WO2006035726A1 - Aqueous polytetrafluoroethylene dispersion composition, poly- tetrafluoroethylene resin film, and products impregnated with polytetrafluoroethylene resin - Google Patents

Aqueous polytetrafluoroethylene dispersion composition, poly- tetrafluoroethylene resin film, and products impregnated with polytetrafluoroethylene resin Download PDF

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Publication number
WO2006035726A1
WO2006035726A1 PCT/JP2005/017643 JP2005017643W WO2006035726A1 WO 2006035726 A1 WO2006035726 A1 WO 2006035726A1 JP 2005017643 W JP2005017643 W JP 2005017643W WO 2006035726 A1 WO2006035726 A1 WO 2006035726A1
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Prior art keywords
ptfe
mass
aqueous dispersion
dispersion composition
polytetrafluoroethylene
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PCT/JP2005/017643
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French (fr)
Japanese (ja)
Inventor
Yasukazu Nakatani
Toshirou Miura
Yasuhiko Sawada
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Daikin Industries, Ltd.
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Priority to JP2006537730A priority Critical patent/JPWO2006035726A1/en
Publication of WO2006035726A1 publication Critical patent/WO2006035726A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • 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

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 particles have heretofore been impregnated into glass fibers, carbon fibers, Kepler fibers, etc., and include roofing materials, etc. of membrane structure buildings. It has been used in the manufacture of immersion bodies, and has been used for film formation by coating and baking on objects to be coated in applications such as high-frequency printed circuit boards, conveyor belts, and packing.
  • PTFE polytetrafluoroethylene
  • a silicone emulsion is blended (for example, see Patent Document 1), a silicone emulsion, and a specific nonionic property.
  • Patent Document 2 A combination of a surfactant and a specific anionic surfactant (see, for example, Patent Document 2), and a thermal decomposition component mainly composed of a nonionic surfactant is 9 to 12% of PTFE
  • Patent Document 3 A blended material (for example, see Patent Document 3) has been proposed.
  • the primary particle diameter is limited to 0.3 to 0.6 m (see, for example, Patent Document 4).
  • a mixture of a PTFE dispersion having an average particle diameter of 180 to 400 nm and a PTFE dispersion having the same particle diameter of 20 to 60 nm (for example, see Patent Document 5) has also been proposed.
  • any of these PTFE aqueous dispersion compositions has a crack limit film thickness. There was still a problem that was not suitable for low thick coating.
  • the roof material of the membrane structure building is required to have high light transmittance.
  • a method for enhancing light transmittance a method of applying an aqueous PTFE dispersion composition to an improved base material (for example, see Patent Documents 6 and 7) has been proposed, but an improvement in the aqueous PTFE dispersion composition has been proposed. It ’s a well-known method.
  • Patent Document 1 Japanese Patent Laid-Open No. 61-34032
  • Patent Document 2 Japanese Patent Laid-Open No. 4-292673
  • Patent Document 3 Japanese Patent Laid-Open No. 2001-89624
  • Patent Document 4 JP-A-5-337439
  • Patent Document 5 JP 2000-53834 A
  • Patent Document 6 Japanese Patent Laid-Open No. 4-300363
  • Patent Document 7 Japanese Patent Laid-Open No. 9-256277
  • the object of the present invention is that the crack limit film thickness is extremely large.
  • a thick film can be formed by a single coating or impregnation, and when modified polytetrafluoroethylene is used. Even so, an object of the present invention is to provide an aqueous PTFE dispersion composition capable of forming a film having excellent crack limit film thickness and transparency.
  • the present invention relates to a polytetrafluoroethylene [PTFE] aqueous dispersion composition
  • PTFE polytetrafluoroethylene
  • the PTFE aqueous dispersion composition has a PTFE rosin solids concentration of 30 to 70% by mass of the PTFE aqueous dispersion composition and a viscosity at 25 ° C of 0.1 lPa's or less.
  • the polyoxyalkylene alkyl ether compound (B) is 9 to 20 parts by mass with respect to 100 parts by mass of the PTFE resin solid content, and constitutes the polytetrafluoroethylene resin particles (A).
  • the polytetrafluoroethylene resin is a PTFE aqueous dispersion composition characterized by being a resin having a modified polytetrafluoroethylene power.
  • the present invention can be obtained by coating the PTFE aqueous dispersion composition on an object to be coated.
  • PTFE resin film characterized by
  • the present invention is a PTFE resin-impregnated body characterized by having an object to be impregnated and a film obtained by impregnating the object to be impregnated with the PTFE aqueous dispersion composition.
  • the PTFE aqueous dispersion composition of the present invention is a composition comprising an aqueous dispersion containing PTFE rosin particles (A) and a specific range of amounts of a polyoxyalkylene alkyl ether compound (B). It has a specific range of PTFE resin solids concentration and a specific range of viscosity.
  • 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 or impregnated on an object to be coated, so that a film made of PTFE resin is coated on the object or the surface of the object to be impregnated. Can be formed on top.
  • “V” is sometimes referred to as “substrate” as a concept that can include both the above-mentioned object to be coated and the object to be impregnated.
  • Coating and impregnation generally involve applying the PTFE aqueous dispersion composition of the present invention onto an object to be coated or immersing the object to be coated (as a concept that can include application and immersion for the purposes of this specification). It may be referred to as “application”), and is an operation consisting of drying by heating, etc., if necessary, and then baking to a temperature above the melting point of PTFE resin.
  • the PTFE aqueous dispersion composition of the present invention reduces both mud cracks that have conventionally occurred during drying after application, and shrinkage cracks that have conventionally occurred due to the shrinkage of the grease accompanying cooling after firing. Also, the crack limit film thickness by one coating or impregnation is extremely large. Thick film can be formed by one coating or impregnation (thick coating property).
  • film-forming property the property that can form a film while reducing the occurrence of the above-mentioned cracks is sometimes referred to as “film-forming property”.
