WO2006095825A1 - Polytetrafluoroethylene aqueous dispersion composition, polytetrafluoroethylene resin film and polytetrafluoroethylene resin impregnated article - Google Patents

Polytetrafluoroethylene aqueous dispersion composition, polytetrafluoroethylene resin film and polytetrafluoroethylene resin impregnated article Download PDF

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Publication number
WO2006095825A1
WO2006095825A1 PCT/JP2006/304627 JP2006304627W WO2006095825A1 WO 2006095825 A1 WO2006095825 A1 WO 2006095825A1 JP 2006304627 W JP2006304627 W JP 2006304627W WO 2006095825 A1 WO2006095825 A1 WO 2006095825A1
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ptfe
aqueous dispersion
polytetrafluoroethylene
mass
dispersion composition
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PCT/JP2006/304627
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French (fr)
Japanese (ja)
Inventor
Yasukazu Nakatani
Toshirou Miura
Yasuhiko Sawada
Hiroshi Torii
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Daikin Industries, Ltd.
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Publication of WO2006095825A1 publication Critical patent/WO2006095825A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/02—Dextran; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/06—Pectin; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C08L89/005—Casein
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C08L89/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C08L89/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin, e.g. gelatin
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/034—Organic insulating material consisting of one material containing halogen

Definitions

  • the present invention relates to a polytetrafluoroethylene aqueous dispersion composition, a polytetrafluoroethylene resin film, and a polytetrafluoroethylene resin impregnated body.
  • Aqueous dispersion compositions containing polytetrafluoroethylene [PTFE] resin have been conventionally impregnated into glass fibers, carbon fibers, Kepler fibers (registered trademark), etc. It has been used for the production of impregnated bodies, and has also been used for film formation by coating and baking on an object to be coated in applications such as high-frequency printed circuit boards, conveyor belts, and packing.
  • PTFE polytetrafluoroethylene
  • a conventional aqueous dispersion composition containing a PTFE resin has a problem that the particles tend to settle due to the high true specific gravity of the PTFE resin particles.
  • There is a means to increase the viscosity of the system in order to suppress sedimentation of particles in the composition but there is not much room for considering the processing method of the composition such as impregnation and coating. Therefore, since the particles settled during the storage of the composition at rest, it was necessary to redisperse each use. Furthermore, if the standing period is long, the settled particles may aggregate and redispersion may not be possible.
  • a pyrolysis component such as a nonionic surfactant is 9 to 12 mass% with respect to the PTFE resin. What has been blended (for example, see Patent Document 1) has been proposed.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-89624
  • the object of the present invention is to provide polytetrafluorocarbon when the composition is stored at rest.
  • An object of the present invention is to provide a polytetrafluoroethylene aqueous dispersion composition in which sedimentation of ethylene resin particles is suppressed and redispersion is unnecessary or easy.
  • the present invention includes a polytetrafluoroethylene resin (A), a hydrocarbon nonionic compound (B), and a polysaccharide'polyamino acids (C), This is an ethylene aqueous dispersion composition.
  • the present invention is a polytetrafluoroethylene resin film obtained by coating the polytetrafluoroethylene aqueous dispersion composition on an object to be coated.
  • the present invention comprises an impregnated body and a coating obtained by impregnating the impregnated body with the polytetrafluoroethylene aqueous dispersion composition. Is the body.
  • the polytetrafluoroethylene [PTFE] aqueous dispersion composition of the present invention comprises a polytetrafluoroethylene [PTFE] resin (A), a hydrocarbon-based nonionic compound (B), and a polysaccharide / polyamino acids.
  • a PTFE aqueous dispersion composition comprising (C).
  • the PTFE aqueous dispersion composition of the present invention is not particularly limited, but is suitable as a coating composition.
  • the PTFE aqueous dispersion composition of the present invention is coated on the object to be coated or impregnated into the object to be impregnated, whereby the PTFE resin (A) force, It can be formed on the surface to be impregnated.
  • the PTFE resin (A) force It can be formed on the surface to be impregnated.
  • Coating and impregnation are generally performed by applying the PTFE aqueous dispersion composition of the present invention onto an object to be coated or immersing the object to be impregnated (referred to herein as “application” as a concept that may include application and immersion).
  • application as a concept that may include application and immersion.
  • the operation consists of drying by heating, etc., if necessary, and then baking to a temperature equal to or higher than the melting point of PTFE resin (A).
  • the PTFE aqueous dispersion composition of the present invention is excellent in static stability, and when the composition is stored at rest, the precipitation of PTFE resin (A) particles is suppressed, and redispersion is unnecessary or easy. It is a thing.
  • the aqueous PTFE dispersion composition of the present invention contains PTFE resin (A).
  • the PTFE resin (A) constitutes PTFE resin (A) particles.
  • the PTFE resin (A) particles are dispersed in an aqueous medium described later in the PTFE aqueous dispersion composition of the present invention.
  • the PTFE resin (A) is a resin having a tetrafluoroethylene [TFE] homopolymer and / or a modified polytetrafluoroethylene [modified PTFE] force.
  • the modified PTFE is a copolymer of TFE and a trace amount of monomer copolymerizable with TFE.
  • the trace amount of monomer include fluoroolefin, fluorinated (alkyl vinyl ether), cyclic fluorinated monomer, perfluoroalkylethylene, and the like.
  • Examples of the fluorination include perfluoro (alkyl butyl ether) [PAVE].
  • PAVE perfluoro (methyl butyl ether) [PMVE] and perfluoro (ethyl).
  • the trace monomer unit derived from the trace monomer is preferably in the range of 0.001 to 2 mass% of the total polymer chain of the modified PTFE.
  • the range is more preferable.
  • Specific properties include the transparency of processed products.
  • the trace monomer unit derived from the trace monomer is a powder obtained by coagulating, washing and drying a PTFE aqueous dispersion or a PTFE aqueous dispersion composition. It is a value obtained by performing infrared absorption spectrum measurement.
  • PP VE unit is a part of the molecular structure of the modified PTFE and is a part derived from PPVE, and is represented by _ [CF -CF (-0-C F)]-.
  • the PTFE resin (A) preferably has a number average molecular weight of 1 million to 20 million. More preferably, it is from 0,000 to 15 million.
  • the coating tends to be brittle, and when it exceeds 20 million, the melt viscosity is too high and the particles tend not to be fused.
  • the number average molecular weight can be determined by measuring by the method described in “Journal of Applied Polymer Science”, Vol. 17, pages 3253-3257 (1973).
  • the PTFE resin (A) particles preferably have an average particle diameter of 3 ⁇ 400 to 500 nm.
  • a more preferable lower limit of the average particle diameter is 220 nm, and a more preferable upper limit is 400 nm.
  • the film-forming property is remarkably improved.
  • it exceeds 500 nm the particles are liable to settle and the stability of the aqueous dispersion composition is lowered.
  • the average particle diameter is defined as the transmittance of projection light of 550 nm with respect to the unit length of the PTFE aqueous dispersion composition or PTFE aqueous dispersion prepared to a solid content concentration of 0.22 mass%. It is a value determined from the above transmittance based on a calibration curve with the average particle diameter determined by measuring the constant direction diameter in a transmission electron micrograph.
  • the PTFE aqueous dispersion composition of the present invention is preferably such that the PTFE resin (A) is 30 to 70% by mass of the PTFE aqueous dispersion composition. If it is less than 30% by mass, painting and impregnation may be required many times. If it exceeds 70% by mass, the viscosity may increase and handling may be difficult.
  • the concentration of the PTFE resin (A) is more preferably 40 mass% of the PTFE aqueous dispersion composition, more preferably 65 mass% of the PTFE aqueous dispersion composition.
  • the concentration of the PTFE resin (A) is 3 g of PTFE aqueous dispersion composition.
  • the mass of the residue obtained by drying at a temperature of 80 ° C. for 45 minutes was determined as a percentage of the mass of the PTFE aqueous dispersion composition before the drying.
  • the PTFE resin (A) is obtained by polymerizing TFE or TFE and the above-mentioned trace amount of monomer in the presence of an aqueous medium by a known polymerization method such as emulsion polymerization or suspension polymerization. Obtained by
  • It can be supplied by an aqueous PTFE dispersion.
  • the polymerization is preferably performed by emulsion polymerization.
  • aqueous medium used in the polymerization include water and a mixed liquid of water and a known water-soluble solvent.
  • the above polymerization can be carried out by appropriately setting conditions according to the type and amount of the PTFE resin (A) to be used and the type of emulsifier.
  • the PTFE aqueous dispersion composition of the present invention includes a hydrocarbon-based nonionic compound (B) and a polysaccharide 'polyamino acids (C) in addition to the PTFE resin (A).
  • the PTFE aqueous dispersion composition of the present invention comprises a protective colloid effect caused by adsorption of polysaccharide / polyamino acids (C) on the surface of PTFE resin (A) particles, and polysaccharides' polyamino acids (C ) It is thought that the ability S of PTFE resin (A) particles to exist stably in the composition can be achieved by loosely associating each other.
  • hydrocarbon-based nonionic compound (B) in the aqueous PTFE dispersion composition of the present invention include, for example, formula (I):
  • R is a linear or branched alkyl group having 8 to 19, and preferably 10 to 16 carbon atoms;
  • a 1 is a polyoxyalkylene chain having 8 to 58 carbon atoms
  • R is a linear or branched alkyl group having 2 to 13, preferably 4 to 12 carbon atoms;
  • a 1 is a polyoxyalkylene chain having 8 to 58 carbon atoms
  • the polyoxyalkylene alkyl phenyl ether represented by these is preferable.
  • the above A 1 is preferably a polyoxyalkylene chain having 4 to 20 oxyethylene units and 0 to 6 oxypropylene units.
  • hydrocarbon-based nonionic compound (B) examples include polyoxyalkylene alkyl ether represented by the above formula (I) and polyoxyalkylene alkyl phenyl ether represented by the above formula (II). You can use either one or both.
  • the polyoxyalkylene alkyl ether represented by the above formula (I) and the polyoxyalkylene alkyl phenyl ether represented by the above formula (II) only one kind each may be used, or two kinds The above may be used.
  • the polyoxyalkylene alkyl ether is represented by the formula (III):
  • x is an integer of 1 or more
  • y is an integer of 1 or more
  • N is an integer from 4 to 20
  • a polyoxyalkylene alkyl ether represented by
  • a 2 is preferably a polyoxyalkylene chain having 4 to 20 oxyethylene units and 0 to 6 oxypropylene units.
  • the polyoxyalkylene alkyl phenyl ether is represented by the formula (V):
  • a 3 is preferably a polyoxyalkylene chain having 4 to 20 oxyethylene units and 0 to 6 oxypropylene units.
  • Polyoxyalkylene alkyl phenyl ether represented by the following formula can be preferably used.
  • the hydrocarbon-based nonionic compound (B) is gradually decomposed from around 150 ° C in terms of film-forming properties of the resulting aqueous dispersion composition, and a temperature range of 350 to 400 ° C. When heated for about 5 minutes at 1 to 10% by weight, it is preferable that it remains before heating.
  • the hydrocarbon-based nonionic compound (B) preferably has an average HLB in the range of 10 to 16 and more preferably in the range of 11 to 15.
  • the H LB is a value calculated based on the Griffin equation.
  • the hydrocarbon-based nonionic compound (B) is preferably 2 to 12 parts by mass with respect to 100 parts by mass of the PTFE resin (A). If the hydrocarbon-based nonionic compound (B) is less than 2 parts by mass relative to 100 parts by mass of the PTFE resin (A), the stability of the composition may be impaired, and the PTFE resin (A) 100 parts by mass If the content exceeds 12 parts by weight, the physical properties of the PTFE coating may deteriorate, for example, the coating obtained using the aqueous dispersion composition may be colored.
  • hydrocarbon nonionic compound (B) with respect to 100 parts by mass of PTFE resin (A) is A more preferred lower limit is 3 parts by mass, a still more preferred lower limit is 4 parts by mass, and a more preferred upper limit is 10 parts by mass.
  • the polysaccharide 'polyamino acids (C) may be any of those obtained by synthesis or naturally occurring.
  • polysaccharides' polyamino acids may be those generally referred to as polysaccharides or polyamino acids, or may be derivatives of those generally referred to as polysaccharides or polyamino acids.
  • polyamino acids can include peptides and proteins. Examples of the above-mentioned “derivatives of what are generally called polysaccharides or polyamino acids” include etherified forms, esterified forms, hydroxyalkylated forms, salts, and the like that are chemically possible.
  • Examples of the above-mentioned polysaccharides' polyamino acids (C) include cellulose, starch, dextrin, alginic acid, dextran, xanthan gum, punoleran, chitosan, gum arabic, casein, guar gum, gelatin and vectin and these And at least one selected from the group consisting of derivatives.
  • polysaccharides-polyamino acids such polysaccharides-polyamino acids that are generally referred to as polysaccharides and / or derivatives of those generally referred to as polysaccharides are preferred.
  • the class (C) include cellulose, starch, dextrin, alginic acid, dextran, xanthan gum, punoleran, chitosan, gum arabic, guar gum and bectin, and derivatives thereof.
  • cellulose ether, Alginate, alginate, xanthan gum, chitosan, chitosan salt, hydroxypropyl chitosan and guar gum are preferred.
  • the polysaccharide / polyamino acids (C) are preferably those having an average molecular weight of 10,000 to 20,000,000. The higher the average molecular weight, the better the static stability. However, if the average molecular weight is too high, the viscosity of the aqueous dispersion may increase and handling may be difficult. A more preferred lower limit is 20,000, and a more preferred upper limit is 10 million.
