TW202313728A - 粉體塗料組成物 - Google Patents
粉體塗料組成物 Download PDFInfo
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- TW202313728A TW202313728A TW111127420A TW111127420A TW202313728A TW 202313728 A TW202313728 A TW 202313728A TW 111127420 A TW111127420 A TW 111127420A TW 111127420 A TW111127420 A TW 111127420A TW 202313728 A TW202313728 A TW 202313728A
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- 239000000843 powder Substances 0.000 title claims abstract description 103
- 239000008199 coating composition Substances 0.000 title claims abstract description 73
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- 238000002844 melting Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims abstract description 25
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 14
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 24
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- 150000004982 aromatic amines Chemical class 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
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- KMYAABORDFJSLR-UHFFFAOYSA-N (carbamothioyltrisulfanyl) carbamodithioate Chemical compound NC(=S)SSSSC(N)=S KMYAABORDFJSLR-UHFFFAOYSA-N 0.000 description 1
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 1
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- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- SRLLDMVISOTQFV-UHFFFAOYSA-N 2-methylpiperidine-1-carbodithioic acid Chemical compound CC1CCCCN1C(S)=S SRLLDMVISOTQFV-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- KZNDXCVEWRZEEU-UHFFFAOYSA-N 4-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1CCCCC1 KZNDXCVEWRZEEU-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- SKZDCEBGIKCGLG-UHFFFAOYSA-N C(CCCCC)N.SC=1SC2=C(N1)C=CC=C2 Chemical compound C(CCCCC)N.SC=1SC2=C(N1)C=CC=C2 SKZDCEBGIKCGLG-UHFFFAOYSA-N 0.000 description 1
