing of extrusion forming etc. designs the style shape again.
The example of scale has: the scale at expression water levels such as cookers is represented with lettering; Represent its explanation etc.; The example of expression has in oil can etc.: use the optical illusion of grade etc. of the obvious expression of marking device of the deterioration color that is easy to discern oil, can a glance just judge the deterioration level of oil.
Under the situation of fluorine resin enclose material with intermediate layer of containing above-mentioned filler, then form its outermost fluororesin kind and can select PTFE, PFA, FEP or their mixture arbitrarily for use, contain additives such as pigment or filler and also can.Under the situation of paying attention to non-cohesive and corrosion resistance, its outermost layer is advisable not contain additives such as pigment.Again, outermost layer by contain the MFR that accounts for PFA total amount 20～100 weight % ratios be 0.2～10g/10 minute PFA formed, thickness is the PFA layer of 10～90 μ m.Therefore, can improve durability.Priming coat is formed by PTFE, PFA, FEP or their mixture, and its thickness is 5～100 μ m normally, preferred about 10～60 μ m.There is no particular restriction for the thickness in intermediate layer, normally 5～100 μ m, preferably about 10～60 μ m.
Like this, the wearability of fluorine resin enclose material of the present invention, traumatic resistance, corrosion resistance, anti-foaming characteristic are superior, and the research by to the configuration in intermediate layer then can further improve wearability.And, also additional pattern and deixis etc.Fluorine resin enclose material of the present invention directly or by pressure processing etc. is shaped to the article shaped of different shape after forming fluororesin layer on the base material, promptly applicable to the extensive fields based on the cooking appliance field.
Embodiment
Below enumerate embodiment and comparative example, with specific description the present invention, but the present invention is not subjected to the restriction of these embodiment.
Moreover the assay method of rerum natura is as follows:
(1) surface roughness
Determination method folder according to the center line average boldness (Ra) of JIS-B-0607 defined is measured surface roughness.Its unit is μ m.
(2) pinprick degree
Fluorine resin enclose material be impregnated in the sodium-chloride water solution of 2.5 weight %, then, with the metal_based material of fluorine resin enclose material as negative electrode, electrode is put into solution as anode, be converted into the electric current of unit are and try to achieve with the switch on electric current (mA) that partly flows out from pinprick of gained after 5 seconds of 10V, its unit is mA/cm
2
(3) Scotland Bu Laite (ス コ Star チ Block ラ イ ト) abrasion test
Make Scotland Bu Laite testing machine with fluorine resin enclose material laminar surface state of contact under rotate, represent at that time abrasion loss to wipe the thick required rotation number of PFA layer of 1 μ m off, its unit is 10
3Commentaries on classics/μ m.
(4) corrosion resistance
The raw material (Ha Wusi (Ha ゥ ス) food industry system) 25 of mixture (お In ん) is restrained in the experimental liquid that is dissolved in 1 premium on currency, and the dipping test piece 90～100 ℃ of insulations, is determined at the time that corrosion takes place on the coated surface.
Embodiment 1
(light metals industry corporate system in Sumitomo is MG-110) as alumina-base material for the aluminium plectane of use thickness of slab 1.2m1.At first with this aluminium plectane as anode, in aqueous ammonium chloride solution, with 25 coulombs/cm
2Electric weight carry out electrochemical corrosion and handle, fine concavo-convex on aluminium plectane surface, to form.On this fine male and fomale(M﹠F), the PTFE dispersant (the system D-IF of band gold (ダ イ キ Application) industrial group) that does not contain filler is carried out spin coating, secondly, after making moisture drying, 400 ℃ of following roastings 10 minutes, forming thick was film (ground floor) of 25 μ m.
Secondly, with average grain diameter 15 μ m, melt flow is PFA powder (E.I.Du Pont Company's system of 1.6g/10 minute, MP-103) 33.3 weight % are scattered in the aqueous solvent, this aqueous solvent is surfactant (ユ ニ ダ イ Application, DS-401 are already made in the band metal working) 1.0 weight % and a hydrocarbon system surfactant (Japanese grease system by water 34.8 weight %, fluorine, ニ オ Application K-204) 0.5 weight % mixes, and adds average grain diameter 0.4 μ m therein, melt flow is about 25g/10 minute PFA spherical particle 47 weight %, surfactant 6 weight %.The PFA dispersion liquid that water 47 weight % are formed (band metal working industry corporate system, AD-2CR) 30.4 weight % fully mix, and are modulated into fluorine resin coating.The weight ratio of the PFA particle of the PFA particle of average grain diameter 15 μ m and average grain diameter 0.4 μ m is 70: 30.On above-mentioned ground floor with this fluorine resin coating spin coating, secondly, make moisture drying after, 390 ℃ of following sintering 30 minutes, forming thick was film (second layer) of 15 μ m, the results are shown in table 1.