  • the polysaccharides'polyamino acids (C) are preferably prepared and used in an aqueous dispersion or an aqueous solution.
  • the corresponding compound may be used alone. Two or more types may be used in combination.
  • the polysaccharides' polyamino acids (C) are preferably 0.00001 to:! Parts by mass with respect to 100 parts by mass of the PTFE resin (A).
  • PTFE resin (A) If it is less than 0.0001 part by mass relative to 100 parts by mass, the static stability may be insufficient, and 1 part by mass for 100 parts by mass of PTFE resin (A). If it exceeds, the viscosity of the composition becomes high and handling may be difficult.
  • a more preferred lower limit is 0.0001 parts by mass with respect to 100 parts by mass of the PTFE resin (A).
  • each amount of the hydrocarbon-based nonionic compound (B) and the polysaccharide 'polyamino acid (C) is determined by the concentration of the PTFE resin (A) and the PTFE aqueous dispersion of the present invention. From the amount blended when preparing the composition (including the blended amount when blended at the time of preparing the PTFE aqueous dispersion), it can be determined as the mass with respect to 100 parts by mass of the PTFE resin (A).
  • the aqueous PTFE dispersion composition of the present invention comprises the above-mentioned PTFE resin (A), hydrocarbon-based nonionic compound (B) and polysaccharide / polyamino acids (C) in an aqueous medium.
  • the aqueous medium is not particularly limited, and may be water, a mixed solution of water and a known water-soluble solvent, or the like, and may further contain an organic solvent. It is preferable that it is a thing.
  • the aqueous medium in the present invention for example, the aqueous medium in emulsion polymerization for obtaining the above-mentioned PTFE resin (A) can be used as it is.
  • the PTFE aqueous dispersion composition of the present invention may contain various known additives as long as the effects of the present invention are not impaired.
  • the additive include pigments, fillers, antifoaming agents, drying retarders, film-forming agents, leveling agents, repellency inhibitors, and film-forming aids.
  • the pigment is not particularly limited, and examples thereof include known pigments such as titanium oxide, carbon black, and bengara.
  • Examples of the antifoaming agent include toluene, xylene, and nonpolar solvents such as hydrocarbons having 9 to 11 carbon atoms.
  • Examples of the drying retarder include a solvent having a boiling point of about 200 to 300 ° C., and such a solvent is preferably a water-soluble solvent.
  • Examples of the film forming agent include acrylic resin and urethane resin.
  • leveling agent and repellency inhibitor examples include fluorine-based surfactants and silicone-based surfactants.
  • the PTFE aqueous dispersion composition of the present invention may be one that does not contain a pigment, and one that does not contain a heat-resistant resin other than the above-mentioned PTFE resin (A) is preferred.
  • the PTFE aqueous dispersion composition of the present invention preferably has a viscosity at 25 ° C of not more than 0.1 Pa's. If the viscosity is too high, handling may be difficult.
  • a more preferred upper limit is 0.06 Pa's, and if it is within the above range, it may be 0. OlPa's or more.
  • the viscosity is measured at a temperature of 25 ° C. according to JIS K 6893 using a B-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.).
  • the PTFE aqueous dispersion composition of the present invention is not particularly limited.
  • the hydrocarbon-based nonionic compound (B) while stirring the PTFE aqueous dispersion obtained by polymerization, the hydrocarbon-based nonionic compound (B), polysaccharides' Ability to prepare by adding and mixing amino acids (C) and other additives as desired.
  • the hydrocarbon-based nonionic compound (B) can also be added when preparing the PTFE aqueous dispersion.
  • the aqueous dispersion that is a polymerization product is added.
  • it may be added as a dispersant conventionally used for concentration, it is usually preferable to add it after preparation of the PTFE aqueous dispersion to adjust the viscosity of the target aqueous PTFE dispersion composition. Good.
  • Conditions for each of the above stirring, addition and mixing operations can be appropriately set depending on the components and amounts of the composition to be used, but it is preferably performed at a temperature of 5 to 30 ° C.
  • the PTFE aqueous dispersion composition of the present invention has the above-described configuration, it is excellent in stationary stability as described above.
  • the above-mentioned standing stability refers to the time-dependent change of the cloudy layer containing PTFE resin by leaving a graduated cylinder containing 100 ml of the PTFE aqueous dispersion composition at 25 ° C.
  • the volume of the transparent supernatant layer after 3 months is measured as a ratio (volume%) to the initial volume of 100 ml, and this is evaluated as a static stability index.
  • the static stability index is preferably 6.0% by volume or less.
  • a PTFE resin film obtained by coating the above-mentioned PTFE aqueous dispersion composition of the present invention on an object to be coated is also one aspect of the present invention.
  • the material to be coated is not particularly limited, and examples thereof include various metals, enamel, glass, various ceramics, and various heat-resistant resin molded products.
  • the object to be coated may have any shape.
  • the above coating can usually be performed by applying the PTFE aqueous dispersion composition of the present invention, drying and then baking.
  • the PTFE aqueous dispersion composition of the present invention may be directly coated on a substrate, but in order to improve adhesion to the substrate, a primer layer may be provided and formed as an overcoat layer. .
  • the application is not particularly limited, and can be performed by a known coating method such as a dating method, a spray method, a roll coating method, a doctor blade method, a flow coating method, or the like.
  • the drying can be appropriately set according to the type of hydrocarbon-based nonionic compound (B), polysaccharides' polyamino acids (C), etc. to be used, but room temperature to 150 ° C, preferably 80 to 1 It is preferably performed at a temperature of 50 ° C for 5 to 20 minutes.
  • the firing is generally at or above the melting temperature of the PTFE resin (A) used, usually 340-415.
  • Trowel capable of performing for 5-60 minutes S, capable of performing for 30-30 minutes at 360-400 ° C.
  • the PTFE resin film of the present invention may be peeled off from the object to be coated after the above-mentioned firing depending on the type of object to be coated. It may be in contact with an object through a primer layer or the like.
  • the PTFE resin film of the present invention is formed by coating the above-mentioned PTFE aqueous dispersion composition of the present invention, it is usually 5 ⁇ m or more, preferably about 10 to 100 ⁇ m. It has a thickness.
  • the PTFE resin film of the present invention can be obtained without particular limitation as long as the object to be coated does not substantially deteriorate upon firing.
  • the PTFE resin film obtained from the composition of the present invention can be suitably used as a coating material for high-frequency printed circuit boards, transport belts, packings, and the like.
  • a PTFE resin-impregnated body having an impregnated body and a film obtained by impregnating the above-mentioned impregnated body with the above-mentioned PTFE aqueous dispersion composition of the present invention is also one aspect of the present invention.
  • the impregnated material is not particularly limited, and examples thereof include a fiber base material, a woven fabric'nonwoven fabric, and the like.
  • the fiber substrate is not particularly limited, and examples thereof include glass fiber, carbon fiber, and aramid fiber (Kepler fiber (registered trademark), etc.).
  • the impregnation can be performed by a known method.
  • the coating film is formed by impregnating the above-mentioned PTFE aqueous dispersion composition of the present invention, the force depending on the shape and thickness of the substrate usually has a thickness of about 10 to 100 / im. .
  • the PTFE aqueous dispersion composition of the present invention has the above-described configuration, it has excellent stationary stability, and the sedimentation of PTFE resin particles can be suppressed when the composition is stored at rest. Distribution can be made unnecessary or easy.
  • the PTFE resin film of the present invention Since the PTFE resin film of the present invention has the above-described configuration, it can be easily formed into a uniform film free from defects such as foreign matters.
  • the PTFE resin impregnated body of the present invention has the above-described configuration, it is easy to form a uniform film free from defects such as foreign matters.
  • a graduated cylinder containing 100 ml of PTFE aqueous dispersion composition is allowed to stand at 25 ° C, the time-dependent change of the cloudy layer containing PTF E resin is observed, and the volume of the transparent supernatant layer after 3 months is measured. It was measured as a percentage (% by volume) with respect to the initial volume of 100 ml.
  • PTFE resin (A) As the PTFE resin (A), an aqueous PTFE dispersion having an average particle size of 325 nm and a PTFE resin (A) concentration [P. C.] of 30. 2% by mass was obtained by emulsion polymerization.
  • a concentrated PTFE aqueous dispersion was prepared in which PC was 69.5% by mass and the hydrocarbon-based nonionic compound (B) concentration [NC] was 2.9 parts by mass with respect to 100 parts by mass of PTFE resin (A).
  • PTFE resin (A) As the PTFE resin (A), an aqueous PTFE dispersion having an average particle size of 325 nm and a PTFE resin (A) concentration [P. C.] of 30. 2% by mass was obtained by emulsion polymerization.
  • PTFE resin (A) As the PTFE resin (A), an aqueous PTFE dispersion having an average particle size of 325 nm and a PTFE resin (A) concentration [P. C.] of 30. 2% by mass was obtained by emulsion polymerization.
  • the force S tried to concentrate in the liquid temperature range of 20 to 80 ° C, and it was never concentrated beyond the original concentration (30.2 mass%).
  • PTFE aqueous dispersion concentrate 300 g PTFE aqueous dispersion concentrate, Neugen TDS- 80 6.3 g, Guar gum aqueous dispersion as polysaccharide 'polyamino acids (C) (Mitsui Co., Ltd., molecular weight 200,000, resin concentration 2% by mass) 1.0 g , pure water 35. 5 g with added Caro, PC 60. 8 mass 0/0, NC force S PTFE Kitsuki effect (a) 9 parts by weight 5. 100 parts by mass, polysaccharides * polyamino acids (C PTFE resin (A) was 100 parts by weight of PTFE resin (A).
  • the viscosity of the resulting aqueous PTFE dispersion composition 2. 95 X 10- 2 Pa 's , standing stability index 4. was 1% by volume.
  • PTFE aqueous dispersion concentrate 300 g PTFE aqueous dispersion concentrate, Neugen TDS- 80 6.3 g, xanthan gum aqueous dispersion as polysaccharide 'polyamino acids (C) (Mitsui Co., Ltd., molecular weight 2 million, resin concentration 2 mass%) 1.0 g , pure water 35. 5 g with added Caro, 9 parts by mass 5.
  • PC 60. 8 mass 0/0 NC force SPTFE Kimune
  • a 100 parts by mass of a polysaccharide-polyamino acids (C) is PTFE resin
  • A An aqueous PTFE dispersion composition having a mass of 0.01 parts by mass with respect to 100 parts by mass was obtained.
  • the resulting PTFE aqueous dispersion composition has a viscosity of 3.70 X 10 " 2 Pa-s, and the static stability index is
  • PTFE aqueous dispersion concentrate 300 g PTFE aqueous dispersion concentrate, Neugen TDS-80 6.3 g, alginate aqueous dispersion as polysaccharide 'polyamino acids (C) (Kimiru Co., Ltd., molecular weight 100,000, resin concentration 2% by mass) 5. 2g, 35.5g of pure water are added, 60.1% by weight of PC, NC is 5.9 parts by weight with respect to 100 parts by weight of PTFE resin (A), polysaccharide'polyamino acids (C) is PTFE resin ( A) A PTFE aqueous dispersion composition in an amount of 0.05 part by mass with respect to 100 parts by mass was obtained.
  • the viscosity of the resulting aqueous PTFE dispersion composition 2. 70 X 10- 2 Pa 's , standing stability index was 5.0 vol%.
  • PTFE aqueous dispersion concentrate 300g, Neugen TDS- 80 6.3g, Hydroxypropylmethylcellulose aqueous dispersion as polysaccharide 'polyamino acids (C) (Shin-Etsu Chemical Co., Ltd., molecular weight 100,000, resin concentration 2% by mass) 10 4g, 35.5g of pure water, 59.2% by mass of PC, N.
  • C. is 5.9 parts by mass of 100% by mass of PTFE resin (A).
  • a PTFE aqueous dispersion composition in which C) was 0.1 part by mass with respect to 100 parts by mass of PTFE resin (A) was obtained.
  • the obtained PTFE aqueous dispersion composition had a viscosity of 2.80 ⁇ 10 ” 2 Pa-s and a static stability index of 5.6% by volume.
  • PTFE aqueous dispersion concentrate 300g, Neugen TDS- 80 6.3g, Chitosan aqueous dispersion as polysaccharide 'polyamino acids (C) (manufactured by Dainichi Seiki Co., Ltd., molecular weight 100,000, resin concentration 15% by mass) 0 . 7 g, pure water 35. 5 g with added Caro, PC 60. 9 mass 0/0, NC force SPTFE Kimune (a) 9 parts by weight 5. respect 10 0 parts by mass, polysaccharides' polyamino acids ( A PTFE aqueous dispersion composition in which C) was 0.05 parts by mass with respect to 100 parts by mass of the PTFE resin (A) was obtained.
  • C polysaccharide 'polyamino acids
  • Example 6 The glass fiber was impregnated with the PTFE aqueous dispersion composition prepared in Example 1 and fired to form an impregnated body.
  • the glass fiber used had a thickness of 50 ⁇ and a width of 30 cm, and was moved at a speed of 1.2 m / min.
  • the composition was maintained at 25 ° C when impregnated, the firing temperature was 380 ° C, and the firing time was 40 hours shorter.
  • the impregnation and baking were performed for 125 minutes to form an impregnated body having a coating thickness of 10 zm and a length of 150 m, but no foreign matter was observed.
  • Neugen TDS-80C had a solid content of 4% by mass when heated at 350 ° C. for 5 minutes, and the molded impregnated body was not colored.
