KR100346796B1 - fluorin resin coated product and process for producing the same - Google Patents
fluorin resin coated product and process for producing the same Download PDFInfo
- Publication number
- KR100346796B1 KR100346796B1 KR1020000008636A KR20000008636A KR100346796B1 KR 100346796 B1 KR100346796 B1 KR 100346796B1 KR 1020000008636 A KR1020000008636 A KR 1020000008636A KR 20000008636 A KR20000008636 A KR 20000008636A KR 100346796 B1 KR100346796 B1 KR 100346796B1
- Authority
- KR
- South Korea
- Prior art keywords
- pfa
- fluorine resin
- layer
- coating
- particle diameter
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 114
- 239000011347 resin Substances 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims description 24
- 238000000576 coating method Methods 0.000 claims abstract description 155
- 239000011248 coating agent Substances 0.000 claims abstract description 150
- 239000011737 fluorine Substances 0.000 claims abstract description 115
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 115
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000000155 melt Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 140
- 239000002245 particle Substances 0.000 claims description 113
- 239000000463 material Substances 0.000 claims description 45
- 239000000654 additive Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 11
- 238000009499 grossing Methods 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 4
- 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
- 239000011342 resin composition Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 22
- 238000005299 abrasion Methods 0.000 abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 15
- 238000010411 cooking Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- 230000007547 defect Effects 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
- 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
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003746 surface roughness Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 241000047703 Nonion Species 0.000 description 3
- 101150060820 Pfas gene Proteins 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002221 fluorine Chemical class 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
- 239000003973 paint Substances 0.000 description 3
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 3
- 230000009255 platelet function activity Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 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
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000467686 Eschscholzia lobbii Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 239000006229 carbon black Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000004446 fluoropolymer coating Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 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
- 239000011261 inert gas Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 101150054634 melk gene Proteins 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide 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
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 238000005406 washing 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
Landscapes
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Radiology & Medical Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Cookers (AREA)
- Coating Apparatus (AREA)
Abstract
본 발명은, 내마모성, 내상성, 내식성, 내블리스터성 등이 뛰어난 불소수지피복물과 그 제조방법을 제공하는 것을 과제로 한 것이며, 그 해결수단으로서, 기재위에 1층 또는 2층이상의 불소수지층이 피복된 불소수지피복물에 있어서, 그 최외층이, ASTM-D-3307에 규정된 멜트플로레이트가 0.2∼10g/10분인 테트라플루오로에틸렌/퍼플루오로알킬비닐에테르공중합체(PFA)를 PFA전체량속에 20∼100중량%의 비율로 함유하는 PFA로 이루어진 두께 10∼90㎛인 PFA층인 것을 특징으로 하는 불소수지피복물 및 그 제조방법이 제공된다.It is an object of the present invention to provide a fluorine resin coating having excellent abrasion resistance, scratch resistance, corrosion resistance, blister resistance and the like and a method for producing the same, wherein one or more fluorine resin layers are provided on the substrate. In the coated fluororesin coating, the outermost layer is a PFA containing tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) having a melt flow rate of 0.2 to 10 g / 10 min as specified in ASTM-D-3307. Provided is a fluororesin coating and a method for producing the same, characterized in that the PFA layer has a thickness of 10 to 90 µm and is made of PFA contained in a total amount of 20 to 100% by weight.
Description
본 발명은, 불소수지피복물과 그 제조방법에 관한 것이며, 더욱 상세하게는, 내마모성, 내상(耐傷)성, 내식성, 내블리스터성 등이 뛰어난 불소수지피복물과 그 제조방법에 관한 것이다. 또, 본 발명은, 상기 여러 특성이 뛰어난 불소수지피복물을 제조하는 데 적합한 불소수지도료에 관한 것이다.TECHNICAL FIELD The present invention relates to a fluorine resin coating and a method for producing the same, and more particularly, to a fluorine resin coating having excellent abrasion resistance, scratch resistance, corrosion resistance, blister resistance, and the like. Moreover, this invention relates to the fluorine resin material suitable for manufacturing the fluororesin coating material which is excellent in the said various characteristic.
종래부터, 금속기재 등의 기재(基材)위에 불소수지를 피복한 불소수지피복물은, 비점착성의 표면을 가지기 때문에, 남비, 솥, 프라이팬, 자(jar)취반기내부솥 등의 조리기구; 핫플레이트, 그릴팬, 오토베이커리, 떡치는 기구 등의 가전조리기구; 오일포트 등으로서, 광범위한 분야에 응용되고 있다(일본국 특개소 60-234618호 공보, 동 특공평 7-55182호 공보). 불소수지로서는, 일반적으로, 내열성이 뛰어난 폴리테트라플루오로에틸렌(PTFE)이나 테트라플루오로에틸렌/퍼플루오로알킬비닐에테르공중합체(PFA) 등이 사용되고 있다.Conventionally, since the fluorine resin coating which coated the fluorine resin on the base materials, such as a metal base, has a non-stick surface, cooking utensils, such as a pot, a pot, a frying pan, and a jar cooker internal pot; Home appliance cooking appliances such as hot plates, grill pans, auto bakeries and rice cakes; As an oil pot etc., it is applied to a wide range of fields (Japanese Unexamined-Japanese-Patent No. 60-234618, 7-55182). As the fluororesin, polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), etc. which are excellent in heat resistance are generally used.
불소수지피복물은, 통상, 기재위에 불소수지도료를 도포하고, 베이킹해서, 불소수지도막을 형성함으로써 제조되고 있다. 불소수지피복물을 남비, 솥, 프라이팬, 자취반기내부솥 등의 용기형상으로 성형하는 경우에는, 기재로서 금속기재를 사용해서 불소수지피복물을 제작하고, 필요에 따라서 원판형상 등의 소정의 형상으로 펀칭가공한 후, 프레스가공 등에 의해 소망의 형상으로 성형가공하고 있다. 미리 원판형상 등의 소정의 형상으로 펀칭가공한 금속기재를 사용해서, 불소수지피복물을 제작해도 된다. 불소수지층은, 1층 또는 2층이상으로 형성한다. 불소수지피복물은, 비점착성, 내열성, 내식성의 표면을 가지고 있으며, 조리식품의 달라붙음이 없기 때문에, 특히 조리기구의 분야에 알맞다.Fluorine resin coatings are usually produced by coating a fluorine resin on a substrate, baking, and forming a fluorine resin film. In the case of forming a fluorine resin coating into a container shape such as a pot, a pot, a frying pan, or a self-contained inner pot, a fluorine resin coating is prepared using a metal substrate as a base material, and punched into a predetermined shape such as a disc shape if necessary. After processing, it is molded into a desired shape by press working or the like. The fluorine resin coating may be produced by using a metal substrate punched into a predetermined shape such as a disc in advance. The fluororesin layer is formed of one layer or two or more layers. The fluororesin coating has a non-tacky, heat resistant, and corrosion resistant surface, and is suitable for the field of cooking utensils, especially since there is no stickiness of the cooked food.
그런데, 종래의 불소수지피복물은, 내마모성이나 내상성이 반드시 충분하지는 않고, 반복사용하는 중에, 마모하거나, 상처가 나기 쉽다고하는 문제가 있었다. 그 원인으로서는, 불소수지피막의 기계적 강도나 내스트레스크랙성이 충분하지 않은 것에 있다고 추정된다. 종래, 불소수지로서는, 도막에의 가공성의 관점에서, 비교적 분자량이 높은 PTFE를 미소 입자분산액으로서 도포가공하여 사용하거나, 또는 비교적 저분자량의 PFA를 비교적 큰 입자직경의 건식의 정전분말체도료로서 사용하고 있었다. 기계적 강도나 내스트레스크랙성 등을 개선하기 위해서는, 사용하는 불소수지의 분자량을 더욱 높이는 것을 생각할 수 있으나, 초고분자량의 PTFE나 고분자량PFA는, 도장에 의해 균일하고 평활한 도막을 형성하는 일이 매우 곤란하다.By the way, the conventional fluorine resin coating has a problem that abrasion resistance and abrasion resistance are not necessarily enough, and it is easy to abrasion or a wound during repeated use. The reason for this is presumably due to insufficient mechanical strength and stress crack resistance of the fluororesin coating film. Conventionally, as a fluororesin, from the viewpoint of processability to a coating film, PTFE having a relatively high molecular weight is applied as a fine particle dispersion, or PFA having a relatively low molecular weight is used as a dry electrostatic powder coating having a relatively large particle diameter. Was doing. In order to improve mechanical strength, stress crack resistance, etc., it is conceivable to further increase the molecular weight of the fluorine resin to be used, but ultra high molecular weight PTFE and high molecular weight PFA may form a uniform and smooth coating film by coating. Very difficult.
본 발명의 목적은, 내마모성, 내상성, 내식성, 내블리스터성 등이 뛰어난 불소수지피복물과 그 제조방법을 제공하는 데 있다.An object of the present invention is to provide a fluorine resin coating having excellent abrasion resistance, scratch resistance, corrosion resistance, blister resistance, and a method for producing the same.
본 발명의 다른 목적은, 이와 같은 제특성이 뛰어난 불소수지도막을 형성할 수 있는 불소수지도료를 제공하는 데 있다.Another object of the present invention is to provide a fluorine resin which can form a fluorine resin film excellent in such various characteristics.
본 발명자들은, 상기 종래기술의 문제점을 극복하기 위하여 예의 연구한 결과, 멜트플로레이트(MFR:Melt Flow Rate)가 작은 고분자량 테트라플루오로에틸렌/퍼플루오로알킬비닐에테르 공중합체(PFA)를 사용해도, 평균입자직경이 5∼40㎛(큰 입자직경)인 PFA입자와 평균입자직경 0.1∼0.5㎛(작은입자직경)의 PFA입자를 조합시킴으로써, 실용성이 뛰어난 도막을 용이하게 형성할 수 있고, 그에 의해서, 기계적 강도나 내스트레스크랙성이 뛰어난 도막을 형성할 수 있는 것을 발견했다. 큰 입자직경의 PFA입자와 작은 입자직경의 PFA입자로서, 모두 고분자량 PFA입자를 사용할 수 있으나, 작은 입자직경의 PFA입자로서 종래의 MFR이 큰 저분자량 PFA입자로 해도 된다. 또, 분말체도장법을 채용하고, 평균입자직경을 선택하는 등을 하면, 고분자량 PFA단독이라도, 실용성이 있는 도막을 형성하는 일이 가능하다.The present inventors have diligently studied to overcome the problems of the prior art, and as a result, high molecular weight tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) having a low melt flow rate (MFR) Even if used, by combining PFA particles having an average particle diameter of 5 to 40 µm (larger particle diameter) and PFA particles having an average particle diameter of 0.1 to 0.5 µm (small particle diameter), a coating film having excellent practicality can be easily formed. It discovered that the coating film excellent in mechanical strength and stress crack resistance can be formed thereby. Both high molecular weight PFA particles can be used as the PFA particles having a large particle diameter and the PFA particles having a small particle diameter, but the low molecular weight PFA particles having a large MFR can be used as the PFA particles having a small particle diameter. In addition, by adopting the powder coating method and selecting the average particle diameter, it is possible to form a practical coating film even in a high molecular weight PFA alone.
