CA2216404C - Aqueous polytetrafluoroethylene dispersion composition and use thereof - Google Patents

Aqueous polytetrafluoroethylene dispersion composition and use thereof Download PDF

Info

Publication number
CA2216404C
CA2216404C CA002216404A CA2216404A CA2216404C CA 2216404 C CA2216404 C CA 2216404C CA 002216404 A CA002216404 A CA 002216404A CA 2216404 A CA2216404 A CA 2216404A CA 2216404 C CA2216404 C CA 2216404C
Authority
CA
Canada
Prior art keywords
dispersion
aqueous
polytetrafluoroethylene
polyoxyethylene alkyl
alkyl ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CA002216404A
Other languages
French (fr)
Other versions
CA2216404A1 (en
Inventor
Toshiro Miura
Tadao Hayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=14278526&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CA2216404(C) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of CA2216404A1 publication Critical patent/CA2216404A1/en
Application granted granted Critical
Publication of CA2216404C publication Critical patent/CA2216404C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions 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
    • C08L27/02Compositions 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
    • C08L27/12Compositions 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
    • C08L27/18Homopolymers or copolymers or tetrafluoroethene
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02Polyalkylene oxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • H01M4/622Binders being polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • H01M4/622Binders being polymers
    • H01M4/623Binders being polymers fluorinated polymers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides an aqueous polytetrafluoroethylene dispersion composition characterized in that the composition comprises 30 to 65 wt. % of polytetrafluoroethylene and a polyoxyethylene alkyl ether in an amount of 2 to 10 wt. % based on the polytetrafluoro- ethylene, the polyoxyethylene alkyl ether being represented by the formula RO (CH2 CH2 O) nH wherein R is a saturated or unsaturated hydrocarbon group having 8 to 18 carbon atoms, and n is 5 to 18, having a cloud point of over 45 .degree.C to not higher than 85 .degree.C- and containing 6 5 to 70 wt. % of ethylene oxide in the molecule.