  • the obtained PTFE aqueous dispersion composition had a viscosity of 2.70 ⁇ 10 ” 2 Pa-s and a static stability index of 9.8% by volume.
  • PTFE aqueous dispersion concentrate 300 g PTFE aqueous dispersion concentrate, Neugen TDS-80 6.3 g, polyvinyl alcohol aqueous dispersion (Nippon Vinegar's Poval, molecular weight 150,000, resin concentration 10% by mass) 4.2 g, pure water 35. the 5g and added Caro, PC 60. 3 mass 0/0, NC force ⁇ PTFE Kitsuki effect (a) 9 parts by 5. per 100 parts by weight, poly Bulle alcohols force SPTFE resin (a) 100 parts by weight A PTFE aqueous dispersion composition having a content of 0.2 parts by mass was obtained.
  • PTFE aqueous dispersion concentrate 300g, Neugen TDS- 80 6.3g, polyacrylic acid aqueous dispersion (manufactured by Nippon Pure Chemical Co., Ltd., molecular weight 1 million, resin concentration 5% by mass) 0.4g, pure water 35.5g and added Caro, 9 parts by mass 5.
  • PC 60 9 mass 0/0, NC force PTFE Kitsuki effect (A) 100 parts by mass of polyacrylic acid with respect to PTFE resin (A) 100 parts by mass of 0.
  • a PTFE aqueous dispersion composition of 01 parts by mass was obtained.
  • the resulting PTFE aqueous dispersion composition has a viscosity of 4. 50 X 10 " 2 Pa-s and a static stability index of
  • PTFE aqueous dispersion concentrate Neugen TDS- 80 6.3 g, polyethylene oxide aqueous dispersion (Madesei Chemical Co., Ltd., molecular weight 80,000, resin concentration 20% by mass) 7.3 g, pure water 35.5 g and Caro, PC 59. 7 wt 0/0, NC force PTFE Kitsuki effect (A) 9 parts by 5. per 100 parts by weight, 0.1 polyethylene O dimethylsulfoxide Whereas PTFE resin (A) 100 parts by mass of 7 A PTFE aqueous dispersion composition having a mass part was obtained.
  • PTFE aqueous dispersion concentrate 300 g PTFE aqueous dispersion concentrate, Neugen TDS- 80 6.3 g, polybulurpyrrolidone aqueous dispersion (manufactured by Nippon Shokubai Co., Ltd., molecular weight 1.1 million, resin concentration 20% by mass) 2. lg, pure water 35.5 g and Caro, PC 60. 6 wt 0/0, NC force SPTFE Kitsuki effect (A) 9 parts by 5. per 100 parts by weight of polyvinyl pyrrolidone PTFE resin (A) 0. 2 mass relative to 100 parts by weight Part of a PTFE aqueous dispersion composition was obtained.
  • the viscosity of the obtained PTFE aqueous dispersion composition was 3.15 ⁇ 10 ” 2 Pa-s, and the static stability index was 7.0% by volume.
  • the PTFE aqueous dispersion composition of the present invention has the above-described configuration, the settling of PTFE resin particles can be suppressed when the composition is stored at rest, and redispersion is unnecessary or easy. It can be.
  • the PTFE resin film of the present invention Since the PTFE resin film of the present invention has the above-described configuration, it can be easily formed into a uniform film free from defects such as foreign matters.
  • the PTFE resin-impregnated body of the present invention has the above-described configuration, it can be formed into a uniform film free from defects such as foreign matters.

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Abstract

Provided is a polytetrafluoroethylene [PTFE] aqueous dispersion composition, which is excellent in static stability, is inhibited in the precipitation of polytetrafluoroethylene [PTFE] resin particles when it is stored in static state, and thus requires no operation for re-dispersion or can be re-dispersed with ease. A polytetrafluoroethylene [PTFE] aqueous dispersion composition, characterized in that it comprises a polytetrafluoroethylene [PTFE] resin (A), a hydrocarbon based non-ionic compound (B) and a polysaccharide/polyamino acid (C).

Description

明 細 書  Specification
ポリテトラフルォロエチレン水性分散液組成物、ポリテトラフルォロェチレ ン榭脂フィルム及びポリテトラフルォロエチレン樹脂含浸体  Polytetrafluoroethylene aqueous dispersion composition, polytetrafluoroethylene resin film, and polytetrafluoroethylene resin impregnated body
技術分野  Technical field
[0001] 本発明は、ポリテトラフルォロエチレン水性分散液組成物、ポリテトラフルォロェチレ ン樹脂フィルム及びポリテトラフルォロエチレン樹脂含浸体に関する。  The present invention relates to a polytetrafluoroethylene aqueous dispersion composition, a polytetrafluoroethylene resin film, and a polytetrafluoroethylene resin impregnated body.
背景技術  Background art
[0002] ポリテトラフルォロエチレン〔PTFE〕樹脂を含む水性分散液組成物は、従来、ガラス 繊維、カーボン繊維、ケプラー繊維 (登録商標）等に含浸して膜構造建築物の屋根 材等の含浸体の製造に用いられ、また、高周波プリント基板、搬送用ベルト、パツキ ン等の用途において、被塗装物上に塗布し焼成することよりなるフィルム形成に用い られてきた。  [0002] Aqueous dispersion compositions containing polytetrafluoroethylene [PTFE] resin have been conventionally impregnated into glass fibers, carbon fibers, Kepler fibers (registered trademark), etc. It has been used for the production of impregnated bodies, and has also been used for film formation by coating and baking on an object to be coated in applications such as high-frequency printed circuit boards, conveyor belts, and packing.
[0003] 従来の PTFE樹脂を含む水性分散液組成物では、 PTFE樹脂粒子の高い真比重の ために粒子が沈降しやすいという課題があった。組成物中の粒子の沈降を抑えるに は系の粘度を高める手段があるが、含浸、塗装といった組成物の加工法を考慮する と、その余地は大きくない。したがって、組成物を静置保存している間にも粒子が沈 降するために、使用毎に再分散させるなどの必要があった。さらに、静置期間が長く なれば沈降した粒子が凝集し、再分散が不可能となることもあった。  [0003] A conventional aqueous dispersion composition containing a PTFE resin has a problem that the particles tend to settle due to the high true specific gravity of the PTFE resin particles. There is a means to increase the viscosity of the system in order to suppress sedimentation of particles in the composition, but there is not much room for considering the processing method of the composition such as impregnation and coating. Therefore, since the particles settled during the storage of the composition at rest, it was necessary to redisperse each use. Furthermore, if the standing period is long, the settled particles may aggregate and redispersion may not be possible.
[0004] このような静置安定性の改善を目的とした PTFEの水性分散液組成物としては、非ィ オン系界面活性剤などの熱分解成分を PTFE樹脂に対して 9〜： 12質量％配合した もの (例えば、特許文献 1参照)等が提案されてレ、る。  [0004] As an aqueous dispersion composition of PTFE for the purpose of improving the standing stability, a pyrolysis component such as a nonionic surfactant is 9 to 12 mass% with respect to the PTFE resin. What has been blended (for example, see Patent Document 1) has been proposed.
[0005] し力しながら、このような PTFEの水性分散液組成物は静置安定性が依然として低く 、 PTFE樹脂粒子の沈降を十分には防止できない問題があった。  [0005] However, such an aqueous dispersion composition of PTFE still has a low standing stability, and there is a problem that the precipitation of PTFE resin particles cannot be sufficiently prevented.
[0006] 特許文献 1 :特開 2001— 89624号公報  [0006] Patent Document 1: Japanese Patent Laid-Open No. 2001-89624
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0007] 本発明の目的は、上記現状に鑑み、組成物を静置保存する際にポリテトラフルォロ エチレン樹脂粒子の沈降が抑えられ、再分散が不要、あるいは容易であるポリテトラ フルォロエチレン水性分散液組成物を提供することにある。 [0007] In view of the above-mentioned present situation, the object of the present invention is to provide polytetrafluorocarbon when the composition is stored at rest. An object of the present invention is to provide a polytetrafluoroethylene aqueous dispersion composition in which sedimentation of ethylene resin particles is suppressed and redispersion is unnecessary or easy.
課題を解決するための手段  Means for solving the problem
[0008] 本発明は、ポリテトラフルォロエチレン樹脂 (A)、炭化水素系非イオン性化合物 (B) 及び多糖類'ポリアミノ酸類（C)を含むことを特徴とするポリテトラフルォロエチレン水 性分散液組成物である。  [0008] The present invention includes a polytetrafluoroethylene resin (A), a hydrocarbon nonionic compound (B), and a polysaccharide'polyamino acids (C), This is an ethylene aqueous dispersion composition.
[0009] 本発明は、被塗装物上に上記ポリテトラフルォロエチレン水性分散液組成物を塗装 することにより得られることを特徴とするポリテトラフルォロエチレン樹脂フィルムである  [0009] The present invention is a polytetrafluoroethylene resin film obtained by coating the polytetrafluoroethylene aqueous dispersion composition on an object to be coated.
[0010] 本発明は、被含浸体と、上記被含浸体に上記ポリテトラフルォロエチレン水性分散液 組成物を含浸することにより得られる被膜とを有することを特徴とするポリテトラフルォ 口エチレン樹脂含浸体である。 [0010] The present invention comprises an impregnated body and a coating obtained by impregnating the impregnated body with the polytetrafluoroethylene aqueous dispersion composition. Is the body.
以下に本発明を詳細に説明する。  The present invention is described in detail below.
[0011] 本発明のポリテトラフルォロエチレン〔PTFE〕水性分散液組成物は、ポリテトラフルォ 口エチレン〔PTFE〕樹脂 (A)、炭化水素系非イオン性化合物 (B)及び多糖類 ·ポリア ミノ酸類（C)を含む PTFE水性分散液組成物である。  [0011] The polytetrafluoroethylene [PTFE] aqueous dispersion composition of the present invention comprises a polytetrafluoroethylene [PTFE] resin (A), a hydrocarbon-based nonionic compound (B), and a polysaccharide / polyamino acids. A PTFE aqueous dispersion composition comprising (C).
[0012] 本発明の PTFE水性分散液組成物は、特に限定されないが、コーティング用組成物 として好適である。コーティング用組成物として用いる際、本発明の PTFE水性分散 液組成物を被塗装物上に塗装又は被含浸体に含浸することにより、 PTFE樹脂 (A) 力、らなる被膜を被塗装物上又は被含浸体表面上に形成することができる。本明細書 において、上記被塗装物と被含浸体との両方を含み得る概念として「基材」ということ 力 Sある。塗装及び含浸は、一般に、本発明の PTFE水性分散液組成物を被塗装物 上に塗布し又は被含浸体を浸漬し (本明細書において、塗布及び浸漬を含み得る概 念として「適用」ということがある）、必要に応じて加熱等を行うことにより乾燥し、次い で、 PTFE樹脂 (A)の融点以上の温度に焼成することよりなる操作をいう。  [0012] The PTFE aqueous dispersion composition of the present invention is not particularly limited, but is suitable as a coating composition. When used as a coating composition, the PTFE aqueous dispersion composition of the present invention is coated on the object to be coated or impregnated into the object to be impregnated, whereby the PTFE resin (A) force, It can be formed on the surface to be impregnated. In this specification, there is a force S called “base material” as a concept that can include both the object to be coated and the object to be impregnated. Coating and impregnation are generally performed by applying the PTFE aqueous dispersion composition of the present invention onto an object to be coated or immersing the object to be impregnated (referred to herein as “application” as a concept that may include application and immersion). In some cases, the operation consists of drying by heating, etc., if necessary, and then baking to a temperature equal to or higher than the melting point of PTFE resin (A).
[0013] 本発明の PTFE水性分散液組成物は、静置安定性に優れ、組成物を静置保存する 際に PTFE樹脂 (A)粒子の沈降が抑えられ、再分散が不要又は容易であるものであ る。 [0014] 本発明の PTFE水性分散液組成物は、 PTFE樹脂 (A)を含むものである。 [0013] The PTFE aqueous dispersion composition of the present invention is excellent in static stability, and when the composition is stored at rest, the precipitation of PTFE resin (A) particles is suppressed, and redispersion is unnecessary or easy. It is a thing. [0014] The aqueous PTFE dispersion composition of the present invention contains PTFE resin (A).
本発明の PTFE水性分散液組成物において、上記 PTFE樹脂 (A)は、 PTFE樹脂（ A)粒子を構成している。該 PTFE樹脂 (A)粒子は、本発明の PTFE水性分散液組 成物において後述の水性媒体中に分散している。  In the PTFE aqueous dispersion composition of the present invention, the PTFE resin (A) constitutes PTFE resin (A) particles. The PTFE resin (A) particles are dispersed in an aqueous medium described later in the PTFE aqueous dispersion composition of the present invention.
[0015] 本明細書にぉレ、て、 PTFE樹脂（A)は、テトラフルォロエチレン〔TFE〕単独重合体 及び/又は変性ポリテトラフルォロエチレン〔変性 PTFE〕力 なる樹脂である。  In the present specification, the PTFE resin (A) is a resin having a tetrafluoroethylene [TFE] homopolymer and / or a modified polytetrafluoroethylene [modified PTFE] force.
[0016] 上記変性 PTFEは、 TFEと、 TFEと共重合可能な微量の単量体との共重合体である 。上記微量の単量体としては、例えば、フルォロォレフイン、フッ素化（アルキルビニ ルエーテル）、環式のフッ素化された単量体、パーフルォロアルキルエチレン等が挙 げられる。  [0016] The modified PTFE is a copolymer of TFE and a trace amount of monomer copolymerizable with TFE. Examples of the trace amount of monomer include fluoroolefin, fluorinated (alkyl vinyl ether), cyclic fluorinated monomer, perfluoroalkylethylene, and the like.