불소수지도막을 형성하기 위한 불소수지도료로서는, 큰 입자직경의 PFA입자로 이루어진 분말체라도 좋으나, 큰 입자직경의 PFA입자와 작은 입자직경의 PFA입자를 액상매체속에 분산시킨 디스퍼젼(dispersion)형태의 불소수지도료가 도료로서의 안정성과 도막성형성이 뛰어나고, 동시에 이것만으로 평활화 효과가 있으므로, 특히 바람직하다. 이와 같은 PFA도막을 기재위에 직접 또는 적어도 1층의 불소수지층을 개재해서, 최외층으로서 형성함으로써, 내마모성과 내상성이 현저하게 개선되고, 내식성이나 내블리스터성도 양호한 불소수지피복물을 얻을 수 있다.The fluorine resin coating material for forming the fluorine resin film may be a powder composed of PFA particles having a large particle diameter, but a dispersion form in which PFA particles having a large particle diameter and PFA particles having a small particle diameter are dispersed in a liquid medium. Fluorine resin is particularly preferred because of its excellent stability and coating film formation as a coating and at the same time only a smoothing effect. By forming such a PFA coating film on the substrate directly or via at least one fluorine resin layer as the outermost layer, abrasion resistance and scratch resistance are remarkably improved, and a fluororesin coating having good corrosion resistance and blister resistance can be obtained. .
또, 기재위에 적어도 3층의 불소수지층을 형성하고, 중간층에, 안료나 충전재 등의 첨가재를 특정 비율로 함유하는 불소수지층을 배치함으로써, 내마모성이나 내상성을 높일 수 있다. 또, 상기 중간층을 무늬나 눈금, 문자 등의 패턴형상으로 형성함으로써, 불소수지피복물에 의장성이나 지시기능성 등을 부여할 수 있다. 본 발명은, 이들 지견에 의거해서 완성하기에 이르렀던 것이다.Moreover, abrasion resistance and flaw resistance can be improved by forming at least 3 fluorine resin layers on a base material, and arrange | positioning the fluorine resin layer which contains additives, such as a pigment and a filler, in a specific ratio in an intermediate | middle layer. In addition, by forming the intermediate layer into a pattern such as a pattern, a scale, a letter, or the like, designability, indicating functionality, and the like can be imparted to the fluorine resin coating. The present invention has been completed based on these findings.
본 발명에 의하면, 기재위에 1층 또는 2층이상의 불소수지층이 피복된 불소수지피복물에 있어서, 그 최외층이, ASTM-D-3307에 규정된 멜트플로레이트가 0.2∼10g/10분인 테트라플루오로에틸렌/퍼플루오로알킬비닐에테르공중합체(PFA)를 PFA전체량속에 20∼100중량%의 비율로 함유하는 PFA로 이루어진 두께 10∼90㎛인 PFA층인 것을 특징으로 하는 불소수지피복물이 제공된다.According to the present invention, in a fluorine resin coating coated with one or two or more layers of fluorine resin layers on a substrate, the outermost layer is a tetrafluoride having 0.2 to 10 g / 10 minutes of a melt fluoride specified in ASTM-D-3307. Provided is a fluororesin coating comprising a fluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) comprising a PFA layer having a thickness of 10 to 90 탆 made of PFA containing 20 to 100% by weight in the total amount of PFA. do.
또, 본 발명에 의하면, 기재위에 1층 또는 2층이상의 불소수지층이 피복된 불소수지피복물의 제조방법에 있어서, 상기 기재위에 직접 또는 적어도 1층의 불소수지층을 개재해서, ASTM-D-3307에 규정된 멜트플로레이트가 0.2∼10g/10분인 PFA를 PFA전체량속에 20∼100중량%의 비율로 함유하는 PFA로 이루어진 불소수지를 도포하고, 베이킹해서, 두께 10∼90㎛인 PFA층으로 이루어진 최외층을 형성하는 것을 특징으로 하는 불소수지피복물의 제조방법이 제공된다.Further, according to the present invention, in the method for producing a fluorine resin coating wherein one layer or two or more layers of fluorine resin layers are coated on a base material, directly or at least one layer of fluorine resin layer on the base material, ASTM-D- PFA having a melt flow rate of 0.2 to 10 g / 10 minutes specified in 3307 is coated with a PFA containing PFA containing 20 to 100% by weight in the total amount of PFA. Provided is a method for producing a fluororesin coating, which forms an outermost layer composed of layers.
또, 본 발명에 의하면, 평균입자직경 5∼40㎛이고 ASTM-D-3307에 규정된 멜트플로레이트가 0.2∼10g/10분인 PFA입자와 평균입자직경 0.1∼0.5㎛이고 ASTM-D-3307에 규정된 멜트플로레이트가 0.2∼40g/10분인 PFA입자가 중량비 20:80∼80:20으로 액상매체속에 분산되어서 이루어진 불소수지도료가 제공된다.Further, according to the present invention, PFA particles having an average particle diameter of 5 to 40 µm and a melt florate specified in ASTM-D-3307 of 0.2 to 10 g / 10 minutes and an average particle diameter of 0.1 to 0.5 µm are ASTM-D-3307. Provided is a fluororesin comprising a PFA particle having a melt flow rate of 0.2 to 40 g / 10 minutes as defined in the above, dispersed in a liquid medium in a weight ratio of 20:80 to 80:20.
또한, 본 발명에 의하면, 기재위에 불소수지층이 피복된 불소수지피복물에있어서,Further, according to the present invention, in a fluorine resin coating having a fluorine resin layer coated on a base material,
(1) 불소수지피복층이, 기재에 접하는 베이스코트층, 적어도 1층의 중간층 및 최외층으로 이루어진 3층이상의 불소수지층으로 형성되고, 또한,(1) The fluorine resin coating layer is formed of three or more layers of fluorine resin layers composed of a base coat layer in contact with a substrate, at least one intermediate layer, and an outermost layer, and
(2) 적어도 1층의 중간층이, 유기안료, 무기안료, 유기충전재 및 무기충전재로 이루어진 군으로부터 선택되는 적어도 1종의 첨가재를 0.5∼10중량%의 비율로 함유하는 불소수지조성물로 형성되어 있는(2) At least one intermediate layer is formed of a fluororesin composition containing at least one additive selected from the group consisting of organic pigments, inorganic pigments, organic fillers and inorganic fillers in a proportion of 0.5 to 10% by weight.
것을 특징으로 하는 불소수지피복물이 제공된다.A fluorine resin coating is provided, which is characterized by the above-mentioned.
본 발명의 불소수지피복물은, 기재위에 1층 또는 2층이상의 불소수지층이 피복된 불소수지피복물이다. 기재로서는 알루미늄이나 알루미늄합금 등의 알루미늄계 기재, 자성 또는 비자성 스테인레스기재, 혹은 알루미늄-SUS 등의 이들 복합기재 등의 각종 금속기재를 사용할 수 있다. 또, 기재로서, 세라믹기재나 유리기재 등을 사용할 수도 있다. 이들 기재중에서도, 조리기구의 용도에는, 열전도성이나 성형가공성이 양호한 것때문에, 알루미늄계 기재가 바람직하다.The fluorine resin coating of the present invention is a fluorine resin coating wherein one or two or more layers of fluorine resin layers are coated on a base material. As a base material, various metal base materials, such as aluminum base materials, such as aluminum and an aluminum alloy, magnetic or nonmagnetic stainless base materials, and these composite base materials, such as aluminum-SUS, can be used. Moreover, as a base material, a ceramic base material, a glass base material, etc. can also be used. Among these substrates, aluminum-based substrates are preferred for the use of cookware because of their good thermal conductivity and molding processability.
본 발명의 불소수지피복물에 있어서, 최외층을 ASTM-D-3307에 규정된 MFR이 0.2∼10g/10분인 PFA를 20∼100중량%의 비율로 함유하는 PFA로 이루어진 PFA층으로 하는 경우에는, PFA에 안료나 충전재를 첨가해도 좋으나, 내마모성이나 내상성, 도막형성성 등의 관점에서, PFA만인 것이 바람직하다. 본 발명에서 사용하는 MFR이 0.2∼10g/10분인 PFA는, 고분자량의 PFA이다. 이 MFR이 0.2g/10분미만에서는, 코팅가공성이 나빠져, 균일하고 평활한 도막을 형성하는 것이 곤란하게 된다. MFR이 10g/10분을 초과하면, 내마모성이나 내상성의 개선효과가 작아, 종래품과 큰 차이가 없어져, 충분한 내구성을 얻을 수 없다. MFR은, 바람직하게는 0.5∼5g/10분, 보다 바람직하게는 1∼4g/10분이다.In the fluorine resin coating of the present invention, when the outermost layer is a PFA layer made of PFA containing PFA having a MFR specified in ASTM-D-3307 of 0.2 to 10 g / 10 minutes at a ratio of 20 to 100% by weight, Although a pigment and a filler may be added to PFA, it is preferable that it is only PFA from a viewpoint of abrasion resistance, scratch resistance, coating film formation property, etc. PFA whose MFR used in this invention is 0.2-10 g / 10min is high molecular weight PFA. If the MFR is less than 0.2 g / 10 min, the coating workability deteriorates, making it difficult to form a uniform and smooth coating film. When MFR exceeds 10 g / 10 minutes, the improvement effect of abrasion resistance and abrasion resistance is small, there is no big difference with a conventional product, and sufficient durability cannot be obtained. MFR becomes like this. Preferably it is 0.5-5 g / 10min, More preferably, it is 1-4 g / 10min.