Description

CA 02216404 1997-09-24 1 AQUEOUS POLYTETRAFLUOROETHYLENE DISPERSION COMPOSITION AND USE THEREOF TECHNICAL FIELD The present invention relates to a composition which is an aqueous polytetrafluoroethylene dispersion as concentrated, and to the use thereof. The aqueous polytetrafluoroethylene dispersion composition of the invention is useful, for example, for coating base materials such as glass fibers, carbon fibers and aramide fibers (hereinafter referred to as "fibrous base materials") for preparing conveyor belts, roof materials (tent fabrics) for architectural fabric structure, packings, high-frequency printed boards, etc., and is also suited as it is for use as a battery binder and a material for coating compositions- BACKGROUND ART It is already known to concentrate an aqueous polytetrafluoroethylene dispersion by adding a surfactant to the dispersion, thereafter heating the dispersion to form a transparent aqueous solution as an upper layer and to concentrate polymer particles as contained in a lower aqueous layer, and removing the upper.layer by decantation. The surfactant used is an ethylene oxide adduct of an alkylphenol (polyoxyethylene alkyl phenyl ether). However, the concentrated dispersion has many problems, such as those given below, for use in impregnating fibrous base materials. (1) In the impregnating-baking step, the surfactant i" ~ CA 02216404 1997-09-24 ~ 2 thermally decomposes, converting into a harmful organic aromatic compound (such as benzene, toluene or xylene) as an exhaust gas to cause air pollution. (2) The surfactant partially undergoes thermal decomposition to produce a tarlike substance, which accumulates on the inner wall of the baking furnace of the impregnating-baking apparatus. The substance falls onto or adheres to the fibrous base material passing through the furnace to lower the yield from the viewpoint of quality. (3) The surfactant, which is difficult to thermally decompose or dissipate, partly remains in the fibrous base material after baking, assuming a brown color to seriously impair the hand of the impregnated material. (4) Because the remaining portion of the surfactant is carbonized, use of the impregnated material in preparing high-frequency printed boards entails impaired electric characteristics. When the dispersion is used as a battery binder, the surfactant is left undissipated almost entirely under the drying condition (about 250 to about 300 C ) for the electrode material, remaining in the electrode material and contributing to impaired performance. To solve these problems, aqueous polytetrafluoro- ethylene dispersion compositions are known in which an ethoxylated aliphatic alcohol (polyoxyethylene alkyl ether) is used (see, for example, JP-B-21532/1977) . It is known that polyoxyethylene alkyl ethers are lower than polyoxyethylene alkyl phenyl ethers in decomposition temperature, therefore = CA 02216404 1997-09-24 ~ 3 readily dissipate on thermal decomposition in many cases, are less likely to remain in polymers, and form films which are apparently advantageous in yellow index of plastics (ASTM D- 1925- 63T) measured. Polyoxyethylene alkyl ethers, which contain no benzene ring in the structure, do not convert into a harmful organic aromatic compound (such as benzene, toluene or xylene) on thermal decomposition, giving rise to no air pollution. Thus, the aqueous polytetrafluoroethylene dispersion comprising a polyoxyethylene alkyl ether has various advantages and yet is not in wide use because in the field of fibrous base materials impregnated with aqueous polytetrafluoroethylene dispersions wherein the dispersion is used most frequently, the following properties are required of the dispersion. (1) For impregnation, the dispersion is relatively stabilized in viscosity and low in viscosity-temperature dependence. (2) The dispersion has a relatively low viscosity of 10 to 30 cp at room temperature (25 C) and smoothly penetrates into fibrous base materials. (3) When the dispersion is repeatedly applied in layers, the resulting coating still remains free of cissing or coagulation. JP-B-21532/1977 mentions nothing about such impregnation. We have conducted intensive research on the invention of JP-B-21532/1977 and found that this invention is CA 02216404 1997-09-24 h T 4 characterized by using as surfactants two kinds of polyoxyethylene alkyl ethers, i.e., one having a cloud point of up to 45 C and the other having a cloud point at least 10 C higher than the former and not lower than 50 C . Examples of the invention indicate that the ethylene oxide content is as high as 73.5 to 82 wt. % to give marked hydrophilic properties, such that when the composition is applied repeatedly, cissing occurs. An object of the present invention is to provide an aqueous polyoxyethylene alkyl ether dispersion composition having excellent impregnating properties, releasing none of harmful organic aromatic compounds such as benzene into the atmosphere and less likely to cause pollution. Another object of the invention is to provide a coated product which is diminished in the amount of residue (carbide) of a surfactant, has good hand (high degree of whiteness) and is also excellent in electric properties. Another object of the invention is to provide a binder for use in batteries which is excellent in electric characteristics, or a coating composition for giving a clear color of high lightness. DISCLOSURE OF THE INVENTION The present invention provides an aqueous dispersion composition comprising polytetrafluoroethylene and a surfactant, the aqueous polytetrafluoroethylene dispersion composition being characterized in that the composition has a polytetrafluoroethylene concentration of 30 to 65 wt. % the surfactant comprising a polyoxyethylene alkyl ether represented by the formula CA 02216404 1997-09-24 RO (CH2 CH2 0) nH wherein R is a saturated or unsaturated hydrocarbon group having 8 to 18 carbon atoms, and n is 5 to 18, having a cloud point of over 45 C to not higher than 85 C and containing 65 to 70 wt. % of ethylene oxide in the molecule, the concentration of the surfactant being 2 to 10 wt. % based on the polytetrafluoroethylene. The invention relates also to the use of the composition. Although the polytetrafluoroethylene present in the aqueous polytetrafluoroethylene dispersion of the present invention can be of any particle size, the preferred particle size is usually 0.15 to 0.40 f,c m. The aqueous polytetrafluoro- ethylene dispersion as prepared, which generally contains 25 to 35 wt. % of polytetrafluoroethylene, is heated in the presence of the surfactant specified above and thereby separated into two layers to obtain the desired concentrated aqueous polytetrafluoroethylene dispersion containing 30 to 65 wt. % of polytetrafluoroethylene. The polytetrafluoroethylene includes not only a homopolymer of polytetrafluoroethylene but also a modified polytetrafluoroethylene prepared by copolymerizing tetrafluoroethylene with other copolymerizable monomer in a small amount that will not impart fluidity to the modified product on melting. Examples of such copolymerizable monomers are hexafluoropropene, chlorotrifluoroethylene, perfluoro(alkyl vinyl ether), perfluoro(alkoxy vinyl ether), trifluoroethylene and perfluoroalkylethylene. While the proportion of the monomer to be copolymerized varies depending on the kind of the monomer, for example, a perfluoro(alkyl CA 02216404 1997-09-24 6 vinyl ether) or perfluoro(alkoxy vinyl ether) is used for copolymerization usually in an amount of up to 2 wt. % preferably 0.01 to 1 wt. %. The surfactant to be used in the invention is represented by the formula RO (CH2 CH2 0) nH wherein R is a saturated or unsaturated hydrocarbon group having 8 to 18 carbon atoms, and n is 5 to 18, has a cloud point of over 45 C to not higher than 85 C and contains 65 to 70 wt. % of ethylene oxide in the molecule. Examples of preferable hydrocarbon groups are octyl, decyl, tridecyl, stearyl, lauryl, cetyl and oleyl. It is important that the surfactant have a cloud point of over 45 C to not higher than 85 C and contain 65 to 70 wt. % , preferably 65.5 to 68 wt. % , of ethylene oxide in the molecule. One or at least two surfactants of the type described are usable. When the aqueous dispersion is concentrated by the method described, the surfactant becomes incorporated in the resulting concentrate in an amount of at least 2% . If the