  • the PTFE aqueous dispersion composition of the present invention contains PTFE rosin particles (A).
  • the PTFE resin particles (A) are particles made of PTFE resin.
  • PTFE resin includes a resin made of modified polytetrafluoroethylene [modified PTFE]. If the PTFE resin contains a resin that also has a modified PTFE power, it may be a tetrafluoroethylene [TFE] homopolymer or a modified PTFE card. Fat may be sufficient.
  • the PTFE resin constituting the PTFE resin particles (A) is a resin made of a modified PTFE cartridge.
  • the aqueous PTFE dispersion composition of the present invention can improve the light transmittance of the resulting coating, particularly when the resin made of modified PTFE is used as the PTFE resin. Therefore, the processed article having a coating film having the composition power of the PTFE aqueous dispersion of the present invention can be suitably used as a roofing material for a membrane structure building.
  • the modified PTFE is a copolymer of TFE and a small amount of monomer copolymerizable with TFE.
  • examples of the trace amount of monomer include fluoroolefin, fluorinated (alkyl vinyl ether), cyclic fluorinated monomer, and perfluoroalkylethylene.
  • fluorination examples include perfluoro (alkyl butyl ether) [PAVE], and examples of the PAVE include perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl butyl ether) [ PEVE], perfluoro (propyl butyl ether) [PPVE] and the like.
  • trace amounts of monomers include PAVE, hexafluoropropylene, black trifluoride. PP is more preferred. PVE is more preferred.
  • the trace monomer unit derived from the above trace monomer is preferably in the range of 0.001 to 2% by mass of the entire polymer chain of the modified PTFE, and is in the range of 0.01 to 1% by mass. It is more preferable.
  • the content of the trace monomer unit derived from the trace monomer is determined by using an infrared absorption scan using a powder obtained by coagulating, washing and drying the PTFE aqueous dispersion. It is the value obtained by measuring the petal, or the value obtained by measuring the residual amount in the reaction system by gas chromatography and calculating the consumption power consumption.
  • “monomer unit” such as the above-mentioned trace monomer unit means a part of the molecular structure of the modified PTFE and derived from the corresponding monomer.
  • the PP VE unit is a part of the molecular structure of modified PTFE, which is derived from PPVE. Yes, represented by [CF—CF (OCF;)] —.
  • the PTFE resin preferably has a number average molecular weight of 2 ⁇ 10 4 to 1 ⁇ 10 7 , more preferably 2 ⁇ 10 5 to 8 ⁇ 10 6 .
  • the coating film tends to be brittle, and when it exceeds 1 ⁇ 10 7 , the melt viscosity tends to be too high and the particles tend not to be fused.
  • the number average molecular weight can be determined by measurement by the method described in “Journal of Applied Polymer Science”, Vol. 17, pages 3253-3257 (1973).
  • the PTFE resin particles (A) have an average particle diameter of S200 to 500 nm.
  • a more preferable lower limit of the average particle diameter is 300 nm, and a more preferable upper limit is 400 nm. If it is 200 nm or more, the force that dramatically increases the crack limit film thickness exceeds 500 nm, the particles tend to settle, and the stability of the aqueous dispersion composition decreases.
  • the PTFE aqueous dispersion composition of the present invention enables a large particle size of 300 nm or more, which is not generally achieved with modified PTFE.
  • the average particle size is large in this way, it is easy to increase the film thickness by a single application. Therefore, even when the film is finally made thick, the number of applications can be reduced, and the work becomes easier. It can also suppress mud cracks that are more likely to occur than conventional TFE homopolymers.
  • the average particle size is defined as the transmittance of 550 nm projection light with respect to the unit length of the PTF E aqueous dispersion prepared at a solid content concentration of 0.22% by mass, and the unidirectional diameter in the transmission electron micrograph. Based on the calibration curve with the average particle diameter determined by measuring the above, the transmittance was determined from the above.
  • PTFE aqueous dispersion composition of the present invention is PTFE ⁇ solid concentration is 30 to 70 mass 0/0 aqueous PTFE dispersion composition.
  • the PTFE rosin solid content concentration is preferably U, the lower limit is 40% by mass of the PTFE aqueous dispersion composition, and the upper limit is preferably 65% by mass of the PTFE aqueous dispersion composition.
  • the PTFE aqueous dispersion composition of the present invention has the above-mentioned PTFE rosin solid content concentration within the above range, it is excellent in film forming property and can be easily formed into a thick film.
  • the concentration of the solid content of PTFE resin is the mass of the residue obtained by drying 10 g of the PTFE aqueous dispersion composition described later at a temperature of 380 ° C. for 45 minutes. Determined as a percentage of the mass of the PTFE aqueous dispersion composition
  • the PTFE rosin particles (A) are obtained by polymerizing TFE and the above-mentioned trace amount of monomers in the presence of an aqueous medium by a known polymerization method such as emulsion polymerization or suspension polymerization. Supplied PTFE aqueous dispersion.
  • the polymerization is preferably performed by emulsion polymerization.
  • aqueous medium used in the polymerization examples 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 PTFE resin used and the type of emulsifier.
  • the PTFE aqueous dispersion composition of the present invention contains a polyoxyalkylene alkyl ether compound (B) in addition to the PTFE rosin particles (A).
  • the gap between the PTFE rosin particles (A) in the coating is formed into a polyoxyalkylene alkyl ether.
  • the compound (B) is buried and can act as a binder during drying after application to suppress the generation of cracks and improve the film-forming property.
  • the polyoxyalkylene alkyl ether compound (B) suppresses shrinkage cracks that have conventionally occurred due to grease shrinkage by some action even during cooling after firing the coating.
  • the polyoxyalkylene alkyl ether compound (B) is considered to contribute to the dispersion stability of the PTFE resin particles (A).
  • polyoxyalkylene alkyl ether compound (B) examples include those represented by the formula (I): R—O—A 1 —H (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
  • the polyoxyalkylene alkyl ether represented by these is preferable.