그런데, 종래, 불소수지피복물의 기술분야에서 사용되고 있는 PFA는, MFR이 10g/10분초과, 40g/10분이하 정도인 비교적 저분자량의 것이다. 예를 들면, 일본국 미쯔이듀폰플로로케미컬회사제의 PFA(상품명 MP102)는, MFR이 13g/10분이고, 용융점도가 380℃에서 4×104Poise이며, 분자량이 약 50만으로 추정된다. 또 상기 미쯔이듀폰플로로케미컬회사제의 PFA(상품명 MP10)는, MFR이 16이고, 용융점도가 MP102와 동등한 380℃에서 4×104Poise이며, 분자량도 약 50만으로 추정된다. 동등한 레벨의 분자랑의 PFA는, 일본국 다이킹공업회사나 일본국 아사히초자회사로부터도 시판되고, 이 기술분야에서 실용에 제공되고 있다. 이들 PFA는, 구(球)형상 또는 분쇄된 이형의 분말체나, 디스퍼젼으로서 공급된다. 디스퍼젼에서는, 분자량이 약 20만정도로 추정되는 PFA가 상기 다이킨공업회사로부터 시판되고 있으며, MFR이 16∼35이고, 용융점도가 380℃에서 1.5×104Poise라고 언급되어 있다. 그러나, 이들 PFA를 사용했다면, 코팅가공성은 양호하나, 얻어진 불소수지피복물의 내마모성이 불충분하게 된다.By the way, PFA conventionally used in the technical field of a fluororesin coating has a relatively low molecular weight whose MFR is more than 10g / 10min and about 40g / 10min or less. For example, PFA (trade name MP102) made by Mitsui Dupont Phloro Chemical Co., Ltd., Japan, has an MFR of 13 g / 10 minutes, a melt viscosity of 4 × 10 4 Poise at 380 ° C., and an estimated molecular weight of about 500,000. The PFA (trade name MP10) manufactured by Mitsui DuPont Floro Chemical Company is MFR of 16, a melt viscosity of 4 × 10 4 Poise at 380 ° C. equivalent to MP102, and a molecular weight of approximately 500,000. The PFA of the molecular sieve of the same level is marketed also by the Japanese diking industry company and the Japan Asahi Choza company, and is provided for practical use in this technical field. These PFAs are supplied as a spherical or pulverized release powder or as a dispersion. In the dispersion, PFA, which is estimated to have a molecular weight of about 200,000, is commercially available from Daikin Industries Co., Ltd., and has an MFR of 16 to 35 and a melt viscosity of 1.5 × 10 4 Poise at 380 ° C. However, if these PFAs were used, the coating workability was good, but the wear resistance of the obtained fluororesin coating was insufficient.
이에 대해서, 본 발명에서는, MFR이 0.2∼10g/10분인 고분자량 PFA를 특정비율로 사용한다. 이와 같은 고분자량 PFA로서는, 시판품을 적합하게 사용할 수 있다. 시판으로서는, 예를 들면, 듀폰회사로부터 제조판매되고 있는 PFA(상품명 MP103)를 들 수 있다. 이 MP103은, MFR이 약 2정도로 작고, 용융점도가 380℃에서 3×105Poise로 지극히 높기 때문에, 가공이 곤란하다. 그 때문에, 이와 같은 고분자량 PFA는, 자취반기내부솥이나 남비, 솥, 프라이팬 등의 주방조리기구에의 코팅용도에는 사용이 곤란하였다. 한편, 이 PFA는, 분자량이 약 90만이상으로 간주되고, 기계적 강도나 내스트레스크랙성이 뛰어나기 때문에, 이것을 불소수지피복물의 기술분야에 적용을 할 수 있다면, 마모내구성이나 내상성 등이 뛰어난 도막을 얻게되는 것을 기대할 수 있다. 본 발명자들은, 이와 같은 고분자량 PFA를 사용해서, 압축성형에 의해 시험편을 제조하였던 바, 종래의 PFA성형품의 2배이상의 마모내구성이 얻어지는 것이 확인되었다.On the other hand, in this invention, high molecular weight PFA whose MFR is 0.2-10 g / 10min is used by specific ratio. As such high molecular weight PFA, a commercial item can be used suitably. As a commercial item, the PFA (brand name MP103) manufactured and sold by the DuPont company is mentioned, for example. This MP103 has a small MFR of about 2, and has a very high melt viscosity of 3 × 10 5 Poise at 380 ° C., which makes machining difficult. Therefore, such high molecular weight PFA was difficult to use for coating application to kitchen cooking appliances, such as an internal pot half pot, a pot, a pot, and a frying pan. On the other hand, this PFA is considered to have a molecular weight of about 900,000 or more, and is excellent in mechanical strength and stress crack resistance. Therefore, if it can be applied to the technical field of fluorocarbon resin coating, it has excellent wear durability and resistance to scratches. You can expect to get a coating. The present inventors produced the test piece by compression molding using such a high molecular weight PFA, and it was confirmed that more than twice the wear durability of the conventional PFA molded product is obtained.
그러나, 이와 같은 MFR이 작은 고분자량의 PFA는, 그 입자를 액상매체속에 분산시킨 디스퍼젼도료로서 도장해도 또는 분말체도장해도, 치밀하고 도막결함이 없는, 균일한 두께의 도막을 형성하는 것이 곤란하다. 이 문제를 해결하는 방법으로서는, 예를 들면, 고분자량 PFA의 평균입자직경을 크게 해서, 분말체도장하는 방법을 생각할 수 있다. 또, 본 발명자들은, 더욱 검토를 행한 결과, 평균입자직경 5∼40㎛이고 MFR이 0.2∼10g/10분인 PFA입자와, 평균입자직경 0.1∼0.5㎛이고 MFR이 0.2∼40g/10분인 PFA입자를 중량비 20:80∼80:20으로 함유하는 불소수지도료를 사용함으로써, 가공성이 양호하고, 도막결함이 없는 도막을 형성할 수 있고, 또한, 이 도막을 평활화하기 쉽다는 것을 발견했다. 평균입자직경이 0.1∼0.5㎛인 작은 입자직경의 PFA입자로서는, MFR이 0.2∼10g/10분인 고분자량 PFA입자를 사용해도 되나, MFR이 10g/10분초과 40g/10분이하인 저분자량 PFA입자를 사용하는 것이 바람직하다. 여기서, 평균입자직경 5∼40㎛인 큰 입자직경의 PFA입자의 배합비율이 지나치게 작으면 도막형성성이 뒤떨어지고, 지나치게 크면 습식도료(디스퍼젼)로 했을 경우에 안정성이 저하한다. 큰 입자직경의 PFA입자와 작은 입자직경의 PFA입자의 배합비율은, 바람직하게는 50:50∼80:20이다.However, high molecular weight PFAs having such a low MFR are difficult to form a uniform and uniform coating film without coating defects, even if coated or powder coated as a dispersion coating in which the particles are dispersed in a liquid medium. Do. As a method of solving this problem, for example, a method of increasing the average particle diameter of the high molecular weight PFA and coating the powder can be considered. Further, the inventors conducted further studies, and as a result, the PFA particles having an average particle diameter of 5 to 40 µm and an MFR of 0.2 to 10 g / 10 minutes, and PFA particles having an average particle diameter of 0.1 to 0.5 µm and an MFR of 0.2 to 40 g / 10 minutes. By using the fluorine resin material containing 20: 80-80: 20 by weight ratio, it discovered that the processability is favorable, the coating film without a coating-film defect can be formed, and it is easy to smooth this coating film. As small PFA particles having an average particle diameter of 0.1 to 0.5 µm, high molecular weight PFA particles having an MFR of 0.2 to 10 g / 10 minutes may be used, but low molecular weight PFA particles having an MFR of more than 10 g / 10 minutes and 40 g / 10 minutes or less. Preference is given to using. When the blending ratio of PFA particles having a large particle size of 5 to 40 µm in average particle size is too small, the coating film formability is inferior, and when too large, stability is reduced when a wet coating (dispersion) is used. The blending ratio of the large particle diameter PFA particles and the small particle diameter PFA particles is preferably 50:50 to 80:20.
본 발명에서 사용하는 PFA입자를 함유하는 불소수지도료는, 분말체도료라도되나, 상기 2종류의 PFA입자를 액상 매체속에 분산시킨 디스퍼젼(습식도료)으로서 사용하는 것이, 도료의 입자간격이 패킹되기 쉽고, 평활화도 용이하기 때문에 바람직하다. 또, 큰 입자직경의 PFA입자와 작은 입자직경의 PFA입자의 어느 한쪽을 고분자량 PFA입자로 해도 되나, 큰 입자직경의 PFA입자로서, MFR이 작고 고분자량의 PFA입자를 사용하면, 가공성이 보다 양호하게 되고, 도막결함의 발생을 억제하기 쉬워지므로 바람직하다. MFR이 작은 고분자량 PFA입자의 전체 PFA입자속에 차지하는 비율은, 20∼100중량%이나, 가공성과 여러 물성이 균형을 이루는 점에서, 바람직하게는 20∼80중량%, 보다 바람직하게는 50∼80중량%로 하는 것이 바람직하다. 이 비율을 20중량%이상으로 함으로써, 도막의 내마모성을 현저하게 개선할 수 있다.The fluorine resin coating material containing the PFA particles used in the present invention may be a powder coating material, but the particle spacing of the coating material may be used as a dispersion (wet paint) in which the two kinds of PFA particles are dispersed in a liquid medium. Since it is easy to be smooth and smoothing, it is preferable. In addition, either PFA particles having a large particle diameter or PFA particles having a small particle diameter may be high molecular weight PFA particles. Since it becomes favorable and it becomes easy to suppress generation | occurrence | production of a coating film defect, it is preferable. The ratio of MFR to the total PFA particles of the small high molecular weight PFA particles is 20 to 100% by weight, but from the viewpoint of balancing workability and various physical properties, preferably 20 to 80% by weight, more preferably 50 to 80 It is preferable to set it as weight%. By setting this ratio to 20% by weight or more, the wear resistance of the coating film can be remarkably improved.
상기 PFA입자를 함유하는 불소수지도료는, 예를 들면, 분말체정전도장, 디스퍼젼의 스프레이코팅, 전사, 플로코트, 스크린코트 그밖의 인쇄수법, 스핀코트, 롤코트 등에 의해 도장할 수 있다. 이들 도장법중에서도, 디스퍼젼의 스프레이코팅은, 도막결함이 없고, 평활화가 용이한 도막을 얻기 쉬우므로 바람직하다.The fluororesin containing the PFA particles can be coated by, for example, powder coating, coating of dispersion, spraying, flow coating, screen coating or other printing method, spin coating, roll coating or the like. Among these coating methods, the spray coating of the dispersion is preferable because there is no coating film defect and an easy to obtain smooth coating film is obtained.