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- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
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- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- BDSYEKLSEKMQDH-UHFFFAOYSA-N ethyl(phenyl)carbamodithioic acid Chemical compound CCN(C(S)=S)C1=CC=CC=C1 BDSYEKLSEKMQDH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 229910000765 intermetallic Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- 229910052618 mica group Inorganic materials 0.000 description 1
- WGARMULIELDQEH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfinamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)NC1CCCCC1 WGARMULIELDQEH-UHFFFAOYSA-N 0.000 description 1
- XBRUGMQPHDONFS-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfinamide Chemical compound C1=CC=C2SC(S(=O)NC(C)(C)C)=NC2=C1 XBRUGMQPHDONFS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DHHVAGZRUROJKS-UHFFFAOYSA-N phentermine Chemical compound CC(C)(N)CC1=CC=CC=C1 DHHVAGZRUROJKS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/031—Powdery paints characterised by particle size or shape
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/12—Applying particulate materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/20—Homopolymers or copolymers of hexafluoropropene
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Abstract
本發明提供一種粉體塗料組成物,其無論塗裝次數,皆可形成具有良好的表面平滑性之皮膜。
一種粉體塗料組成物,其含有四氟乙烯系共聚物,且特徵在於:上述四氟乙烯系共聚物為9.0~13.0質量%之六氟丙烯及0.8~3.0質量%之全氟烷基乙烯醚和四氟乙烯之共聚物,熔體流動速率為13~26(g/10分鐘),熔點為240~270℃。
Description
本發明係關於一種粉體塗料組成物。
於硬管(tube)、管道管(pipe)、球管等配管材料等為使用時與化學藥品類等接觸者之情形時,為了具備對於化學藥品類等之耐受性,較理想為實施有耐蝕襯裏者。作為耐蝕襯裏用材料,自具有對於酸、鹼、氧化還原劑、各種溶劑等化學藥品類之優異之耐受性之面而言,可較佳地使用氟樹脂。
氟樹脂除了耐蝕性以外,亦具有非黏著性,因此,自能以化學方式防止汙染物質附著於耐蝕襯裏之表面之方面而言,亦有助於賦予防汙性。
近年來,尤其針對半導體製造設備之配管材料等,對於具有更高之防汙性之耐蝕襯裏用材料的需求不斷增長。關於使用有氟樹脂之耐蝕襯裏,作為提高防汙力之方法,有以下方法,亦即,藉由提升耐蝕襯裏之表面平滑性,以物理方式抑制汙染物質之附著。
關於氟樹脂,以作為耐蝕襯裏用材料,可配合被加工物之各種形狀,以足以發揮耐蝕性之充分的量進行加工,並且,操作性容易等之觀點而言,可較佳地用作粉體塗料。