  • A polyoxyalkylene chain preferably having 4 to 20 amino Okishiechiren units and 0-6 O carboxymethyl propylene Unit.
  • 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 5 to 20 oxyethylene units and 1 to 2 oxypropylene units.
  • the polyoxyalkylene alkyl ether compound (B) further includes the following formula (IV):
  • R 4 is a linear or branched alkyl group having 4 to 12 carbon atoms, and A 3 is a polyoxyalkylene chain having 8 to 58 carbon atoms). Examples thereof include oxyethylene alkyl ether.
  • a 3 is preferably a polyoxyalkylene chain having 5 to 20 oxyethylene units and 0 to 12 oxypropylene units, and 5 to 20 oxyshethylene units and 1 to More preferred is a polyoxyalkylene chain having 12 oxypropylene units.
  • the polyoxyalkylene alkyl ether compound (B) exceeds 12 parts by mass with respect to 100 parts by mass of PTFE rosin solids, and 20 parts by mass. It may be 9 to 12 parts by mass with respect to 100 parts by mass of PTFE resin solid content.
  • the film-forming property is insufficient.
  • Kirene alkyl ether compound (B) strength When the content exceeds 20 parts by mass with respect to 100 parts by mass of the solid content of PTFE resin, the physical properties of the PTFE film may deteriorate, for example, the film may be colored.
  • the content of the polyoxyalkylene alkyl ether compound (B) with respect to 100 parts by mass of the PTFE rosin solid content is preferably 12 parts by mass, more preferably 12.1 parts by mass, and preferably 16 parts by mass. is there.
  • the amount of the polyoxyalkylene alkyl ether compound (B) is determined based on the solid content concentration of the PTFE resin and the amount blended when preparing the PTFE aqueous dispersion composition of the present invention ( (Including the blending amount at the time of preparation of the PTFE aqueous dispersion), and can be obtained as a mass with respect to 100 parts by mass of the PTFE resin solids, or 10 g of the PTFE aqueous dispersion composition at a temperature of 100 ° C.
  • the residue obtained by drying for 60 minutes is extracted with hexane, and then the mass of the residue obtained by volatilizing the hexane is expressed as a percentage of the mass of the PTFE resin solid before drying. You can ask for it.
  • the crack limit film thickness is a force evaluated by baking a film on an aluminum plate at 380 ° C for 15 minutes, which is a practical processing condition.
  • PTFE resin solid content 10 0 Cracks do not occur even when the polyoxyalkylene alkyl ether compound (B) is 9 parts by mass or more with respect to parts by mass. If cracks do not occur under these conditions, there will be no major problems in practical use.
  • the firing time can be shortened according to practical use.
  • a PTFE aqueous dispersion composition is fired for a long time, the actual thermal decomposition amount increases and cracks are likely to occur. .
  • the force depending on the heat capacity of the substrate For example, in the case of glass cloth impregnation, the coating is exposed to an atmosphere of 380 ° C. for about 5 minutes or less. After that, it takes about 15 to 20 minutes for the film to be exposed to an atmosphere of 380 ° C when applied to kitchen equipment.
  • the polyoxyalkylene alkyl ether compound (B) is 9 to 20 parts by mass with respect to 100 parts by mass of the PTFE resin solid content
  • the polyoxyalkylene alkyl ether compound (B) is: It is preferable that the average HLB contains a polyoxyalkylene alkyl ether compound of 12 or more, preferably 12-14.
  • the polyoxyalkylene alkyl ether compound (B) exceeds 12 parts by mass with respect to 100 parts by mass of the PTFE resin solid content, and 20 parts by mass.
  • the polyoxyalkylene alkyl ether compound (B1) having an average HLB of 14 or more is preferred! / ,.
  • the polyoxyalkylene alkyl ether compound (B) is more than 12 parts by mass and less than 20 parts by mass with respect to 100 parts by mass of the PTFE resin solid content, and
  • the polyoxyalkylene alkyl ether compound (B) includes the polyoxyalkylene alkyl ether compound (B1), the film-forming property is particularly excellent.
  • the average HLB is a value calculated based on the Griffin equation.
  • the polyoxyalkylene alkyl ether compound (B1) is more than 12 parts by mass and less than 20 parts by mass with respect to 100 parts by mass of the PTFE resin solid content. In some cases, it is preferably 1 to 99% by mass of the polyoxyalkylene alkyl ether compound (B).
  • the content of the polyoxyalkylene alkyl ether compound (B1) is such that the polyoxyalkylene alkyl ether compound (B) exceeds 12 parts by mass and 20 parts by mass or less based on 100 parts by mass of the PTFE resin solid content.
  • a more preferable lower limit is 10% by mass of the polyoxyalkylene alkyl ether compound (B)
  • a further preferable lower limit is 20% by mass
  • a more preferable upper limit is 95% by mass
  • a further preferable upper limit is 90% by mass.
  • the PTFE aqueous dispersion composition of the present invention has the polyoxyalkylene alkyl ether compound (B1) in an amount within the above range, it has an appropriate viscosity, and further has excellent film-forming properties. It will be a thing.
  • the polyoxyalkylene alkyl ether compound (B) is 9 to 12 parts by mass with respect to 100 parts by mass of the PTFE resin solid content
  • the polyoxyalkylene alkyl ether compound (B) is: It is preferred that the polyoxyalkylene alkyl ether compound (B2) has an average HLB of 12 or more and less than 14.
  • the aqueous PTFE dispersion composition of the present invention comprises the above polyoxyalkylene alkyl ether.
  • Compound (B) is 9 to 12 parts by mass with respect to 100 parts by mass of the PTFE resin solid content, and the polyoxyalkylene alkyl ether compound (B2) is used as the polyoxyalkylene alkyl ether compound (B). )
  • the polyoxyalkylene alkyl ether compound (B2) exhibiting particularly excellent film-forming properties is preferably those having an average HLB of 12.5 to 13.7 in terms of film-forming properties.
