CN1137803A - 氟聚合物涂料组合物及涂层制品 - Google Patents
氟聚合物涂料组合物及涂层制品 Download PDFInfo
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- CN1137803A CN1137803A CN95191099.XA CN95191099A CN1137803A CN 1137803 A CN1137803 A CN 1137803A CN 95191099 A CN95191099 A CN 95191099A CN 1137803 A CN1137803 A CN 1137803A
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron 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
- 150000002576 ketones Chemical class 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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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
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
本发明提供一种氟聚合物涂料组合物及用其作为面层的制品,该氟聚合物涂料组合物是由氟聚合物的微粒子、按该微粒子的重量基准的0.1-300重量%的聚醚类高分子表面活性剂及液态载体组成,可以进行厚涂层,可以形成耐磨损性、耐腐蚀性及非粘合性优良的涂膜。
Description
本发明涉及氟聚合物涂料组合物及涂层制品。
先前,在氟聚合物涂料组合物中通常添加阴离子表面活性剂作为成膜助剂,但由于容易发泡,在涂膜上容易产生小孔(pin hole),另外由于成膜性不充分、厚涂层困难,所以还存在由于涂膜的磨损而使耐腐蚀性或非粘合性降低等缺点。
本发明的目的在于提供一种可以厚涂层的、能够形成耐磨损性、非粘合性优良的涂膜的配合有特定的聚醚类高分子表面活性剂的氟聚合物涂料组合物及其涂层制品。
本发明涉及由氟聚合物的微粒子、按该微粒子的重量基准的0.1-300重量%的特定的聚醚类高分子表面活性剂及液态载体组成的氟聚合物涂料组合物。
另外,本发明还涉及由上述氟聚合物涂料组合物在物品上形成至少30μm厚的熔融膜层作为面层的制品。
本发明中的氟聚合物是指由被氟原子、氯原子或二者完全取代的单乙烯类不饱和烃的单体的均聚物及由该单体的至少2种组成的共聚物的均聚物及共聚物的至少2种组成的混合物。
上述均聚物为聚四氟乙烯(PTFE)。
上述共聚物例如有四氟乙烯-全氟(烷基乙烯基醚)(PFA)(其中烷基的碳原子数为1-5)、四氟乙烯-六氟丙烯(FEP),从非粘合性、耐热性优良方面考虑优选PEA。
上述均聚物及共聚物的混合物例如有PTFE与PFA、PTFE与FEP、PTFE与PFA及FEP、PFA与FEP等,从非粘合性及耐热性优良方面考虑优选PTFE与PFA的混合物。
上述氟聚合物的数均分子量为2×104-l×107,优选2×105-8×106,如数均分子量小于2×104则涂膜有变脆的倾向;如超过1×107则熔融粘度过高,粒子之间有不熔合的倾向。
PTFE的数均分子量例如可以按照〔Journal of Applied Poly-mer Science〕第17卷、第3253-3257页(1973年)中记载的方法测定求出。
上述氟聚合物的微粒子可以是根据氟烯烃的乳化聚合等方法得到的微粒子,其平均粒径为0.01-100μm,优选0.1-5μm,如该粒径小于0.01μm,则成膜性有变差的倾向,如超过100μm则用于喷涂的喷枪管有堵塞的倾向。
另外,在本发明中,可以使用由上述乳化聚合得到的氟聚合物的微粒子的水性分散液或由该分散液得到的粉末状的微粒子,从带电粒子之间互相排斥而使乳浊液稳定方面考虑优选以分散液的形态使用,从涂膜形成方面考虑其固态成分的浓度为20-80重量%,优选40-70重量%。
本发明中的特定的聚醚类高分子表面活性剂例如为,