專利文獻1揭示了一種粉體塗料,其作為尤其適於藉由滾襯(rotolining)方法之塗裝之粉體塗料,含有由六氟丙烯、全氟(乙烯醚)及四氟乙烯構成之四氟乙烯系共聚物。
[先前技術文獻]
[專利文獻]
[專利文獻1]國際公開第2003/006566號
[發明所欲解決之課題]
本發明之目的在於:提供一種粉體塗料組成物,其無論塗裝次數,皆可形成具有良好的表面平滑性之皮膜。
[解決課題之技術手段]
本發明為一種粉體塗料組成物,其由四氟乙烯系共聚物構成,且特徵在於:上述四氟乙烯系共聚物為9.0~13.0質量%之六氟丙烯及0.8~3.0質量%之全氟烷基乙烯醚和四氟乙烯之共聚物,熔體流動速率為13~26 g/10分鐘,熔點為240~270℃。
上述四氟乙烯系共聚物的平均粒徑較佳為5~500 μm,視密度較佳為0.5~1.1 g/ml。
本發明之粉體塗料組成物亦可含有熱穩定劑及/或著色顏料。
上述熱穩定劑較佳為選自由胺系抗氧化劑、含有機硫之化合物及金屬粉末所組成之群中之至少1種。
本發明亦為一種皮膜,其係由上述粉體塗料組成物所形成者。
又,本發明亦為一種皮膜,其係由上述粉體塗料組成物以靜電塗裝法所形成者。
本發明亦為一種積層體,其含有上述皮膜。
本發明亦為一種積層體,其在表面層含有上述皮膜。
本發明亦為一種塗裝物品,其在金屬基材上設有上述皮膜。
本發明亦為一種塗裝物品,其係在金屬基材之內表面設有上述皮膜者,上述金屬基材為配管、管道管(pipe)或導管(duct)。
本發明亦為一種皮膜成形方法,其具有下述步驟:
在被塗裝物形成基底(primer)層之步驟(1),及
使用上述粉體塗料組成物,藉由靜電塗裝法在基底層之表面形成皮膜之步驟(2)。
[發明之效果]
藉由本發明,可提供一種粉體塗料組成物,其無論塗裝次數,皆可形成具有良好的表面平滑性之皮膜。。
以下,針對本發明進行詳細說明。
本發明之粉體塗料組成物含有四氟乙烯系共聚物,且特徵在於:上述四氟乙烯系共聚物為9.0~13.0質量%之六氟丙烯及0.8~3.0質量%之全氟烷基乙烯醚和四氟乙烯之共聚物,熔體流動速率為13~26 g/10分鐘,熔點為240~270℃。
本發明之粉體塗料組成物在塗布於被塗裝物後,可藉由加熱焙燒來製膜而進行加工。進行此般加工而得之皮膜可作為耐蝕襯裏等而用於各種用途。
於將粉體塗料組成物塗裝於被塗裝物而得之皮膜中,為了獲得良好的表面平滑性,研究了視塗裝次數而調整TFE系共聚物之熔體流動速率(MFR)。
本發明之粉體塗料組成物係藉由使用具有特定之四氟乙烯系共聚物之組成比、MFR及熔點之四氟乙烯系共聚物,而無論塗裝次數,皆可形成具有良好的表面平滑性之皮膜者。
關於本發明之粉體塗料組成物,視其用途,例如可設為使用靜電塗裝、滾襯等塗布方法,且焙燒後之膜厚為50~200 μm之薄塗、或焙燒後之膜厚超過200 μm且5000 μm以下之值的厚塗。
本發明之粉體塗料組成物通常可尤佳地用於藉由進行複數次塗裝之靜電塗裝的塗布方法。
再者,於本發明中,將「本發明之粉體塗料組成物塗布於被塗裝物後,進行加熱焙燒來製膜之步驟」作為1次的塗裝來計算塗裝次數。
所謂上述焙燒後之膜厚,為上述塗裝次數為1次之情形時所得之膜厚、或藉由重複進行上述步驟2次以上而上述塗裝次數為2次以上之情形時所得之膜厚。於本說明書中,有時將上述塗裝次數為2次以上之情形稱作疊塗。
本發明之粉體塗料組成物係含有四氟乙烯(以下,稱作「TFE」)系共聚物者。
於本說明書中,所謂上述TFE系共聚物意指「作為共聚組成,主成分具有TFE之共聚物」。於本說明書中,所謂上述共聚組成,意指「上述TFE系共聚物之化學結構之基本單元即單體單元之種類、及上述各種單體單元於上述TFE系共聚物中之量(質量%)」
本發明之粉體塗料組成物所含之上述TFE系共聚物為六氟丙烯(以下,稱作「HFP」)9.0~13.0質量%及全氟烷基乙烯醚(以下,稱作「PAVE」)0.8~3.0質量%和四氟乙烯之共聚物。
由於本發明之粉體塗料組成物含有具有上述共聚組成之TFE系共聚物作為基體樹脂,故可獲得表面平滑性、耐化學品性皆優異之皮膜。
作為上述PAVE並無特別限定,可列舉:全氟甲基乙烯醚(PMVE)、全氟乙基乙烯醚(PEVE)、全氟丙基乙烯醚(PPVE)等之1種或2種以上,尤佳為全氟丙基乙烯醚(PPVE)。
上述HFP之量為9.0~13.0質量%。若HFP之量未達9.0質量%,則上述TFE系共聚物之熔點變得過高,結晶化度變大,故塗裝時熔融不充分,表面平滑性降低。若超過13.0質量%,則上述TFE系共聚物之熔點變得過低,而所得之塗膜之耐熱性降低。又,若塗裝次數過多,則有產生發泡或滴落之情形。