Comparative example 1
In embodiment 1, as the fluorine resin coating of the second layer, be two kinds of original PFA particles of PFA particle displacement of 13g/10 minute with average grain diameter 13 μ m, melt flow, all identical in addition with embodiment 1, make fluorine resin enclose material, the results are shown in table 1.
Table 1
| Routine number | The powder PFA that uses | Scotland Bu Laite abrasion test (10 3Commentaries on classics/μ m) | Pinprick degree (mA/cm 2) | Surface roughness Ra (μ m) |
| Comparative example 1 | MP-102 | 1.0 | 0 | 1.0～1.2 |
| Embodiment 1 | MP-103 | 2.1 | 0 | 2.3～ 2.5 |
As shown in table 1, as the PFA particle, the MP-102 (comparative example 1) big with using MFR compares, and uses the wearability of the little MP-103 (embodiment 1) of MFR can improve about 2 times.
Embodiment 2
The surface roughness Ra of the outermost layer (second layer) of embodiment 1 gained fluorine resin enclose material is 2.3～2.5 μ m.Above the fluorine resin enclose material, overlapped surfaces rugosity Ra is the corrosion resistant plate of 1.0 μ m at this, under 27 ℃ of heating, under 0.5 atmospheric decompression the pressurization 500kgf/cm
2Hot pressing is 20 minutes under the pressure, and obtaining surface roughness Ra is surface 1.2～1.5 μ m, that flatness is enhanced.
Embodiment 3
The aluminium sheet (Sumitomo light metals industry system, MG-110) that uses thickness of slab 1.2mm is as alumina-base material.At first, with this aluminium plectane as anode, in aqueous ammonium chloride solution, with 25 coulombs/cm
2Electric weight carry out electrochemical corrosion, it is concavo-convex that aluminium plectane surface is formed.
With average grain diameter 15 μ m, melt flow is PFA powder (E.I.Du Pont Company's system of 1.6g/10 minute, MP-103) 33.3 weight % are dispersed in by water 34.8 weight %, fluorine is a surfactant (band metal working industry corporate system, ユ ニ グ イ Application DS-204) 1.0 weight % and hydrocarbon system surfactant (Japanese grease, ニ オ Application K-204) in the aqueous solvent that 0.5 weight % mixes, add therein by average grain diameter 0.4 μ m, melt flow is about 25g/10 minute PFA spherical particle 47 weight %, surfactant 6 weight %, the PFA dispersion liquid that water 4.7 weight % are formed (band metal working industry corporate system, AD-2CR) 30.4 weight %, fully mix, be modulated into fluorine resin coating.The weight ratio of the PFA particle of the PFA particle of average grain diameter 15 μ m and average grain diameter 0.4 μ m is 70: 30.
This fluorine resin coating is sprayed on the micro concavo-convex face of above-mentioned aluminium plectane, and after with moisture drying, 390 ℃ of roastings 30 minutes, forming thick was filming of 25 μ m.Be shaped to a pot shape with forming this test portion of filming, carry out the corrosion resistance evaluation.The result does not almost see corrosion in 90 hours corrosion resistance test, obtaining can be for practical fluorine resin enclose material.
Comparative example 2
Remove and to change two kinds of PFA particles among the embodiment 3 into average grain diameter 13 μ m, melt flow be 13g/10 minute PFA particle (MP 102) in addition, other press embodiment 3 and prepares fluorine resin enclose materials equally, similarly estimates.As a result, in 90 hours corrosion resistance test, almost do not see corrosion, obtaining can be for practical fluorine resin enclose material.Also promptly, with comparative example 2 contrast as can be known, according to the fluorine resin enclose material of embodiment 3, can reach the corrosion resistance that is equal to mutually with employee always.