  • the polyoxyalkylene alkyl ether compound (B2) is a polyoxyalkylene alkyl ether compound (B2) when the polyoxyalkylene alkyl ether compound (B) is 9 to 12 parts by mass with respect to 100 parts by mass of the PTFE resin solid content. It is preferably 1 to 99% by mass of the alkylene alkyl ether compound (B).
  • the content of the polyoxyalkylene alkyl ether compound (B2) is more when the polyoxyalkylene alkyl ether compound (B) is 9 to 12 parts by mass with respect to 100 parts by mass of the PTFE resin solid content.
  • a preferable lower limit is 10% by mass of the polyoxyalkylene alkyl ether compound (B), a further preferable lower limit is 20% by mass, a more preferable upper limit is 95% by mass, and a further preferable upper limit is 90% by mass.
  • the PTFE aqueous dispersion composition of the present invention has the polyoxyalkylene alkyl ether compound (B2) in an amount within the above range, it has an appropriate viscosity, and further has excellent film-forming properties. It becomes.
  • the PTFE aqueous dispersion composition of the present invention can be adjusted to an appropriate value for the surface tension by adding a trace amount of a fluorosurfactant, a silicone surfactant, or the like. . Since the addition amount of these surfactants is very small, the viscosity of the aqueous PTFE dispersion composition does not change greatly.
  • the aqueous PTFE dispersion composition of the present invention further contains a film-forming improver (C).
  • the film-forming modifier (C) is a polyoxyalkylene alkyl ether compound (B) in which PTFE It is considered that the film forming property is improved by supplementing the filling of the gaps between the resin particles.
  • the PTFE aqueous dispersion composition of the present invention uses, in particular, a resin made of a modified PTFE resin as the PTFE resin, cracks are more likely to occur than a TFE homopolymer.
  • C) is also preferably included.
  • the PTFE aqueous dispersion composition of the present invention also has a polyoxyalkylene alkyl ether compound (B) strength. Since it is 9 to 20 parts by mass with respect to 100 parts by mass of the solid content of PTFE resin, the crack generation inhibiting power is improved. In view of this, it is preferable that the film-forming improver (C) is included.
  • the film-forming improver (C) depends on the type of film-forming improver (C) to be used, but it is 10 parts by mass or less with respect to 100 parts by mass of PTFE oil solid content. If it is in the above-mentioned range, it is more preferable that it is 0.1 part by mass or more, and it is more preferable that it is 1 part by mass or more.
  • the film-forming improver (C) is not particularly limited, but is a nonionic surfactant having an acrylic resin, a silicone-based surfactant, and a decomposition residue at 5% or more at 380 ° C.
  • a nonionic surfactant having an acrylic resin, a silicone-based surfactant, and a decomposition residue at 5% or more at 380 ° C.
  • acrylic resin, silicone surfactant, nonionic surfactant having a decomposition residue at 5% or more at 380 ° C. and Z or drying retarder refers to these four types. Of these, one or two or more can be used.
  • the acrylic polymer constituting the acrylic resin is not particularly limited, but a polymer obtained by polymerizing a methacrylate monomer is preferred.
  • metatalylate monomer examples include methyl metatalylate, ethyl methacrylate, propyl methacrylate, dimethylpropyl methacrylate, butyl methacrylate, and pentyl methacrylate.
  • the acrylic resin can be prepared as a stable aqueous dispersion even if it is a homopolymer.
  • the polymer is a polymer having a monomer having a ru group as appropriate as a comonomer.
  • a nonionic surfactant may be added to the aqueous dispersion as necessary in order to further enhance the stability.
  • the above-mentioned acrylic resin remains in a temperature range of 300 to 320 ° C, approximately 25 to 50% by mass before heating, and a temperature range of 330 to 345 ° C. It is preferable that 10 to 20% by mass before heating remains.
  • the acrylic resin when acrylic resin is used as the film-forming improver (C), the acrylic resin is 10 parts by mass with respect to 100 parts by mass of PTFE resin solids. It is preferable that
  • a more preferable upper limit of the above-mentioned acrylic resin relative to 100 parts by mass of PTFE resin is 8 parts by mass, and the lower limit is not particularly limited, but is preferable in that it obtains an effect by blending the above-mentioned acrylic resin.
  • the lower limit is 1 part by mass.
  • silicone surfactant examples include the following general formula:
  • R 1 may be the same or different and has 1 to 30 carbon atoms.
  • R 2 is a formula —R 3 — (CHO)
  • R 3 represents a substituent represented by r.
  • q and r are the same or different and represent an integer of 0 to 20, and q + r> l. ).
  • a compound having such a general formula is sold as a modified silicone oil, but in this application, it is treated as a silicone surfactant.
  • the silicone-based surfactant when a silicone-based surfactant is used as the film-forming improver (C), the silicone-based surfactant is used with respect to 100 parts by mass of the solid content of PTFE resin. It is preferable that the amount is 10 parts by mass or less.
  • the upper limit of the silicone-based surfactant is 100 parts by weight based on PTFE rosin solid content, and the lower limit is not particularly limited.
  • a preferable lower limit is 0.1 part by mass in terms of obtaining the effect of the above.
  • Examples of the nonionic surfactant whose decomposition residue at 380 ° C is 5% or more include various polyoxyethylene derivatives.
  • the decomposition residue at 380 ° C. is 5% or more
  • the residue after heating at 380 ° C. for at least 10 minutes is 5% by mass or more before the heating. Means that.
  • the PTFE aqueous dispersion composition of the present invention uses the nonionic surfactant when the nonionic surfactant whose decomposition residue at 380 ° C is 5% or more is used as the film-forming improver (C).
  • the agent is preferably 10 parts by mass or less with respect to 100 parts by mass of the solid content of PTFE resin.