較佳之HFP量之下限為10質量%,較佳之上限為12質量%。
上述PAVE之量為0.8~3.0質量%。若PAVE之量未達0.8質量%,則所得之皮膜之耐化學品性無法充分提升。若超過3.0質量%,則由於無法獲得與含有率之增加相對應之效果,故於經濟性之方面而言較不佳。較佳之PAVE之量之下限為0.9質量%,較佳之上限為2.6質量%。
又,於無損本發明之目的之範圍,亦可含有其他單體。
上述TFE系共聚物之熔體流動速率(MFR)必須為13~26 g/10分鐘。若MFR未達13 g/10分鐘,則塗裝時之流動性變差,表面平滑性變低。又,為了獲得作為目的之皮膜之平滑性而變得需要長時間之加熱,故有上述TFE系共聚物之劣化成為問題之情況。若超過26 g/10分鐘,則於塗膜次數較多之情形時,會產生發泡或滴落,表面平滑性變差。
於本發明中,藉由將MFR設為上述範圍,於將粉體塗料組成物進行複數次塗布之情形時,即便於由粉體塗料組成物形成之皮膜上進而塗裝粉體塗料組成物,亦為皮膜之表面平滑性良好者。
較佳之MFR之下限為15質量%,較佳之MFR之上限為25質量%。
上述MFR為於上述TFE系共聚物熔融之情形時顯示出流動性者。於本發明中,藉由設為上述MFR之範圍,於無論塗裝次數,皆可獲得良好的表面平滑性之方面而言較優異。
關於上述TFE系共聚物,藉由調整分子量,可成為具有上述範圍內之MFR者。
於本說明書中,上述MFR係根據ASTM D2116,設定為溫度372℃、荷重5 kg進行測定而得之值。
上述TFE系共聚物之熔點為240~270℃。若熔點未達240℃,則耐熱性降低。若超過270℃,則難以獲得平滑之表面。
於本說明書中,上述熔點係根據ASTM D2116進行測定而得之值。
作為製造上述TFE系共聚物之方法並無特別限定,例如可藉由使用乳化聚合、懸浮聚合等先前公知之聚合方法等進行共聚而獲得上述TFE系共聚物。
本發明之粉體塗料組成物的平均粒徑較佳為5~500 μm。若未達5 μm,則有於進行塗布之情形時容易產生靜電排斥,厚膜化變得困難之傾向,若超過500 μm,則有所獲得之皮膜之平滑性等變差之情形。
關於上述粉體塗料組成物的平均粒徑,可視塗布方法來決定更佳之範圍,於用於靜電塗裝之情形時,更佳為10~70 μm,於用於滾襯之情形時,更佳為150~400 μm。
關於上述粉體組成物的平均粒徑,亦可依據欲藉由視需要之靜電塗裝而形成之膜厚來決定更佳之範圍,於用於上述薄塗之情形時,更佳為10~40 μm,於用於上述厚塗之情形時,更佳為40~70 μm。
關於上述粉體塗料組成物的平均粒徑,於下述之本發明之粉體塗料組成物之製造方法中,藉由調整粉碎或分級之條件,可製為上述範圍內者。
於本說明書中,上述平均粒徑為藉由雷射繞射法而測定之值。具體而言,為藉由Microtrac公司製造之MT-3300II所測定之體積基準之中值粒徑。
本發明之粉體塗料組成物之視密度較佳為0.5~1.1 g/ml。若未達0.5 g/ml,則有於塗裝時發生發泡,或導致塗裝次數之增加,而靜電塗裝變得困難之情形,若超過1.1 g/ml,則於工業上製造此種粉體塗料組成物變得不容易。較佳之視密度之下限為0.7 g/ml,較佳之上限為1.0 g/ml。
於本說明書中,上述視密度(g/ml)係藉由根據JIS K 6891之測定而得之值。
本發明之粉體塗料組成物亦可含有熱穩定劑。若本發明之粉體塗料組成物為含上述熱穩定劑者,則於熔點附近之溫度以上進行加熱之情形時,可防止「上述TFE系共聚物變得不穩定而會產生之塗膜之著色或發泡」。
作為上述熱穩定劑,自防止上述TFE系共聚物之氧化之方面而言,較佳為選自由胺系抗氧化劑、含有機硫之化合物及金屬粉末所組成之群中之至少1種。
作為上述胺系抗氧化劑,例如可列舉:分子中具有苯基、萘基等芳香族性烴基之芳香族胺,例如可列舉:N,N’-二苯基對苯二胺、N,N’-二-2-萘基對苯二胺、二苯胺與二異丁烯之反應產物等苯二胺系化合物;二萘胺、苯基-α-萘胺、苯基-β-萘胺、4,4’-雙(α,α’-二甲基芐基)二苯胺、苯基環己基對苯二胺、苯乙烯化二苯胺等其他芳香族2級胺化合物等。