최외층을 PFA도막(PFA층)에 의해 형성하는 경우, 그 막두께를 10∼90㎛의 범위로 하는 것이 필요하다. 불소수지피복물은, 내마모성(마모내구성)외에, 실용상필요한 특성으로서, 내식성과 내블리스터성(블리스터내구성)을 구비하고 있는 것이 요구된다. 내식성은, 음식물 등을 조리했을 때에, 도막의 미소한 결함 등으로부터 침입하는 염이나 유기물에 의해 기재의 금속이 부식되는 데 견디는 내구성이다. 블리스터내구성은, 반복하여 조리를 행하는 실사용중에, 도막사이나 도막과 기재사이에 블리스터라 호칭되는 박리나 부풀림이 발생하지 않도록 견디는 성능이다. 블리스터는, 도막내부나 도막사이나 도막과 기재사이에 괸 수분이 조리 등의 급속가열시에 가스로서 빠질 때에, 접착력을 상회해서 도막을 밀어올리기 때문에 발생한다고 추정된다. 실험의 결과, 최외층의 PFA층의 평균두께가 90㎛를 초과하면, 블리스터발생빈도가 높아지는 것을 알았다. 마모내구성을 높이려면, PFA층의 막두께는 두꺼울수록 바람직하나, 블리스터내구성의 관점에서는 얇은 쪽이 바람직하다. PFA층의 막두께가 지나치게 작으면, 도막을 관통하는 핀홀 등의 도막결함이 발생하기 쉬워, 내식성이 저하한다. 그래서, 블리스터내구성과 내식성과의 균형을 취하는 데다가, 최외층의 막두께를 10∼90㎛로 하거나, 15∼60㎛로 하는 것이 바람직하다.When forming an outermost layer by a PFA coating film (PFA layer), it is necessary to make the film thickness into the range of 10-90 micrometers. Fluoropolymer coatings are required to have corrosion resistance and blister resistance (blister durability) in addition to wear resistance (wear resistance) as practically necessary characteristics. Corrosion resistance is the durability which withstands corrosion of the metal of a base material by the salt or organic substance which invades from the minute defect of a coating film, etc. when food or the like is cooked. Blister durability is a performance which endures peeling and swelling called a blister between a coating film, a coating film, and a base material in actual use which repeats cooking. It is presumed that blisters occur because the moisture contained in the coating film, between the coating film, the coating film and the base material escapes as a gas during rapid heating such as cooking, because it pushes the coating film beyond the adhesive force. As a result of the experiment, it was found that when the average thickness of the outermost PFA layer exceeds 90 µm, the blister occurrence frequency increases. In order to increase abrasion durability, the thicker the film thickness of the PFA layer is, the better, but from the viewpoint of blister durability, the thinner side is preferable. When the film thickness of a PFA layer is too small, coating film defects, such as a pinhole penetrating a coating film, will likely arise, and corrosion resistance will fall. Therefore, it is preferable to balance the blister durability and the corrosion resistance, and to set the outermost layer to have a thickness of 10 to 90 m or 15 to 60 m.
본 발명의 불소수지피복물은, 기재위에 직접 또는 적어도 1층의 불소수지층을 개재해서, 평균입자직경이 5∼40㎛이고 MFR이 0.2∼10g/10분인 PFA입자와 평균입자직경이 0.1∼0.5㎛이고 MFR이 0.2∼40g/10분인 PFA입자를 중량비 20:80∼80:20으로 함유하는 불소수지도료를 도포하고, 베이킹함으로써 제조할 수 있다. 이 제조방법에 의해, MFR이 0.2∼10g/10분인 PFA를 PFA전체량속에 20∼100중량%의 비율로 함유하는 PFA로 이루어진 도막(PFA층)이 형성된다. 최외층의 PFA층의 두께는, 10∼90㎛의 범위로 한다. 베이킹조건 등은, 통상의 PFA도막의 형성방법에 따라서 적당히 정할 수 있다.The fluororesin coating of the present invention has PFA particles having an average particle diameter of 5 to 40 µm and an MFR of 0.2 to 10 g / 10 minutes and an average particle diameter of 0.1 to 0.5 directly or on at least one layer of fluorine resin layer on the substrate. It can manufacture by apply | coating and baking fluorine resin material containing PFA particle | grains with a micrometer and MFR of 0.2-40 g / 10min by weight ratio 20: 80-80: 20. By this manufacturing method, a coating film (PFA layer) made of PFA containing PFA having an MFR of 0.2 to 10 g / 10 minutes in a proportion of 20 to 100% by weight in the total amount of PFA is formed. The thickness of the PFA layer of an outermost layer shall be 10-90 micrometers. Baking conditions can be suitably determined according to the usual method of forming a PFA coating film.
본 발명의 불소수지피복물에는, 필요에 따라서, 평활화처리를 실시할 수 있다. 평활화는, 큰 입자직경의 PFA입자와 작은 입자직경의 PFA입자를 함유하는 습식도료의 코팅으로도 달성할 수 있고, 후술의 가열가압으로도 가능하며, 이들을 단독으로 행하여도 되나, 조합하면 더욱 좋다. 본 발명의 불소수지피복물은, 최외층을 상기의 특정 PFA층에 의해 형성하고 있기 때문에, 표면의 평활화처리를 용이하게 행할 수 있다. 이 평활화처리는, PFA층으로 이루어진 최외층을 형성한 뒤, PFA의 결정융점미만의 온도로 가열하면서, 최외층의 표면에 직각방향으로 가압함으로써 행한다. 가압방법은, 실온이상으로 가열하면서, 핀치롤이나 레벨러 등의 압착하고 있는 롤사이를 통과시키는 방법이나, 이종(異種) 금속의 접합 등에 사용하는 핫프레스법 등에 의해, 가열하는 동시에 도장면에 직각방향으로 가압하는 방법을 들 수 있다. 핫프레스법에 의해 평활화처리를 행하는 경우, 통상 150℃∼300℃, 바람직하게는 220∼280℃의 가열하에, 질소가스, 아르곤가스 등의 불활성 가스분위기속, 상압하 또는 대기속의 1.5기압이하의 감압하에, 통상 200∼1,000kgf/㎠, 바람직하게는 300∼800kgf/㎠의 프레스압력으로, 통상 5∼60분간, 바람직하게는 10∼30분간 프레스하는 것이 일반적이다.The fluorine resin coating of the present invention can be subjected to a smoothing treatment if necessary. Smoothing can be achieved by the coating of a wet paint containing PFA particles having a large particle diameter and PFA particles having a small particle diameter, and also by heating and pressing described below, which may be performed alone or in combination. . Since the outermost layer is formed by said specific PFA layer, the fluorine resin coating of this invention can perform the surface smoothing process easily. This smoothing treatment is performed by pressing the surface of the outermost layer at right angles while forming the outermost layer made of the PFA layer, while heating it to a temperature below the crystal melting point of the PFA. The pressurization method is heated at a room temperature or higher, and is heated at the same time by a method such as passing between the press rolls such as a pinch roll or a leveler, a hot press method used for joining dissimilar metals, or the like, and perpendicular to the painted surface. The method of pressurizing to a direction is mentioned. When the smoothing treatment is performed by a hot press method, the heating is usually performed at a temperature of 150 ° C. to 300 ° C., preferably 220 to 280 ° C., at an atmosphere of inert gas such as nitrogen gas and argon gas, at atmospheric pressure or at most 1.5 atm in air. Under reduced pressure, it is generally pressurized at a press pressure of usually 200 to 1,000 kgf / cm 2, preferably 300 to 800 kgf / cm 2, for 5 to 60 minutes, preferably for 10 to 30 minutes.
본 발명의 불소수지피복물의 표면의 평활성은, 도장조건이나 평활화처리조건등에도 따르나, 표면거칠기(Ra)를 약 0.1㎛∼약 5㎛의 범위로 마무리하는 것이 가능하다. 여러 조건의 선택에 의해, 자취반기내부솥이나 조리기구 등의 용도에 적합한 0.2∼3㎛의 범위의 표면거칠기로 하는 것도 가능하다.Although the smoothness of the surface of the fluororesin coating of the present invention depends on the coating conditions, the smoothing treatment conditions, and the like, it is possible to finish the surface roughness Ra in the range of about 0.1 µm to about 5 µm. By the selection of various conditions, it is also possible to make surface roughness of the range of 0.2-3 micrometers suitable for uses, such as an internal cooking pot and a cooking utensil.
금속기재 등의 기재에는, 미리 프라이머를 도포해서, 불소수지도막과의 사이의 밀착성을 높일 수 있다. 금속기재의 경우에는, 화학적 또는 전기화학적인 에칭처리에 의해, 금속기재의 표면에 미세한 요철(凹凸)을 형성해서, 불소수지도막과의 사이의 밀착성을 높이는 것이 바람직하다. 에칭처리를 실시한 금속기재를 사용하면, 판재에 불소수지도막을 형성한 후, 임의의 형상으로 성형가공이 가능하고, 또, 습식도료에 의한 도장이나 가압에 의한 평활화처리를 행하기 쉽다. 비교적 저농도의 접착제를 배합한 프라이머를 에칭처리면에 코트하게 되는, 접착제방식과 에칭처리 등에 의한 물리적 접착방식과의 혼합방식도 적합하게 사용할 수 있다. 프라이머처리나 에칭처리 등은, 상법에 따라서 행할 수 있다.The base material, such as a metal base material, can be apply | coated beforehand and adhesiveness with a fluororesin film can be improved. In the case of a metal base material, it is preferable to form fine unevenness | corrugation on the surface of a metal base material by chemical or electrochemical etching process, and to improve adhesiveness with a fluorine resin film. When the etched metal substrate is used, after forming the fluorine resin film on the plate, it can be molded into any shape, and it is easy to perform the smoothing treatment by coating or pressing with a wet paint. The mixing method of the adhesive method and the physical adhesion method by an etching process etc. which coat the primer which mix | blended the comparatively low concentration adhesive agent on the etching process surface can also be used suitably. Primer treatment, an etching process, etc. can be performed according to a conventional method.