以通式(I):〔式中R为氢原子或碳原子数1-20的烷基,Y为醚基、酯基、尿烷基、亚硫酰基或磷酸基,A为环氧乙烷残基,B为环氧丙烷残基,a为30-2000的整数,b为20-500的整数,c为1-10的整数(其中括号内表示由交替共聚或无规共聚得到的残基)〕、以通式(II):R-Y-Aa-Bb-Ad-Y-R (II)(式中R、Y、A、B及b与上述相同,a与d的总数为30-2000的整数)、
以通式(III):R-Y-Ba-Ab-Bd-Y-R (III)(式中R、Y、A及B与上述相同,a与d的总数为20-500的整数,b为30-2000的整数)表示的表面活性剂或由其中的2种以上组成的聚醚类高分子表面活性剂及液态载体组成。
另外,本发明中特定的聚醚类高分子表面活性剂有:
以通式(IV):〔式中Z为碳原子数1-5的多价脂肪族饱和烃基,R为氢原子或碳原子数1-20的烷基,Y为醚基、酯基、尿烷基、亚硫酰基或磷酸基,A为环氧乙烷残基,B为环氧丙烷残基,a为30-2000的整数,b为20-500的整数,c为1-10的整数,e为1-4的整数(括号内表示由交替共聚或无规共聚得到的残基)〕、以通式(V):Z[-Y-Aa-Bb-Ad-Y-R]e (V)(式中Z、R、Y、A、B及b与上述相同,a与d的总数为30-2000的整数,e为1-4的整数)、以通式(VI):Z[-Y-Ba-Ab-Bd-Y-R]e (VI)(式中Z、R、Y、A、B及b与上述相同,a与d的总数为20-500的整数,b为30-2000的整数,e为1-4的整数)表示的聚醚类高分子表面活性剂或由其中的2种或2种以上组成的聚醚类高分子表面活性剂。
在通式(I)中,在R为烷基的情况下从热分解性方面考虑,其碳原子数优选为1-18、Y从热分解性方面考虑优选为醚基或酯基。a从成膜性及热分解性方面考虑优选为40-600的整数,b从增粘性方面考虑优选为30-120的整数。c从涂平性方面考虑优选为1-5。
在通式(II)中,在R为烷基的情况下,从热分解性方面考虑,其碳原子数优选为1-18。Y从热分解性方面考虑优选醚基或酯基。a从成膜性及热分解性方面考虑优选为20-300的整数,b从增粘性方面考虑优选为30-120的整数,d从成膜性及热分解性方面考虑优选为20-300的整数。
在通式(III)中,在R为烷基的情况下,从热分解性方面考虑,其碳原子数优选为1-18。Y从热分解性方面考虑优选为醚基或酯基,a从增粘性及热分解性方面考虑优选为15-60的整数,b从成膜性方面考虑优选为40-600的整数,d从增粘性及热分解性方面考虑优选为15-60的整数。
在通式(IV)中,Z的碳原子数从增粘性及热分解性方面考虑优选为2或3,在R为烷基的情况下,从增粘性、热分解性方面考虑其碳原子数优选为1-18。Y从热分解性方面考虑优选为醚基或酯基。a从成膜性及热分解性方面考虑优选为40-600的整数,b从增粘性方面考虑优选为30-120的整数,c从涂平性方面考虑优选为1-5,e从烘烤时的分解性良好方面考虑优选为1。
在通式(V)中,Z从增粘性及热分解性方面考虑优选为2或3。在R为烷基的情况下,从热分解性方面考虑碳原子数优选为1-18。Y从热分解性方面考虑优选为醚基或酯基。a从成膜性及热分解性方面考虑优选为20-300的整数,b从增粘性方面考虑优选30-120的整数,d从成膜性及热分解性方面考虑优选为20-300,e从烘烤时的分解性良好方面考虑优选为1。
在通式(VI)中,Z的碳原子数从增粘性及热分解性方面考虑优选为2或3。在R为烷基的情况下其碳原子数从热分解性方面考虑优选为1-18。Y从热分解性方面考虑优选为醚基或酯基。a从增粘性及热分解性方面考虑优选为15-60的整数,b从成膜性方面考虑优选为40-600的整数,d从增粘性及热分解性方面考虑优选为15-60,e从烘烤时的分解性良好方面考虑优选为1。
上述特定的聚醚类高分子表面活性剂具有增粘性、成膜性的功能,例如具有以丙二醇部分作为亲油基、以乙二醇部分作为亲水基的构造的高分子表面活性剂,在从250℃附近至上述氟聚合物的熔融温度的范围内分解气化,可以有交替共聚物(如通式(I)或(IV)中a=b=1时)、嵌段共聚物(如通式(II)、(III)、(V)或(VI))、无规共聚物(如通式(I)或(IV))等形态,从容易增粘方面考虑,最优选以通式(II)表示的至少一种嵌段共聚物。