surfactant content exceeds 10% , the surfactant gives the aqueous dispersion prepared an increased viscosity and impaired viscosity- temperature dependence, apparently remaining in the fibrous base material impregnated with the dispersion to produce an undesirable result. In impregnating fibrous base materials with the aqueous polytetrafluoroethylene dispersion, the ethylene oxide content of the surfactant exerts a great influence not only on the basic properties of the dispersion such as viscosity and CA 02216404 1997-09-24 7 viscosity-temperature dependence but also on the impregnating properties thereof such as the wetting property and surface tension of the polymer. When the surfactant, i.e., polyoxyethylene alkyl ether, as used singly or in the form of a mixture for the aqueous polytetrafluoroethylene dispersion is less than 65 wt. % in ethylene oxide content, the dispersion has an excessively high viscosity at room temperature (25 C) and is not suited to impregnation. If the fibrous base material is impregnated with the dispersion, an excess of resin will deposited on the fibers by a single application, rendering the coating liable to develop mud cracks. Such an aqueous dispersion exhibits great viscosity-temperature dependence as shown in FIG. 1, is prone to become more viscous with a slight rise in temperature, and is difficult to control in viscosity. The amount of resin to be deposited on the base material per application by impregnation depends largely on the viscosity of the aqueous dispersion, and when having great viscosity-temperature dependence, the aqueous dispersion has problems in quality. If the ethylene oxide content exceeds 70 wt. % , on the other hand, the dispersion becomes excessively hydrophilic, with the result that when the fibrous base material impregnated with the dispersion the second time and further repeatedly, cissing is likely to occur on the polytetrafluoroethylene coating on the base material. Similarly, the cloud point of the surfactant is also an important factor. Generally the cloud point rises with an CA 02216404 1997-09-24 t 8 increase in the number of moles added of ethylene oxide which is the hydrophilic group of the surfactant. For the reason already given, therefore, the cloud point also affects the impregnating properties. According to JP-B-21532/1977, a polyoxyethylene alkyl ether of low cloud point (30 to 45 C is used in concentrating an aqueous polytetrafluoroethylene dispersion, and a surfactant of high cloud point is added to give improved storage stability at room temperature (25 C). However, the cloud point of the former surfactant is approximate to room temperature and too low, so that even if the aqueous dispersion is allowed to cool to room temperature, it is difficult to obtain a transparent supernatant after concentration and to separate off a concentrated aqueous polytetrafluoroethylene dispersion. Furthermore, since the supernatant occurs readily at room temperature (further progress of concentration), the latter surfactant must be added in an early stage for stabilization. Consequently, although a highly concentrated aqueous polytetrafluoroethylene dispersion is available from the concentration step, addition of an aqueous solution of the latter surfactant reduces the concentration of polytetrafluoroethylene in the aqueous dispersion, conversely increasing the surfactant concentration. On the other hand, the polyoxyethylene alkyl ether having a cloud point of over 45 C to not higher than 85 C and used in the invention affords an aqueous polytetrafluoroethylene dispersion having a relatively high storage stability without adding the latter surfactant or with CA 02216404 1997-09-24 9 use of only a small amount of the latter surfactant. More specifically, the aqueous polytetrafluoroethylene dispersion of the invention can be obtained, for example, by heating an aqueous polytetrafluoroethylene dispersion immediately after the preparation thereof in the presence of a polyoxyethylene alkyl ether represented by the formula RO (CH2 CH2 O) nH wherein R is a saturated or unsaturated hydrocarbon group having 8 to 18 carbon atoms, and n is 5 to 18, having a cloud point of over 45 C to not higher than 85 C and containing 65 to 70 wt. % of ethylene oxide in the molecule to separate the dispersion into two layers and obtain a concentrated aqueous polytetrafluoroethylene dispersion containing 30 to 65% of polytetrafluoroethylene, and adding to the dispersion a small amount of a polyoxyethylene alkyl ether represented by the formula RO (CH2 CH2 O) nH wherein R is a saturated or unsaturated hydrocarbon group having 8 to 18 carbon atoms, and n is 5 to 18, or without adding the ether. The polyoxyethylene alkyl ether of the above formula is used singly, or such ethers are used in the form of a mixture, as will be apparent from Examples. Thus, the invention provides an aqueous polytetrafluoroethylene dispersion having a high solids CA 02216404 2006-05-30 9/1 content and low surfactant concentration by a method which basically differs from the method disclosed in JP-B- 21532/1977. In fields other than the field of impregnation, i.e., in the field, for example, of battery binders, there is a demand for such aqueous polytetrafluoroethylene dispersions. While the aqueous polytetrafluoroethylene dispersion of the invention is useful, for example, for coating fibrous base materials to prepare conveyor belts, roof materials (tent fabrics) of buildings of architectural fabric structure, packings, high-frequency printed boards, etc., the dispersion is also suited for use as a battery binder and material for coating compositions. Examples of base materials are glass fibers, KevlarrM fibers, carbon fibers, ceramic fibers, metal fibers, silicon carbide fibers, etc. An electrode material for batteries, for example, for nonaqueous electrolyte cells called lithium cells wherein Li is used as the negative electrode active substance is prepared by adding 1 to 20% of polytetrafluoroethylene to a powder of positive electrode active substance such as carbon fluoride or manganese dioxide, kneading the mixture with heating and rolling the mixture. At this time, the polytetrafluoroethylene is supplied in the form of an aqueous dispersion, and the desired surfactant is one which is easily thermally decomposable. Pigments, solvents, additives, etc. are usable for CA 02216404 1997-09-24 preparing coating compositions. Suitable pigments are those having such thermal resistance as to free of degradation at temperatures not lower than the melting point of polytetrafluoroethylene. Stated more specifically, examples of 5 inorganic pigments usable are compound oxide pigments comprising combinations of oxides of Cr, Ti, Co, Ni, Fe, Mn, Cu, Sb, etc., calcined pigments such as cadmium pigments, carbon black, ultramarine, etc. Examples of organic pigments usable are Phthalocianine Blue, Phthalocyanine Green, 10 perylene-type pigments, etc. as improved in heat resistance. The pigment is used in an amount of about 1 to about 40 wt. % based on the weight of polytetrafluoroethylene. It is usually desired that the pigment be added in the form of a slurry. Also usable are commercial aqueous coloring agents intended for fluorine-containing resins and containing about 1 to about 50 wt. % of such pigments. Examples of useful solvents are N,N- dimethylformamide, N,N-dimethylacetamide, N-methyl-2- pyrrolidone, dimethyl sulfoxide, methyl ethyl ketone, methyl glycol acetate, 2-nitropropane, ethylene glycol acetate, toluene, etc. Examples of additives are fillers such as glass, talc, mica, clay, Si02, Ti02, A12 03 and ceramic compounds, thickeners such as methyl cellulose, coating composition additives such as leveling agents, etc. Such additives can be used in an amount of 0.1 to 40 parts per 100 parts of the dispersion. The coating composition obtained can be used as such for metal cooking utensils (frying pans), CA 02216404 1997-09-24 , 11 household electric devices such as irons and jars, industrial machines such as copying machine rolls. BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a graph showing the viscosity-temperature dependence of aqueous polytetrafluoroethylene dispersions of Example 3 and Comparative Examples 3 and 5. BEST MODE OF CARRYING OUT THE INVENTION The present invention will be described in greater detail with reference to the following examples. The percentages are by weight