  • the decomposition residue at 380 ° C is 5% or more with respect to 100 parts by mass of PTFE resin solid content.
  • a more preferable upper limit of the nonionic surfactant is 5 parts by mass, and the lower limit is not particularly limited.
  • a preferable lower limit is 0.1 part by mass in that an effect is obtained by adding a nonionic surfactant whose decomposition residue at 380 ° C is 5% or more.
  • drying retardant examples include those having a boiling point of about 200 to 300 ° C, as long as they are normally recognized by those skilled in the art as “drying retardants”.
  • a solvent a water-soluble solvent is preferable.
  • water-soluble solvent examples include glycerin, diethylene glycol monoethyl ether (ethyl carbitol), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol, ethylene glycol, 1,3 propanediol, 1,3 butanediol, 1 1,4-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, 2-ethyl-2-hydroxymethyl-1,3-propanediol and the like are preferred.
  • the drying retardant is obtained by reducing or removing water, polyoxyalkylene alkyl ether compound (B), etc. by drying or heating from a coating obtained by applying the PTFE aqueous dispersion composition of the present invention to a substrate.
  • the film-forming property is improved by remaining in the coating and acting to fill the gaps between the PTFE resin particles.
  • the amount of the drying retarder is appropriately set according to the type of the drying retarder. It is possible The strength is preferably 10 parts by mass or less with respect to 100 parts by mass of the solid content of PTFE resin.
  • diethylene glycol monoalkyl ether has a function of dissolving acrylic resin, so that the film forming property can be further improved by using it together with acrylic resin.
  • the PTFE aqueous dispersion composition of the present invention has, as the film-forming improver (C), an allyl resin, a silicone-based surfactant, or a decomposition residue at 380 ° C of 5% or more. It is more preferable to include an acrylic resin which preferably includes a certain nonionic surfactant.
  • the acrylic resin used as the film-forming modifier (C) in the present invention maintains the binder effect on the PTFE resin particles (A) when the PTFE aqueous dispersion composition of the present invention is applied and dried and then fired. Since it gradually decomposes, the occurrence of shrinkage cracks can be effectively prevented.
  • the PTFE aqueous dispersion composition of the present invention can be blended with various known additives as long as the effects of the present invention are not impaired.
  • the additive include pigments, fillers, antifoaming agents, drying agents, thickeners, leveling agents, repellency inhibitors, and the like.
  • the pigment is not particularly limited, and examples thereof include known pigments such as titanium oxide, carbon black, and bengara.
  • antifoaming agent examples include toluene, xylene, non-polar solvents such as hydrocarbons having 9 to 11 carbon atoms, and silicone oil.
  • Examples of the desiccant include acid cobalt.
  • thickener examples include methyl cellulose, polybulal alcohol, carboxylated bulle polymer, and the like.
  • the PTFE aqueous dispersion composition of the present invention has a viscosity at 25 ° C of 0.1 Pa's or less.
  • the PTFE aqueous dispersion composition of the present invention preferably has a viscosity of 0.06 Pa's or less, and may be 0.0 OlPa's or more as long as it is within the above range.
  • the viscosity is measured at a temperature of 25 ° C. according to JIS K6893 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. For example, while stirring the PTFE aqueous dispersion obtained by polymerization, the polyoxyalkylene alkyl ether compound (B), and as necessary, Depending on the situation, the film-forming improver (C) and other additives can be added and mixed.
  • the polyoxyalkylene alkyl ether compound (B) can be added when preparing an aqueous PTFE dispersion, and has been conventionally used, for example, for concentrating an aqueous dispersion that is a polymerization product. Although it may be added as a dispersant, it is usually preferable to add after the preparation of the PTFE aqueous dispersion to adjust to the target viscosity.
  • the conditions for the above-mentioned stirring, addition and mixing operations are preferably performed at a force of 5 to 30 ° C., which can be appropriately set according to the type and amount of the composition to be used.
  • the PTFE aqueous dispersion composition of the present invention has the above-described configuration, it improves the crack resistance and thick coatability as described above, and also has an extremely large crack limit film thickness by one application.
  • the crack limit film thickness by one application can be achieved only up to about 2 m in the past, especially when using a PTFE resin particle (A) as a modified PTFE resin.
  • it can be about 20 m or more.
  • the crack limit film thickness is determined by dropping a PTFE aqueous dispersion composition (5 ml) on an aluminum plate of 20 cm ⁇ 10 cm ⁇ l. 5 mm and using a coating applicator (manufactured by Yasuda Seiki Co., Ltd.).
  • a coating applicator manufactured by Yasuda Seiki Co., Ltd.
  • the coating thickness is greater than O / zm and continuously changes between 200 m and below, when dried at 100 ° C for 10 minutes and then baked at 380 ° C for 15 minutes, no cracks occur. The film thickness was measured.
  • modified PTFE can provide a coating with better transparency than a TFE homopolymer, but the aqueous PTFE dispersion composition of the present invention has a modified PTFE strength as a PTFE resin.
  • the resin is used, it is possible to obtain a thick film with high light transmittance despite the extremely large crack limit film thickness.
  • the PTFE resin film of the present invention is obtained by coating the above-mentioned PTFE aqueous dispersion composition of the present invention on an object to be coated.
  • 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 coating can usually be performed by applying the PTFE aqueous dispersion composition of the present invention, drying, and then firing.
  • aqueous PTFE dispersion composition of the present invention may be directly applied to a substrate, but in order to improve the 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 polyoxyalkylene alkyl ether compound (B), film-forming improver (C), etc. to be used, but it is room temperature to 150 ° C, preferably 80 to 150 °. It is preferably performed at a temperature of C for 5 to 20 minutes.
  • the firing can be performed for 5 to 60 minutes at a temperature equal to or higher than the melting temperature of the PTFE resin to be used, usually 340 to 415 ° C, and is performed at 360 to 400 ° C for 10 to 30 minutes. That power S is preferable.