这些特定的聚醚类高分子表面活性剂的乙二醇部分的重均分子量为1×103-2×105,优选2×103-2×104,更优选8×103-8×104,另外丙二醇部分的重均分子量为1×102-3×104,优选1×103-3×104,更优选2×103-1×104。
上述乙二醇部分的重均分子量如果低于1×103则引起相分离,有不能均匀分散的倾向,如大于2×105则增粘过度,有不能喷雾的倾向,另外上述丙二醇部分的重均分子量如果低于1×102则增粘不足,涂料容易滴垂,滴垂部分在烧制时容易发生裂缝,如高于3×104则增粘过度,有不能喷雾的倾向。
通式(I)的具体例例如有:(1)HO(CH2CH2O)a(CH(CH3)CH2O)bH(式中a为300,b为75)表示的无规共聚物、(2)C17H35COO(CH2CH2O)a(CH(CH3)CH2O)bCOC17H35(式中a为300,b为75)表示的无规共聚物等,从热分解性方面考虑优选(1)的结构。
通式(II)的具体例例如有:(3)HO(CH2CH2O)a(CH(CH3)CH2O)b(CH2CH2O)dH(式中a与d的总数364,b为69)(4)C17H35COO(CH2CH2O)a(CH(CH3)CH2O)b(CH2CH2O)dCOC17H35(式中a与d的总数为300,b为60)表示的嵌段共聚物等,从热分解性方面考虑优选(3)的结构。
通式(III)的具体例例如有:(5)HO(CH(CH3)CH2O)a(CH2CH2O)b(CH(CH3)CH2O)dH(式中a与d的总数64,b为350)、(6)C17H35COO(CH(CH3)CH2O)a(CH2CH2O)b(CH(CH3)CH2O)dCOC17H(式中a与d的总数为60,b为310)表示的嵌段共聚物等,从热分解性方面考虑优选(5)的结构。
在本发明中,在单独使用以通式(I)-(III)所示的高分子表面活性剂的情况下,从容易增粘方面考虑优选通式(II),另外,在使用2种以上的情况下,作为通式(I)-(III)中的组合,例如可以有所有的组合,但从增粘并赋予涂平性方面考虑优选(IV)与(V)的组合。这种情况下具体的组合例有上述具体例子中的(7)与(9)或(10)的组合,(8)与(9)或(10)的组合等,从热分解性方面考虑是优选的。
本发明中的液态载体例如有水及水与甲醇、乙醇、丙醇、异丙醇等醇类、乙二醇、二乙二醇、三乙二醇、甘油等多元醇类,丙酮等酮类、二乙胺、三乙胺、乙醇胺、二乙醇胺、三乙醇胺等胺类、四氢呋喃等醚类等的混合物,其中从防止氟原子类粒子的凝集、成膜性等方面考虑优选水及水与二乙醇胺的组合。
另外,在本发明中,在不损害组合物的物性的范围内,例如在组合物中以15%(重量,以下同)以下的比例,可以使用甲苯、二甲苯、C9-C11的芳香族烃等非极性溶剂作为液态载体。
本发明中,可以添加云母粒子、被颜料包裹的云母粒子、金属片或这些的2种以上的填料。这些填料可以提高耐磨损性、其中的云母还可以使涂膜美观。
云母粒子的粒径为10-100μm,优选15-50μm,如粒径小于10μm则涂膜的耐磨损性有变差的倾向,如大于100μm则非粘合性能有降低的倾向。
被颜料包裹的云母粒子例如有将TiO2、Fe2O3等颜料利用烧结蒸镀方法包裹在上述云母粒子上而得到的产物。
金属片例如有钛、锆、铝、锌、锑、锡、铁、镍等,从不生锈方面考虑优选钛、锆,其大小为10-100μm,更优选15-50μm,其大小如小于10μm,则涂膜的耐磨损性有变差的倾向,如大于100μm,则非粘合性能有降低的倾向。
在本发明中可以使用各种添加剂,例如将氧化钴等干燥剂、硅酮油等消泡剂、甲基纤维素、PVA、羧化乙烯基聚合物等增粘剂、C9-C11的芳香族烃类、乙二醇类溶剂等涂平剂、氧化钛、氧化铁红、碳黑等颜料利用常法添加,其添加量为按上述氟聚合物的重量基准的50%以下,优选35%以下,如果该添加量大于50%则有失去非粘合性的倾向。
上述特定的聚醚类高分子表面活性剂的使用量为按上述氟聚合物的微粒子的重量基准的0.1-300%,优选0.5-100%,更优选1-30%,该使用量如低于0.1%则看不出效果,如超过300%则不能形成涂膜。
上述填料的使用量为按其与PTFE类聚合物的总重量基准的0.2-20%,优选1-15%,更优选2-10%,该使用量如果低于0.2%则涂膜的耐磨损性有变差的倾向,如大于20%则非粘合性有降低的倾向。
本发明的氟聚合物的涂料组合物的固态成分的浓度为20-80%,优选40-70%,如果该浓度低于20%则有不能形成涂膜的倾向,如果超过80%则有不能喷雾的倾向。