unless otherwise specified. The amounts of the components used other than that of fluorine- containing resin are all expressed in percent by weight based on the weight of the fluorine-containing resin. In the following description, HLB=ethylene content/5. Example 1 A starting aqueous dispersion of polytetrafluoroethylene particles was prepared by an emulsion polymerization process wherein tetrafluoroethylene was polymerized with stirring under pressure in an aqueous solution of polymerization emulsifier such as ammonium polyfluorocarboxylate in the presence of ammonium persulfate or succinic acid peroxide serving as a polymerization initiator. The dispersion contained 30% of the polymer based on the weight of the dispersion, and the polymer was 0.20 ,u m in mean particle diameter. To the dispersion was added 10% (based on the weight of solids of the polymer) of a nonionic surfactant represented by C1 3 H2 70(CH2 CHZ 0) nH [registered trademark " DISPANOL TOC" (product of Nippon Oils & Fats Co., CA 02216404 1997-09-24 12 Ltd.), about 8.5 in n, the number of moles of ethylene oxide added, 49 C in cloud point and 65% in calculated ethylene oxide content]. Aqueous ammonia was further added to the dispersion in an amount sufficient to raise the pH of the dispersion from about 3 to about 10. The resulting dispersion was gently stirred for several minutes, heated at 55 C and allowed to stand for 24 hours. A transparent supernatant produced was removed to obtain a concentrated dispersion, which was about 70% in solids content and about 2.7% in surfactant (DISPANOL TOC) content based on the weight of the dispersion. To 1 liter of this dispersion as a specimen was further added about 3.3% of DISPANOL TOC to adjust the specimen to a solids content of about 60% and surfactant content of about 6% Example 2 The same procedure as in Example 1 was repeated with the exception of changing the nonionic surfactant from DISPANOL TOC to a surfactant represented by C1 s H27 0(CHZ CHZ O) nH [product of Nippon Oils & Fats Co., Ltd., about 9_5 in n, 58.8 C in cloud point and 65.5% in calculated ethylene oxide content]. The dispersion concentrate obtained was about 66% in solids content and about 2.4% in surfactant content based on the weight of the dispersion. To 1 liter of this dispersion as a specimen was further added 3.6% of the surfactant to adjust the specimen to a solids content of about 60% and surfactant content of about 6% . Example 3 CA 02216404 1997-09-24 13 The concentration procedure of Example 1 was repeated_ To 1 liter of the dispersion as a specimen were added about 2% of DISPANOL TOC, and about 1.3% of a nonionic surfactant represented by C, 2 H2 s O(CH2 CH2 0) nH [registered trademark "EMULGEN 120" (product of Kao Co., Ltd.), about 11.7 in n, 98 C in cloud point and 76% in calculated ethylene oxide content] to adjust the specimen to a solids content of about 60% and surfactant content of about 6% . The ethylene oxide content of the surfactant mixture in the dispersion was 67.5% . Example 4 The same procedure as in Example 1 was repeated with the exception of changing the nonionic surfactant from DISPANOL TOC to a surfactant represented by C1 3 H2 70(CH2 CH2 O) nH [product of Nippon Oils & Fats Co., Ltd., about 10.5 in n, 72.6 C in cloud point and 68.0% in calculated ethylene oxide content]. The dispersion concentrate obtained was about 65% in solids content and about 2.5% in surfactant content. To 1 liter of this dispersion as a specimen was further added 3.5% of the surfactant to adjust the specimen to a solids content of about 60% and surfactant content of about 6% Comparative Example 1 The same concentration procedure as in Example 1 was repeated with the exception of changing the nonionic surfactant from DISPANOL TOC to Nonion P-208 [C1 6 H3 s 0(CH2 CH2 0) nH, product of Nippon Oils & Fats Co., Ltd., about 8.0 in n, 48 C in cloud point and 59.5% in calculated ethylene oxide content], whereas it was impossible to obtain CA 02216404 1997-09-24 14 any concentrate. Comparative Example 2 The same concentration procedure as in Example 1 was performed with the exception of changing the surfactant from DISPANOL TOC to EMULGEN 108 [C1 2 H2 5 0(CH2 CH2 0) nH, product of Kao Co., Ltd., about 6.3 in n, 40 C in cloud point and 60.5% in calculated ethylene oxide content], whereas it was difficult to detect the interface between the concentrated aqueous polytetrafluoroethylene dispersion and the supernatant. The resulting dispersion was 61.5% in solids content and 2.5% in surfactant content. To 1 liter of this dispersion as a specimen was further added 3.5% of the surfactant to adjust the specimen to a solids content of about 60% and surfactant content of about 6% . The dispersion obtained had an excessively high viscosity and deposited an increased amount of resin by a single application when tested for impregnation, consequently developing mud cracks and faults in the coating. Comparative Example 3 The same concentration procedure of Example 1 was performed using a lot, lower in cloud point, of the surfactant DISPANOL TOC (product of Nippon Oils & Fats Co., Ltd.), i.e., C, 3 H2 , 0(CH2 CH2 O) nH [about 8.3 in n, 44.5 C in cloud point and 64.5% in calculated ethylene oxide content] . The dispersion concentrate obtained was about 69.3% in solids content and about 2.9% in surfactant content based on the weight of the dispersion. To 1 liter of this dispersion as a specimen was further added 3.1% of the surfactant to adjust the specimen CA 02216404 2006-05-30 to a solids content of about 60% and surfactant content of about 6% . The dispersion obtained had a slightly high viscosity of 55 cp at 25 C . The dispersion had great viscosity-temperature dependence as shown in FIG. 1, 5 increasing in viscosity with a slight rise in temperature. Like the dispersion of Comparative Example 2, this dispersion was not suited for impregnation. Comparative Example 4 For comparison, the same concentration procedure as 10 above was performed with the exception of replacing DISPANOL TOC by Triton X-100 [C8 H, 7 Cs H9 0(CH2 CHZ O) nH, product of Union Carbide Corporation, about 9.0 in n, 65 'C in cloud point and 67.5% in ethylene oxide content] to obtain a dispersion having a solids content of about 65% and surfactant content 15 of about 3.2% . To the dispersion was added 2.8% of TritoriMX- 100 to adjust the dispersion to a solids content of about 60% and surfactant content of about 6% . The dispersion had the problem of air pollution and faults such as impaired hand. Comparative Example 5 The concentration procedure of Example 1 was repeated. To 1 liter of the dispersion as a specimen were added about 0.4% of DISPANOL TOC, and about 2.9% of a nonionic surfactant represented by C12HZ 5 0(CH2 CH2 0) nH [registered trademark "EMULGEN 120" (product of Kao Co., Ltd.), about 11.7 in n, 98 C in cloud point and about 76.5% in calculated ethylene oxide content] to adjust the specimen to a solids content of about 60% and surfactant content of about 6% . The ethylene oxide content of the surfactant CA 02216404 1997-09-24 16 mixture in the dispersion was 70.5% . When the dispersion obtained was repeatedly applied to a base material in an impregnation test, cissing occurred on the second and subsequent polytetrafuoroethylene coatings on the base material. Comparative Example 6 The same procedure as in Example 1 was performed except that the surfactant used was C$ H1 70(CH2 CHZ O) nH [product of Nippon Oils & Fats Co., Ltd., about 7.0 in n, 67.6 C in cloud point and 70.5% in calculated ethylene oxide content], whereas it was impossible to obtain any concentrate. 20 CA 02216404 1997-09-24 17 Table 1 Example 1 2 surfactant for concentration kind C13H270(CH2CH2O)nH C1gH270(CH2CH2O)nH n 8.5 9.5 amount 10% 10% cloud point 49 C 58.8 C EO content 65% 65.5% HLB 13.0 13_1 dispersion concentrate solid content 70% 66% surfactant content 2.7% 2.4% surfactant for adjustment kind C1,H270(CH2CH2O)nH C13H27O(CH2CH2O)nH n 8.5 9.5 amount 3.3% 3.6% cloud point 49 C 58.8 C EO content 65% 65.5% HLB 13.0 13.1 dispersion prepared solid content 60.3% 60.0% surfactant content 5.8% 5.9% viscosity 18.5cp 22.Ocp pH 9.4 9.8 specific gravity 1.522 1.515 cloud point 49 C 58.8 C EO content 65% 65.5% HLB 13.0 13.1 CA 02216404 1997-09-24 18 Table 2 Example 3 4 surfactant for concentration kind C13H270(CH2CH20)nH Ci3H270(CH2CH2O)nH n 8.5 10.5 amount 10% 10% cloud point 49 C 72.6 C EO content 65% 68% HLB 13.0 13.5 dispersion concentrate solid content 70% 65% surfactant content 2.7% 2.5% surfactant for adjustment kind Q C12H250(CH2CH2O)nH C,gH270(CH2CH2O)nH 0 C13H270(CH2CH20)nH n ~i 11.7 0 8.5 10.5 amount (D 1.3% (Z 2.0% 3.5% cloud point Q 98 C OO 49 C 72.6 C EO content 67.5% 68% HLB 13.5 13.6 dispersion prepared solid content 60.8% 60.2% surfactant content 6.0% 6.4% viscosity 21.9cp 23.8cp pH 9.5 9.4 specific gravity 1.528 1.518 cloud point 59.6 C 72.6 C EO content 67.5% 68.0% HLB 13.5 13.6 CA 02216404 1997-09-24 19 x 0 U o 0 U o ~ Lf=1 LP1 Ol M ~ . . . . p1 U O ~ ~r c~ rn ~-- 00 ~ cr t0 ~ 0 tV O N x t~ a~ ~ cu x 0 W N a o 0 ~ U .7 N o Ln Ln \ =~ x M \ oU . . . . Lfy -P N U = O O O cV fL7 V l0 - d' lo N 3-+ O E x O N U U M a~ x .