  • 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 the coated product via a primer layer or the like.
  • the PTFE resin film of the present invention is formed by coating the PTFE aqueous dispersion composition of the present invention described above, it is usually about 5 to: LOO ⁇ m, preferably about 10 to: It has a thickness of LOO ⁇ m.
  • 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, it can be obtained, for example, metal cooking utensils, bearings, valves, etc. , Electric wire, metal foil, boiler, pipe, ship bottom, oven lining, iron bottom plate, ice tray, snow shovel, plow, chute, conveyor, roll, mold, die, saw, file, cutting tool, knife, Scissors, hoppers, other industrial containers (especially for the semiconductor industry), and scissors can be used.
  • metal cooking utensils, bearings, valves, etc. Electric wire, metal foil, boiler, pipe, ship bottom, oven lining, iron bottom plate, ice tray, snow shovel, plow, chute, conveyor, roll, mold, die, saw, file, cutting tool, knife, Scissors, hoppers, other industrial containers (especially for the semiconductor industry), and scissors can be used.
  • the PTFE resin film of the present invention can be suitably used as a coating material for high-frequency printed circuit boards, conveyor belts, packings and the like.
  • the PTFE resin-impregnated body of the present invention has 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.
  • the impregnated body is not particularly limited, and examples thereof include a fiber base material, a woven fabric and a non-woven fabric.
  • the fiber substrate is not particularly limited, and examples thereof include glass fiber, carbon fiber, and aramid fiber (Kepler fiber, etc.).
  • Examples of the woven fabric'nonwoven fabric include a roof material (tent membrane) of a membrane structure building. When light transmission is required as the roofing material, it is preferable to use a modified PTFE resin as the PTFE resin.
  • 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, it usually depends on the shape and thickness of the substrate, but is usually about 5 to: LOO ⁇ m, preferably About 10 ⁇ : having a thickness of LOO ⁇ m.
  • the PTFE aqueous dispersion composition of the present invention has the above-mentioned constitution, it can be suitably used as a coating yarn and composition that does not cause cracks despite being a thick film. Togashi.
  • the PTFE resin film of the present invention has the above-described configuration, it can be easily formed into a thick film free from defects such as cracks.
  • the PTFE resin impregnated body of the present invention has the above-mentioned constitution, it can be a thick film without cracks and the like.
  • aqueous PTFE dispersion composition of the present invention contains a resin made of modified PTFE, the resulting coating is highly light transmissive.
  • the mass of the residue obtained by drying 10 g of the PTFE aqueous dispersion at a temperature of 380 ° C. for 45 minutes was determined as a percentage of the mass of the PTFE aqueous dispersion before the drying.
  • PTFE rosin solid concentration determined in (3) above and the amount to be blended when preparing the PTFE aqueous dispersion composition of the present invention (including the blending amount at the time of preparing the PTFE aqueous dispersion), PT FE It calculated
  • composition concentrations other than (3) and (4) are values in which mass force at the time of addition is also converted.
  • PC 71.2% by mass polyoxy A PTFE aqueous dispersion concentrate A having an ethylene alkyl ether concentration [NC] of 2.9% by mass of PTFE rosin solids was prepared.
  • NC force SPTFE Kitsuki PTFE aqueous dispersion concentrated product B is 1.9% by weight of the fact solids.
  • a PTFE aqueous dispersion composition in which “(Bl) Z (B)” and “)” were 54 mass% was obtained.
  • the obtained PTFE aqueous dispersion composition had a viscosity of 2.05 X 10 " 2 Pa-s and a crack limit film thickness force SlO / zm.
  • the obtained PTFE aqueous dispersion composition had a viscosity of 5.80 ⁇ 10 ” 2 Pa-s, crack limit film thickness force ⁇ 4; ⁇ ⁇ .
  • PTFE aqueous dispersion concentrate A 300 g, TDS-120 21.6 g, acrylic resin aqueous dispersion (Nihon Shokubai Co., Ltd., solid concentration 40% by mass) 16. Og, ethyl carbitol (Nippon Shokubai Co., Ltd.) (Boiling point: 202 ° C) 8.
  • the obtained PTFE aqueous dispersion composition had a viscosity of 4.80 ⁇ 10 ” 2 Pa-s and a crack limit film thickness of 20 / zm.
  • PTFE aqueous dispersion concentrate A 300 g, TDS-120 19.4 g, acrylic resin aqueous dispersion (Nippon Shokubai Co., Ltd., solid concentration 40% by mass) 16. Og, Emargen A-60 (manufactured by Kao Corporation) Polyoxyethylene derivatives) 2. lg, ethyl carbitol 4.
  • the obtained PTFE aqueous dispersion composition had a viscosity of 3.55 ⁇ 10 ” 2 Pa-s and a crack limit film thickness of 20 / zm.
  • PTFE aqueous dispersion concentrate A 300 g, TDS-120 21.6 g, acrylic resin aqueous dispersion (Nippon Shokubai Co., Ltd., solid content 40% by mass) 16.0 g, ethyl carbitol 8.0 g, g glycerin 2. lg and pure water 55. 2 g of ⁇ Ka ⁇ , PC 53 mass 0/0, NC force 13 mass% of PTFE ⁇ solids, 3% by weight of acrylic ⁇ is PTFE ⁇ solids, Ethylcarbitol is 50% by mass of the aqueous dispersion of acrylic resin, and glycerin is a part of the solid content of PTFE resin.
  • the obtained PTFE aqueous dispersion composition had a viscosity of 5.70 ⁇ 10 ” 2 Pa-s, a crack limit film thickness force of 8; ⁇ .
  • PTFE aqueous dispersion concentrate A 300 g, TDS-120 21.6 g, Silwet L-77 (manufactured by Nippon Carker, silicone surfactant) 2. Add Ig and 79.3 g of pure water, .53% by mass, NC is 13% by mass of PTFE resin solids, Silicone surfactant is 1% by mass of PTFE resin solids, (Bl) Z (B)
  • the obtained PTFE aqueous dispersion composition had a viscosity of 5.70 ⁇ 10 ” 2 Pa-s, crack limit film thickness force ⁇ 2; ⁇ .