作為上述含有機硫之化合物,例如可列舉: 2-巰基苯并咪唑、2-巰基甲基苯并咪唑等巰基苯并咪唑系化合物;2-巰基苯并噻唑、2-巰基苯并噻唑之環己胺鹽、二硫化二苯并噻唑、2-(4’-(N-𠰌啉基)二硫基)苯并噻唑、N-環己基-2-苯并噻唑基亞磺醯胺、N-氧二伸乙基-2-苯并噻唑基亞磺醯胺、N-第三丁基-2-苯并噻唑基亞磺醯胺等巰基苯并噻唑系化合物;2-巰基咪唑啉等巰基咪唑啉系化合物;五亞甲基二硫基胺基甲酸、哌可二硫基胺基甲酸(pipecolyl dithiocarbamic acid)、二甲基二硫基胺基甲酸、二乙基二硫基胺基甲酸、二丁基二硫基胺基甲酸、N-乙基-N-苯基二硫基胺基甲酸等二硫基胺基甲酸類等,該等例如亦可為Zn、Sn、Cd、Cu、Fe等之金屬鹽;哌啶鹽、哌可鹽等有機鹽等。
作為上述含有機硫之化合物,例如可列舉:秋蘭姆(thiuram)系化合物,例如可列舉:四甲基秋蘭姆單硫化物等秋蘭姆單硫化物;四甲基秋蘭姆二硫化物、四乙基秋蘭姆二硫化物、四丁基秋蘭姆二硫化物等秋蘭姆二硫化物;二(五亞甲基)秋蘭姆四硫化物等其他秋蘭姆系化合物等。
又,作為上述含有機硫之化合物,例如亦可為N,N’-二乙基硫脲、二丁基硫脲、二月桂基硫脲等硫脲衍生物等。
作為上述金屬粉末,可列舉:鈷粉末、鐵粉末、鋅粉末、錫粉末或銅粉末之1種或2種以上。關於金屬粉末,相較於單獨使用,較佳為與上述含有機硫之化合物及/或胺系抗氧化劑併用。
關於上述熱穩定劑,其中,自要求於本發明之粉體塗料組成物所含之TFE系共聚物之熔點附近之溫度以上,例如於約250℃之高溫之穩定性之方面而言,較佳為含芳香環之化合物,更佳為芳香族胺、巰基苯并噻唑系化合物及巰基苯并咪唑系化合物。
作為上述熱穩定劑,於本發明之粉體塗料組成物用於化學、醫療用器具、半導體製造設備等之用途之情形時,較佳為不殘留金屬殘渣之非金屬化合物。
作為上述熱穩定劑,可藉由先前公知之方法進行製造,但通常可使用市售品。
相對於上述TFE系共聚物100質量份,上述熱穩定劑較佳為0.001~5質量份。若未達0.001質量份,則有上述TFE系共聚物之熱穩定性惡化之情形,若超過5質量份,則在所獲得之皮膜會發生著色或由上述熱穩定劑之分解所致之發泡,故較不佳。更佳為0.003~2質量份。
本發明之粉體塗料組成物亦可含有著色顏料。作為著色顏料,可列舉:氧化鈦、氧化鈷、碳、氧化鉻、氧化鐵、雲母等。
相對於上述TFE系共聚物100質量份,上述著色顏料較佳為0.001~5質量份。若未達0.001質量份,則有無法獲得作為目的之著色之情形,若超過5質量份,則有於所獲得之皮膜產生發泡之情形。更佳為0.003~2質量份。
本發明之粉體塗料組成物可為與上述TFE系共聚物以及依期望而使用之上述穩定劑及/或著色顏料併用,並視需要含有添加劑等者。作為上述添加劑等並無特別限定,例如可列舉:一般用於粉體塗料組成物者等。
作為上述添加劑等,例如,以防鏽等為目的,可列舉:防鏽顏料、焙燒顏料等其他顏料;以防止塗膜之收縮為目的,可列舉:碳纖維、玻璃纖維、玻璃薄片、雲母等塗膜補強材;以賦予導電性為目的,可列舉:導電性碳等導電性賦予材等,亦可為調平劑、抗靜電劑等。
相對於上述粉體塗料組成物,上述添加劑之含量較佳為0~10.0質量%,更佳為0~5.0質量%。
上述熱穩定劑、著色顏料及添加劑的平均粒徑較佳為0.1~70 μm,更佳為0.1~50 μm。若該等之粒徑在此範圍,則能夠均勻地分散於組成物中並穩定地進行塗裝。
該等平均粒徑為藉由雷射繞射法而測定之值。具體而言,為藉由Microtrac公司製造之MT-3300II所測定之體積基準之中值粒徑。
作為本發明之粉體塗料組成物之製造方法並無特別限定,例如可列舉:粉碎方法、造粒方法、噴霧乾燥法等先前公知之方法等,例如,可列舉如日本特開昭63-270740號公報所揭示之方法等,該方法為:以輥將上述TFE系共聚物壓縮為片狀,將藉由粉碎機粉碎並分級而獲得之粉末與上述穩定劑及著色顏料、視需要而使用之導電性賦予劑等添加劑等進行乾式混合。
作為上述粉體塗料之製造方法,亦可使用以下方法:預先以混合機將上述TFE系共聚物、上述穩定劑及視需要之上述添加劑等進行混合,繼而,以捏合機、熔融擠出機等進行熔融混練後,進行粉碎,並視需要進行分級。
如此獲得之本發明之粉體塗料組成物通常可於塗布於被塗裝物後,利用加熱焙燒而製膜,藉此來進行加工。
作為上述被塗裝物並無特別限定,可較佳地使用被期望賦予耐蝕性者。作為此種被塗裝物,例如可列舉:槽(tank)、容器(vessel)、塔、閥、泵、接頭、其他配管材料、零件、密封材等實施有耐蝕襯裏者等。
本發明之粉體塗料組成物可尤佳地用於金屬基材。作為上述金屬基材,具體而言,可列舉:配管、管道管、導管等工業零件相關用途等。可將粉體塗料組成物塗布於該等之內表面。