本发明的氟聚合物涂料组合物的制造例如可按以下方法进行。
在带有搅拌机的容器中加入氟聚合物微粒子的水性分散液90-110份(重量份,以下同),搅拌下依次加入填料2-10份、特定的聚醚类高分子表面活性剂的15-30重量%的水溶液3-500份、液态载体2-22份、及根据需要的添加剂0.05-10份,在5-30℃下搅拌10-40分钟至搅拌均匀,得到本发明的氟聚合物涂料组合物。
在各种基底材料上涂覆本发明组合物可按常法进行,例如将金属、搪瓷制品、玻璃、陶瓷等的表面吹砂磨蚀使成粗糙表面后,用底漆混合物(Daikin(大金)工业(株)制、PolyflonTEE enamel EK-1909BKN)涂底层,在组合物中浸渍或将组合物以喷雾、辊涂或刮刀法涂覆,为使涂覆的组合物中的氟聚合物熔融,在足够的温度(340-415℃)下烘烤10-30分钟。
此时的熔融膜层的厚度为30μm以上,对于上限没有特别限定,但如果超过70μm则聚醚类高分子表面活性剂的淤渣残留在涂膜中,非粘合性能急剧降低,因此优选30-70μm。
本发明的组合物对于金属餐具特别是煎锅的涂层最为有用,该组合物也可用于需要具有耐腐蚀性的其他制品的涂层。其他制品例如有由玻璃或能够经受得住所使用的烘烤温度的物质制成的物品,例如轴承、阀门、电线、金属箔、锅炉、管、船底、烘箱内衬、熨斗的底板、煎锅锅底、饭煲、烤肉锅、电水壶、制冰盘、除雪铲、锄、滑槽、传动机、辊、金属模具、铸模、锯、锉、锥子等工具、菜刀、漏斗及其他的工业用容器及铸模。
下面,利用实施例进一步详细说明本发明,但本发明并不受这些实施例的限定。
实施例1
将如下所示的成分按记载的顺序混合。(1)PTFE水性分散液(大金工业(株)制Polyflon TEE DispersionD-1、固态成分为60%的水性分散液(相对于PTFE,含有用作分散稳定剂的聚环氧乙烷基苯酚醚(EO=10)6%))
240.0份(2)被TiO2包裹的云母粒子(粒径30μm)
14.4份(3)氧化乙烯-氧化丙烯嵌段共聚物(三洋化成工业(株)制NewpolePE 128、25%水溶液(相当于上述通式(II),R为H,Y为氧原子,a为182,b为69,d为182))
57.6份(4)三乙醇胺
7.2份
对于制得的组合物进行有关涂料物性的试验。
试验如下进行。涂料物性
粘度:使用B型旋转粘度计(No.2转子),转子的转数为60rpm,使旋转2分钟进行测定(温度25℃)。ph:使用pH计按常法进行测定。固态成分:在铝制杯子上称量10g涂料,在380℃下烧制45分钟,测定重量并计算出固态成分量。结果如表1所示。
将铝制煎锅预先进行吹砂磨蚀处理,之后用底漆混合物(大金工业(株)制Polyflon TEE Enamel EK-1909BKN(含有聚酰胺亚胺))进行底层涂漆,使底漆厚度达到15μm,然后将上述(1)-(4)的各成分混合形成的本发明组合物在煎锅上喷雾涂覆,使厚度达到35μm,在380℃下烘烤15分钟,得到膜的厚度总计为50μm的涂覆有本发明组合物的制品,进行有关涂膜物性的试验。试验如下进行。涂膜物性临界开裂膜厚:在未经喷砂处理的铝板上喷涂,在上述烘烤条件下烧制,用电磁式膜厚计测定。铅笔硬度:根据JIS K5400的涂料一般试验标准进行。描绘试验:根据JIS K5400的涂料一般试验标准进行。耐滑动摩擦试验:根据JIS K5400的涂料一般试验标准进行。热水试验:根据JIS K5400的涂料一般试验标准进行。在无剥离时以“无异常”评价,在有剥离时以“有起泡”评价。盐水喷雾试验:根据JIS K5400的涂料一般试验标准进行。在无剥离时以“无异常”评价,在有剥离时以“有起泡”评价。非粘合试验:在用PTFE制成的容器中安装2mm2的不锈钢制的筛网(内径3.5cm、外径4.8cm、厚度1.5cm),在其中加入小麦粉20g、砂糖10g、水40g的混合物,将该容器载置于涂层表面,在200℃下加热6分钟后将该容器用弹簧称拉起,测定每单位面积的密着力。结果如表1所示。
实施例2
在实施例1中,氧化乙烯-氧化丙烯嵌段共聚物的种类采用如下所示的物质,除采用表1中所示的量之外,按照与实施例1同样的方法,得到本发明的组合物及涂覆有该组合物的制品,进行与实施例1同样的试验。
氧化乙烯-氧化丙烯嵌段共聚物(三洋化成工业(株)制、New-pole V-10-C 25%水溶液(相当于上述通式(V),R为H,Y为氧原子,a为182,b为69,d为182,Z为3价脂肪族饱和烃,e为30)结果如表1所示。