~ ro o 0 H a-) d) x 0 +3 U \ a~ co x o ~ oU . . sz 4-) U = O CO rn - =-i C oo <- u-i - m a) O rn U 0 C t3F ~ 0 =~i U C 0 -r-t 4-) ~ la -I-) N C +-) O co U S-i +-J C +J C O C a) U C S i C =I-) 0 O 0 C U 4-) U N C =N I-) +~ 4-) =~ C C C C C 0 N 0 0 c6 c0 a -N =ri U +=) =P -t-) C tn U U C 't'1 0 t-+ ZS f (0 Z? C C U N =rl va 4-+ C 0 0 Oq R ~ S-+ w =I+ C 5 .-1 0 a v) 0 zi zi ac co U w x -1 U) m Ui V CA 02216404 1997-09-24 0 x o P \ \ o ~ N P \ U ~ Lf1 LC1 Ol N LC1 N Lf1 LC1 01 M ~- = = = = = -~f Ln = = m "~T'. = = d' 'cH N C) = Lf-1 = = d' ~N N U 00 C+') lD Lfl L1l Ol c- d~ lD ~ 0 ~ x U ~ r-+ x s~ a ~n ~ co c/a o a) v N ~ w x U o \ \ o n, o \ Q) N ~ Ln U 4-) Ln > x c=n Ln P = = ao 0 0o P -.-t CV U = = C) O= N (D = -ZN = d) C) o. N a--> '=-~ l0 M l0 Lf1 N Ol r-i =V 1~0 (0 ~ L1 w ~ =ra N CO V] G1, x [A 5 0 O A., 4) U U ~ ..GZ ~ E-~ ~ m Pi En 4-) r-i 4) G Cf !-i 4) R7 RI +j =fJ 0. c -rl !.a a) +-) O > O S-+ c: U 2T w=+ -1~ CL 4) G +~ 4--) C r- G G ~ ====1 ~ O N 0 0 c0 +-) U 0 N c0 Aa -t~ =r-I U -i, = --I -r-1 a -P -P 41 Ul U Ul 4-1 r- U r- Z5 0 !.a TS [6 0 =H 10 0 tQ ''o =j U m =ri 4-+ U U U y-+ 0 0 a, -+ S-1 Cm a) 0 [1m $-, -~ gi e -1 o a u~ o a ~ Q c~. -+ o a v~ U w x ca U w x =~ m m > m ~a CA 02216404 1997-09-24 21 0 o -J a~ N o 'N co U o io ui ~ ~ t=-i = S~ -I~ N O = o= ~o x = o ~ ~r ~ ~ ul a) ai U o 0 [ a 0 U x ri U x x ~' x o 0 ~ x x c0 O D U ~ N N N w x o x x 'r o 0 0 0 \ U U V o x x RS N a x v v e M ~ O O x x c c ~ o 0 Q N N ~r x x H U U U O o ~ ~ O N ~ . \ U . . . . O rn O tn [~ C=n tn t~ O v - l0 l0 e- l0 x x U U x x U U O -N -1-> co +-) N ~ ~ -4) u) ro En U S=-i +) ::5 +-) C -+" O N 'c$ U N -I--) R1 U G f.a S-a c: +-3 0 O 0 U 0 v-~ -+-J U (1) w ~ -F-~ -I=' 4-) G C 4-) 0 N 0 0 c0 [Q f.1 +-) =1I U +' RJ -1~ 4-) r- fA U =+=) U r- '0 0 La 10 [0 U cci :5 U N -1 4-4 cQ '0 v-.i 0 0 Ix1 ~, =-i w v-+ r- -4 0 1l m 0 =1 S.a =1i :5 x co U w x -+ m m =3 ac v) z~ v2 CA 02216404 1997-09-24 . ' 22 io a~ L, c0 = = o~ co O zzr ~ ~ a U o W o 0 o U ~ o ~ Lf1 Lf=1 Lf1 N l- Lll Q) Lf1 O O O = = = pp = L(1 Lll = = ~ > 0 O = ~fl = = N 0 =ri l- ~- lD LIl N Ol [- -F-~ co c0 = m Q ~- CN rn ~ 0 N () --I .C~ (0 E o \ \ o M ~ LC1 LC1 N N Ln Lf1 o= = m oU . . . O = l0 ,.r, oU . ~ LCl l~ M O = c- = = LC1 l~ M Ol fV lD l0 =- l0 l0 N 01 ~ l0 l0 -F=~ ~ ~ -1--~ rn :5 i-) =r~ 4) ~ a w a) Rf f6 -h~ a==) L~ C =.-i Si O -F-) 0 > O 1=-~ C U c0 w -F-~ L~. 4) 1=- +~ 4> -E=i -N 2T ~ =F-) .N =~ a a z r- >1 0 d) 0 0 c0 -I, U 0 O c[3 CL 1~ H U -I, -=i ='-I fL +-) +~ 1, C Ul U fll 4-4 C U r- 'O 0 S-i 'O c0 0 =H 'CS 0 t0 U a) =ri w U U U 00 0 0 PO 0a 02 a) 0 E -1 0 a V] 0 z -,-1 CL f)~ r--l 0 1-1 ca L) w x =r+ m m > m U w x ~ ~ CA 02216404 1997-09-24 23 [Impregnating Properties] Glass fibers were impregnated by the following procedure with each of the aqueous polytetrafluoroethylene dispersions obtained in the examples. Used as glass fibers was a plain-woven fabric having a yarn density of 60 warps/25 mm and 46 wefts/25 mm and a thickness of 0.05 mm and subjected to heat cleaning. 1) The fabric was impregnated with the aqueous polytetrafluoroethylene dispersion of the example once, dried at about 100 C and baked at about 380 C for 3 minutes. 2) The impregnated fabric was immersed in the same aqueous dispersion for impregnation, dried at about 100 C and baked at about 380 C for 3 minutes. In this step, the dispersion was checked for cissing on the fluorine-containing resin coating. 3) The step 2) of impregnation, drying and baking was repeated to obtain a fabric having a fluorine-containing resin content of about 60 to about 65% . Table 5 shows the impregnating properties of the aqueous polytetrafluoroethylene dispersions of Examples and Comparative Examples. The fabrics treated with the dispersion of Example 3 or Comparative Example 4 were checked for the degree of whiteness by a color difference meter, SM color computer MODEL SM-4 (Suga Shikenki Co., Ltd.) and for light transmittance by a haze meter (Toyo Seiki Co., Ltd.)_ Table 6 shows the results. CA 02216404 2006-05-30 24 .,.i El) ,--i OD M = ~õ~ . a Lr, U Q x E ro ~ o ~ x W ~ +-) > ..., 4-) co M o kD r 01 N ~., . . . . . . o L~ a O Q Q E D 4) 0 U U co 4-4 N r r I I rn a, X Q Q ~4 Ln o ko U) = r ~ ~ O ~ 0 ~ C) o rM in p~ O= -[ O Ln Ln o Ln Q Q Qo v d' O N d~ rn \O ~ ~ O 'U ts ~ o O N v~ ~p rn -,-{ X U) m M r O ~p N d 'f' .-' CD r- M w to Q Q O N -U)i a .- U E a> ~ O =~ x CD l!l M =- M ,- RS N ~ (~ . . . . 4-1 .1-1 r rn u-i 0 0 Qo E~~ o N M Cp U) RS ro a~ > O d' ko o -qr >-, o lD O N M Q Q O "A 3 V~ rn r-- M CO lD '- ~ O U O r-1 U) ,O -=-i b) > ul rl tn .c: m O .,~ --! =.~ E U) U H O O O 1 y~ tf O O m ?j, En J-! 1-) ro v1 .i C p O O "-' O, Z z ~ o w =.A! [n o =., o c ~ ~ 4-1 -~ .. .. w =.4 +.Y .=i w a i, c x x Q '0 +' ~ +~ o o ,-Q .,_, ta c co w m -.~ CT C CS C ~ c0 a O N w 3 ~ d+ a' p' +-) +) +) L; '+-+ a, l..i - c c 0+ a w v Zs '~ o O w a O a) C >, E O 0) O c a E a CT U -4 -+-) ., I > O C +J E ~ E 1 4-) =,4 tn Li C7 C7 c.!) 11 zs 14 G ~ -.i a ~ i ~ a E + +-) -a c H .n +) .ri Q O OO ts ~ o i..~ a s., c ro (o ~ O f i U O 0 =.1 S-i C v +-) a, E 7 Ln a a, a -4 m +~ w cn +J ro E E N -a co 4--4 1- -.-! m s i 3 ~ cv M CA 02216404 1997-09-24 y L Table 6 L value a value b value light transmittance (Tt) Ex.3 56.95 0.05 -1.24 63.7% Com.Ex.4 55.13 0.44 1.19 60.9% The L value indicates the degree of whiteness, and the a value the degree of redness. The a value indicates a reddish color when higher and a greenish color when lower. The b value indicates the degree of yellowness. The b value indicates a yellowish color when higher and a bluish color when lower. The impregnated fabric of Example 3 is smaller in the degree of yellowness and greater in the degree of whiteness than that of Comparative Example 4. This result is well in match with the result of Table 5 as to the whiteness determined with the unaided eye- [Temperature Dependence of Viscosity] The aqueous polytetrafluoroethylene dispersion of Example 3 and Comparative Examples 3 and 5 were.heated from 20 C to 50 C and checked for viscosity upon rise of every 5 C FIG. 1 shows the results. The graphs shows that the lower the ethylene oxide content, the greater is the viscosity- temperature dependence of the aqueous dispersion and the greater is the difficulty encountered in controlling the viscosity of the dispersion for use in impregnation. While base materials are actually impregnated with the dispersion usually as controlled to a temperature of about 25 C , the CA 02216404 1997-09-24 ~ 26 dispersion of Comparative Example 3 has an excessively high viscosity and is therefore unsuited for impregnation. The dispersion of Comparative Example 5 has the drawback of cissing when used for impregnation although acceptable in viscosity-temperature dependence. INDUSTRIAL APPLICABILITY The use of a surfactant having a specified cloud point and specified ethylene oxide content affords aqueous polytetrafluoroethylene dispersions which have good storage stability without the necessity of using an adjusting surfactant or with use of only a small amount of such surfactant. The aqueous polytetrafluoroethylene dispersion of the invention has excellent impregnating properties and is unlikely to release any harmful organic aromatic compound such as benzene into the atmosphere. The aqueous dispersion of the invention is further expected to provide coated articles which are diminished in the residue (carbide) of the surfactant, satisfactory in hand (high degree of whiteness) and also excellent in electric characteristics. The aqueous dispersion of the invention further provides a binder for batteries, etc. which has high electric characteristics, or a coating composition for giving a clear color of high lightness.