「將本發明之粉體塗料組成物用於上述金屬基材」在可防止基材之腐蝕之方面而言有利。
作為上述金屬,可列舉:鐵、鋁、銅等金屬單體及該等之合金類等。作為上述合金類,可列舉:不鏽鋼(SUS)等。上述基材除包含金屬外,亦可包含其他材料。
作為上述基材,尤其更佳為由鐵、鋁、或不鏽鋼構成者。
上述被塗裝物亦可為視需要而進行洗淨、噴砂等表面處理或基底塗裝而得者。
作為基底,可列舉一般使用之含氟樹脂之基底等。
上述基底皮膜之膜厚較佳為20~150 μm。更佳為30~100 μm。
可將本發明之粉體塗料組成物塗布於上述基底皮膜上,並藉由加熱焙燒而形成皮膜。
作為本發明之粉體塗料之塗布方法並無特別限定,例如可列舉:靜電塗裝法、滾襯法、流動浸漬塗裝法等先前公知之方法等,自本發明之粉體塗料組成物無論塗裝次數,皆可獲得表面平滑性優異之皮膜之方面而言,可較佳地用於靜電塗裝法。
根據用途,本發明之粉體塗料組成物亦能以成為目標之膜厚之方式而分為複數次來進行塗裝。本發明之粉體塗料組成物無關其塗裝次數,皆可使塗裝表面之平滑性良好。塗裝次數並無特別限定,視目的進行1次至10次即可。
作為視需要進行了疊塗之焙燒後之膜厚,例如可列舉:20~5000 μm等,於以耐蝕襯裏等耐蝕性賦予作為目的之情形時,較佳為300~5000 μm。於使用靜電塗裝方法之情形時,通常為50~1000 μm。
作為上述加熱焙燒之溫度,例如可列舉:250~350℃等。
如上所述,由本發明之粉體塗料組成物所形成之皮膜亦為本發明之一。
又,如上所述,由本發明之粉體塗料組成物以靜電塗裝法所形成之皮膜亦為本發明之一。
進而,含有上述皮膜之積層體亦為本發明之一。又,在表面層含有上述皮膜之積層體亦為發明之一。
作為本發明之積層體,如上所述,可列舉:將本發明之粉體塗料組成物進行複數次塗裝,並將皮膜進行積層而得者、或將自本發明之粉體塗料組成物形成之皮膜設置於基底皮膜上而得者等。於此種積層體中,較佳為由本發明之粉體塗料組成物構成之皮膜為最外層者。
如上所述,在金屬基材上設有本發明之皮膜之塗裝物品亦為本發明之一。
又,在金屬基材之內表面設有本發明之皮膜,且金屬基材為配管、管道管或導管之塗裝物品亦為本發明之一。
關於本發明之皮膜,可直接設置在金屬基材上,亦可介隔基底皮膜來設置。
如上所述,具有以下步驟之皮膜形成方法以為本發明之一:
在被塗裝物形成基底皮膜之步驟(1),及
使用請求項1至4中任一項之粉體塗料組成物,藉由靜電塗裝法在基底皮膜之表面形成皮膜之步驟(2)。
由於本發明之粉體塗料組成物具有上述特定之共聚組成、MFR及熔點,因此,具有以下優異之加工性,亦即,無論塗裝次數,皆可獲得皮膜之表面平滑性。又,可獲得耐化學品性優異、不會產生因化學品或溫度衝擊所致之裂痕的皮膜。此種有利功效即便於將被膜設為厚塗之情形時亦可充分發揮,尤其於以耐蝕性賦予為目的之情形亦優異。
[實施例]
以下,根據實施例來具體說明本發明。
以下實施例中,於未特別提及之情形時,「份」「%」分別表示「質量份」「質量%」。
(實施例1)
利用輪壓機(roller compactor)將TFE系共聚物粉末A(HFP11.1%、PPVE1.0%、於372℃之熔體流動速率17.0 g/10分鐘、熔點258℃)壓縮為片狀,分解碎裂為數mm程度之大小後,以鎚磨機進行粉碎,獲得平均粒徑50~60 μm、視密度0.80~0.90 g/ml之粉體塗料組成物A。
將作為80網目之氧化鋁之TOSA EMERY(宇治電化學工業公司製造)以0.5 MPa之壓力噴擊於經脫脂之鐵基材(100 mm×200 mm×5 mm),利用空氣去除噴擊粉。並且,將TC-11000(大金工業公司製造)作為基底來進行塗裝、乾燥而獲得30~50 μm之皮膜。
於此基底皮膜上藉由靜電塗裝法塗布粉體塗料組成物A後,將其垂直懸吊於乾燥爐中並以285℃焙燒30分鐘,獲得膜厚約150 μm之皮膜。
進而,於該皮膜上重複4次藉由粉體塗料組成物A之塗布、焙燒的步驟,獲得總膜厚約500 μm之皮膜。
(實施例2)
使用TFE共聚物粉末B(HFP11.7(質量%)、PPVE1.0(質量%)、於372℃之熔體流動速率25.0 g/10分鐘、熔點255℃)來代替TFE共聚物粉末A而獲得粉體塗料組成物B,除此之外,實施與實施例1相同之步驟,獲得膜厚約150 μm之皮膜及總膜厚約500 μm之皮膜。
實施例3