[0017] 上記フッ素化（アルキルビュルエーテル）としては、例えば、パーフルォロ（アルキル ビュルエーテル） [PAVE]が挙げられ、上記 PAVEとしては、例えば、パーフルォロ（ メチルビュルエーテル） [PMVE]、パーフルォロ（ェチルビニルエーテル） [PEVE] 、パーフルォロ（プロピルビエルエーテル） [PPVE]等が挙げられる。  [0017] Examples of the fluorination (alkyl butyl ether) include perfluoro (alkyl butyl ether) [PAVE]. Examples of the PAVE include perfluoro (methyl butyl ether) [PMVE] and perfluoro (ethyl). Vinyl ether) [PEVE] and perfluoro (propyl biether) [PPVE].
[0018] 上記微量の単量体に由来する微量単量体単位は、変性 PTFEのポリマー鎖全体の 0. 001〜2質量％の範囲であることが好ましぐ 0. 01〜1質量％の範囲であることが より好ましい。上記微量単量体単位が上記範囲内であると、一般的に溶融成形でき ないという特徴をもちながらも TFE単独共重合体では達成不可能な性状を有する加 ェ品が得られるという効果がある。具体的な性状としては、加工品の透明性などが挙 げられる。  [0018] The trace monomer unit derived from the trace monomer is preferably in the range of 0.001 to 2 mass% of the total polymer chain of the modified PTFE. The range is more preferable. When the amount of the monomer unit is within the above range, there is an effect that it is possible to obtain an additive having properties that cannot be achieved with a TFE homopolymer, while generally having a feature that it cannot be melt-molded. . Specific properties include the transparency of processed products.
[0019] 本明細書において、上記微量の単量体に由来する微量単量体単位は、 PTFE水性 分散体又は PTFE水性分散液組成物を凝析、洗浄、乾燥して得られたパウダーを用 いて、赤外吸収スペクトル測定を行って得られた値である。  [0019] In the present specification, the trace monomer unit derived from the trace monomer is a powder obtained by coagulating, washing and drying a PTFE aqueous dispersion or a PTFE aqueous dispersion composition. It is a value obtained by performing infrared absorption spectrum measurement.
[0020] 本明細書にぉレ、て、上記微量単量体単位等の「単量体単位」は、変性 PTFEの分子 構造上の一部分であって、対応する単量体に由来する部分を意味する。例えば、 PP VE単位は、変性 PTFEの分子構造上の一部分であって、 PPVEに由来する部分で あり、 _ [CF -CF (-0-C F ) ]—で表される。  [0020] As used herein, "monomer unit" such as the above-mentioned trace monomer unit is a part of the molecular structure of the modified PTFE and is a part derived from the corresponding monomer. means. For example, the PP VE unit is a part of the molecular structure of the modified PTFE and is a part derived from PPVE, and is represented by _ [CF -CF (-0-C F)]-.
2 3 7  2 3 7
[0021] 上記 PTFE樹脂 (A)は、数平均分子量が 100万〜 2000万であることが好ましぐ 15 0万〜 1500万であることがより好ましい。 [0021] The PTFE resin (A) preferably has a number average molecular weight of 1 million to 20 million. More preferably, it is from 0,000 to 15 million.
上記数平均分子量が 100万未満であると、被膜が脆くなる傾向があり、 2000万を超 えると、溶融粘度が高すぎて粒子同士が融着しにくくなる傾向がある。  When the number average molecular weight is less than 1 million, the coating tends to be brittle, and when it exceeds 20 million, the melt viscosity is too high and the particles tend not to be fused.
本明細書において、上記数平均分子量は、 journal of Applied Polymer Sci ence」第 17卷、第 3253〜3257頁（1973)に記載の方法により測定して求めること ができる。  In the present specification, the number average molecular weight can be determined by measuring by the method described in “Journal of Applied Polymer Science”, Vol. 17, pages 3253-3257 (1973).
[0022] 本発明の PTFE水性分散液組成物にぉレ、て、 PTFE樹脂 (A)粒子は、平均粒子径 力 ¾00〜500nmであるものが好ましレ、。上記平均粒子径のより好ましい下限は 220 nmであり、より好ましい上限は 400nmである。 200nm以上であると、造膜性が飛躍 的に高まるが、 500nmを超えると、粒子が沈降しやすくなり、水性分散液組成物の 安定性が低下する。  In the aqueous PTFE dispersion composition of the present invention, the PTFE resin (A) particles preferably have an average particle diameter of ¾00 to 500 nm. A more preferable lower limit of the average particle diameter is 220 nm, and a more preferable upper limit is 400 nm. When it is 200 nm or more, the film-forming property is remarkably improved. However, when it exceeds 500 nm, the particles are liable to settle and the stability of the aqueous dispersion composition is lowered.
[0023] 本明細書において、上記平均粒子径は、固形分濃度 0. 22質量％に調製した PTF E水性分散液組成物又は PTFE水性分散体の単位長さに対する 550nmの投射光 の透過率と、透過型電子顕微鏡写真における定方向径を測定して決定された平均 粒径との検量線をもとにして、上記透過率から決定した値である。  [0023] In the present specification, the average particle diameter is defined as the transmittance of projection light of 550 nm with respect to the unit length of the PTFE aqueous dispersion composition or PTFE aqueous dispersion prepared to a solid content concentration of 0.22 mass%. It is a value determined from the above transmittance based on a calibration curve with the average particle diameter determined by measuring the constant direction diameter in a transmission electron micrograph.
[0024] 本発明の PTFE水性分散液組成物は、 PTFE樹脂 (A)が PTFE水性分散液組成物 の 30〜70質量％であるものが好ましい。 30質量％未満であると、塗装、含浸を多数 回要する場合があり、 70質量％を超えると、粘度が高くなり取扱いが困難となることが ある。  [0024] The PTFE aqueous dispersion composition of the present invention is preferably such that the PTFE resin (A) is 30 to 70% by mass of the PTFE aqueous dispersion composition. If it is less than 30% by mass, painting and impregnation may be required many times. If it exceeds 70% by mass, the viscosity may increase and handling may be difficult.
上記 PTFE樹脂 (A)濃度は、より好ましい下限が PTFE水性分散液組成物の 40質 量％、より好ましレ、上限が PTFE水性分散液組成物の 65質量％である。  The concentration of the PTFE resin (A) is more preferably 40 mass% of the PTFE aqueous dispersion composition, more preferably 65 mass% of the PTFE aqueous dispersion composition.
[0025] 本明細書にぉレ、て、上記 PTFE樹脂 (A)濃度は、 PTFE水性分散液組成物 10gを 3[0025] In the present specification, the concentration of the PTFE resin (A) is 3 g of PTFE aqueous dispersion composition.
80°Cの温度にて 45分間乾燥して得られた残渣の質量を、該乾燥前の上記 PTFE水 性分散液組成物の質量に占める割合の百分率として求めたものである。 The mass of the residue obtained by drying at a temperature of 80 ° C. for 45 minutes was determined as a percentage of the mass of the PTFE aqueous dispersion composition before the drying.
[0026] 上記 PTFE樹脂（A)は、 TFE、又は、 TFEと上述の微量の単量体とを、乳化重合、 懸濁重合等、公知の重合方法にて水性媒体の存在下に重合することにより得られる[0026] The PTFE resin (A) is obtained by polymerizing TFE or TFE and the above-mentioned trace amount of monomer in the presence of an aqueous medium by a known polymerization method such as emulsion polymerization or suspension polymerization. Obtained by
PTFE水性分散体により供給することができる。 It can be supplied by an aqueous PTFE dispersion.
上記重合は、乳化重合にて行うことが好ましい。 上記重合において、使用する水性媒体としては、例えば、水、水と公知の水溶性溶 媒との混合液等が挙げられる。 The polymerization is preferably performed by emulsion polymerization. Examples of the aqueous medium used in the polymerization include water and a mixed liquid of water and a known water-soluble solvent.
上記重合は、使用する PTFE樹脂 (A)の種類及び量、並びに、乳化剤の種類等に 応じて、条件を適宜設定して行うことができる。  The above polymerization can be carried out by appropriately setting conditions according to the type and amount of the PTFE resin (A) to be used and the type of emulsifier.
[0027] 本発明の PTFE水性分散液組成物は、上記 PTFE樹脂 (A)にカ卩え、炭化水素系非 イオン性化合物（B)及び多糖類 'ポリアミノ酸類（C)をも含むものである。 [0027] The PTFE aqueous dispersion composition of the present invention includes a hydrocarbon-based nonionic compound (B) and a polysaccharide 'polyamino acids (C) in addition to the PTFE resin (A).
[0028] 本発明の PTFE水性分散液組成物は、 PTFE樹脂 (A)粒子表面に多糖類 ·ポリアミ ノ酸類 (C)が吸着することによる保護コロイド効果、及び、多糖類'ポリアミノ酸類 (C) 同士が緩やかに会合することにより、 PTFE樹脂 (A)粒子が組成物中で安定して存 在すること力 Sできるものと考えられる。 [0028] The PTFE aqueous dispersion composition of the present invention comprises a protective colloid effect caused by adsorption of polysaccharide / polyamino acids (C) on the surface of PTFE resin (A) particles, and polysaccharides' polyamino acids (C ) It is thought that the ability S of PTFE resin (A) particles to exist stably in the composition can be achieved by loosely associating each other.
[0029] 本発明の PTFE水性分散液組成物中における炭化水素系非イオン性化合物（B)と しては、例えば、式 (I)： [0029] Examples of the hydrocarbon-based nonionic compound (B) in the aqueous PTFE dispersion composition of the present invention include, for example, formula (I):
R— O— A1— H (I) R— O— A 1 — H (I)
(式中、 Rは、直鎖状又は分岐鎖状の炭素数 8〜19、好ましくは 10〜： 16のアルキル 基; A1は、炭素数 8〜58のポリオキシアルキレン鎖） (Wherein R is a linear or branched alkyl group having 8 to 19, and preferably 10 to 16 carbon atoms; A 1 is a polyoxyalkylene chain having 8 to 58 carbon atoms)
で表されるポリオキシアルキレンアルキルエーテルや、式（II)：  Or a polyoxyalkylene alkyl ether represented by formula (II):
R-C H一〇一 A1— H (II) RC H1001 A 1 — H (II)
6 4  6 4
(式中、 Rは、直鎖状又は分岐鎖状の炭素数 2〜13、好ましくは 4〜： 12のアルキル基 ； A1は、炭素数 8〜58のポリオキシアルキレン鎖） (Wherein R is a linear or branched alkyl group having 2 to 13, preferably 4 to 12 carbon atoms; A 1 is a polyoxyalkylene chain having 8 to 58 carbon atoms)
で表されるポリオキシアルキレンアルキルフエニルエーテルが好ましい。  The polyoxyalkylene alkyl phenyl ether represented by these is preferable.
上記 A1としては、 4〜20個のォキシエチレン単位及び 0〜6個のォキシプロピレン単 位を有するポリオキシアルキレン鎖が好ましレ、。 The above A 1 is preferably a polyoxyalkylene chain having 4 to 20 oxyethylene units and 0 to 6 oxypropylene units.
[0030] 上記炭化水素系非イオン性化合物（B)としては、上記式 (I)で表されるポリオキシァ ルキレンアルキルエーテル及び上記式（II)で表されるポリオキシアルキレンアルキル フエニルエーテルを何れか一方のみを用いてもよいし、両方とも用いてもよレ、。また、 上記式 (I)で表されるポリオキシアルキレンアルキルエーテル及び上記式 (II)で表さ れるポリオキシアルキレンアルキルフエニルエーテルとしては、それぞれ、 1種のみを 用いてもよいし、 2種以上を用いてもよい。 [0031] 上記ポリオキシアルキレンアルキルエーテルとしては、式（III)： [0030] Examples of the hydrocarbon-based nonionic compound (B) include polyoxyalkylene alkyl ether represented by the above formula (I) and polyoxyalkylene alkyl phenyl ether represented by the above formula (II). You can use either one or both. In addition, as the polyoxyalkylene alkyl ether represented by the above formula (I) and the polyoxyalkylene alkyl phenyl ether represented by the above formula (II), only one kind each may be used, or two kinds The above may be used. [0031] The polyoxyalkylene alkyl ether is represented by the formula (III):
C H CH (C H ) C H 0 (C H O) H (III)  C H CH (C H) C H 0 (C H O) H (III)
x 2x+ l y 2y+ l z 2z 2 4 n  x 2x + l y 2y + l z 2z 2 4 n
(式中、 xは 1以上の整数、 yは 1以上の整数、 zは 0又は 1以上の整数、但し、 x、 y及 び zは x + y + z = 7〜： 18の関係にある。 nは、 4〜20の整数である）  (In the formula, x is an integer of 1 or more, y is an integer of 1 or more, z is 0 or an integer of 1 or more, provided that x, y and z are in a relationship of x + y + z = 7 to 18: N is an integer from 4 to 20)
で表わされるポリオキシエチレンアルキルエーテル、及び/又は、式（IV)：  And / or formula (IV):
C H -0-A2-H (IV) CH -0-A 2 -H (IV)
p 2p + l  p 2p + l
(式中、 pは 8〜19の整数、 A2は、炭素数 13〜46のポリオキシアルキレン鎖である。 ) で表わされるポリオキシアルキレンアルキルエーテルが好適に使用できる。 (Wherein p is an integer of 8 to 19 and A 2 is a polyoxyalkylene chain having 13 to 46 carbon atoms.) A polyoxyalkylene alkyl ether represented by
上記式（IV)において、 A2は、 4〜20個のォキシエチレン単位及び 0〜6個のォキシ プロピレン単位を有するポリオキシアルキレン鎖が好ましい。 In the above formula (IV), A 2 is preferably a polyoxyalkylene chain having 4 to 20 oxyethylene units and 0 to 6 oxypropylene units.