实施例3
用如下所示的物质替换实施例1中的氧化乙烯-氧化丙烯嵌段共聚物,除采用表1所示的量之外,按照与实施例1同样的方法得到本发明的组合物及涂覆有该组合物的制品,进行与实施例1同样的试验。
氧化乙烯-氧化丙烯无规共聚物(三洋化成工业(株)制,New-pole 75H-90000,25%水溶液(相当于上述通式(I),R为H,Y为氧原子,a为300,b为75,c为1))结果如表1所示。
实施例4
将如下所示的成分按记载的顺序混合。(1)PTFE水性分散液(大金工业(株)制Polyflon TFE DispersionD-1,固态成分占60%的水性分散液(相对于PTFE,含有作为分散稳定剂的聚环氧乙烷烷基苯酚醚(EO=10)6%))
240.0份(2)被TiO2包裹的云母粒子(粒径30μm)
14.4份(3)Mill base(将去离子水55份及氧化钴蓝45份用球磨机混合得到的混合物)
7.2份(4)氧化乙烯-氧化丙烯嵌段共聚物(三洋化成工业(株)制Newpole
PE-128,25%水溶液(相当于上述通式(II),R为H,Y为氧原子,a为182,b为69,d为182))
57.6份(5)三乙醇胺 7.2份
对于制得的组合物进行与实施例1同样的试验。结果如表1所示。
另外,除本发明的组合物的干燥后的厚度为45μm之外,其余按与实施例1同样的方法得到涂层制品,进行同样的试验,结果如表1所示。
比较例1
除在实施例1中不使用氧化乙烯-氧化丙烯嵌段共聚物且组合物的上涂层的涂膜干燥后的厚度为10μm(膜厚总计为25μm)之外,用同样的方法得到组合物及涂覆有该组合物的制品,进行与实施例1同样的试验。结果如表1所示。
比较例2
将如下所示成分按记载的顺序混合。(1)PTFE水性分散液(大金工业(株)制Polyflon TFE DispersionD-1,固态成分占60%的水性分散液(相对于PTFE,含有作为分散稳定剂的聚环氧乙烷烷基苯酚醚(EO=10)6%))
240.0份(2)去离子水 29.1份(3)阴离子表面活性剂(月桂基硫酸钠盐) 17.1份与甲苯5.7份的混合溶液 22.8份
对于制得的组合物进行与实施例1同样的试验。结果如表1所示。
另外,使用上述(1)-(3)组成的组合物替代实施例1中的本发明的组合物,且上涂层涂膜的干燥后的厚度为15μm(膜厚总计为30μm),其余与实施例1同样得到涂层制品,进行同样的试验。结果如表1所示。
比较例3
将如下所示成分按照记载的顺序混合。(1)PTFE水性分散液(大金工业(株)制Polyflon TFE DispersionD-1,固态成分占60%的水性分散液(相对于PTFE,含有作为分散稳定剂的聚环氧乙烷烷基苯酚醚(EO=10)6%))
240.0份(2)去离子水 29.1份(3)Millbase(将去离子水55份及氧化钴蓝45份用球磨机混合得到的混合物) 7.2份(4)阴离子表面活性剂(月桂基硫酸钠盐) 17.1份与甲苯5.7份的混合溶液 22.8份
对于得到的组合物进行与实施例1同样的试验。
结果如表1所示。
另外,使用由上述(1)-(4)的成分组成的组合物替代实施例1中的本发明的组合物,且上涂层涂膜的干燥后的厚度为20μm(膜厚总计为35μm),其余与实施例1方法相同,得到涂层制品,进行同样的试验。结果如表1所示。
表1
实施例 | 比较例 | ||||||||
1 | 2 | 3 | 4 | 1 | 2 | 3 | |||
配合量︵份︶ | PTFE水性分散液 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
氧化乙烯-氧化丙烯嵌段共聚物(相当于通式(II)) | 6 | - | - | 6 | - | - | - | ||
氧化乙烯-氧化丙烯嵌段共聚物(相当于通式(V)) | - | 6 | - | - | - | - | - | ||
氧化乙烯-氧化丙烯嵌段共聚物(相当干通式(I)) | - | - | 8 | - | - | - | - | ||
阴离子表面活性剂 | - | - | - | - | - | 9 | 9 | ||
被TiO2包裹的云母粒子 | - | - | - | 6 | - | - | - | ||