  • the resulting PTFE aqueous dispersion composition had a viscosity of 4.40 ⁇ 10 ” 2 Pa-s and a crack limit film thickness of 12 / zm.
  • the obtained PTFE aqueous dispersion composition had a viscosity of 4.90 ⁇ 10 ” 2 Pa-s and a crack limit film thickness force m.
  • the obtained PTFE aqueous dispersion composition had a viscosity of 5.70 ⁇ 10 ” 2 Pa-s and a crack limit film thickness force SlO / zm.
  • the obtained PTFE aqueous dispersion composition had a viscosity of 4.95 ⁇ 10 ” 2 Pa-s and a crack limit film thickness of 29 / zm.
  • PTFE aqueous dispersion concentrate A 300g coconut, TDS-80 13. Add Og and pure water 90.Og, PC 53% by mass, NC is 9% by mass of PTFE oil solids, (Bl) Z ( B) A 0% by mass PTFE aqueous dispersion was obtained.
  • the obtained aqueous dispersion composition had a viscosity of 1.80 ⁇ 10 ” 2 Pa ′s and a crack limit film thickness of 5 ⁇ m.
  • the obtained aqueous dispersion composition had a viscosity of 7.45 ⁇ 10_2 Pa's and a crack limit film thickness of 5 m.
  • the resulting aqueous dispersion composition has a viscosity of 2.00 X 10 _2 Pa's and a crack limit film thickness of 8 m.
  • the obtained aqueous dispersion composition had a viscosity of 2.00 ⁇ 10 ” 2 Pa-s and a crack limit film thickness of 29 ⁇ m.
  • the resulting aqueous dispersion composition had a viscosity of 0.60 ⁇ 10 ” 2 Pa-s and a crack limit film thickness of 1 ⁇ m.
  • the resulting aqueous dispersion composition had a viscosity of 13.90 ⁇ 10 ” 2 Pa-s and a crack limit film thickness of 6 ⁇ m.
  • the resulting aqueous dispersion composition had a viscosity of 15.05 ⁇ 10 ” 2 Pa-s and a crack limit film thickness of 5 ⁇ m.
  • PTFE aqueous dispersion concentrate C 300g, TDS-80 7.lg, TDS-120 15.lg, acrylic resin aqueous dispersion (Nippon Shokubai Co., Ltd., solid content concentration 40% by mass) 16.2g, Ethylcal Bitoru 8. added lg and pure water 60.
  • the obtained aqueous dispersion composition had a viscosity of 3.05 X 10 " 2 Pa-s and a crack limit film thickness of 41 ⁇ m.
  • PTFE aqueous dispersion concentrated product A 300g, TDS-808.8g and pure water 94.2g added, 53% PC by weight, NC 7% by weight PTFE solids, (Bl) Z (B) A PTFE aqueous dispersion with 0 mass% was obtained.
  • the obtained aqueous dispersion composition had a viscosity of 1.55 ⁇ 10 ” 2 Pa-s and a crack limit film thickness of 2 m.
  • the PTFE aqueous dispersion composition obtained from Example 3 and the aqueous dispersion compositions obtained from Comparative Example 1 and Comparative Example 5 were coated on an aluminum plate (20 cm ⁇ 15 cm ⁇ l.5 mm) with a film thickness of 10 Apply to ⁇ 20 m, dry at 100 ° C for 10 minutes, peel off the film obtained by baking at 380 ° C for 15 minutes, and use a direct reading haze meter (Toyo Seiki Seisakusho) Then, the total light transmittance and haze value of the portion having a film thickness of 15 m were measured.
  • the total light transmittance indicates the light transmission ratio, and the larger the value, the better the light transmittance.
  • the haze value indicates the ratio of diffused light in the transmitted light, and the smaller the value, the better the transparency.
  • Table 1 shows the total light transmittance and haze value of the coatings obtained in Example 3, Comparative Example 1 and Comparative Example 5.
  • Example 3 9 4 .9% 8.0% Comparative Example 1 9 2.5% 2 3.7% Comparative Example 5 9 3 .5% 1 9 .4%
  • Example 3 PPVE-modified PTFE is used, while in Comparative Examples 1 and 5, PTFE homopolymer (Homo PTFE) is used! It can be seen that the coating containing the modified PTFE-strengthened resin is superior in light transmission, and has a low ratio of diffused light, and thus excellent in transparency.
  • PTFE homopolymer Homo PTFE
  • the PTFE aqueous dispersion composition of the present invention also has the above-mentioned constitutional power, it is suitable as a coating yarn and composition that does not cause cracks despite being easy to form a thick film. Can be used.
  • the PTFE resin film of the present invention has the above-described configuration, it can be easily formed into a thick film free from defects such as cracks.
  • the PTFE resin impregnated body of the present invention has the above-mentioned constitution, it can be a thick film without cracks and the like.
  • aqueous PTFE dispersion composition of the present invention contains a resin made of modified PTFE, the resulting coating is highly light transmissive.

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Abstract

An aqueous polytetrafluoroethylene (PTFE) dispersion composition which has a great film crack threshold thickness and permits the formation of thick film by single application or impregnation and which can give film excellent in crack threshold thickness and transparency even though a modified PTFE is used. The dispersion composition is one comprising PTFE resin particles (A) and a polyoxyalkylene alkyl ether compound (B) which is characterized in that the concentration of solid PTFE resin is 30 to 70 % by mass based on the dispersion composition, that the viscosity of the composition at 25˚C is 0.1Pa·s or below, that the polyoxyalkylene alkyl ether compound (B) is contained in an amount of 9 to 20 parts by mass per 100 parts by mass of the solid PTFE, and that the PTFE resin constituting the particles (A) is a modified PTFE resin.