上記ポリオキシアルキレンアルキルフエニルエーテルとしては、式 (V)：  The polyoxyalkylene alkyl phenyl ether is represented by the formula (V):
C H -C H -0-A3-H (V) CH -CH -0-A 3 -H (V)
q 2q+ l 6 4  q 2q + l 6 4
(式中、 qは 2〜： 13、好ましくは 4〜12の整数、 A3は、 4〜20個のォキシエチレン単位 及び 0〜6個のォキシプロピレン単位を有するポリオキシアルキレン鎖が好ましレ、。 ) で表わされるポリオキシアルキレンアルキルフエニルエーテルが好適に使用できる。 (Wherein q is an integer of 2 to: 13, preferably 4 to 12, and A 3 is preferably a polyoxyalkylene chain having 4 to 20 oxyethylene units and 0 to 6 oxypropylene units. Polyoxyalkylene alkyl phenyl ether represented by the following formula can be preferably used.
[0032] 上記炭化水素系非イオン性化合物（B)は、得られる水性分散液組成物の造膜性の 点で、 150°C前後から徐々に分解が始まり、 350〜400°Cの温度範囲で 5分程度加 熱した場合、加熱前の 1〜 10質量％残存するものが好ましレ、。  [0032] The hydrocarbon-based nonionic compound (B) is gradually decomposed from around 150 ° C in terms of film-forming properties of the resulting aqueous dispersion composition, and a temperature range of 350 to 400 ° C. When heated for about 5 minutes at 1 to 10% by weight, it is preferable that it remains before heating.
上記炭化水素系非イオン性化合物（B)は、平均 HLBが 10〜： 16の範囲にあることが 好ましぐさらに 11〜： 15の範囲にあることがより好ましレ、。本明細書において、上記 H LBは、 Griffinの式に基づき算出した値である。  The hydrocarbon-based nonionic compound (B) preferably has an average HLB in the range of 10 to 16 and more preferably in the range of 11 to 15. In the present specification, the H LB is a value calculated based on the Griffin equation.
[0033] 本発明の PTFE水性分散液組成物において、炭化水素系非イオン性化合物（B)は PTFE樹脂 (A) 100質量部に対して 2〜： 12質量部であることが好ましい。炭化水素 系非イオン性化合物（B)が PTFE樹脂 (A) 100質量部に対して 2質量部未満である と、組成物の安定性が損なわれることがあり、 PTFE樹脂 (A) 100質量部に対して 12 質量部を超えると、水性分散液組成物を用いて得られる被膜が着色するなど、 PTF E被膜としての物性が低下することがある。  [0033] In the aqueous PTFE dispersion composition of the present invention, the hydrocarbon-based nonionic compound (B) is preferably 2 to 12 parts by mass with respect to 100 parts by mass of the PTFE resin (A). If the hydrocarbon-based nonionic compound (B) is less than 2 parts by mass relative to 100 parts by mass of the PTFE resin (A), the stability of the composition may be impaired, and the PTFE resin (A) 100 parts by mass If the content exceeds 12 parts by weight, the physical properties of the PTFE coating may deteriorate, for example, the coating obtained using the aqueous dispersion composition may be colored.
炭化水素系非イオン性化合物（B)の PTFE樹脂 (A) 100質量部に対する含有量は 、より好ましい下限が 3質量部であり、更に好ましい下限が 4質量部であり、より好まし い上限が 10質量部である。 The content of hydrocarbon nonionic compound (B) with respect to 100 parts by mass of PTFE resin (A) is A more preferred lower limit is 3 parts by mass, a still more preferred lower limit is 4 parts by mass, and a more preferred upper limit is 10 parts by mass.
[0034] 本発明の PTFE水性分散液組成物において、多糖類'ポリアミノ酸類（C)としては、 合成により得られるもの又は天然に存在するものの何れであってもよい。 [0034] In the PTFE aqueous dispersion composition of the present invention, the polysaccharide 'polyamino acids (C) may be any of those obtained by synthesis or naturally occurring.
上記多糖類 'ポリアミノ酸類（C)は、一般に多糖類又はポリアミノ酸と称されるもので あってもよいし、一般に多糖類又はポリアミノ酸と称されるものの誘導体であってもよ レ、。本明細書において、ポリアミノ酸は、ペプチド及びタンパク質を含み得る。上記「 一般に多糖類又はポリアミノ酸と称されるものの誘導体」としては、化学的に可能であ るものについて、エーテル化体、エステル化体、ヒドロキシアルキル化体、塩等が挙 げられる。  The polysaccharides' polyamino acids (C) may be those generally referred to as polysaccharides or polyamino acids, or may be derivatives of those generally referred to as polysaccharides or polyamino acids. As used herein, polyamino acids can include peptides and proteins. Examples of the above-mentioned “derivatives of what are generally called polysaccharides or polyamino acids” include etherified forms, esterified forms, hydroxyalkylated forms, salts, and the like that are chemically possible.
[0035] 上記多糖類'ポリアミノ酸類（C)としては、例えば、セルロース、澱粉、デキストリン、ァ ルギン酸、デキストラン、キサンタンガム、プノレラン、キトサン、アラビアゴム、カゼイン、 グァーガム、ゼラチン及びべクチン並びにこれらの誘導体よりなる群から選ばれる少 なくとも 1つが挙げられる。  [0035] Examples of the above-mentioned polysaccharides' polyamino acids (C) include cellulose, starch, dextrin, alginic acid, dextran, xanthan gum, punoleran, chitosan, gum arabic, casein, guar gum, gelatin and vectin and these And at least one selected from the group consisting of derivatives.
[0036] 上記多糖類 ·ポリアミノ酸類（C)としては、一般に多糖類と称されるもの、及び/又は 、一般に多糖類と称されるものの誘導体が好ましぐこのような多糖類 ·ポリアミノ酸類 (C)としては、例えば、セルロース、澱粉、デキストリン、アルギン酸、デキストラン、キ サンタンガム、プノレラン、キトサン、アラビアゴム、グァーガム及びべクチン、並びに、 これらの誘導体等が挙げられ、なかでも、セルロースエーテル、アルギン酸塩、アル ギン酸エステル、キサンタンガム、キトサン、キトサン塩、ヒドロキシプロピルキトサン、 グァーガムが好ましい。  [0036] As the above-mentioned polysaccharides-polyamino acids (C), such polysaccharides-polyamino acids that are generally referred to as polysaccharides and / or derivatives of those generally referred to as polysaccharides are preferred. Examples of the class (C) include cellulose, starch, dextrin, alginic acid, dextran, xanthan gum, punoleran, chitosan, gum arabic, guar gum and bectin, and derivatives thereof. Among these, cellulose ether, Alginate, alginate, xanthan gum, chitosan, chitosan salt, hydroxypropyl chitosan and guar gum are preferred.
[0037] 上記多糖類 ·ポリアミノ酸類（C)としては、平均分子量が 1万〜 2000万であるものが 好ましい。平均分子量が高いほど静置安定性が向上するが、平均分子量が高すぎる と水性分散体の粘度が高くなり、取扱いが困難となることがある。より好ましい下限は 2万であり、より好ましい上限は 1000万である。  [0037] The polysaccharide / polyamino acids (C) are preferably those having an average molecular weight of 10,000 to 20,000,000. The higher the average molecular weight, the better the static stability. However, if the average molecular weight is too high, the viscosity of the aqueous dispersion may increase and handling may be difficult. A more preferred lower limit is 20,000, and a more preferred upper limit is 10 million.
上記多糖類'ポリアミノ酸類 (C)は、水性分散体又は水溶液に調製して使用すること が好ましい。  The polysaccharides'polyamino acids (C) are preferably prepared and used in an aqueous dispersion or an aqueous solution.
上記多糖類 ·ポリアミノ酸類（C)としては、該当する化合物を単独で使用してもよいし 、 2種以上併用してもよい。 As the above polysaccharide / polyamino acids (C), the corresponding compound may be used alone. Two or more types may be used in combination.
[0038] 本発明の PTFE水性分散液組成物において、多糖類'ポリアミノ酸類（C)は PTFE 樹脂 (A) 100質量部に対して 0. 00001〜：!質量部であることが好ましい。 PTFE榭 脂 (A) 100質量部に対して 0. 00001質量部未満であると、静置安定性が不充分で あることがあり、 PTFE樹脂 (A) 100質量部に対して 1質量部を超えると、組成物の粘 度が高くなり、取扱いが困難となることがある。より好ましい下限は PTFE樹脂 (A) 10 0質量部に対して 0. 0001質量部である。  [0038] In the aqueous PTFE dispersion composition of the present invention, the polysaccharides' polyamino acids (C) are preferably 0.00001 to:! Parts by mass with respect to 100 parts by mass of the PTFE resin (A). PTFE resin (A) If it is less than 0.0001 part by mass relative to 100 parts by mass, the static stability may be insufficient, and 1 part by mass for 100 parts by mass of PTFE resin (A). If it exceeds, the viscosity of the composition becomes high and handling may be difficult. A more preferred lower limit is 0.0001 parts by mass with respect to 100 parts by mass of the PTFE resin (A).
[0039] 本明細書において、上記炭化水素系非イオン性化合物（B)、上記多糖類 'ポリアミノ 酸類 (C)の各量は、上記 PTFE樹脂 (A)濃度と、本発明の PTFE水性分散液組成 物を調製する際に配合する量 (PTFE水性分散体調製時に配合した場合はその配 合量も含む）とから、 PTFE樹脂 (A) 100質量部に対する質量として求めることができ る。  [0039] In the present specification, each amount of the hydrocarbon-based nonionic compound (B) and the polysaccharide 'polyamino acid (C) is determined by the concentration of the PTFE resin (A) and the PTFE aqueous dispersion of the present invention. From the amount blended when preparing the composition (including the blended amount when blended at the time of preparing the PTFE aqueous dispersion), it can be determined as the mass with respect to 100 parts by mass of the PTFE resin (A).
[0040] 本発明の PTFE水性分散液組成物は、水性媒体中に上述の PTFE樹脂 (A)、炭化 水素系非イオン性化合物（B)及び多糖類 ·ポリアミノ酸類（C)を有するものである。上 記水性媒体としては特に限定されず、例えば、水、水と公知の水溶性溶媒との混合 液等であってよぐ更に有機溶剤をも含むものであってもよいが、有機溶剤は含まな レ、ものであることが好ましい。本発明における水性媒体としては、例えば、上述の PT FE樹脂 (A)を得るための乳化重合における水性媒体をそのまま使用することもでき る。  [0040] The aqueous PTFE dispersion composition of the present invention comprises the above-mentioned PTFE resin (A), hydrocarbon-based nonionic compound (B) and polysaccharide / polyamino acids (C) in an aqueous medium. is there. The aqueous medium is not particularly limited, and may be water, a mixed solution of water and a known water-soluble solvent, or the like, and may further contain an organic solvent. It is preferable that it is a thing. As the aqueous medium in the present invention, for example, the aqueous medium in emulsion polymerization for obtaining the above-mentioned PTFE resin (A) can be used as it is.
[0041] 本発明の PTFE水性分散液組成物は、本発明の効果を損なわないかぎり、種々の 公知の添加剤を配合することができる。上記添加剤としては、例えば、顔料、充填剤 、消泡剤、乾燥遅延剤、造膜剤、レべリング剤、ハジキ防止剤、造膜助剤等が挙げら れる。  [0041] The PTFE aqueous dispersion composition of the present invention may contain various known additives as long as the effects of the present invention are not impaired. Examples of the additive include pigments, fillers, antifoaming agents, drying retarders, film-forming agents, leveling agents, repellency inhibitors, and film-forming aids.
上記顔料としては、特に限定されず、例えば、酸化チタン、カーボンブラック、ベンガ ラ等、公知の顔料が挙げられる。  The pigment is not particularly limited, and examples thereof include known pigments such as titanium oxide, carbon black, and bengara.
上記充填剤としては、特に限定されず、公知のものが挙げられる。  It does not specifically limit as said filler, A well-known thing is mentioned.
上記消泡剤としては、例えば、トルエン、キシレン、炭素数 9〜： 11の炭化水素系など の非極性溶剤等が挙げられる。 上記乾燥遅延剤としては、例えば、 200〜300°C程度の沸点を有する溶剤等が挙げ られ、このような溶剤としては、水溶性溶剤が好ましい。 Examples of the antifoaming agent include toluene, xylene, and nonpolar solvents such as hydrocarbons having 9 to 11 carbon atoms. Examples of the drying retarder include a solvent having a boiling point of about 200 to 300 ° C., and such a solvent is preferably a water-soluble solvent.
上記造膜剤としては、例えば、アクリル樹脂、ウレタン樹脂等が挙げられる。  Examples of the film forming agent include acrylic resin and urethane resin.
上記レべリング剤やハジキ防止剤としては、例えば、フッ素系界面活性剤、シリコーン 系界面活性剤等が挙げられる。  Examples of the leveling agent and repellency inhibitor include fluorine-based surfactants and silicone-based surfactants.
本発明の PTFE水性分散液組成物は、顔料を含まないものであってよいし、また、上 述の PTFE樹脂 (A)以外の耐熱性樹脂を含まなレ、ものが好ましい。  The PTFE aqueous dispersion composition of the present invention may be one that does not contain a pigment, and one that does not contain a heat-resistant resin other than the above-mentioned PTFE resin (A) is preferred.