涂料物性 | 粘度(cp) | 180 | 190 | 140 | 160 | 23 | 180 | 140 | |
pH | 9 | 9 | 9 | 9 | 9 | 9 | 9 | ||
固态成分(%) | 47 | 47 | 47 | 50 | 60 | 46 | 49 | ||
涂膜物性 | 临界开裂膜厚(μm) | 45 | 50 | 47 | 70 | 15 | 21 | 30 | |
铅笔硬度 | 室 温 | H | H | H | 2H | 2B | H | 2H | |
200℃ | HB | HB | HB | H | 6B以下 | B | H | ||
描绘试验 | 4.5 | 4.5 | 4.5 | 5 | 1 | 4.5 | 4.5 | ||
耐滑动摩擦试验 (mg/1000次) | 14 | 14 | 15 | 1O | 25 | 24 | 19 | ||
热水试验 100hrs | 无异常 | 无异常 | 无异常 | 无异常 | 有起泡 | 无异常 | 有起泡 | ||
盐水试验 100hrs | 无异常 | 无异常 | 无异常 | 无异常 | 有起泡 | 有起泡 | 有起泡 | ||
非粘合试验 (g/cm2) | 12 | 12 | 12 | 14 | 20 | 13 | 16 |
由表1可以看出,配合有由通式(II)表示的特定的聚醚类高分子表面活性剂的本发明的组合物(实施例1),其临界开裂膜厚、200℃的铅笔硬度、耐滑动摩擦量、热水及盐水试验、非粘合性均良好。
另外,配合有由通式(III)表示的特定的聚醚类高分子表面活性剂的本发明的组合物(实施例2),其临界开裂膜厚、200℃的铅笔硬度、耐滑动摩擦量、热水及盐水试验、非粘合性均良好。
另外,配合有由通式(I)表示的特定的聚醚类高分子表面活性剂的本发明的组合物(实施例3),其临界开裂膜厚、200℃的铅笔硬度、耐滑动摩擦量、热水及盐水试验、非粘合性均良好。
另外,配合有由通式(II)表示的特定的聚醚类高分子表面活性剂及被TiO2包裹的云母粒子的本发明的组合物(实施例4),其临界开裂膜厚、铅笔硬度、耐滑动摩擦量均良好。
由上述结果可知,本发明的氟聚合物涂料组合物可以进行厚涂层、可以形成耐磨损性、耐腐蚀性、非粘合性优良的涂膜,以该组合物为外涂层的制品,可长期保持品质。
Claims (8)
1.氟聚合物涂料组合物,由氟聚合物的微粒子、按该微粒子的重量基准的0.1-300重量%的聚醚类高分子表面活性剂及液态载体组成。
2.氟聚合物涂料组合物,由氟聚合物的微粒子及、按该微粒子重量基准的0.1-300重量%的
以通式(I):〔式中R为氢原子或碳原子数1-20的烷基,Y为醚基、酯基、尿烷基、亚硫酰基或磷酸基,A为环氧乙烷残基,B为环氧丙烷残基,a为30-2000的整数,b为20-500的整数,c为1-10的整数(其中括号内表示由交替共聚或无规共聚得到的残基)〕、以通式(II):R-Y-Aa-Bb-Ad-Y-R (II)(式中R、Y、A、B及b与上述相同,a与d的总数为30-2000的整数)、以通式(III):R-Y-Ba-Ab-Bd-Y-R (III)(式中R、Y、A及B与上述相同,a与d的总数为20-500的整数,b为30-2000的整数)表示的聚醚类高分子表面活性剂或其中的2种或2种以上的聚醚类高分子表面活性剂及液态载体组成。
3.氟聚合物涂料组合物,由氟聚合物的微粒子及、按该微粒子的重量基准的0.1-300重量%的
以通式(IV):〔式中Z为碳原子数1-5的多价脂肪族饱和烃基,R为氢原子或碳原子数1-20的烷基,Y为醚基、酯基、尿烷基、亚硫酰基或磷酸基,A为环氧乙烷残基,B为环氧丙烷残基,a为30-2000的整数,b为20-500的整数,c为1-10的整数,e为1-4的整数(括号内表示由交替共聚或无规共聚得到的残基)〕、以通式(V):Z[-Y-Aa-Bb-Ad-Y-R]e (V)(式中Z、R、Y、A、B及b与上述相同,a与d的总数为30-2000的整数,e为1-4的整数)、以通式(VI):Z[-Y-Ba-Ab-Bd-Y-R]e (VI)(式中Z、R、Y、A及B与上述相同,a与d的总数为20-500的整数,b为30-2000的整数,e为1-4的整数)表示的聚醚类高分子表面活性剂或其中的2种或2种以上的聚醚类高分子表面活性剂及液态载体组成。
4.权利要求1-3中任一项记载的氟聚合物涂料组合物,其中的氟聚合物为四氟乙烯类聚合物。