使用TFE共聚物粉末C(HFP11.4(質量%)、PPVE0.8(質量%)、於372℃之熔體流動速率21.8 g/10分鐘、熔點257℃)來代替TFE共聚物粉末A而獲得粉體塗料組成物C,除此之外,實施與實施例1相同之步驟,獲得膜厚約150 μm之皮膜及總膜厚約500 μm之皮膜。
實施例4
使用TFE共聚物粉末D(HFP9.8(質量%)、PPVE2.6(質量%)、於372℃之熔體流動速率20.5 g/10分鐘、熔點265℃)來代替TFE共聚物粉末A而獲得粉體塗料組成物D,除此之外,實施與實施例1相同之步驟,獲得膜厚約150 μm之皮膜及總膜厚約500 μm之皮膜。
實施例5
使用TFE共聚物粉末E(HFP12.5(質量%)、PPVE1.0(質量%)、於372℃之熔體流動速率25.6 g/10分鐘、熔點250℃)來代替TFE共聚物粉末A而獲得粉體塗料組成物E,除此之外,實施與實施例1相同之步驟,獲得膜厚約150 μm之皮膜及總膜厚約500 μm之皮膜。
比較例1
使用TFE共聚物粉末F(HFP11.5(質量%)、PPVE0.9(質量%)、於372℃之熔體流動速率35.0 g/10分鐘、熔點257℃)來代替TFE共聚物粉末A而獲得粉體塗料組成物F,除此之外,實施與實施例1相同之步驟,獲得膜厚約150 μm之皮膜及總膜厚約500 μm之皮膜。
比較例2
使用TFE共聚物粉末G(HFP11.0(質量%)、PPVE1.0(質量%)、於372℃之熔體流動速率7.0 g/10分鐘、熔點258℃)來代替TFE共聚物粉末A而獲得粉體塗料組成物G,除此之外,實施與實施例1相同之步驟,獲得膜厚約150 μm之皮膜及總膜厚約500 μm之皮膜。
比較例3
使用TFE共聚物粉末H(HFP6.8(質量%)、PPVE1.3(質量%)、於372℃之熔體流動速率18.3 g/10分鐘、熔點280℃)來代替TFE共聚物粉末A而獲得粉體塗料組成物H,除此之外,實施與實施例1相同之步驟,獲得膜厚約150 μm之皮膜及總膜厚約500 μm之皮膜。
比較例4
使用TFE共聚物粉末I(HFP15.0(質量%)、PPVE0.1(質量%)、於372℃之熔體流動速率20.0 g/10分鐘、熔點230℃)來代替TFE共聚物粉末A而獲得粉體塗料組成物I,除此之外,實施與實施例1相同之步驟,獲得膜厚約150 μm之皮膜及總膜厚約500 μm之皮膜。
針對上述所獲得皮膜,藉由下述方法算出表面粗糙度,並評價皮膜之外觀。
將其結果一併示於表1。
(表面粗糙度Ra)
關於表面粗糙度Ra(算術平均粗糙度),使用表面粗糙度形狀測定機(Mitutoyo股份有限公司製造,SJ-210),根據JIS B 0601-1994,將測定點數5點之測定值進行平均來算出。
[表1]
[產業上之可利用性]
共聚物組成(質量%) | MFR | 溶點 | 表面粗糙度Ra(µm) | 皮膜之外觀 | |||
HFP | PPVE | (g/10分鐘) | (℃) | 1層 | 5層 | ||
實施例1 | 11.1 | 1.0 | 17.0 | 258 | 0.55 | 0.22 | 平滑性良好 |
實施例2 | 11.7 | 1.0 | 25.0 | 255 | 0.41 | 0.19 | 平滑性良好 |
實施例3 | 11.4 | 0.8 | 21.8 | 257 | 0.50 | 0.24 | 平滑性良好 |
實施例4 | 9.8 | 2.6 | 20.5 | 265 | 0.57 | 0.28 | 平滑性良好 |
實施例5 | 12.5 | 1.0 | 25.6 | 250 | 0.46 | 0.18 | 平滑性良好 |
比較例1 | 11.5 | 0.9 | 35.0 | 257 | 0.34 | (有發泡、有滴落) | 有發泡、有滴落 |
比較例2 | 11.0 | 1.0 | 7.0 | 258 | 1.06 | 0.59 | 平滑性不足 |
比較例3 | 6.8 | 1.3 | 18.3 | 280 | 7.78 | 6.95 | 熔融不足 |
比較例4 | 15.0 | 0.1 | 20.0 | 230 | 0.59 | (有發泡、有滴落) | 有發泡、有滴落 |
由於本發明之粉體塗料組成物具有上述構成,故皮膜之表面平滑性良好,且可尤佳地作為適於金屬基材之粉體塗料組成物。
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Claims (11)