본 발명의 불소수지피복물은, 소망에 의해, 기재와 최외층과의 사이에 1층이상의 불소수지층을 형성한 것이라도 된다. 이와 같은 불소수지층은, 폴리테트라플루오로에틸렌(PTFE), PFA, 테트라플루오로에틸렌/헥사플루오로프로필렌(FEP) 등의 불소수지를 각각 단독으로 또는 2종이상을 조합해서 도장함으로써 형성할 수 있다. 하층에 사용하는 불소수지도료의 종류나 도포, 베이킹 등의 여러 조건은, 상법에 따라서 적당히 선택할 수 있다. 하층에 사용하는 PFA로서는, 최외층과 동일 종류의 것이라도 되나, 종래의 MFR이 큰 저분자량 PFA를 사용해도 된다. 불소수지층을 2층이상으로 함으로써, 핀홀 등의 도막결함을 없애고, 내마모성을 보다 한층 향상시킬 수 있다. 또, 하층의 불소수지층을 착색하거나, 무늬 등을 형성시킴으로써, 의장성 등의 기능을 부가할 수도 있다. 하층에 불소수지층을 배치할 경우는, 층수는, 특별히 한정되지 않으나, 통상 1∼3층정도로 하고, 그 두께의 합계는, 통상 5∼100㎛, 바람직하게는 10∼60㎛정도로 한다.The fluorine resin coating of the present invention may be one in which one or more fluorine resin layers are formed between the base material and the outermost layer as desired. Such a fluorine resin layer can be formed by coating fluorine resins such as polytetrafluoroethylene (PTFE), PFA, tetrafluoroethylene / hexafluoropropylene (FEP), alone or in combination of two or more thereof. have. Various conditions, such as the kind, application | coating, baking, etc. of the fluororesin used for a lower layer, can be suitably selected according to a conventional method. As PFA used for a lower layer, although it may be the same kind as an outermost layer, you may use the low molecular weight PFA with large conventional MFR. By using two or more fluororesin layers, coating film defects, such as a pinhole, can be eliminated and abrasion resistance can be improved further. Moreover, functions, such as design, can also be added by coloring the lower fluororesin layer or forming a pattern. In the case of disposing the fluorine resin layer on the lower layer, the number of layers is not particularly limited, but is usually about 1 to 3 layers, and the total of the thickness is usually 5 to 100 µm, preferably about 10 to 60 µm.
본 발명에 의하면, 기재위에 불소수지층이 피복된 불소수지피복물에 있어서, 불소수지피복층을, 기재에 접하는 베이스코트층, 적어도 1층의 중간층 및 최외층으로 이루어진 3층이상의 불소수지층을 형성하고, 또한, 적어도 1층의 중간층으로서, 유기안료, 무기안료, 유기충전제 및 무기충전제로 이루어진 군으로부터 선택되는 적어도 1종의 첨가제를 0.5∼10중량%의 비율로 함유하는 불소수지조성물로 형성한 불소수지층을 배치함으로써, 내마모성 등이 뛰어난 불소수지피복물을 얻을 수 있다. 이 경우, 최외층은, 반드시 상기의 PFA도막으로 형성된 것일 필요는 없다. 각 층을 형성하는 불소수지로서는, PTFE, PFA, FEP 등을 들 수 있다.According to the present invention, in the fluorine resin coating coated with the fluorine resin layer on the substrate, the fluorine resin coating layer is formed of three or more layers of fluorine resin layers comprising a base coat layer in contact with the substrate, at least one intermediate layer and an outermost layer. In addition, fluorine formed of a fluororesin composition containing at least one additive selected from the group consisting of organic pigments, inorganic pigments, organic fillers and inorganic fillers in a proportion of 0.5 to 10% by weight as at least one intermediate layer. By disposing a resin layer, a fluorine resin coating having excellent abrasion resistance and the like can be obtained. In this case, the outermost layer does not necessarily need to be formed of the above PFA coating film. PTFE, PFA, FEP, etc. are mentioned as a fluororesin which forms each layer.
중간층은, 1층이라도 되나, 2층이상의 다층이어도 된다. 중간층은, 핀홀 등의 도막결함의 보수, 내마모성의 보강, 의장성이나 지시기능의 부여에 이용할 수 있다. 핀홀 등의 도막결함의 보수를 위한 것뿐이라면, 중간층에 굳이 첨가제를 함유시킬 필요는 없으나, 내마모성의 보강, 의장성이나 지시기능성의 부여에는 첨가제를 배합하는 일이 필수적이며, 중간층의 적어도 1층에는 유기안료, 무기안료, 유기충전제 및 무기충전제로 이루어진 군으로부터 선택되는 적어도 1종의 첨가제를 0.5∼10중량%의 비율로 함유시킨다.The intermediate layer may be one layer or a multilayer of two or more layers. The intermediate layer can be used for repairing coating defects such as pinholes, reinforcing abrasion resistance, and providing designability and indicating function. It is not necessary to include an additive in the intermediate layer as long as it is only for the repair of coating defects such as pinholes, but it is necessary to add the additive to reinforce the wear resistance, to impart designability or indicating functionality, and to add at least one layer of the intermediate layer. Contains at least one additive selected from the group consisting of organic pigments, inorganic pigments, organic fillers and inorganic fillers in a proportion of 0.5 to 10% by weight.
유기 첨가제로서는, 예를 들면, 폴리아미드이미드, 폴리이미드, 폴리에테르이미드, 폴리에테르술폰, 폴리술폰, 폴리벤즈이미다졸, 폴리페닐렌술피드, 폴리에테르에테르케톤 등의 엔지니어링플라스틱을 들 수 있다. 이들 유기 첨가제는, 통상, 서브미크론이하의 미세입자에서부터 수십미크론의 비교적 큰 입자형상으로 배합한다. 무기 첨가제로서는, 예를 들면, 티탄화이트, 티탄옐로, 카본블랙, 철단(iron oxide), 군청 등을 대표로 하는 안료; 마이카, 안료피복마이카, 금속박분(薄粉), 유리박분, 그래파이트, 불화카본 등을 대표로 하는 비늘조각형상(鱗片狀) 안료류: 유리입자, 금속입자, 금속산화물입자, 세라믹입자 등의 보강용 충전제 등을 들 수 있다. 단, 첨가제는, 상기의 것에 한정되지 않고, 입수가능한 모든 첨가제를 적당히 사용할 수 있다. 첨가제의 배합비율이 지나치게 작으면, 상기와 같은 작용효과를 얻는 일이 곤란하게 되며, 지나치게 크면, 도막강도를 오히려 저하시키거나, 층간의 접착력이나 핀홀 등의 도막결함을 발생시키는 일이 있으므로 바람직하지 않다. 첨가제의 배합비율은, 목적에 따라서 적당히 설정할 수 있으나, 일반적으로는, 1∼5중량%가 바람직하다.Examples of the organic additives include engineering plastics such as polyamideimide, polyimide, polyetherimide, polyether sulfone, polysulfone, polybenzimidazole, polyphenylene sulfide, and polyether ether ketone. These organic additives are normally mix | blended in sub-micron or less microparticles | fine-particles in comparatively large particle shape of several tens of microns. As an inorganic additive, For example, pigments represented by titanium white, titanium yellow, carbon black, iron oxide, ultramarine blue, etc .; Scaly pigments such as mica, pigment coated mica, metal foil, glass foil, graphite, carbon fluoride, etc .: reinforcement of glass particles, metal particles, metal oxide particles, ceramic particles, etc. Solvent fillers; and the like. However, an additive is not limited to said thing, All available additives can be used suitably. If the blending ratio of the additive is too small, it is difficult to obtain the above-described effects, and if it is too large, the coating film strength may be lowered or coating film defects such as adhesion between layers and pinholes may be undesirable. not. Although the compounding ratio of an additive can be set suitably according to the objective, Generally, 1 to 5 weight% is preferable.
중간층의 형성방법은, 스크린인쇄, 스탬프인쇄, 잉크젯프린트, 스프레이코트, 스핀코트, 롤코트 등의 임의의 코트법이나 인쇄법을 적용할 수 있다. 중간층을 전체면 코트하지 않고 부분코트로 할 경우에는, 스크린인쇄, 스탬프인쇄, 잉크젯프린트 등의 인쇄수단을 사용하는 것이 적합하다.As the method for forming the intermediate layer, any coating method or printing method such as screen printing, stamp printing, inkjet printing, spray coating, spin coating, roll coating or the like can be applied. When the intermediate layer is partially coated without coating the entire surface, it is suitable to use printing means such as screen printing, stamp printing, inkjet printing, or the like.
불소수지피복물이 핫플레이트, 그릴팬, 오토베이커리, 떡치는 기구 등으로 대표되는 가전조리기구, 남비, 솥, 프라이팬 등의 일반적 조리기구, 자취반기내부솥 등의 용도로 사용되는 경우에는, 조리나 쌀씻기 등에 있어서, 마멸되거나, 상처나기 쉬운 개소에 중간층을 부분적으로 배치할 수 있다. 특히, 취반기 내부솥이나, 남비, 솥, 프라이팬 등의 용기형상으로 성형된 불소수지피복물의 경우에는, 용기형상 성형물의 안쪽의 바닥면 또는 바닥면과 측면의 아래절반의 위치에 중간층을 형성하는 것이 바람직하다. 중간층은, 다른 부분에 있어도 좋으나, 가공도가 엄격한 측면중간부, 측면상부, 플랜지부근방에는, 첨가제를 함유하는 중간층이 없는 편이 도막결함의 발생이 어렵고, 내식성의 점에서 바람직한 경우가 많다. 첨가제를 함유하는 중간층을 형성하는 부분의 위치나 디자인은, 불소수지피복물의 용법, 용도, 기능, 볼품 등에 따라서 적당히 결정되나, 일반적으로는, 용기형상 성형물로 형성했을 때의 측면의 높이중앙 근처이하에서부터 바닥면까지 중간층을 배치하는 것이 좋다. 내구성이 높다고 하는 성능을 의장에 의해 인상을 주면서 표시할 수 있는 점에서도, 충전제를 함유하는 중간층을 배치하는 것이 바람직하다.When the fluorine resin coating is used for general purpose cooking utensils such as hot plates, grill pans, auto bakeries, rice cakes, cooking utensils such as pots, cookers, and frying pans, and internal cooking pots, etc. In rice washing etc., an intermediate | middle layer can be partially arrange | positioned in the place which is abrasion-prone or abrasion. In particular, in the case of a fluorine resin coating molded into a container shape such as an inner pot, a pot, a pot, a frying pan, or the like, an intermediate layer is formed at the bottom half or the bottom half of the container shape molding. It is preferable. Although the intermediate | middle layer may be in another part, when there is no intermediate | middle layer containing an additive in the lateral middle part, upper side part, and flange part vicinity which are severe in workability, it is difficult to produce a coating film defect and it is preferable at the point of corrosion resistance. The position and design of the part forming the intermediate layer containing the additive is appropriately determined depending on the usage, use, function, and look of the fluororesin coating, but generally, it is less than or equal to the height center of the side when formed into a container-shaped molding. It is better to arrange the intermediate layer from the bottom to the bottom. It is preferable to arrange | position the intermediate | middle layer containing a filler also from the point which can display the performance of high durability, giving impression by a design.