5.权利要求4中记载的氟聚合物涂料组合物,其中的四氟乙烯类聚合物为聚四氟乙烯、四氟乙烯-全氟(烷基乙烯基醚)共聚物、四氟乙烯-六氟丙烯共聚物或其中的2种以上。
6.权利要求1-3中任一项记载的氟聚合物涂料组合物进一步含有下列成分:(1)添加云母粒子、被颜料包裹的云母粒子、金属片或其中的2种以上,(2)氟聚合物为聚四氟乙烯、四氟乙烯-全氟(烷基乙烯基醚)共聚物、四氟乙烯-六氟丙烯共聚物或其中的2种以上,以成分(1)与成分(2)的总量为基准,成分(2)占80-99.8重量%,成分(1)占20-0.2重量%。
7.权利要求1-6中任一项记载的氟聚合物涂料组合物,其中的液态载体为水。
8.将权利要求1-7中任一项记载的氟聚合物涂料组合物在物品表面形成至少30μm厚的熔融膜作为面层而制得的成品。
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TW375646B (en) | 1996-04-24 | 1999-12-01 | Daikin Ind Ltd | Fluoropolymer coating composition and coated article |
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EP1059333B1 (en) * | 1998-02-24 | 2006-10-11 | Asahi Glass Company, Limited | Aqueous polytetrafluoroethylene dispersion composition |
DE19857111A1 (de) | 1998-12-11 | 2000-06-15 | Dyneon Gmbh | Wäßrige Dispersionen von Fluorpolymeren |
GB2349113B (en) * | 1999-04-21 | 2003-07-02 | Gates Corp | Wear resistant belts and a process for their manufacture |
US20030125421A1 (en) * | 2001-08-03 | 2003-07-03 | Hermann Bladel | Aqueous dispersions of fluoropolymers |
US7279522B2 (en) | 2001-09-05 | 2007-10-09 | 3M Innovative Properties Company | Fluoropolymer dispersions containing no or little low molecular weight fluorinated surfactant |
US7217426B1 (en) | 2002-06-21 | 2007-05-15 | Advanced Cardiovascular Systems, Inc. | Coatings containing polycationic peptides for cardiovascular therapy |
US7638154B2 (en) * | 2003-01-21 | 2009-12-29 | Hap International, Inc. | Pan spray formulation and delivery system |
EP1452571B1 (en) * | 2003-02-28 | 2005-08-17 | 3M Innovative Properties Company | Fluoropolymer dispersion containing no or little low molecular weight fluorinated surfactant |
US8791171B2 (en) | 2003-05-01 | 2014-07-29 | Abbott Cardiovascular Systems Inc. | Biodegradable coatings for implantable medical devices |