Claims

27 The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows: 1. An aqueous polytetrafluoroethylene dispersion B which is obtained by the following steps: heating an aqueous polytetrafluoroethylene dispersion A, after the preparation thereof, with a polyoxyethylene alkyl ether represented by the formula: RO ( CH2CH2O ) n H wherein R is a saturated hydrocarbon group having 8 to 18 carbon atoms, and n is 5 to 18, wherein said polyoxyethylene alkyl ether has a cloud point of over 49.degree.C to not higher than 85.degree.C and an ethylene oxide content of 65 to 70 wt %, to separate the dispersion A into two layers and obtain a concentrated aqueous polytetrafluoroethylene dispersion containing 30 to 65% of polytetrafluoroethylene; recovering the concentrated aqueous polytetrafluoroethylene dispersion; and thereafter optionally mixing the concentrated aqueous polytetrafluoroethylene dispersion with an amount of a polyoxyethylene alkyl ether represented by the formula: RO ( CH2CH2O ) n H wherein R is a saturated hydrocarbon group having 8 to 18 carbon atoms, and n is 5 to 18 to obtain the aqueous polytetrafluoroethylene dispersion B, wherein said amount of polyoxyethylene alkyl ether results in a concentration of 2 to 10 wt. %, based on the polytetrafluoroethylene, of the polyoxyethylene alkyl ether in the dispersion B. 28 2. The aqueous polytetrafluoroethylene dispersion B according to claim 1, wherein said ethylene oxide content of the polyoxyethylene alkyl ether is 65.5 to 68 wt %. 3. An article prepared by coating a base material with the aqueous polytetrafluoroethylene dispersion B as defined in claim 1 or 2. 4. A binder for batteries comprising the aqueous polytetrafluoroethylene dispersion B as defined in claim 1 or 2. 5. A coating composition comprising the aqueous polytetrafluoroethylene dispersion B as defined in claim 1 or 2, and a pigment, solvent or additive admixed therewith. 6. A process for preparing an aqueous polytetrafluoroethylene dispersion comprising the following steps: heating an aqueous polytetrafluoroethylene dispersion in the presence of a polyoxyethylene alkyl ether represented by the formula: RO ( CH2CH2O ) n H wherein R is a saturated hydrocarbon group having 8 to 18 carbon atoms, and n is 5 to 18, wherein said polyoxyethylene alkyl ether has a cloud point of over 49.degree.C to not higher than 85.degree.C and an ethylene oxide content of 65 to 70 wt.%, to separate the dispersion into two layers and obtain a concentrated aqueous polytetrafluoroethylene dispersion containing 30 to 65 wt.% of polytetrafluoroethylene; and 29 optionally, adding to the concentrated aqueous dispersion further polyoxyethylene alkyl ether to adjust the amount of polyoxyethylene alkyl ether to 2 to 10 wt.%, based on the polytetrafluoroethylene. 7. An aqueous polytetrafluoroethylene dispersion obtained by the process as defined in claim 6. 8. The aqueous dispersion according to claim 7, wherein said ethylene oxide content of the polyoxyethylene alkyl ether is 65.5 to 68 wt %. 9. An article prepared by coating a base material with the aqueous dispersion as defined in claim 7 or B. 10. A binder for batteries comprising the aqueous dispersion as defined in claim 7 or 8. 11. A coating composition comprising the aqueous dispersion as defined in claim 7 or 8, and a pigment, solvent or additive admixed therewith. 12. An aqueous dispersion composition comprising 30 to 65 wt. % of polytetrafluoroethylene and 2 to 10 wt % of a surfactant based on the polytetrafluoroethylene, wherein the surfactant comprises a polyoxyethylene alkyl ether represented by the formula: RO ( CH2CH2O ) n H wherein R is a saturated hydrocarbon group having 8 to 18 carbon atoms, and n is 5 to 18, wherein the surfactant has a cloud point of over 49.degree.C to not higher than 85.degree.C and 30 contains 65 to 70 wt. % of ethylene oxide in the polyoxyethylene alkyl ether molecule. 13. The aqueous dispersion composition according to claim 12, wherein said ethylene oxide content of the polyoxyethylene alkyl ether is 65.5 to 68 wt %. 14. An article prepared by coating a base material with the aqueous dispersion composition as defined in claim 12 or 13. 15. A binder for batteries comprising the aqueous dispersion composition as defined in claim 12 or 13. 16. A coating composition comprising the aqueous dispersion composition as defined in claim 12 or 13, and a pigment, solvent or additive admixed therewith.
CA002216404A 1995-03-31 1996-03-26 Aqueous polytetrafluoroethylene dispersion composition and use thereof Expired - Lifetime CA2216404C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP7/100606 1995-03-31
JP10060695A JP3346090B2 (en) 1995-03-31 1995-03-31 Polytetrafluoroethylene aqueous dispersion composition and use thereof
PCT/JP1996/000778 WO1996030445A1 (en) 1995-03-31 1996-03-26 Aqueous polytetrafluoroethylene dispersion composition and use thereof

Publications (2)

Publication Number Publication Date
CA2216404A1 CA2216404A1 (en) 1996-10-03
CA2216404C true CA2216404C (en) 2008-02-05

Family

ID=14278526

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002216404A Expired - Lifetime CA2216404C (en) 1995-03-31 1996-03-26 Aqueous polytetrafluoroethylene dispersion composition and use thereof

Country Status (9)

Country Link
US (1) US6153688A (en)
EP (1) EP0818506B9 (en)
JP (1) JP3346090B2 (en)
KR (1) KR100228448B1 (en)
CN (1) CN1125131C (en)
CA (1) CA2216404C (en)
DE (1) DE69608675T3 (en)
TW (1) TW340120B (en)
WO (1) WO1996030445A1 (en)