첨가제를 함유하는 불소수지조성물로 이루어진 중간층은, 패턴형상으로 형성할 수 있다. 패턴으로서는, 특별히 한정되지 않으며, 각종 무늬나 문자, 눈금 등을 들 수 있다. 의장성의 점에서는, 기하학무늬나 인물, 풍경, 정물 등의 일러스트, 회화, 사진, 서화 또는 캐릭터디자인, 문장(紋章)등의 기호, 기업 등의 로고마크, 메시지 등을 중간층으로서 패턴형상으로 형성하는 것이 바람직하다. 형성장소는, 어디라도 좋으나, 그림무늬가 변형되지 않는 것을 원할 경우는 바닥면에 형성하는 편이 생산상 유리하다. 물론, 측면이나 플랜지근방에도 패턴을 성형가능하나, 그 경우는, 프레스성형 등의 후가공에 의한 변형을 미리 예측한 패턴형상의 설계가 필요하다.The intermediate layer made of a fluorine resin composition containing an additive can be formed in a pattern shape. It does not specifically limit as a pattern, Various patterns, a letter, a scale, etc. are mentioned. In terms of design, the pattern of geometric patterns, figures, landscapes, still lifes, illustrations, paintings, photographs, calligraphy or character designs, symbols such as letters, logos of companies, etc. are formed in a pattern form as an intermediate layer. It is preferable. The place of formation may be anywhere, but if it is desired that the picture pattern is not deformed, it is advantageous to produce on the bottom surface. Of course, the pattern can be formed on the side surface or in the vicinity of the flange, but in this case, it is necessary to design a pattern shape that predicts deformation in advance by post-processing or the like.
눈금은, 자취반기 등에서 수위를 표시하는 눈금을 인자하는 예나, 그 설명을 표시하는 예 등이 있다. 또, 오일포트 등에 표시하는 예로서, 오일의 열악화색을 알기 쉬운 인디케이터를 밝은 색으로 표시하거나, 그러데이션(gradation) 등의 착시를 이용해서, 오일열악화레벨을 한눈에 알 수 있도록 하는 것이 가능해진다.Examples of the scale include printing a scale for displaying the water level in the track and the like, an example for displaying the explanation, and the like. Moreover, as an example to display on an oil pot etc., it is possible to display the indicator which is easy to understand the heat deterioration color of oil in a bright color, or to be able to know oil deterioration level at a glance using optical illusions, such as gradation.
상기의 충전제를 함유하는 중간층을 가진 불소수지피복물의 경우, 최외층을 형성하는 불소수지의 종류는, 임의이며, PTFE, PFA, FEP 또는 이들의 혼합물이라도 되고, 안료나 충전제 등의 첨가제재를 함유해도 된다. 비점착성이나 내식성을 중시하는 경우는, 최외층은, 안료 등의 첨가제를 함유하지 않는 것이 바람직하다. 또, 최외층을, MFR이 0.2∼10g/10분인 PFA를 PFA전체량속에 20∼100중량%의 비율로 함유하는 PFA로 이루어진 두께 10∼90㎛인 PFA층으로 할 수 있으며, 이에 의해서 내구성을 높일 수 있다. 베이스코트층은, PTFE, PFA, FEP, 또는 이들의 혼합물로 형성하고, 그 두께는, 통상 5∼100㎛, 바람직하게는 10∼60㎛정도로 한다. 중간층의 두께는, 특별히 한정되지 않으며, 통상 5∼100㎛, 바람직하게는 10∼60㎛정도로 한다.In the case of the fluorine resin coating having the intermediate layer containing the above filler, the kind of fluorine resin forming the outermost layer may be arbitrary, and may be PTFE, PFA, FEP or a mixture thereof, and may contain additives such as pigments and fillers. You may also In the case where emphasis is placed on non-tackiness and corrosion resistance, it is preferable that the outermost layer does not contain additives such as pigments. The outermost layer may be a PFA layer having a thickness of 10 to 90 µm made of PFA containing PFA having an MFR of 0.2 to 10 g / 10 minutes at a ratio of 20 to 100% by weight in the total amount of PFA, thereby providing durability. It can increase. The base coat layer is formed of PTFE, PFA, FEP, or a mixture thereof, and the thickness thereof is usually 5 to 100 µm, preferably about 10 to 60 µm. The thickness of the intermediate layer is not particularly limited, and is usually 5 to 100 µm, preferably about 10 to 60 µm.
이와 같이, 본 발명의 불소수지피복물은, 내마모성, 내상성, 내식성, 내블리스터성 등이 뛰어나고, 또, 중간층의 배치를 연구함으로써, 내마모성 등을 더욱 향상시키고, 또한, 의장성이나 지시기능성 등을 부가할 수 있다. 본 발명의 불소수지피복물은, 기재에 불소수지층을 형성한 채로 또는 프레스가공 등에 의해 각종 형상의 성형물로 성형함으로써, 조리기구의 분야를 비롯하여, 광범위한 분야에 적용할 수 있다.As described above, the fluorine resin coating of the present invention is excellent in wear resistance, scratch resistance, corrosion resistance, blister resistance, and the like, and further studies on the arrangement of the intermediate layer further improves the wear resistance and the like, and further improves the designability, the indicating function, and the like. Can be added. The fluorine resin coating of the present invention can be applied to a wide range of fields, including the field of cooking utensils, by forming a fluorine resin layer on a base material or by molding into molded articles of various shapes.
이하에 실시예 및 비교예를 들어서, 본 발명에 대해서 보다 구체적으로 설명하나, 본 발명은, 이들 실시예만으로 한정되는 것은 아니다.Although an Example and a comparative example are given to the following and this invention is demonstrated more concretely, this invention is not limited only to these Examples.
또한, 물성의 측정방법은, 다음과 같다.In addition, the measuring method of a physical property is as follows.
(1) 표면거칠기(1) surface roughness
JIS-B-0601에 규정되어 있는 중심선평균거칠기(Ra)의 측정법에 따라서, 표면거칠기를 측정했다. 단위는 ㎛이다.Surface roughness was measured according to the measuring method of centerline average roughness (Ra) prescribed | regulated to JIS-B-0601. The unit is μm.
(2) 핀홀도(2) pinhole diagram
불소수지피복물을 2.5중량%염화나트륨수용액에 담그고, 그리고, 불소수지피복물의 금속기재를 음극으로 하고, 수용액속에 전극을 넣어서 양극으로 하고, 10V로 5초간 통전했을 때 핀홀부분으로부터 흐르는 전류(㎃)를 단위면적당으로 환산해서 구했다. 단위는, ㎃/㎠이다.The fluorine resin coating was immersed in a 2.5% by weight aqueous sodium chloride solution, the metal base of the fluorine resin coating was used as the cathode, the electrode was placed in an aqueous solution as the anode, and the current flowing from the pinhole part was energized at 10V for 5 seconds. It was calculated in terms of unit area. The unit is dl / cm 2.
(3) 스코치브라이트 내마모테스트(3) scorch bright abrasion test
불소수지피복물층의 표면에 스코치브라이트를 접촉시킨 상태에서 회전시켜서, 그 때의 마모량을 두께 1㎛인 PFA층이 깎이는 데 소요되는 회전수로 표시했다. 단위는, 103회전/㎛이다.The scorch bright was rotated in contact with the surface of the fluororesin coating layer, and the amount of wear at that time was expressed by the number of revolutions required to cut the PFA layer having a thickness of 1 µm. The unit is 10 3 revolutions / micrometer.
(4) 내식성(4) corrosion resistance
오덴노모토(상품명)(일본국 하우스식품공업회사제) 25g을 1ℓ의 물에 용해한 시험액속에 시험조각을 담가서, 90∼100℃로 보온하여, 도막면에 부식이 발생할 때까지의 시간을 측정한다.Dip 25 g of Odennomoto (trade name) (manufactured by Japan House Food Industry Co., Ltd.) in a test solution dissolved in 1 liter of water, and keep it at 90 to 100 ° C to measure the time until corrosion occurs on the coating surface. .
[실시예 1]Example 1
알루미늄기재로서 판두께 1.2㎜의 알루미늄원판(일본국 스미토모경금속공업회사제, MG-110)을 사용했다. 먼저, 이 알루미늄원판을 양극으로 해서, 염화암모늄수용액속, 25쿨롱/㎠의 전기량으로 전기화학적 에칭처리를 행하여, 알루미늄원판표면에 미세한 요철을 형성시켰다. 이 미세한 요철면에, 충전제를 함유하지 않는 PTFE디스퍼젼(일본국 다이킹공업회사제, D-1F)을 스핀코팅하고, 이어서 수분을 건조시킨 후, 400℃에서 10분간 베이킹하여, 두께 25㎛인 도막(제 1층)을 형성했다.As an aluminum base material, an aluminum disc of 1.2 mm in thickness (manufactured by Sumitomo Light Metal Industries, Japan, MG-110) was used. First, using this aluminum disc as an anode, electrochemical etching was carried out in an ammonium chloride aqueous solution and an electric quantity of 25 coulombs / cm 2 to form fine irregularities on the surface of the aluminum disc. On this fine uneven surface, spin-coated a PTFE dispersion (D-1F manufactured by Nippon Diking Co., Ltd.) containing no filler, and then dried the moisture, baked at 400 ° C for 10 minutes, and had a thickness of 25 µm. Phosphorus coating film (1st layer) was formed.
다음에, 평균입자직경 15㎛, 멜트플로레이트가 1.6g/10분인 PFA분말체(듀폰회사제, M-103) 33.3중량%를, 물 34.8중량%, 불소계 계면활성제(다이킹공업회사제, 유니다인 DS-401) 1.0중량% 및 탄화수소계 계면활성제(닛뽄유시제, 노니온 K-204) 0.5중량%를 혼합해서 이루어진 액상매체속에 분산시키고, 이것에, 평균입자직경 0.4㎛, 멜트플로레이트 약 25g/10분인 PFA구형상 입자 47중량%, 계면활성제 6중량%, 물 47중량%로 이루어진 PFA분산액(다이킹공업회사제, AD-2CR) 30.4중량%를 첨가하여 충분히 혼합해서 불소수지도료를 조제했다. 평균입자직경 15㎛인 PFA입자와 평균입자직경 0.4㎛인 PFA입자의 중량비는, 70:30이었다. 상기 제 1층위에, 이 불소수지도료를 스핀코팅하고, 이어서, 수분을 건조시킨 후, 390℃에서 30분간 베이킹하여, 두께 15㎛인 도막(제 2층)을 형성했다. 결과를 표 1에 표시한다.Next, 33.3 weight% of PFA powder (M-103 by Dupont, M-103) whose average particle diameter is 15 micrometers and melt-florate is 1.6g / 10min, 34.8 weight% of water, and a fluorine-type surfactant (made by Diking Industries, Ltd.) , 1.0% by weight of Unidine DS-401) and 0.5% by weight of a hydrocarbon-based surfactant (Nippon Chemical, Nonion K-204) were dispersed in a liquid medium, which had an average particle diameter of 0.4 µm and melted liquid. 30.4% by weight of PFA dispersion (AD-2CR, manufactured by Diking Industry Co., Ltd.), consisting of 47% by weight of PFA spherical particles, 25% by weight, and 7% by weight of surfactant, and 47% by weight of water, was thoroughly mixed with fluorine. Resin fee was prepared. The weight ratio of PFA particles having an average particle diameter of 15 µm and PFA particles having an average particle diameter of 0.4 µm was 70:30. This fluorine resin was spin-coated on the first layer, and then dried for 30 minutes at 390 ° C to form a coating film (second layer) having a thickness of 15 µm. The results are shown in Table 1.