- 一種粉體塗料組成物,其含有四氟乙烯系共聚物,且特徵在於:上述四氟乙烯系共聚物為9.0~13.0質量%之六氟丙烯及0.8~3.0質量%之全氟烷基乙烯醚和四氟乙烯之共聚物,熔體流動速率為13~26(g/10分鐘),熔點為240~270℃。
- 如請求項1之粉體塗料組成物,其中,上述四氟乙烯系共聚物的平均粒徑為5~500 μm,視密度為0.5~1.1(g/ml)。
- 如請求項1或2之粉體塗料組成物,其含有熱穩定劑及/或著色顏料。
- 如請求項1至3中任一項之粉體塗料組成物,其中,上述熱穩定劑係選自由胺系抗氧化劑、含有機硫之化合物及金屬粉末所組成之群中之至少1種。
- 一種皮膜,其係由請求項1至4中任一項之粉體塗料組成物所形成者。
- 一種皮膜,其係由請求項1至4中任一項之粉體塗料組成物以靜電塗裝法所形成者。
- 一種積層體,其含有請求項5之皮膜。
- 一種積層體,其在表面層含有請求項5之皮膜。
- 一種塗裝物品,其在金屬基材上設有請求項5之皮膜。
- 一種塗裝物品,其係在金屬基材之內表面設有請求項5之皮膜者,上述金屬基材為配管、管道管(pipe)或導管(duct)。
- 一種皮膜成形方法,其具有下述步驟: 在被塗裝物形成基底(primer)皮膜之步驟(1),及 使用請求項1至4中任一項之粉體塗料組成物,藉由靜電塗裝法在基底皮膜之表面形成皮膜之步驟(2)。
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JPH075743B2 (ja) | 1986-12-22 | 1995-01-25 | ダイキン工業株式会社 | テトラフルオロエチレン系共重合体粉末およびその製造法 |
JP4135741B2 (ja) * | 1997-06-23 | 2008-08-20 | ダイキン工業株式会社 | テトラフルオロエチレン共重合体フィルム |
JP2000026767A (ja) * | 1998-05-01 | 2000-01-25 | Daikin Ind Ltd | 熱硬化性粉体塗料組成物 |
WO2001036504A1 (fr) * | 1999-11-16 | 2001-05-25 | Daikin Industries, Ltd. | Fluorocopolymere |
DE60209224T2 (de) * | 2001-06-18 | 2006-07-27 | Daikin Industries, Ltd. | Verwendung von Pulverlack |
JP2003003111A (ja) * | 2001-06-18 | 2003-01-08 | Daikin Ind Ltd | 粉体塗料 |
US7169854B2 (en) * | 2001-09-11 | 2007-01-30 | Daikin Industries, Ltd. | Fluororesin composition, process for preparing the same and cable coated with the same |
JP3594950B2 (ja) * | 2002-10-22 | 2004-12-02 | 三井・デュポンフロロケミカル株式会社 | 粉末加工用フッ素樹脂粉末組成物 |
WO2008047759A1 (fr) * | 2006-10-20 | 2008-04-24 | Daikin Industries, Ltd. | Copolymère contenant du fluor et article moulé de celui-ci |
CN103554326B (zh) * | 2008-02-15 | 2016-06-15 | 大金美国股份有限公司 | 四氟乙烯/六氟丙烯共聚物和其生产方法以及电线 |
JP2009263609A (ja) * | 2008-03-31 | 2009-11-12 | Daikin Ind Ltd | 粉体塗料及びプライマー |
JP5744410B2 (ja) * | 2010-03-25 | 2015-07-08 | 日本フッソ工業株式会社 | 塗料組成物、それを用いた被膜製造方法および被膜体 |
WO2013146078A1 (ja) * | 2012-03-26 | 2013-10-03 | ダイキン工業株式会社 | 複合粒子、粉体塗料、塗膜、積層体、及び、複合粒子の製造方法 |
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