Families Citing this family (80)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1293779B1 (en) 1997-07-25 1999-03-10 Ausimont Spa FLUOROPOLYMER DISPERSIONS
EP1059333B1 (en) * 1998-02-24 2006-10-11 Asahi Glass Company, Limited Aqueous polytetrafluoroethylene dispersion composition
DE19857111A1 (en) * 1998-12-11 2000-06-15 Dyneon Gmbh Aqueous dispersions of fluoropolymers
KR100692163B1 (en) 1999-10-05 2007-03-12 다이낑 고오교 가부시키가이샤 Fluorine rubber vulcanizing aqueous composition and fluorine rubber coating
JP2006040543A (en) * 2000-09-04 2006-02-09 Daikin Ind Ltd Additives for electrodes used in batteries or capacitors
ITMI20010087A1 (en) * 2001-01-18 2002-07-18 Ausimont Spa WATER DISPERSION OF FLUOROPOLYMERS
WO2002064696A1 (en) * 2001-01-30 2002-08-22 Daikin Industries, Ltd. Water- and oil-repellent composition, process for producing the same and use thereof
JP5103702B2 (en) * 2001-07-30 2012-12-19 ダイキン工業株式会社 Resin aqueous dispersion composition
CN1229452C (en) * 2001-07-30 2005-11-30 大金工业株式会社 Aqueous dispersion composition for fluorine-containing resin paint
US7279522B2 (en) 2001-09-05 2007-10-09 3M Innovative Properties Company Fluoropolymer dispersions containing no or little low molecular weight fluorinated surfactant
BR0215428A (en) * 2002-01-04 2004-12-14 Du Pont Aqueous dispersion, aqueous dispersion coating composition, coated substrates and self-supporting film
JP2003338289A (en) * 2002-03-15 2003-11-28 Choichi Furuya Dispersion for gas diffusion electrode and method for producing the same
JP4207442B2 (en) * 2002-03-20 2009-01-14 旭硝子株式会社 Process for producing polytetrafluoroethylene aqueous dispersion composition
WO2003106556A1 (en) 2002-05-20 2003-12-24 ダイキン工業株式会社 Fluorinated resin water dispersion composition and fluorinated water base coating composition
US20040171726A1 (en) * 2003-02-03 2004-09-02 Joseph D'haenens Luk Germain Pierre Stabilized aqueous dispersion of fluoropolymer
DE60301322T2 (en) * 2003-02-28 2006-06-08 3M Innovative Properties Co., St. Paul A fluoropolymer dispersion containing no or little fluorine-containing low molecular weight wetting agent
US20040185728A1 (en) * 2003-03-21 2004-09-23 Optimer, Inc. Textiles with high water release rates and methods for making same
US7258925B2 (en) * 2003-07-11 2007-08-21 E.I. Du Pont De Nemours And Company Fluorochemical finishes for paint applicators
KR100794435B1 (en) * 2003-09-25 2008-01-16 로렐 프로덕츠, 엘엘씨 High Stability Polytetrafluoroethylene Dispersion and How to Obtain Them
DE60336400D1 (en) 2003-10-24 2011-04-28 3M Innovative Properties Co Aqueous dispersions of polytetrafluoroethylene particles
CA2545001C (en) * 2003-11-13 2010-07-06 Nova Wildcat Shur-Line, Llc Paint applicators including paint application element having non-stick coating
ATE529451T1 (en) 2003-11-17 2011-11-15 3M Innovative Properties Co AQUEOUS PTFE DISPERSIONS WITH A LOW CONTENT OF FLUORINATED EMULSIFIERS
US8178612B2 (en) * 2004-01-22 2012-05-15 E. I. Du Pont De Nemours And Company Fluoropolymer emulsion coatings
EP1570917B1 (en) * 2004-03-01 2009-06-10 3M Innovative Properties Company Method of coating a substrate with a fluoropolymer dispersion
JP4759931B2 (en) * 2004-04-21 2011-08-31 パナソニック株式会社 Method for producing non-aqueous electrolyte battery
JP4655041B2 (en) * 2004-06-25 2011-03-23 ダイキン工業株式会社 Soil release agent containing fluorine-containing copolymer and method for producing the same
US20070023360A1 (en) 2005-08-01 2007-02-01 Noelke Charles J Removing fluorosurfactant from aqueous fluoropolymer dispersion using sorbent pouches
US7790041B2 (en) 2004-08-11 2010-09-07 E.I. Du Pont De Nemours And Company Removing fluorosurfactant from aqueous fluoropolymer dispersions
WO2006035726A1 (en) * 2004-09-27 2006-04-06 Daikin Industries, Ltd. Aqueous polytetrafluoroethylene dispersion composition, poly- tetrafluoroethylene resin film, and products impregnated with polytetrafluoroethylene resin
US7659335B2 (en) * 2004-10-13 2010-02-09 Dupont-Mitsui Fluorochemicals Co Ltd Fluoropolymer dispersion and electrode composition containing same
WO2006043942A1 (en) 2004-10-15 2006-04-27 Dupont-Mitsui Fluorochemicals Co., Ltd. Fluoropolymer dispersion and electrode composition containing same
US20060135681A1 (en) 2004-12-22 2006-06-22 Cavanaugh Robert J Viscosity control for reduced fluorosurfactant aqueous fluoropolymer dispersions by the addition of cationic surfactant
US7666927B2 (en) * 2004-12-22 2010-02-23 E.I. Du Pont De Nemours And Company Removing fluorosurfactant from aqueous fluoropolymer dispersions using anion exchange polymer with functional groups resistant to degradation to trialkylamines
US7619018B2 (en) * 2004-12-22 2009-11-17 E.I. Du Pont De Nemours And Company Process for removing fluorosurfactant from aqueous fluoropolymer dispersions and reducing scum formation
US7659329B2 (en) * 2004-12-22 2010-02-09 E. I. Du Pont De Nemours And Company Removing fluorosurfactant from aqueous fluoropolymer dispersions using monodisperse ion exchange resin
US20060178472A1 (en) * 2005-02-10 2006-08-10 Johnson David W Process for producing low fluorosurfactant-containing aqueous fluoropolymer dispersions with controlled pH
US7671111B2 (en) * 2005-02-10 2010-03-02 E.I. Du Pont De Nemours And Company Monitoring column breakthrough in a process for removing fluorosurfactant from aqueous fluoropolymer dispersions
US20060183842A1 (en) * 2005-02-10 2006-08-17 Johnson David W Fluoropolymer dispersions with reduced fluorosurfactant content and high shear stability
CN101155858A (en) * 2005-04-13 2008-04-02 大金工业株式会社 Process for producing aqueous fluoropolymer dispersion
US7612139B2 (en) * 2005-05-20 2009-11-03 E.I. Du Pont De Nemours And Company Core/shell fluoropolymer dispersions with low fluorosurfactant content
US20060281845A1 (en) * 2005-06-10 2006-12-14 Ramin Amin-Sanayei Aqueous process for making fluoropolymers
JP5000109B2 (en) * 2005-07-13 2012-08-15 日本曹達株式会社 Binder for electrode preparation, electrode and polymer battery
GB0514398D0 (en) 2005-07-15 2005-08-17 3M Innovative Properties Co Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant
GB0525978D0 (en) 2005-12-21 2006-02-01 3M Innovative Properties Co Fluorinated Surfactants For Making Fluoropolymers
US20080015304A1 (en) 2006-07-13 2008-01-17 Klaus Hintzer Aqueous emulsion polymerization process for producing fluoropolymers
GB0523853D0 (en) 2005-11-24 2006-01-04 3M Innovative Properties Co Fluorinated surfactants for use in making a fluoropolymer
US7671112B2 (en) 2005-07-15 2010-03-02 3M Innovative Properties Company Method of making fluoropolymer dispersion
JP5141256B2 (en) * 2005-10-20 2013-02-13 旭硝子株式会社 Polytetrafluoroethylene aqueous dispersion and product thereof
US7728087B2 (en) 2005-12-23 2010-06-01 3M Innovative Properties Company Fluoropolymer dispersion and method for making the same
JP4521364B2 (en) * 2006-02-17 2010-08-11 ダイキン工業株式会社 Incombustible lighting cover
US7754795B2 (en) 2006-05-25 2010-07-13 3M Innovative Properties Company Coating composition
US20070282044A1 (en) * 2006-05-31 2007-12-06 Robert John Cavanaugh Concentrated fluoropolymer dispersions stabilized with anionic polyelectrolyte dispersing agents
US7666929B2 (en) 2006-05-31 2010-02-23 E.I. Du Pont De Nemours And Company Process for reducing fluorosurfactant content of fluropolymer dispersions using anionic surfactant-treated anion exchange resin
US7666928B2 (en) * 2006-05-31 2010-02-23 E.I. Du Pont De Nemours And Company Staged addition of non-fluorinated anionic surfactant to reduced fluorosurfactant fluoropolymer dispersion
US20090278092A1 (en) * 2006-06-29 2009-11-12 Daikin Industries, Ltd. Aqueous fluororesin dispersion and method for producing the same
JP5050442B2 (en) * 2006-07-12 2012-10-17 旭硝子株式会社 Polytetrafluoroethylene aqueous dispersion
US8119750B2 (en) 2006-07-13 2012-02-21 3M Innovative Properties Company Explosion taming surfactants for the production of perfluoropolymers
KR101453404B1 (en) 2006-08-09 2014-10-22 스미토모덴코파인폴리머 가부시키가이샤 Processes for production of fluororesin composite
US7956112B2 (en) * 2006-12-04 2011-06-07 E. I. Du Pont De Nemours And Company Aqueous fluoropolymer dispersion stabilized with amine oxide surfactant and process for making coagulated fluoropolymer resin
US20100160584A1 (en) * 2008-12-23 2010-06-24 E. I. Du Pont De Nemours And Company Ethylene-Tetrafluoroethylene Carboxylic Acids and Salts
US8058376B2 (en) * 2008-12-23 2011-11-15 E. I. Du Pont De Nemours And Company Fluoropolymer produced by aqueous polymerization using dispersed particulate of fluorinated lonomer produced in situ
US20100160552A1 (en) * 2008-12-23 2010-06-24 E. I. Du Pont De Nemours And Company Aqueous Polymerization of Fluorinated Monomer Using Hydrogen Containing Branched Fluoroether Surfactant
US8835547B2 (en) 2008-12-23 2014-09-16 E I Du Pont De Nemours And Company Fluoropolymer particles having a nucleus of fluorinated ionomer
US8436054B2 (en) * 2008-12-23 2013-05-07 E I Du Pont De Nemours And Company Fluorinated ionomer produced by aqueous polymerization using dispersed particulate of fluorinated ionomer produced in situ
US8436053B2 (en) * 2008-12-23 2013-05-07 E.I. Du Pont De Nemours And Company Fluorinated ionomer produced by aqueous polymerization using dispersed particulate of fluorinated ionomer
US8153738B2 (en) 2008-12-23 2012-04-10 E I Du Pont De Nemours And Company Fluoropolymer produced by aqueous polymerization using dispersed particulate of fluorinated ionomer
RU2522749C2 (en) 2009-07-31 2014-07-20 Зм Инновейтив Пропертиз Компани Fluoropolymer compounds containing multi-atomic compounds and methods of production thereof
CN102558721B (en) 2010-12-31 2014-08-20 杜邦公司 Novel polytetrafluoroethylene aqueous dispersion
JP5830782B2 (en) 2012-01-27 2015-12-09 住友電工ファインポリマー株式会社 Method for producing modified polytetrafluoroethylene microporous membrane and method for producing modified polytetrafluoroethylene porous resin membrane composite
JP5981188B2 (en) * 2012-03-28 2016-08-31 東レ株式会社 Method for producing polytetrafluoroethylene-impregnated yarn
EP2803691B1 (en) 2013-05-17 2016-04-20 3M Innovative Properties Company Fluoropolymer compositions containing a polyhydroxy surfactant
CN103326000B (en) * 2013-05-28 2015-05-13 遵义师范学院 Method for preparing composite material for cathode of lithium ion battery
WO2016020231A1 (en) * 2014-08-04 2016-02-11 Solvay Specialty Polymers Italy S.P.A. Powder composition
CN108431055A (en) 2015-12-17 2018-08-21 3M创新有限公司 Amine-containing polymer, its dispersion and preparation and use their method
KR101714996B1 (en) * 2016-03-16 2017-03-08 박상은 Composition of Coating for preventing the contamination
CN109216659B (en) * 2017-07-06 2022-01-11 宁德时代新能源科技股份有限公司 Binder, electrode plate using same and secondary battery
CN109575312B (en) * 2018-12-19 2021-11-05 山东东岳高分子材料有限公司 High-permeability and stable-viscosity fluoroplastic aqueous dispersion liquid and preparation method thereof
CN110180415A (en) * 2019-05-27 2019-08-30 武汉纳霏膜科技有限公司 A kind of method of hydrophilizing of reverse osmosis membrane
CN114787273A (en) * 2019-12-20 2022-07-22 Agc株式会社 Dispersion liquid, liquid composition and method for producing same
JP7740234B2 (en) * 2020-04-30 2025-09-17 Agc株式会社 Methods for producing dispersions, pastes and doughs