Embodiment 4
The aluminium plectane (Sumitomo light metals industry corporate system, MG-110) of thickness of slab 1.2mm, diameter 360mm is used as alumina-base material.At first, with this aluminium plectane as anode, in aqueous ammonium chloride solution, with 25 coulombs/cm
2Electric weight carry out electrochemical corrosion and handle, make on the aluminium plectane, form fine concavo-convex.On this fine male and fomale(M﹠F), the PTFE dispersion liquid (band metal working industry corporate system, D-IF) that does not contain filler is carried out spin coating, behind moisture drying, 400 ℃ of following roastings 10 minutes, forming thick was film (ground floor) of 25 μ m.
In the PFA dispersion liquid of being formed by PFA spherical particle 47 weight %, surfactant 6 weight %, water 47 weight % (band metal working industry corporate system, D-2CR) sneak into mica (Mel set a date our company's system, IRIODIN 503) 4.4 weight %, surfactant (band metal working industry corporate system ユ ニ イ Application, the DS401 of PFA powder (E.I.Du Pont Company's system, MP 103) 28.1 weight %, coating pigment among the 25.4 weight %; Change into corporate system with Sanyo, オ Network Port-Le 80) 42.1 weight %, be modulated into the fluorine resin coating that contains filler.With this fluorine resin coating on the above-mentioned ground floor with serigraphy from plectane central authorities in diameter 180mm scope after the application, 390 ℃ of roastings 15 minutes, forming thick was film (second layer) of 5 μ m.
With average grain diameter 15 μ m, melt flow is PFA powder (E.I.Du Pont Company's system of 1.6g/10 minute, MP-103) 33.3 weight % are dispersed in by water 34.8 weight %, fluorine is surfactant (band metal working industry corporate system ユ ニ イ Application DS-401) 1.0 weight %, with hydrocarbon system surfactant (Nof Corp.'s system, ニ オ Application K-204) in the aqueous solvent that 0.5 weight % mixes, adds therein by average grain diameter 0.4 μ m, melt flow is about 25g/10 minute PFA spherical particle 47 weight %, surfactant 6 weight %, the PFA dispersion liquid that water 47 weight % are formed (band metal working industry corporate system.AD-2CR) 30.4 weight % fully mix, and are modulated into fluorine resin coating.Average grain diameter is that the PFA particle of 15 μ m and weight ratio that average grain diameter is the PFA particle of 0.4 μ m are 70: 30.This fluorine resin coating is rotated coating on the above-mentioned second layer, behind moisture drying, 390 ℃ of following roastings 30 minutes, forming thick was film (the 3rd layer) of 15 μ m.
In the Bu Laite abrasion test of Scotland of the fluorine resin enclose material that obtains like this, detect up to the rotation number of seeing that bottom layer of aluminum is required.The result is as shown in table 2.In addition, in table 2, also list with the evaluation result that fluorine resin enclose material carried out of this determination method comparative example 1 and embodiment 1 gained.
Table 2
| The examination item number | Thickness (μ m) | Scotland Bu Laite abrasion test rotation number (103 change) | Overall merit |
| Comparative example 1 | 40 | 20 | × |
| Embodiment 1 | 40 | 36.5 | ○ |
| Embodiment 4 | 45 | 44 | ◎ |
Again, because with the fluorine resin enclose material compression moulding of embodiment 4 is the pot shape, the all second layer fluororesin layers (intermediate layer) with the mica that contains coating pigment of bottom surface sections are coated, thus obtain the bottom surface different with the tone of lateral parts, the unprecedented characteristic look of fluorine resin enclose material always.
Embodiment 5
Remove the fluorine resin coating that uses the second layer among the embodiment 4, use serigraphy, application scale, literal on the assigned position of all designs in scope from plectane central authorities to diameter 200mm, and 390 ℃ of roastings 15 minutes, secondly, beyond the 3rd layer of fluororesin of spin coating, other is identical with embodiment 4, makes fluorine resin enclose material.With the extrusion forming of gained fluorine resin enclose material is the fried prawn pot.Use this fried prawn pot as can be known, because oil stain changes the literal outward appearance, the scale in intermediate layer and literal play the effect of oil stain indicator.