[비교예 1]Comparative Example 1
실시예 1에 있어서, 제 2층을 형성하는 불소수지도료로서, 2종류의 PFA입자를 평균입자직경 13㎛, 멜트플로레이트가 13g/10분인 PFA입자로 치환한 것을 사용한 것이외는, 실시예 1과 마찬가지로 해서, 불소수지피복물을 제작했다. 결과를 표 1에 표시한다.Example 1 WHEREIN: Except having used what substituted two types of PFA particle into PFA particle whose average particle diameter is 13 micrometers, and melt-florate is 13 g / 10min as a fluorine resin material which forms a 2nd layer. In the same manner as in 1, a fluorine resin coating was produced. The results are shown in Table 1.
표 1에 표시한 바와 같이, PFA입자로서, MFR이 큰 MP-102를 사용한 것(비교예 1)에 비해, MFR이 작은 MP-103을 사용한 것(실시예 1)은, 내마모성이 약 2배로 개선되어 있는 것을 알 수 있다.As shown in Table 1, the use of MP-103 with a small MFR (Example 1) is about twice as high as the PFA particles used with MP-102 with a large MFR (Comparative Example 1). It can be seen that the improvement.
[실시예 2]Example 2
실시예 1에서 얻게된 불소수지피복물의 최외층(제 2층)의 표면거칠기(Ra)는, 2.3∼2.5㎛였다. 이 불소수지피복물의 상부면에, 표면거칠기(Ra)가 1.0㎛인 SUS판을 포개어, 270℃의 가열하, 대기속 0.5기압의 감압하에 프레스압력 500kgf/㎠에 의해 20분간 핫프레스를 실시하였던 바, 표면거칠기(Ra)가 1.2∼1.5㎛로 평활도가 개선된 표면을 얻었다.The surface roughness Ra of the outermost layer (second layer) of the fluorine resin coating obtained in Example 1 was 2.3-2.5 micrometers. On the upper surface of the fluorine resin coating, a SUS plate having a surface roughness (Ra) of 1.0 μm was superposed and hot-pressed for 20 minutes under a press pressure of 500 kgf / cm 2 under heating at 270 ° C. and a reduced pressure of 0.5 atm. The surface roughness Ra of 1.2-1.5 micrometers was obtained and the smoothness was improved.
[실시예 3]Example 3
알루미늄기재로서 판두께 1.2㎜의 알루미늄원판(스미토모경금속공업회사제, MG-110)을 사용했다. 먼저, 이 알루미늄원판을 양극으로 하여, 염화암모늄수용액속, 25쿨롱/㎠의 전기량으로 전기화학적 에칭처리를 행하여, 알루미늄원판표면에 미세한 요철을 형성시켰다.As an aluminum base material, an aluminum disc of 1.2 mm in thickness (manufactured by Sumitomo Light Metal Industries, Ltd., MG-110) was used. First, using this aluminum disc as an anode, electrochemical etching was carried out in an ammonium chloride aqueous solution and an electric quantity of 25 coulombs / cm 2 to form fine irregularities on the surface of the aluminum disc.
평균입자직경 15㎛, 멜트플로레이트가 1.6g/10분인 PFA분말체(듀폰회사제, M-103) 33.3중량%를 물 34.8중량%, 불소계 계면활성제(다이킹공업회사제, 유니다인 DS-401) 1.0중량% 및 탄화수소계 계면활성제(닛뽄유시회사제, 노니온 K-204) 0.5중량%를 혼합해서 이루어진 액상매체속에 분산시키고, 이것에, 평균입자직경 0.4㎛, 멜트플로레이트 약 25g/10분인 PFA구형상 입자 47중량%, 계면활성제 6중량%, 물 47중량%로 이루어진 PFA분산액(다이킹공업회사제, AD-2CR) 30.4중량%를 첨가하여 충분히 혼합해서 불소수지도료를 조제했다. 평균입자직경 15㎛인 PFA입자와 평균입자직경 0.4㎛인 PFA입자의 중량비는 70:30이였다.33.3% by weight of PFA powder (M-103, manufactured by DuPont, M-103) having an average particle diameter of 15 µm and a melt flow rate of 1.6 g / 10 minutes, 34.8% by weight of water, and a fluorine-based surfactant (manufactured by Diking Industries, Ltd.) -401) dispersed in a liquid medium consisting of 1.0% by weight and 0.5% by weight of a hydrocarbon-based surfactant (Nippon K-204, Nonion K-204), to which an average particle diameter of 0.4㎛, about 30.4% by weight of PFA dispersion (AD-2CR, manufactured by Diking Co., Ltd.) consisting of 47% by weight of PFA spherical particles, 25% by weight, and 6% by weight of surfactant, and 47% by weight of water was added, and the mixture was sufficiently mixed to prepare a fluorine resin. Prepared. The weight ratio of PFA particles having an average particle diameter of 15 µm and PFA particles having an average particle diameter of 0.4 µm was 70:30.
이 불소수지도료를 상기의 알루미늄원판의 미세한 요철면에 스핀코팅하고, 수분을 건조시킨 후, 390℃에서 30분간 베이킹하여, 두께 25㎛의 도막을 형성했다. 이 도막을 형성한 샘플을 남비형상으로 프레스성형하여, 내식성 평가를 행하였다. 그 결과, 90시간의 내식시험에서, 거의 부식은 발견되지 않아 실용에 제공할 수 있는 것을 얻게 되었다.The fluorine resin was spin-coated to the fine concavo-convex surface of the aluminum disc, dried, and then baked at 390 ° C. for 30 minutes to form a coating having a thickness of 25 μm. The sample in which this coating film was formed was press-molded in the pot shape, and corrosion resistance evaluation was performed. As a result, in the corrosion resistance test of 90 hours, almost no corrosion was found and what was provided for practical use was obtained.
[비교예 2]Comparative Example 2
실시예 3에 있어서, 2종류의 PFA입자를 평균입자직경 13㎛, 멜트플로레이트가 13g/10분인 PFA입자(MP102)로 치환한 것이외는, 실시예 3과 마찬가지로 불소수지피복물을 제작하여, 마찬가지로 평가했다. 그 결과, 90시간의 내식성 시험에서, 거의 부식은 발견되지 않아 실용에 제공할 수 있는 것을 얻게 되었다. 즉, 비교예 2와의 대비에서, 실시예 3의 불소피복물에 의해, 종래품에 필적하는 내식성을 달성할 수 있게 된 것을 알 수 있다.In Example 3, a fluororesin coating was produced in the same manner as in Example 3, except that the two kinds of PFA particles were replaced with PFA particles (MP102) having an average particle diameter of 13 µm and a melt flow rate of 13 g / 10 minutes. Similarly evaluated. As a result, in the corrosion resistance test of 90 hours, almost no corrosion was found and what was provided for practical use was obtained. That is, compared with the comparative example 2, it turns out that the fluorine coating of Example 3 was able to achieve the corrosion resistance comparable to a conventional product.
[실시예 4]Example 4
알루미늄기재로서 판두께 1.2㎜, 직경 360㎜인 알루미늄원판(스미토모경금속공업회사제, MG-110)을 사용했다. 먼저, 이 알루미늄원판을 양극으로 해서, 염화암모늄수용액속, 25쿨롱/㎠의 전기량으로 전기화학적 에칭처리를 행하여, 알루미늄원판표면에 미세한 요철을 형성시켰다. 이 미세한 요철면에, 충전제를 함유하지 않은 PTFE디스퍼젼(다이킹공업회사제, D-1F)을 스핀코팅하고, 수분을 건조시킨 후, 400℃에서 10분간 베이킹하여, 두께 25㎛인 도막(제 1층)을 형성했다.As an aluminum base material, an aluminum disc (MG-110, manufactured by Sumitomo Light Metal Industries, Ltd.) having a plate thickness of 1.2 mm and a diameter of 360 mm was used. First, using this aluminum disc as an anode, electrochemical etching was carried out in an ammonium chloride aqueous solution and an electric quantity of 25 coulombs / cm 2 to form fine irregularities on the surface of the aluminum disc. On this fine uneven surface, a PTFE dispersion (D-1F, manufactured by Diking Industries, Ltd.) containing no filler was spin-coated, dried, and then baked at 400 ° C for 10 minutes to form a coating film having a thickness of 25 µm ( 1st layer) was formed.
PFA구형상 입자 47중량%, 계면활성제 6중량%, 물 47중량%로 이루어진 PFA분산액(다이킹공업회사제, D-2CR) 25.4중량%에, PFA분말체(듀폰회사제, MP-103)를 28.1중량%, 안료피복마이카(일본국 멜크저팬회사제, IRIODIN503) 4.4중량%, 계면활성제(다이킹공업회사제, 유니다인 DS-401; 및 일본국 산요카세이회사제 옥타폴 80) 42.1중량%를 혼합해서, 충전제를 함유하는 불소수지도료를 조제했다. 이 불소수지도료를 상기의 제 1층위에 스크린인쇄에 의해 원판의 중앙에서부터 직경 180㎜의 범위내로 도장한 후, 390℃에서 15분간 베이킹하여, 두께 5㎛인 도막(제 2층)을 형성했다.PFA powder (made by DuPont, MP-103) to 25.4% by weight of PFA dispersion (D-2CR) made by 47% by weight of PFA spherical particles, 6% by weight of surfactant, and 47% by weight of water 28.1 weight%, pigment coating mica (manufactured by Japan Melk Japan Co., Ltd., IRIODIN503) 4.4 weight%, surfactant (made by Daiking Industry Co., Ltd., Udine DS-401; and octapol 80 made by Sanyo Kasei Co., Ltd.) 42.1 weight % Was mixed and the fluororesin containing a filler was prepared. After coating this fluorine resin material in the range of 180 mm in diameter from the center of a disk by screen printing on said 1st layer, it baked at 390 degreeC for 15 minutes, and formed the coating film (2nd layer) of 5 micrometers in thickness. .