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3037953A (en) * 1961-04-26 1962-06-05 Du Pont Concentration of aqueous colloidal dispersions of polytetrafluoroethylene
CA930092A (en) 1970-09-15 1973-07-10 A. Holmes David Polytetrafluoroethylene aqueous dispersions which provide coatings of improved gloss
US3704272A (en) * 1970-09-15 1972-11-28 Du Pont Concentration of polytetrafluoroethylene aqueous dispersion
US3925292A (en) 1970-09-15 1975-12-09 Du Pont Polytetrafluoroethylene aqueous dispersions which provide coatings of improved gloss
US3705867A (en) * 1970-12-23 1972-12-12 Du Pont Reduced sludge formation in large particle tetrafluoroethylene polymer aqueous dispersion
CA1015885A (en) 1972-10-27 1977-08-16 Robert V. Poirier Storage stable aqueous dispersion of tetrafluoroethylene polymer
JPS5117914A (en) * 1974-07-24 1976-02-13 Daikin Ind Ltd HIFUKUYO SOSEIBUTSU
DE2908001C2 (en) 1979-03-01 1981-02-19 Hoechst Ag, 6000 Frankfurt Process for the preparation of concentrated dispersions of fluoropolymers
JPS6055070A (en) * 1983-09-06 1985-03-29 Mitsui Toatsu Chem Inc Adhesive composition
JP2730128B2 (en) * 1989-02-03 1998-03-25 日本合成ゴム株式会社 Thermosetting resin composition
JPH031442A (en) * 1989-05-30 1991-01-08 Shin Kobe Electric Mach Co Ltd Paste form cadmium negative electrode for alkaline storage battery
JPH03147254A (en) * 1989-11-01 1991-06-24 Toshiba Battery Co Ltd Nonaqueous solvent secondary battery
JPH0774318B2 (en) * 1990-10-30 1995-08-09 住友電気工業株式会社 Fluororesin coating composition
US5218031A (en) * 1991-06-10 1993-06-08 Man-Gill Chemical Company Aqueous coating compositions, process and coated substrates
JPH05320360A (en) * 1992-05-18 1993-12-03 Nippon Saafuakutanto Kogyo Kk Aqueous dispersion of fluororesin powder
JP3186218B2 (en) * 1992-05-20 2001-07-11 出光興産株式会社 Terminal vinyl ethylene-propylene copolymer and method for producing the same
JPH05339537A (en) * 1992-06-05 1993-12-21 Asahi I C I Furoro Polymer-Zu Kk Formation of coating film
JPH0846932A (en) * 1994-07-29 1996-02-16 Toshiba Corp Television signal system detection circuit

Also Published As

Publication number Publication date
DE69608675D1 (en) 2000-07-06
US6153688A (en) 2000-11-28
EP0818506B9 (en) 2010-05-26
CA2216404A1 (en) 1996-10-03
CN1180364A (en) 1998-04-29
JP3346090B2 (en) 2002-11-18
EP0818506A1 (en) 1998-01-14
EP0818506B2 (en) 2009-11-18
JPH08269285A (en) 1996-10-15
EP0818506A4 (en) 1998-07-15
EP0818506B1 (en) 2000-05-31
KR19980702625A (en) 1998-08-05
CN1125131C (en) 2003-10-22
TW340120B (en) 1998-09-11
DE69608675T2 (en) 2001-02-01
DE69608675T3 (en) 2010-06-10
WO1996030445A1 (en) 1996-10-03
KR100228448B1 (en) 1999-11-01

Similar Documents

Publication Publication Date Title
CA2216404C (en) Aqueous polytetrafluoroethylene dispersion composition and use thereof
US4546141A (en) Primer coating composition for topcoats of fluorocarbon polymers containing a polyarylene sulfide resin, an aromatic polyether-sulfone resin or an aromatic polyether-ketone resin
JP5239111B2 (en) Additive for electrodes
EP1470171B1 (en) Core-shell fluoropolymer dispersions
WO1999043750A1 (en) Aqueous polytetrafluoroethylene dispersion composition
US7361708B2 (en) Fluorinated resin water dispersion composition and fluorinated water base coating composition
EP0159268A2 (en) Fluoropolymer coating and casting compositions and films derived thereform
JPS6350383B2 (en)
CA2472175A1 (en) Concentrated fluoropolymer dispersions
EP0254269A2 (en) Polytetrafluoroethylene containing coating composition and use thereof
JP3552612B2 (en) Polytetrafluoroethylene aqueous dispersion composition, compounding composition, and method for producing coating film
JP2014508193A (en) A novel aqueous dispersion of polytetrafluoroethylene.
EP0395100A2 (en) Water and oil repellent composition
US20230287236A1 (en) Aqueous coating material composition and coated article
JP2022515059A (en) Vinylidene Fluoride Polymer Dispersion
CN109890884A (en) Coating composition
EP0043862A1 (en) Composition for coating fluoroplastics
CN117142771A (en) High-temperature-resistant easy-to-clean kitchen electric glass panel coating agent and preparation method thereof
CN107531846A (en) Fluorinated copolymer and the surface modifier of active ingredient is used as using it
JPWO2006035726A1 (en) Polytetrafluoroethylene aqueous dispersion composition, polytetrafluoroethylene resin film, and polytetrafluoroethylene resin impregnated body
KR100769324B1 (en) Polyaniline-containing composition and production method thereof
JP2001089624A (en) Polytetrafluoroethylene aqueous dispersion composition and method for producing coating film
JP2006117900A (en) Polytetrafluoroethylene aqueous dispersion composition, polytetrafluoroethylene resin film, and polytetrafluoroethylene resin impregnated body
JPS62199663A (en) Conductive paint composition
JPH0125506B2 (en)

Legal Events

Date Code Title Description
EEER Examination request
MKEX Expiry

Effective date: 20160329