According to superior fluorine resin enclose material and manufacture methods thereof such as wearability provided by the invention, traumatic resistance, corrosion resistance, anti-foaming characteristics.Again, according to the fluorine resin coating that the invention provides the fluororesin coating film that can form each excellent.Fluorine resin enclose material of the present invention is as utensils for cooking such as pots in pot, steamer, frying pan, the cooker; Electric hot plate, roaster, automatic bread maker, smash household electrical appliances cooking appliances such as rice cake device; Oil vessels etc. are applicable to extensive fields.
Claims (9)
1. fluorine resin enclose material, on base material, coat in the fluorine resin enclose material of one deck or two layers or above fluororesin layer, it is characterized in that, its outermost layer is that 0.2～10g/10 minute tetrafluoroethylene/perfluoro alkyl vinyl ether co-polymer (PFA) is formed by the melt flow that contains among the ASTM-D-3307 to be measured that accounts for PFA total amount 20-100 weight %, thick is the PFA layer of 10～90 μ m, and this PFA layer is that 0.2～10g/10 minute average grain diameter is the PFA particle of 5～40 μ m and to be 0.2～40g/10 minute average grain diameter PFA particle that is 0.1～0.5 μ m with the melt flow of being measured among the ASTM-D-3307 formed by the fluorine resin coating that was scattered in the aqueous solvent in 20: 80～80: 20 with weight ratio with the melt flow of being measured among the ASTM-D-3307.
2. the manufacture method of fluorine resin enclose material, on base material, coat in the manufacture method of fluorine resin enclose material of one deck or two layers or above fluororesin layer, it is characterized in that, on base material, directly or by one deck fluororesin layer at least be 0.2～10g/10 minute PFA accounting for the melt flow of being measured among the ASTM-D-3307 of PFA total amount 20～100 weight %, be that 0.2～10g/10 minute average grain diameter is the PFA particle of 5～40m and is that the PFA particle that 0.2～40g/10 minute average grain diameter is 0.1～0.5 μ m is that the fluorine resin coating that was scattered in the aqueous solvent in 20: 80～80: 20 is coated with weight ratio with the melt flow of being measured among the ASTM-D-3307 promptly with the melt flow of being measured among the ASTM-D-3307, after roasting, form thickness and be 10～90 μ m by outermost layer that PFA constituted.
3. the manufacture method of the fluorine resin enclose material of putting down in writing according to claim 2 is characterized in that, fluorine resin coating is the fluorine resin coating that is scattered in the PFA particle of the PFA particle of average grain diameter 5～40 μ m in the aqueous solvent and average grain diameter 0.1～0.5 μ m.
4. according to the manufacture method of claim 2 or 3 fluorine resin enclose materials of being put down in writing, it is characterized in that, after the outermost layer that the PFA layer is constituted forms, when under temperature, heating less than the PFA crystalline melt point, with the vertical direction of outermost surface on pressurize, carry out smoothing and handle.
5. according to the manufacture method of each fluorine resin enclose material of putting down in writing in the claim 2 to 4, it is characterized in that, to handle through chemistry or electrochemical corrosion, the plate-shape metal material that forms the micro concavo-convex shape from the teeth outwards is as base material, behind the outermost layer that formation is made up of the PFA layer, by required shape processing and forming.
6. fluorine resin coating, this coating is the employed coating of outermost layer that coats the fluorine resin enclose material of one deck or two layers or above coating fluororesin layer on base material, it is characterized in that, by with average grain diameter 5～40 μ m's, the melt flow of being measured among the ASTM-D-3307 is 0.2～10g/10 minute, what account for PFA total amount 20～100 weight % contains tetrafluoroethylene/perfluoro alkyl vinyl ether co-polymer (PFA) particle and average grain diameter 0.1～0.5 μ m, the melt flow of being measured among the ASTM-D-3307 is that 0.2～40g/10 minute PFA particle is scattered in the aqueous solvent with 20: 80～80: 20 weight ratios and constitutes.