[0042] 本発明の PTFE水性分散液組成物は、 25°Cにおける粘度が 0. lPa' s以下であるも のが好ましい。粘度が高すぎると取扱いが困難になることがある。 [0042] The PTFE aqueous dispersion composition of the present invention preferably has a viscosity at 25 ° C of not more than 0.1 Pa's. If the viscosity is too high, handling may be difficult.
より好ましい上限は 0. 06Pa' sであり、また上記範囲内であれば、 0. OlPa' s以上で あってもよレヽ。  A more preferred upper limit is 0.06 Pa's, and if it is within the above range, it may be 0. OlPa's or more.
本明細書において、上記粘度は、 B型回転粘度計 (東京計器社製)を用いて、 JIS K 6893に準拠して、 25°Cの温度にて測定したものである。  In the present specification, the viscosity is measured at a temperature of 25 ° C. according to JIS K 6893 using a B-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.).
[0043] 本発明の PTFE水性分散液組成物は、特に限定されないが、例えば、重合により得 られた PTFE水性分散体を攪拌しながら、炭化水素系非イオン性化合物 (B)、多糖 類'ポリアミノ酸類 (C)及び所望により他の添加剤を添加し、混合することにより調製 すること力 Sできる。 [0043] The PTFE aqueous dispersion composition of the present invention is not particularly limited. For example, while stirring the PTFE aqueous dispersion obtained by polymerization, the hydrocarbon-based nonionic compound (B), polysaccharides' Ability to prepare by adding and mixing amino acids (C) and other additives as desired.
[0044] 上記調製にぉレ、て、炭化水素系非イオン性化合物 (B)は、 PTFE水性分散体を調 製する際に添加することもでき、例えば、重合生成物である水性分散体を濃縮するに 際し従来用いられてきた分散剤として添加してもよいが、通常、 PTFE水性分散体の 調製後に追加して、 目的とする PTFE水性分散体組成物の粘度に調整することが好 ましい。  [0044] In the above preparation, the hydrocarbon-based nonionic compound (B) can also be added when preparing the PTFE aqueous dispersion. For example, the aqueous dispersion that is a polymerization product is added. Although it may be added as a dispersant conventionally used for concentration, it is usually preferable to add it after preparation of the PTFE aqueous dispersion to adjust the viscosity of the target aqueous PTFE dispersion composition. Good.
上記攪拌、添加及び混合の各操作の条件は、使用する組成物の成分や量により適 宜設定することができるが、 5〜30°Cの温度にて行うことが好ましい。  Conditions for each of the above stirring, addition and mixing operations can be appropriately set depending on the components and amounts of the composition to be used, but it is preferably performed at a temperature of 5 to 30 ° C.
[0045] 本発明の PTFE水性分散液組成物は、上述の構成からなるので、上述のように静置 安定性に優れるものである。 [0045] Since the PTFE aqueous dispersion composition of the present invention has the above-described configuration, it is excellent in stationary stability as described above.
本明細書において、上記静置安定性は、 100mlの PTFE水性分散液組成物が入つ たメスシリンダーを 25°C下で静置し、 PTFE樹脂の含まれる白濁層の経時変化を観 察し、 3力月後の透明上澄層の体積を当初の体積である 100mlに対する割合 (体積 %)として測定し、これを静置安定性指数として評価する。静置安定性指数は 6. 0体 積％以下であることが好ましい。 In the present specification, the above-mentioned standing stability refers to the time-dependent change of the cloudy layer containing PTFE resin by leaving a graduated cylinder containing 100 ml of the PTFE aqueous dispersion composition at 25 ° C. The volume of the transparent supernatant layer after 3 months is measured as a ratio (volume%) to the initial volume of 100 ml, and this is evaluated as a static stability index. The static stability index is preferably 6.0% by volume or less.
[0046] 被塗装物上に上述の本発明の PTFE水性分散液組成物を塗装することにより得られ る PTFE樹脂フィルムもまた、本発明の一つである。 [0046] A PTFE resin film obtained by coating the above-mentioned PTFE aqueous dispersion composition of the present invention on an object to be coated is also one aspect of the present invention.
上記被塗装物としては、特に限定されず、例えば、各種金属、ホーロー、ガラス、各 種セラミックス、各種耐熱樹脂成形品が挙げられる。上記被塗装物は、何れの形状で あってもよい。上記塗装は、通常、本発明の PTFE水性分散液組成物を塗布した後 、乾燥し、次いで焼成することにより行うことができる。本発明の PTFE水性分散液組 成物は、基材に直接塗装してもよいが、基材との密着性を向上させるために、プライ マー層を設けてその上塗り層として形成することもできる。  The material to be coated is not particularly limited, and examples thereof include various metals, enamel, glass, various ceramics, and various heat-resistant resin molded products. The object to be coated may have any shape. The above coating can usually be performed by applying the PTFE aqueous dispersion composition of the present invention, drying and then baking. The PTFE aqueous dispersion composition of the present invention may be directly coated on a substrate, but in order to improve adhesion to the substrate, a primer layer may be provided and formed as an overcoat layer. .
[0047] 上記塗布は、特に限定されないが、デイツビング法、スプレー法、ロールコート法、ド クタ一ブレード法、フローコート法等、公知の塗装方法にて行うことができる。 [0047] The application is not particularly limited, and can be performed by a known coating method such as a dating method, a spray method, a roll coating method, a doctor blade method, a flow coating method, or the like.
上記乾燥は、使用する炭化水素系非イオン性化合物 (B)、多糖類'ポリアミノ酸類 (C )等の種類等に応じて適宜設定することができるが室温〜 150°C、好ましくは 80〜1 50°Cの温度にて、 5〜20分間行うことが好ましい。  The drying can be appropriately set according to the type of hydrocarbon-based nonionic compound (B), polysaccharides' polyamino acids (C), etc. to be used, but room temperature to 150 ° C, preferably 80 to 1 It is preferably performed at a temperature of 50 ° C for 5 to 20 minutes.
上記焼成は、一般に、使用する PTFE樹脂 (A)の溶融温度以上、通常、 340〜415 。 こて、 5〜60分間行うこと力 Sでき、 360〜400°Cにて 10〜30分間行うこと力 S好まし レ、。  The firing is generally at or above the melting temperature of the PTFE resin (A) used, usually 340-415. Trowel, capable of performing for 5-60 minutes S, capable of performing for 30-30 minutes at 360-400 ° C.
本発明の PTFE樹脂フィルムは、用いた被塗装物の種類によっては上記焼成ののち 該被塗装物から剥離したものであってもよいが、被塗装物と接したままのもの、又は、 被塗装物とプライマー層等を介して接したままのものであってもよい。  The PTFE resin film of the present invention may be peeled off from the object to be coated after the above-mentioned firing depending on the type of object to be coated. It may be in contact with an object through a primer layer or the like.
[0048] 本発明の PTFE樹脂フィルムは、上述の本発明の PTFE水性分散液組成物を塗装 してなるものであるので、通常、 5 μ m以上、好ましくは、約 10〜： 100 μ mの厚さを有 する。 [0048] Since the PTFE resin film of the present invention is formed by coating the above-mentioned PTFE aqueous dispersion composition of the present invention, it is usually 5 μm or more, preferably about 10 to 100 μm. It has a thickness.
本発明の PTFE樹脂フィルムは、被塗装物が焼成時に実質的に劣化しなレ、ものであ れば特に限定することなく得ることができ、例えば、金属調理器具、ベアリング、バル ブ、電線、金属箔、ボイラー、パイプ、船底、オーブン内張り、アイロン底板、製氷トレ 一、雪かきシャベル、すき、シュート、コンベア、ロール、金型、ダイス、のこぎり、やす り、きり等の工具、包丁、はさみ、ホッパー、その他の工業用コンテナ（特に半導体ェ 業用）、铸型等の被覆材とすることができる。 The PTFE resin film of the present invention can be obtained without particular limitation as long as the object to be coated does not substantially deteriorate upon firing. For example, a metal cooker, a bearing, a valve, an electric wire, Metal foil, boiler, pipe, ship bottom, oven lining, iron bottom plate, ice tray 1. Snow shovel, plow, plow, chute, conveyor, roll, mold, dice, saw, file tool, knife, scissors, hopper, other industrial containers (especially for semiconductor industry), vertical mold, etc. It can be set as a coating material.
本発明の組成物から得られる PTFE樹脂フィルムは、特に、高周波プリント基板、搬 送用ベルト、パッキン等の被覆材として好適に使用することができる。  In particular, the PTFE resin film obtained from the composition of the present invention can be suitably used as a coating material for high-frequency printed circuit boards, transport belts, packings, and the like.
[0049] 被含浸体と、前記被含浸体に上述の本発明の PTFE水性分散液組成物を含浸する ことにより得られる被膜とを有する PTFE樹脂含浸体もまた、本発明の一つである。  [0049] A PTFE resin-impregnated body having an impregnated body and a film obtained by impregnating the above-mentioned impregnated body with the above-mentioned PTFE aqueous dispersion composition of the present invention is also one aspect of the present invention.
[0050] 上記被含浸体としては特に限定されず、例えば、繊維基材、織布'不織布等が挙げ られる。上記繊維基材としては特に限定されず、例えば、ガラス繊維、カーボン繊維 、ァラミド繊維 (ケプラー繊維 (登録商標)等）が挙げられる。上記含浸は、公知の方法 にて行うことができる。  [0050] The impregnated material is not particularly limited, and examples thereof include a fiber base material, a woven fabric'nonwoven fabric, and the like. The fiber substrate is not particularly limited, and examples thereof include glass fiber, carbon fiber, and aramid fiber (Kepler fiber (registered trademark), etc.). The impregnation can be performed by a known method.
上記被膜は、上述の本発明の PTFE水性分散液組成物を含浸してなるものであるの で、基材の形状や厚みにもよる力 通常、約 10〜： 100 /i mの厚さを有する。  Since the coating film is formed by impregnating the above-mentioned PTFE aqueous dispersion composition of the present invention, the force depending on the shape and thickness of the substrate usually has a thickness of about 10 to 100 / im. .
発明の効果  The invention's effect
[0051] 本発明の PTFE水性分散液組成物は、上述の構成からなるものであるので、静置安 定性に優れ、組成物を静置保存する際に PTFE樹脂粒子の沈降が抑えられ、再分 散を不要、あるいは容易とすることができる。  [0051] Since the PTFE aqueous dispersion composition of the present invention has the above-described configuration, it has excellent stationary stability, and the sedimentation of PTFE resin particles can be suppressed when the composition is stored at rest. Distribution can be made unnecessary or easy.
本発明の PTFE樹脂フィルムは、上述の構成からなるものであるので、異物等の欠陥 がなぐ均一な被膜とすることが容易である。  Since the PTFE resin film of the present invention has the above-described configuration, it can be easily formed into a uniform film free from defects such as foreign matters.
本発明の PTFE樹脂含浸体は、上述の構成からなるものであるので、異物等の欠陥 がなぐ均一な被膜とすることが容易である。  Since the PTFE resin impregnated body of the present invention has the above-described configuration, it is easy to form a uniform film free from defects such as foreign matters.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0052] 本発明を実施例及び比較例により更に詳細に説明するが、本発明はこれらの実施例 及び比較例により限定されるものではなレ、。 [0052] The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.
[0053] 各実験例で行った測定は、以下の方法により行った。 [0053] The measurement performed in each experimental example was performed by the following method.
( 1 )平均粒子径  (1) Average particle size
樹脂固形分濃度を 0. 22質量％に調整した PTFE水性分散体の単位長さに対する 5 50nmの投射光の透過率と、透過型電子顕微鏡写真における定方向径を測定して 決定された平均粒径との検量線をもとにして、上記透過率から決定した。 Measure the transmittance of projection light at 550 nm with respect to the unit length of the PTFE aqueous dispersion with the resin solid content concentration adjusted to 0.22% by mass, and the constant direction diameter in the transmission electron micrograph. Based on the calibration curve with the determined average particle diameter, it was determined from the transmittance.
(2) PTFE樹脂 (A)濃度  (2) PTFE resin (A) Concentration
PTFE水性分散体組成物 10gを 380°Cの温度にて 45分間乾燥して得られた残渣の 質量と、該乾燥前の上記 PTFE水性分散体組成物の質量に占める割合の百分率と して求めた。  Obtained as a mass of the residue obtained by drying 10 g of PTFE aqueous dispersion composition at a temperature of 380 ° C. for 45 minutes and a percentage of the mass of the PTFE aqueous dispersion composition before drying. It was.
(3) PTFE水性分散液組成物における炭化水素系非イオン性化合物（B)濃度 上記（2)により求めた PTFE樹脂 (A)濃度と、本発明の PTFE水性分散液組成物を 調製する際に配合する量 (PTFE水性分散体調製時に配合した場合はその配合量 も含む）とから、 PTFE樹脂 (A) 100質量部に対する質量として求めた。  (3) Hydrocarbon-based nonionic compound (B) concentration in PTFE aqueous dispersion composition When preparing the PTFE resin (A) concentration obtained by (2) above and the PTFE aqueous dispersion composition of the present invention. From the amount to be blended (including the blended amount when blended at the time of preparing the PTFE aqueous dispersion), it was determined as the mass with respect to 100 parts by mass of the PTFE resin (A).