평균입자직경 15㎛, 멜트플로레이트가 1.6g/10분인 PFA분말체(듀폰회사제, MP-103) 33.3중량%를, 물 34.8중량%, 불소계 계면활성제(다이킹공업회사제, 유니다인 DS-401) 1.0중량% 및 탄화수소계 계면활성제(닛뽄유시회사제, 노니온 K-204) 0.5중량%를 혼합해서 이루어진 액상매체속에 분산시키고, 이것에 평균입자직경 0.4㎛, 멜트플로레이트 약 25g/10분인 PFA구형상입자 47중량%, 계면활성제 6중량%, 물 47중량%로 이루어진 PFA분산액(다이킹공업회사제, AD-2CR) 30.4중량%를 첨가하여 충분히 혼합해서 불소수지도료를 조제했다. 평균입자직경 15㎛인 PFA입자와 평균입자직경 0.4㎛인 PFA입자의 중량비는 70:30이었다. 이 불소수지도료를 상기 제 2층위에 스핀코팅하고, 수분을 건조시킨 후, 390℃에서 30분간 베이킹하여, 두께 15㎛인 도막(제 3층)을 형성했다.33.3 weight% of PFA powder (Made by Dupont, MP-103) which has an average particle diameter of 15 micrometers, and a melt-florate 1.6g / 10min, 34.8 weight% of water, and a fluorine-type surfactant (made by Diking Industries Co., Ltd.) DS-401) 1.0% by weight and 0.5% by weight of a hydrocarbon-based surfactant (Nippon Co., Ltd., Nonion K-204) are dispersed in a liquid medium, which has an average particle diameter of 0.4 µm and a melt flow rate of about 30.4% by weight of PFA dispersion (AD-2CR, manufactured by Diking Co., Ltd.) consisting of 47% by weight of PFA spherical particles having 25 g / 10 minutes, 6% by weight of surfactant, and 47% by weight of water was added and mixed sufficiently to prepare a fluorine resin. Prepared. The weight ratio of the PFA particles having an average particle diameter of 15 µm and the PFA particles having an average particle diameter of 0.4 µm was 70:30. This fluorine resin was spin-coated on the second layer, dried, and then baked at 390 ° C. for 30 minutes to form a coating film (third layer) having a thickness of 15 μm.
이렇게 해서 얻게된 불소수지피복물의 스코치브라이트내마모테스트에서, 알루미늄의 밑바탕이 보일 때까지 필요한 회전수를 조사했다. 결과를 표 2에 표시한다. 또한, 표 2는, 비교예 1 및 실시예 1에서 얻게된 불소수지피복물에 대해서도, 이 측정법에 의한 평가결과를 표시한다.In the scorch bright abrasion test of the fluorine resin coating thus obtained, the required number of revolutions until the base of aluminum was visible was investigated. The results are shown in Table 2. In addition, Table 2 shows the evaluation result by this measuring method also about the fluororesin coating material obtained by the comparative example 1 and the Example 1.
또, 실시예 4의 불소수지피복물을 남비형상으로 프레스성형함으로써, 바닥면부분전체가 안료피복마이카를 함유하는 제 2층째의 불소수지층(중간층)에 의해 피복되어, 바닥면부분과 측면부분의 색조가 다르다고 하는 종래품에 없는 특징적인 외관을 얻게 되었다.Further, by press-molding the fluorine resin coating of Example 4 in the shape of a pot, the entire bottom surface portion was covered with the second fluorine resin layer (intermediate layer) containing the pigment coated mica, A distinctive appearance was not found in the prior art that the color tone is different.
[실시예 5]Example 5
실시예 4에 있어서, 제 2층째의 불소수지도료를 사용해서 스크린인쇄에 의해 원판의 중앙에서부터 직경 200㎜의 범위내에 미리 설계된 규정 위치에 눈금, 문자를 도장하고, 390℃에서 15분간 베이킹하고, 이어서, 제 3층째의 불소수지피복을 실시한 것이외에는, 실시예 4와 마찬가지로 해서 불소수지피복물을 제작했다. 얻어진 불소수지피복물을 튀김남비로 프레스성형했다. 이 튀김남비를 사용하면, 기름의 오염상태에 따라, 문자가 보이는 방식이 달라, 중간층의 눈금이나 문자가 기름오염인디케이터의 역할을 다하는 것을 알았다.In Example 4, using the fluorine resin material of the second layer, by screen printing, graduations and letters are painted at predetermined positions within a range of 200 mm in diameter from the center of the original plate, and baked at 390 ° C. for 15 minutes, Subsequently, the fluorine resin coating was produced in the same manner as in Example 4 except that the fluorine resin coating of the third layer was applied. The obtained fluorocarbon resin coating was press-molded with a frying pot. Using this frying pot, it was found that the way the letters looked different depending on the oil contamination condition, and the scales and letters in the middle layer played the role of oil pollution indicators.
본 발명에 의하면, 내마모성, 내상성, 내식성, 내블리스터성 등이 뛰어난 불소수지피복물과 그 제조방법을 제공할 수 있다. 또, 본 발명에 의하면, 이와 같은 여러 특성이 뛰어난 불소수지도막을 형성할 수 있는 불소수지도료를 제공할 수 있다. 본 발명의 불소수지피복물은, 남비, 솥, 프라이팬, 자취반기 내부솥 등의 조리기구; 핫플레이트, 그릴팬, 오토베이커리, 떡치는 기구 등의 가전조리기구; 오일포트 등으로서, 광범위한 분야에 적용할 수 있다.According to the present invention, it is possible to provide a fluororesin coating having excellent abrasion resistance, scratch resistance, corrosion resistance, blister resistance and the like and a method of manufacturing the same. Moreover, according to this invention, the fluorine resin material which can form the fluorine resin film excellent in such various characteristics can be provided. Fluorine resin coating of the present invention, a cooking utensil such as a pot, a pot, a frying pan, a half-pot inner pot; Home appliance cooking appliances such as hot plates, grill pans, auto bakeries and rice cakes; As an oil pot etc., it is applicable to a wide range of fields.
Claims (13)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1999-43919 | 1999-02-22 | ||
JP11043919A JP3080089B1 (en) | 1999-02-22 | 1999-02-22 | Fluororesin coating and production method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20000058146A KR20000058146A (en) | 2000-09-25 |
KR100346796B1 true KR100346796B1 (en) | 2002-07-31 |
Family
ID=12677135
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020000008636A KR100346796B1 (en) | 1999-02-22 | 2000-02-22 | fluorin resin coated product and process for producing the same |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP3080089B1 (en) |
KR (1) | KR100346796B1 (en) |
CN (1) | CN1201872C (en) |
TW (1) | TW527230B (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
KR102455817B1 (en) * | 2014-11-13 | 2022-10-18 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | Coating compositions |
KR101532232B1 (en) * | 2014-11-19 | 2015-06-30 | 유한회사 한국 타코닉 | Breadmaking tray and method of manufacturing the same |
JP6776508B2 (en) * | 2015-04-23 | 2020-10-28 | ダイキン工業株式会社 | Coating composition |
CN107969123A (en) * | 2015-05-14 | 2018-04-27 | 住友电工超效能高分子股份有限公司 | The manufacture method of gluing reinforcing sheet, sliding component and gluing reinforcing sheet |
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 |
WO2021172214A1 (en) * | 2020-02-28 | 2021-09-02 | Agc株式会社 | Coated base material and method for producing same |
JP2020128560A (en) * | 2020-06-03 | 2020-08-27 | ダイキン工業株式会社 | Coating composition |
TW202246407A (en) * | 2021-03-31 | 2022-12-01 | 日商大金工業股份有限公司 | Fluororesin composition and molded object |
JP7445146B2 (en) * | 2021-11-26 | 2024-03-07 | ダイキン工業株式会社 | Liquid coating composition, coating film, fluororesin laminate, and article |
JP7445147B2 (en) * | 2021-11-26 | 2024-03-07 | ダイキン工業株式会社 | Powder coating composition, coating film, fluororesin laminate, and article |
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 |
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 |
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 |
---|---|
KR20000058146A (en) | 2000-09-25 |
CN1265942A (en) | 2000-09-13 |
JP2000239596A (en) | 2000-09-05 |
CN1201872C (en) | 2005-05-18 |
TW527230B (en) | 2003-04-11 |
JP3080089B1 (en) | 2000-08-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100346796B1 (en) | fluorin resin coated product and process for producing the same | |
EP0561981B1 (en) | Non-stick coating system with ptfe and pfa or fep for concentration gradient | |
US8642171B2 (en) | Non-stick coating having improved abrasion resistance, hardness and corrosion on a substrate | |
EP2240056B1 (en) | Article with non-stick finish and improved scratch resistance | |
CN101534966B (en) | Glass articles with adhesion and stain resistant non-stick coatings | |
KR101369624B1 (en) | Method for producing coated article, and coated article | |
EP0561987B1 (en) | Non-stick coating system with ptfe of different melt viscosities for concentration gradient | |
EP2001949B1 (en) | Non-stick finish | |
KR101585356B1 (en) | Fluororesin laminate and method for manufacturing same | |
US20070231563A1 (en) | Non-stick finish | |
EP3580289B1 (en) | Substrate coated with non-stick coating resistant to abrasion and scratching | |
KR102385601B1 (en) | Coating Compositions and Coating Articles | |
US6329042B1 (en) | Fluororesin coating compositon and coated article obtained using the same | |
KR100674521B1 (en) | Method of Forming Layered Fluororesin Product and Coated Article | |
KR100896913B1 (en) | A composition of painting and varnishing for metal coating and forming method for coating layer | |
JP3367508B2 (en) | Fluororesin coating and manufacturing method thereof | |
JPH08118561A (en) | Fluorine resin coated material and manufacture thereof | |
JPH08322732A (en) | Cooking pot | |
JP2006130743A (en) | Fluoroplastic coating material, cooking utensil, electromagnetic induction heating container and formation method of electromagnetic induction heating container | |
JP3293084B2 (en) | Heat-resistant non-adhesive pre-coated steel sheet | |
JPH07233345A (en) | Fluororesin coating composition, production of fluororesin coated plate and production of fluororesin coated product | |
JP2006297870A (en) | Fluorocarbon resin coating, kitchen instruments using it and method for producing fluorocarbon resin coating | |
WO1995007321A1 (en) | Methods for producing fluororesin paint composition, a fluororesin covered plate, and a processed body covered with fluororesin | |
JPH02251440A (en) | Fluoroplastic coating material for inner pot in cooking jar and so on |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
N231 | Notification of change of applicant | ||
E902 | Notification of reason for refusal | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20130621 Year of fee payment: 12 |
|
FPAY | Annual fee payment |
Payment date: 20140626 Year of fee payment: 13 |
|
FPAY | Annual fee payment |
Payment date: 20150618 Year of fee payment: 14 |
|
FPAY | Annual fee payment |
Payment date: 20160617 Year of fee payment: 15 |
|
FPAY | Annual fee payment |
Payment date: 20170616 Year of fee payment: 16 |
|
LAPS | Lapse due to unpaid annual fee |