7. fluorine resin enclose material in the fluorine resin enclose material that is coated by fluororesin layer on base material, is characterized in that,
(1) the fluororesin clad is by the priming coat that joins with base material, the intermediate layer of one deck and the fluororesin layer more than at least three layers that outermost layer is constituted are formed at least; And
(2) intermediate layer of one deck is contained the fluorin resin composition that is selected from least a additive in organic pigment, inorganic pigment, organic filler and the inorganic filler with 0.5～10 weight % ratio and is formed at least;
(3) its outermost layer by account for PFA total amount 20-100 % by weight contain the melt flow of measuring among the ASTM-D-3307 be that 0.2～10g/10 minute tetrafluoroethylene/perfluoro alkyl vinyl ether co-polymer (PFA) forms, thick be the PFA layer of 10～90 μ m, this PFA layer with the melt flow of measuring among the ASTM-D-3307 be 0.2～10g/10 minute average grain diameter be the melt flow measured among the PFA particle of 5～40 μ m and the ASTM-D-3307 be 0.2～40g/10 minute average grain diameter be the PFA particle of 0.1～0.5 μ m take weight ratio by 20: 80)～fluorine resin coating that is scattered in aqueous solvent at 80: 20 formed.
8. the fluorine resin enclose material of putting down in writing according to claim 7, it is characterized in that, on the position of the Lower Half of the fluorine resin enclose material inner surface that is formed as container shapes or bottom surface and side, form by the intermediate layer that fluorin resin composition constituted of containing additive.
9. the fluorine resin enclose material of putting down in writing according to claim 7 is characterized in that, forms the decorative pattern shape by the intermediate layer that fluorin resin composition constituted of containing additive.
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| Application Number | Priority Date | Filing Date | Title |
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| JP43919/1999 | 1999-02-22 | ||
| JP11043919A JP3080089B1 (en) | 1999-02-22 | 1999-02-22 | Fluororesin coating and production method thereof |
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| CN1265942A CN1265942A (en) | 2000-09-13 |
| CN1201872C true CN1201872C (en) | 2005-05-18 |
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| KR (1) | KR100346796B1 (en) |
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| JP4312669B2 (en) * | 2004-03-19 | 2009-08-12 | 株式会社リコー | Fixing member, fixing device using the fixing member, and image forming apparatus |
| JP2006130743A (en) * | 2004-11-04 | 2006-05-25 | Sumitomo Electric Fine Polymer Inc | Fluoroplastic coating material, cooking utensil, electromagnetic induction heating container and formation method of electromagnetic induction heating container |
| JP4882312B2 (en) * | 2005-08-25 | 2012-02-22 | 富士ゼロックス株式会社 | Method for producing fluororesin-coated member |
| JP2012170915A (en) * | 2011-02-23 | 2012-09-10 | Dic Corp | Micromixer |
| WO2013058140A1 (en) * | 2011-10-18 | 2013-04-25 | ダイキン工業株式会社 | Fluororesin laminate and method for manufacturing same |
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| JP2016172026A (en) * | 2016-05-18 | 2016-09-29 | コクヨ株式会社 | Furniture member, resin member for chair, and leg base for chair |
| JPWO2021172214A1 (en) * | 2020-02-28 | 2021-09-02 | ||
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| CN114539857B (en) * | 2022-03-29 | 2023-03-07 | 武汉苏泊尔炊具有限公司 | Modified base oil, modified middle oil, composite coating and cooker |
| CN114479570B (en) * | 2022-03-29 | 2023-10-27 | 武汉苏泊尔炊具有限公司 | Corrosion-resistant material, method for producing the same, and corrosion-resistant coating formed therefrom |
| WO2023191061A1 (en) * | 2022-03-31 | 2023-10-05 | ダイキン工業株式会社 | Fluororesin composition and molded body |
| CN115608590A (en) * | 2022-11-04 | 2023-01-17 | 江苏贝尔机械有限公司 | PTFE spraying process for storing inner wall of viscous material bin |
-
1999
- 1999-02-22 JP JP11043919A patent/JP3080089B1/en not_active Expired - Lifetime
-
2000
- 2000-02-18 CN CNB001023470A patent/CN1201872C/en not_active Expired - Fee Related
- 2000-02-19 TW TW089102905A patent/TW527230B/en not_active IP Right Cessation
- 2000-02-22 KR KR1020000008636A patent/KR100346796B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW527230B (en) | 2003-04-11 |
| JP3080089B1 (en) | 2000-08-21 |
| KR20000058146A (en) | 2000-09-25 |
| JP2000239596A (en) | 2000-09-05 |
| CN1265942A (en) | 2000-09-13 |
| KR100346796B1 (en) | 2002-07-31 |
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