(4) PTFE水性分散液組成物における多糖類'ポリアミノ酸類 (C)濃度  (4) Polysaccharides' polyamino acids (C) concentration in PTFE aqueous dispersion composition
上記（2)により求めた PTFE樹脂 (A)濃度と、本発明の PTFE水性分散液組成物を 調製する際に配合する量とから、 PTFE樹脂 (A) 100質量部に対する質量として求 めた。 From the concentration of PTFE resin (A) determined by the above (2) and the amount to be blended when preparing the aqueous PTFE dispersion composition of the present invention, it was determined as a mass with respect to 100 parts by mass of the PTFE resin (A).
(5)粘度  (5) Viscosity
B型回転粘度計 (東京計器社製）を用い、 JIS K 6893に準拠して、 25°Cにおける 粘度を測定した。  Using a B-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.), the viscosity at 25 ° C was measured according to JIS K 6893.
(6)静置安定性指数  (6) Static stability index
100mlの PTFE水性分散液組成物が入ったメスシリンダーを 25°C下で静置し、 PTF E樹脂の含まれる白濁層の経時変化を観察し、 3力月後の透明上澄層の体積を当初 の体積である 100mlに対する割合（体積％)として測定した。  A graduated cylinder containing 100 ml of PTFE aqueous dispersion composition is allowed to stand at 25 ° C, the time-dependent change of the cloudy layer containing PTF E resin is observed, and the volume of the transparent supernatant layer after 3 months is measured. It was measured as a percentage (% by volume) with respect to the initial volume of 100 ml.
調製例 1 Preparation Example 1
PTFE樹脂 (A)として、乳化重合により平均粒径 325nm、 PTFE樹脂 (A)濃度 [P. C. ] 30. 2質量％の PTFE水性分散体を得た。  As the PTFE resin (A), an aqueous PTFE dispersion having an average particle size of 325 nm and a PTFE resin (A) concentration [P. C.] of 30. 2% by mass was obtained by emulsion polymerization.
得られた PTFE水性分散体を、炭化水素系非イオン性化合物 (B)としてポリオキシェ チレンアルキルエーテル（商品名ノィゲン TDS _ 80、第一工業製薬社製；平均 HLB = 13)を用いて濃縮し、 P. C. 69. 5質量％、炭化水素系非イオン性化合物 (B)濃 度 [N. C. ]が PTFE樹脂 (A) 100質量部に対し 2. 9質量部である PTFE水性分散 液濃縮品を調製した。 [0055] 調製例 2 The obtained PTFE aqueous dispersion was concentrated using a polyoxyethylene alkyl ether (trade name Neugen TDS_80, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; average HLB = 13) as the hydrocarbon-based nonionic compound (B). A concentrated PTFE aqueous dispersion was prepared in which PC was 69.5% by mass and the hydrocarbon-based nonionic compound (B) concentration [NC] was 2.9 parts by mass with respect to 100 parts by mass of PTFE resin (A). [0055] Preparation Example 2
PTFE樹脂 (A)として、乳化重合により平均粒径 325nm、 PTFE樹脂 (A)濃度 [P. C. ] 30. 2質量％の PTFE水性分散体を得た。  As the PTFE resin (A), an aqueous PTFE dispersion having an average particle size of 325 nm and a PTFE resin (A) concentration [P. C.] of 30. 2% by mass was obtained by emulsion polymerization.
得られた PTFE水性分散体に、炭化水素系非イオン性化合物 (B)としてポリオキシェ チレンアルキルエーテル（商品名ノィゲン TDS _ 30、第一工業製薬社製；平均 HLB = 8)をカ卩えて液温 20〜80°Cの範囲で濃縮を試みた力 もとの濃度（30. 2質量％) 以上に濃縮されることはなかった。  Polyoxyethylene alkyl ether (trade name Neugen TDS_30, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; average HLB = 8) was added as a hydrocarbon-based nonionic compound (B) to the obtained PTFE aqueous dispersion. Concentration was attempted in the range of 20 to 80 ° C. Concentration was not higher than the original concentration (30.2% by mass).
[0056] 調製例 3 [0056] Preparation Example 3
PTFE樹脂 (A)として、乳化重合により平均粒径 325nm、 PTFE樹脂 (A)濃度 [P. C. ] 30. 2質量％の PTFE水性分散体を得た。  As the PTFE resin (A), an aqueous PTFE dispersion having an average particle size of 325 nm and a PTFE resin (A) concentration [P. C.] of 30. 2% by mass was obtained by emulsion polymerization.
得られた PTFE水性分散体に、炭化水素系非イオン性化合物 (B)としてポリオキシェ チレンアルキルエーテル（商品名ノィゲン TDS _ 200D、第一工業製薬社製；平均 H LB = 16. 3)を加えて液温 20〜80°Cの範囲で濃縮を試みた力 S、もとの濃度（30. 2 質量％)以上に濃縮されることはなかった。  Polyoxyethylene alkyl ether (trade name Neugen TDS_200D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; average H LB = 16.3) was added to the resulting PTFE aqueous dispersion as a hydrocarbon-based nonionic compound (B). The force S tried to concentrate in the liquid temperature range of 20 to 80 ° C, and it was never concentrated beyond the original concentration (30.2 mass%).
[0057] 実施例 1 [0057] Example 1
PTFE水性分散液濃縮品 300gに、ノィゲン TDS— 80 6. 3g、多糖類'ポリアミノ酸 類 (C)としてグァーガム水性分散体 (三晶社製、分子量 20万、樹脂濃度 2質量％) 1 . 0g、純水 35. 5gを添カロして、 P. C. 60. 8質量0 /0、 N. C.力 S PTFE樹月旨（A) 100 質量部に対し 5. 9質量部、多糖類 *ポリアミノ酸類 (C)が PTFE樹脂 (A) 100質量部 に対し 0. 01質量部である PTFE水性分散液組成物を得た。 300 g PTFE aqueous dispersion concentrate, Neugen TDS- 80 6.3 g, Guar gum aqueous dispersion as polysaccharide 'polyamino acids (C) (Mitsui Co., Ltd., molecular weight 200,000, resin concentration 2% by mass) 1.0 g , pure water 35. 5 g with added Caro, PC 60. 8 mass 0/0, NC force S PTFE Kitsuki effect (a) 9 parts by weight 5. 100 parts by mass, polysaccharides * polyamino acids (C PTFE resin (A) was 100 parts by weight of PTFE resin (A).
得られた PTFE水性分散液組成物の粘度は 2. 95 X 10— 2Pa' s、静置安定性指数は 4. 1体積％であった。 The viscosity of the resulting aqueous PTFE dispersion composition 2. 95 X 10- 2 Pa 's , standing stability index 4. was 1% by volume.
[0058] 実施例 2 [0058] Example 2
PTFE水性分散液濃縮品 300gに、ノィゲン TDS— 80 6. 3g、多糖類'ポリアミノ酸 類 (C)としてキサンタンガム水性分散体 (三晶社製、分子量 200万、樹脂濃度 2質量 %) 1. 0g、純水 35. 5gを添カロして、 P. C. 60. 8質量0 /0、 N. C.力 SPTFE樹旨（A) 100質量部に対し 5. 9質量部、多糖類 ·ポリアミノ酸類（C)が PTFE樹脂 (A) 100質 量部に対し 0. 01質量部である PTFE水性分散液組成物を得た。 得られた PTFE水性分散液組成物の粘度は 3. 70 X 10"2Pa - s,静置安定性指数は300 g PTFE aqueous dispersion concentrate, Neugen TDS- 80 6.3 g, xanthan gum aqueous dispersion as polysaccharide 'polyamino acids (C) (Mitsui Co., Ltd., molecular weight 2 million, resin concentration 2 mass%) 1.0 g , pure water 35. 5 g with added Caro, 9 parts by mass 5. to PC 60. 8 mass 0/0, NC force SPTFE Kimune (a) 100 parts by mass of a polysaccharide-polyamino acids (C) is PTFE resin (A) An aqueous PTFE dispersion composition having a mass of 0.01 parts by mass with respect to 100 parts by mass was obtained. The resulting PTFE aqueous dispersion composition has a viscosity of 3.70 X 10 " 2 Pa-s, and the static stability index is
3. 7体積％であった。 3. 7% by volume.
[0059] 実施例 3 [0059] Example 3
PTFE水性分散液濃縮品 300gに、ノィゲン TDS— 80 6. 3g、多糖類'ポリアミノ酸 類 (C)としてアルギン酸エステル水性分散体 (キミ力社製、分子量 10万、樹脂濃度 2 質量％) 5. 2g、純水 35. 5gを添加して、 P. C. 60. 1質量％、 N. C.が PTFE樹脂 (A) 100質量部に対し 5. 9質量部、多糖類'ポリアミノ酸類 (C)が PTFE樹脂 (A) 10 0質量部に対し 0. 05質量部である PTFE水性分散液組成物を得た。  300 g PTFE aqueous dispersion concentrate, Neugen TDS-80 6.3 g, alginate aqueous dispersion as polysaccharide 'polyamino acids (C) (Kimiru Co., Ltd., molecular weight 100,000, resin concentration 2% by mass) 5. 2g, 35.5g of pure water are added, 60.1% by weight of PC, NC is 5.9 parts by weight with respect to 100 parts by weight of PTFE resin (A), polysaccharide'polyamino acids (C) is PTFE resin ( A) A PTFE aqueous dispersion composition in an amount of 0.05 part by mass with respect to 100 parts by mass was obtained.
得られた PTFE水性分散液組成物の粘度は 2. 70 X 10— 2Pa ' s、静置安定性指数は 5. 0体積％であった。 The viscosity of the resulting aqueous PTFE dispersion composition 2. 70 X 10- 2 Pa 's , standing stability index was 5.0 vol%.
[0060] 実施例 4 [0060] Example 4
PTFE水性分散液濃縮品 300gに、ノィゲン TDS— 80 6. 3g、多糖類'ポリアミノ酸 類 (C)としてヒドロキシプロピルメチルセルロース水性分散体 (信越化学社製、分子量 10万、樹脂濃度 2質量％) 10. 4g、純水 35. 5gを添カ卩して、 P. C. 59. 2質量％、 N . C.が PTFE樹脂 (A) 100質量部に対し 5. 9質量部、多糖類'ポリアミノ酸類 (C)が PTFE樹脂 (A) 100質量部に対し 0. 1質量部である PTFE水性分散液組成物を得 た。  PTFE aqueous dispersion concentrate 300g, Neugen TDS- 80 6.3g, Hydroxypropylmethylcellulose aqueous dispersion as polysaccharide 'polyamino acids (C) (Shin-Etsu Chemical Co., Ltd., molecular weight 100,000, resin concentration 2% by mass) 10 4g, 35.5g of pure water, 59.2% by mass of PC, N. C. is 5.9 parts by mass of 100% by mass of PTFE resin (A). A PTFE aqueous dispersion composition in which C) was 0.1 part by mass with respect to 100 parts by mass of PTFE resin (A) was obtained.
得られた PTFE水性分散液組成物の粘度は 2. 80 X 10"2Pa - s,静置安定性指数は 5. 6体積％であった。 The obtained PTFE aqueous dispersion composition had a viscosity of 2.80 × 10 ” 2 Pa-s and a static stability index of 5.6% by volume.
[0061] 実施例 5 [0061] Example 5
PTFE水性分散液濃縮品 300gに、ノィゲン TDS— 80 6. 3g、多糖類'ポリアミノ酸 類 (C)としてキトサン水性分散体 (大日精ィ匕社製、分子量 10万、樹脂濃度 15質量％ ) 0. 7g、純水 35. 5gを添カロして、 P. C. 60. 9質量0 /0、 N. C.力 SPTFE樹旨（A) 10 0質量部に対し 5. 9質量部、多糖類'ポリアミノ酸類 (C)が PTFE樹脂 (A) 100質量 部に対し 0. 05質量部である PTFE水性分散液組成物を得た。 PTFE aqueous dispersion concentrate 300g, Neugen TDS- 80 6.3g, Chitosan aqueous dispersion as polysaccharide 'polyamino acids (C) (manufactured by Dainichi Seiki Co., Ltd., molecular weight 100,000, resin concentration 15% by mass) 0 . 7 g, pure water 35. 5 g with added Caro, PC 60. 9 mass 0/0, NC force SPTFE Kimune (a) 9 parts by weight 5. respect 10 0 parts by mass, polysaccharides' polyamino acids ( A PTFE aqueous dispersion composition in which C) was 0.05 parts by mass with respect to 100 parts by mass of the PTFE resin (A) was obtained.
得られた PTFE水性分散液組成物の粘度は 3. 15 X 10— 2Pa ' s、静置安定性指数はThe resulting viscosity of the PTFE aqueous dispersion composition 3. 15 X 10- 2 Pa 's , standing stability index
4. 5体積％であった。 4. 5% by volume.
[0062] 実施例 6 ガラス繊維を実施例 1で調製した PTFE水性分散液組成物に含浸、焼成して含浸体 を成形した。用いたガラス繊維の厚みは 50 μ ΐη、幅は 30cmであり、 1. 2m/分の速 度で移動させた。組成物は含浸時 25°Cに保ち、焼成温度は 380°C、焼成時間は 40 禾少であった。 [0062] Example 6 The glass fiber was impregnated with the PTFE aqueous dispersion composition prepared in Example 1 and fired to form an impregnated body. The glass fiber used had a thickness of 50 μΐη and a width of 30 cm, and was moved at a speed of 1.2 m / min. The composition was maintained at 25 ° C when impregnated, the firing temperature was 380 ° C, and the firing time was 40 hours shorter.