DE102004008772A1 (de) * | 2004-02-23 | 2005-09-08 | Institut für Neue Materialien Gemeinnützige GmbH | Abriebbeständige und alkalibeständige Beschichtungen oder Formkörper mit Niedrigenergieoberfläche |
US7244443B2 (en) | 2004-08-31 | 2007-07-17 | Advanced Cardiovascular Systems, Inc. | Polymers of fluorinated monomers and hydrophilic monomers |
GB0523853D0 (en) | 2005-11-24 | 2006-01-04 | 3M Innovative Properties Co | Fluorinated surfactants for use in making a fluoropolymer |
GB0514398D0 (en) | 2005-07-15 | 2005-08-17 | 3M Innovative Properties Co | Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant |
US20070025902A1 (en) | 2005-07-15 | 2007-02-01 | 3M Innovative Properties Company | Recovery of fluorinated carboxylic acid from adsorbent particles |
US20080015304A1 (en) | 2006-07-13 | 2008-01-17 | Klaus Hintzer | Aqueous emulsion polymerization process for producing fluoropolymers |
GB0525978D0 (en) | 2005-12-21 | 2006-02-01 | 3M Innovative Properties Co | Fluorinated Surfactants For Making Fluoropolymers |
EP1795565B1 (en) * | 2005-12-06 | 2016-05-18 | Solvay Specialty Polymers Italy S.p.A. | Water-based fluoropolymer composition |
US7754795B2 (en) | 2006-05-25 | 2010-07-13 | 3M Innovative Properties Company | Coating composition |
US9028859B2 (en) | 2006-07-07 | 2015-05-12 | Advanced Cardiovascular Systems, Inc. | Phase-separated block copolymer coatings for implantable medical devices |
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AU2011233415B2 (en) * | 2010-03-30 | 2015-06-04 | Kuraray Co., Ltd. | Composite structural material, formed product and packaging material using the same, method for producing the composite structural material, and coating liquid |
CN103946324B (zh) * | 2011-11-17 | 2016-09-14 | Lg化学株式会社 | 水分散组合物、生态友好的光伏模块的背板和制造该背板的方法 |
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US6124045A (en) | 2000-09-26 |
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