上記含浸、焼成を 125分間にわたって行い、被膜厚み 10 z m、 150mの長さの含浸 体を成形したが、異物は観察されなかった。  The impregnation and baking were performed for 125 minutes to form an impregnated body having a coating thickness of 10 zm and a length of 150 m, but no foreign matter was observed.
また、ノィゲン TDS— 80Cは 350°Cで 5分間加熱した場合の固形分残存率が 4質量 %であり、成形された含浸体に着色は見られなかった。  Neugen TDS-80C had a solid content of 4% by mass when heated at 350 ° C. for 5 minutes, and the molded impregnated body was not colored.
[0063] 比較例 1 [0063] Comparative Example 1
PTFE水十生分散夜濃縮品 300gに、ノィゲン TDS— 80 6. 3g、純水 35. 5gを添カロ して、 P. C. 61. 0質量％、 N. C.力 PTFE樹脂（A) 100質量部に対し 5. 9質量部 である PTFE水性分散液組成物を得た。  300 g of PTFE water-dispersed nightly concentrated product is mixed with Neugen TDS- 80 6.3 g and pure water 35.5 g, PC 61.0 mass%, NC power PTFE resin (A) 5 parts per 100 mass parts A PTFE aqueous dispersion composition of 9 parts by mass was obtained.
得られた PTFE水性分散液組成物の粘度は 2. 70 X 10"2Pa- s,静置安定性指数は 9. 8体積％であった。 The obtained PTFE aqueous dispersion composition had a viscosity of 2.70 × 10 ” 2 Pa-s and a static stability index of 9.8% by volume.
[0064] 比較例 2 [0064] Comparative Example 2
PTFE水性分散液濃縮品 300gに、ノィゲン TDS— 80 6. 3g、ポリビニルアルコー ル水性分散体（日本酢ビ'ポバール社製、分子量 15万、樹脂濃度 10質量％) 4. 2g 、純水 35. 5gを添カロして、 P. C. 60. 3質量0 /0、 N. C.力 ^PTFE樹月旨（A) 100質量 部に対し 5. 9質量部、ポリビュルアルコール力 SPTFE樹脂 (A) 100質量部に対し 0. 2質量部である PTFE水性分散液組成物を得た。 300 g PTFE aqueous dispersion concentrate, Neugen TDS-80 6.3 g, polyvinyl alcohol aqueous dispersion (Nippon Vinegar's Poval, molecular weight 150,000, resin concentration 10% by mass) 4.2 g, pure water 35. the 5g and added Caro, PC 60. 3 mass 0/0, NC force ^ PTFE Kitsuki effect (a) 9 parts by 5. per 100 parts by weight, poly Bulle alcohols force SPTFE resin (a) 100 parts by weight A PTFE aqueous dispersion composition having a content of 0.2 parts by mass was obtained.
得られた PTFE水性分散液組成物の粘度は 2. 80 X 10— 2Pa' s、静置安定性指数は 6. 6体積％であった。 The resulting viscosity of the PTFE aqueous dispersion composition 2. 80 X 10- 2 Pa 's , standing stability index was 6.6 vol%.
[0065] 比較例 3 [0065] Comparative Example 3
PTFE水性分散液濃縮品 300gに、ノィゲン TDS— 80 6. 3g、ポリアクリル酸水性 分散体（日本純薬社製、分子量 100万、樹脂濃度 5質量％) 0. 4g、純水 35. 5gを添 カロして、 P. C. 60. 9質量0 /0、 N. C.力 PTFE樹月旨（A) 100質量部に対し 5. 9質量 部、ポリアクリル酸が PTFE樹脂 (A) 100質量部に対し 0. 01質量部である PTFE水 性分散液組成物を得た。 得られた PTFE水性分散液組成物の粘度は 4. 50 X 10"2Pa - s,静置安定性指数はPTFE aqueous dispersion concentrate 300g, Neugen TDS- 80 6.3g, polyacrylic acid aqueous dispersion (manufactured by Nippon Pure Chemical Co., Ltd., molecular weight 1 million, resin concentration 5% by mass) 0.4g, pure water 35.5g and added Caro, 9 parts by mass 5. to PC 60. 9 mass 0/0, NC force PTFE Kitsuki effect (A) 100 parts by mass of polyacrylic acid with respect to PTFE resin (A) 100 parts by mass of 0. A PTFE aqueous dispersion composition of 01 parts by mass was obtained. The resulting PTFE aqueous dispersion composition has a viscosity of 4. 50 X 10 " 2 Pa-s and a static stability index of
7. 4体積％であった。 7. 4% by volume.
[0066] 比較例 4 [0066] Comparative Example 4
PTFE水性分散液濃縮品 300gに、ノィゲン TDS— 80 6. 3g、ポリエチレンォキシド 水性分散体 (明成化学社製、分子量 8万、樹脂濃度 20質量％) 7. 3g、純水 35. 5g を添カロして、 P. C. 59. 7質量0 /0、 N. C.力 PTFE樹月旨（A) 100質量部に対し 5. 9 質量部、ポリエチレンォキシドが PTFE樹脂 (A) 100質量部に対し 0. 7質量部である PTFE水性分散液組成物を得た。 300 g of PTFE aqueous dispersion concentrate, Neugen TDS- 80 6.3 g, polyethylene oxide aqueous dispersion (Madesei Chemical Co., Ltd., molecular weight 80,000, resin concentration 20% by mass) 7.3 g, pure water 35.5 g and Caro, PC 59. 7 wt 0/0, NC force PTFE Kitsuki effect (A) 9 parts by 5. per 100 parts by weight, 0.1 polyethylene O dimethylsulfoxide Whereas PTFE resin (A) 100 parts by mass of 7 A PTFE aqueous dispersion composition having a mass part was obtained.
得られた PTFE水性分散液組成物の粘度は 2. 75 X 10— 2Pa ' s、静置安定性指数はThe resulting viscosity of the PTFE aqueous dispersion composition 2. 75 X 10- 2 Pa 's , standing stability index
8. 2体積％であった。 8. 2% by volume.
[0067] 比較例 5 [0067] Comparative Example 5
PTFE水性分散液濃縮品 300gに、ノィゲン TDS— 80 6. 3g、ポリビュルピロリドン 水性分散体（日本触媒社製、分子量 110万、樹脂濃度 20質量％) 2. lg、純水 35. 5gを添カロして、 P. C. 60. 6質量0 /0、 N. C.力 SPTFE樹月旨（A) 100質量部に対し 5. 9質量部、ポリビニルピロリドンが PTFE樹脂 (A) 100質量部に対し 0. 2質量部であ る PTFE水性分散液組成物を得た。 300 g PTFE aqueous dispersion concentrate, Neugen TDS- 80 6.3 g, polybulurpyrrolidone aqueous dispersion (manufactured by Nippon Shokubai Co., Ltd., molecular weight 1.1 million, resin concentration 20% by mass) 2. lg, pure water 35.5 g and Caro, PC 60. 6 wt 0/0, NC force SPTFE Kitsuki effect (A) 9 parts by 5. per 100 parts by weight of polyvinyl pyrrolidone PTFE resin (A) 0. 2 mass relative to 100 parts by weight Part of a PTFE aqueous dispersion composition was obtained.
得られた PTFE水性分散液組成物の粘度は 3. 15 X 10"2Pa - s,静置安定性指数は 7. 0体積％であった。 The viscosity of the obtained PTFE aqueous dispersion composition was 3.15 × 10 ” 2 Pa-s, and the static stability index was 7.0% by volume.
産業上の利用可能性  Industrial applicability
[0068] 本発明の PTFE水性分散液組成物は、上述の構成からなるものであるので、組成物 を静置保存する際に PTFE樹脂粒子の沈降が抑えられ、再分散が不要、あるいは容 易とすることができる。 [0068] Since the PTFE aqueous dispersion composition of the present invention has the above-described configuration, the settling of PTFE resin particles can be suppressed when the composition is stored at rest, and redispersion is unnecessary or easy. It can be.
本発明の PTFE樹脂フィルムは、上述の構成からなるものであるので、異物等の欠陥 がなぐ均一な被膜とすることが容易である。  Since the PTFE resin film of the present invention has the above-described configuration, it can be easily formed into a uniform film free from defects such as foreign matters.
本発明の PTFE樹脂含浸体は、上述の構成からなるものであるので、異物等の欠陥 がなぐ均一な被膜とすることが可能である。  Since the PTFE resin-impregnated body of the present invention has the above-described configuration, it can be formed into a uniform film free from defects such as foreign matters.

Claims

請求の範囲 The scope of the claims
[1] ポリテトラフルォロエチレン樹脂 (A)、炭化水素系非イオン性化合物（B)及び多糖類 •ポリアミノ酸類（C)を含む  [1] Polytetrafluoroethylene resin (A), hydrocarbon non-ionic compound (B) and polysaccharide • Includes polyamino acids (C)
ことを特徴とするポリテトラフルォロエチレン水性分散液組成物。  A polytetrafluoroethylene aqueous dispersion composition characterized by the above.
[2] ポリテトラフルォロエチレン樹脂 (A)は、ポリテトラフルォロエチレン水性分散液組成 物の 30〜70質量％であり、 [2] The polytetrafluoroethylene resin (A) is 30 to 70% by mass of the polytetrafluoroethylene aqueous dispersion composition,
炭化水素系非イオン性化合物（B)は、前記ポリテトラフルォロエチレン樹脂 (A) 100 質量部に対して 2〜 12質量部であり、  The hydrocarbon-based nonionic compound (B) is 2 to 12 parts by mass with respect to 100 parts by mass of the polytetrafluoroethylene resin (A),
多糖類 ·ポリアミノ酸類（C)は、前記ポリテトラフルォロエチレン樹脂 (A) 100質量部 に対して 0. 00001〜1質量部である請求項 1記載のポリテトラフルォロエチレン水性 分散液組成物。  The polytetrafluoroethylene aqueous dispersion according to claim 1, wherein the polysaccharide / polyamino acid (C) is 0.000001 to 1 part by mass with respect to 100 parts by mass of the polytetrafluoroethylene resin (A). Liquid composition.
[3] ポリテトラフルォロエチレン樹脂 (A)粒子は、平均粒子径が 200〜500nmである請 求項 1又は 2記載のポリテトラフルォロエチレン水性分散液組成物。  [3] The aqueous polytetrafluoroethylene dispersion composition according to claim 1 or 2, wherein the polytetrafluoroethylene resin (A) particles have an average particle diameter of 200 to 500 nm.
[4] 多糖類 ·ポリアミノ酸類（C)は、セルロース、澱粉、デキストリン、アルギン酸、デキスト ラン、キサンタンガム、プノレラン、キトサン、アラビアゴム、カゼイン、グァーガム、ゼラ チン及びぺクチン、並びに、これらの誘導体よりなる群から選ばれる少なくとも 1つで ある請求項 1、 2又は 3記載のポリテトラフルォロエチレン水性分散液組成物。  [4] Polysaccharides · Polyamino acids (C) are derived from cellulose, starch, dextrin, alginic acid, dextrane, xanthan gum, punoleran, chitosan, gum arabic, casein, guar gum, gelatin and pectin, and their derivatives. The aqueous polytetrafluoroethylene dispersion composition according to claim 1, 2 or 3, wherein the composition is at least one selected from the group consisting of:
[5] 多糖類'ポリアミノ酸類（C)は、セルロースエーテル、アルギン酸塩、アルギン酸エス テル、キサンタンガム、キトサン、キトサン塩、ヒドロキシプロピルキトサン及びグァーガ ムよりなる群から選ばれる少なくとも 1つである請求項 1、 2又は 3記載のポリテトラフル ォロエチレン水性分散液組成物。  [5] Polysaccharides' polyamino acids (C) are at least one selected from the group consisting of cellulose ether, alginate, ester alginate, xanthan gum, chitosan, chitosan salt, hydroxypropyl chitosan and guagam. The aqueous polytetrafluoroethylene dispersion composition according to 1, 2 or 3.
[6] 被塗装物上に請求項 1、 2、 3、 4又は 5記載のポリテトラフルォロエチレン水性分散液 組成物を塗装することにより得られる  [6] Obtained by coating the polytetrafluoroethylene aqueous dispersion composition according to claim 1, 2, 3, 4 or 5 on an object to be coated.
ことを特徴とするポリテトラフルォロエチレン樹脂フィルム。  A polytetrafluoroethylene resin film characterized by the above.
[7] 被含浸体と、前記被含浸体に請求項 1、 2、 3、 4又は 5記載のポリテトラフルォロェチ レン水性分散液組成物を含浸することにより得られる被膜とを有する [7] An impregnated body and a film obtained by impregnating the impregnated body with the polytetrafluoroethylene aqueous dispersion composition according to claim 1, 2, 3, 4 or 5.
ことを特徴とするポリテトラフルォロエチレン樹脂含浸体。  A polytetrafluoroethylene resin impregnated body characterized by the above.
PCT/JP2006/304627 2005-03-10 2006-03-09 Polytetrafluoroethylene aqueous dispersion composition, polytetrafluoroethylene resin film and polytetrafluoroethylene resin impregnated article WO2006095825A1 (en)

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CN106750425A (en) * 2016-11-23 2017-05-31 宁波大学 A kind of preparation method of the modified fish scale gelatin chitosan complex film of bamboo-leaves flavones
CN113214581A (en) * 2021-05-12 2021-08-06 九江市磐泰复合材料有限公司 Preparation method of high-flexibility folding-resistant polytetrafluoroethylene glass fiber material

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CN113214581A (en) * 2021-05-12 2021-08-06 九江市磐泰复合材料有限公司 Preparation method of high-flexibility folding-resistant polytetrafluoroethylene glass fiber material

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