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  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 ン榭脂フィルム及びポリテトラフルォロエチレン榭脂含浸体に関する。  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〕榭脂粒子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、パッキン等の用 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 particles have heretofore been impregnated into glass fibers, carbon fibers, Kepler fibers, etc., and include roofing materials, etc. of membrane structure buildings. It has been used in the manufacture of immersion bodies, and has been used for film formation by coating and baking on objects to be coated in applications such as high-frequency printed circuit boards, conveyor belts, and packing.
[0003] 従来の PTFE榭脂粒子を含む水性分散液組成物は、 1回あたりの含浸 ·塗布量をあ る膜厚以上にすると、被膜にクラックを生じ、品質が損われる問題があった。この問題 を解決するため、厚膜の加工品が求められる場合、含浸又は塗布の工程を繰返す 方法が行われてきたが、この方法には、生産コストが上昇する問題、はじきが生じる 問題があった。  [0003] Conventional aqueous dispersion compositions containing PTFE rosin particles have had the problem that if the impregnation / coating amount per application exceeds a certain film thickness, the coating cracks and the quality is impaired. In order to solve this problem, when a thick film processed product is required, a method of repeating the impregnation or coating process has been performed. However, this method has a problem that the production cost increases and a problem occurs. It was.
[0004] 耐クラック性の改善を目的とした PTFEの水性分散液組成物としては、シリコーンェ マルジヨンを配合したもの（例えば、特許文献 1参照。）、シリコーンェマルジヨン、特 定の非イオン性界面活性剤及び特定の陰イオン性界面活性剤を配合したもの (例え ば、特許文献 2参照。）、非イオン性界面活性剤を主成分とする熱分解成分を PTFE に対して 9〜12%配合したもの（例えば、特許文献 3参照。）等が提案されている。  [0004] As an aqueous dispersion composition of PTFE for the purpose of improving crack resistance, a silicone emulsion is blended (for example, see Patent Document 1), a silicone emulsion, and a specific nonionic property. A combination of a surfactant and a specific anionic surfactant (see, for example, Patent Document 2), and a thermal decomposition component mainly composed of a nonionic surfactant is 9 to 12% of PTFE A blended material (for example, see Patent Document 3) has been proposed.
[0005] 耐クラック性の改善を目的とした PTFEの水性分散液組成物としては、また、一次粒 子径を 0. 3〜0. 6 mに限定したもの（例えば、特許文献 4参照。）、平均粒子径 18 0〜400nmの PTFE分散体と同 20〜60nmの PTFE分散体とを混合したもの（例え ば、特許文献 5参照。）も提案されている。  [0005] As an aqueous dispersion composition of PTFE for the purpose of improving crack resistance, the primary particle diameter is limited to 0.3 to 0.6 m (see, for example, Patent Document 4). A mixture of a PTFE dispersion having an average particle diameter of 180 to 400 nm and a PTFE dispersion having the same particle diameter of 20 to 60 nm (for example, see Patent Document 5) has also been proposed.
[0006] しかしながら、これらの PTFEの水性分散液組成物は、いずれも、クラック限界膜厚が 依然として低ぐ厚塗りに適さない問題があった。 [0006] However, any of these PTFE aqueous dispersion compositions has a crack limit film thickness. There was still a problem that was not suitable for low thick coating.
[0007] 一方、膜構造建築物の屋根材には高い光透過性が求められる。光透過性を高める 方法として、改良した基材に PTFE水性分散液組成物を塗布する手法 (例えば、特 許文献 6、 7参照。）は提案されているが、 PTFE水性分散液組成物の改良による手 法にっ ヽては知られて ヽな 、。  [0007] On the other hand, the roof material of the membrane structure building is required to have high light transmittance. As a method for enhancing light transmittance, a method of applying an aqueous PTFE dispersion composition to an improved base material (for example, see Patent Documents 6 and 7) has been proposed, but an improvement in the aqueous PTFE dispersion composition has been proposed. It ’s a well-known method.
特許文献 1：特開昭 61— 34032号公報  Patent Document 1: Japanese Patent Laid-Open No. 61-34032
特許文献 2：特開平 4 - 292673号公報  Patent Document 2: Japanese Patent Laid-Open No. 4-292673
特許文献 3：特開 2001— 89624号公報  Patent Document 3: Japanese Patent Laid-Open No. 2001-89624
特許文献 4：特開平 5— 337439号公報  Patent Document 4: JP-A-5-337439
特許文献 5：特開 2000— 53834号公報  Patent Document 5: JP 2000-53834 A
特許文献 6：特開平 4— 300363号公報  Patent Document 6: Japanese Patent Laid-Open No. 4-300363
特許文献 7：特開平 9 - 256277号公報  Patent Document 7: Japanese Patent Laid-Open No. 9-256277
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
[0008] 本発明の目的は、上記現状に鑑み、クラック限界膜厚が極めて大きぐ 1回の塗装又 は含浸によっても厚膜ィ匕が可能で、変性ポリテトラフルォロエチレンを用いた場合で あってもクラック限界膜厚と透明性に優れた被膜を成形することができる PTFE水性 分散液組成物を提供することにある。 [0008] In view of the above situation, the object of the present invention is that the crack limit film thickness is extremely large. A thick film can be formed by a single coating or impregnation, and when modified polytetrafluoroethylene is used. Even so, an object of the present invention is to provide an aqueous PTFE dispersion composition capable of forming a film having excellent crack limit film thickness and transparency.
課題を解決するための手段  Means for solving the problem
[0009] 本発明は、ポリテトラフルォロエチレン [PTFE]榭脂粒子 (A)とポリオキシアルキレン アルキルエーテル系化合物（B)とを含むポリテトラフルォロエチレン [PTFE]水性分 散液組成物であって、上記 PTFE水性分散液組成物は、 PTFE榭脂固形分濃度が 上記 PTFE水性分散液組成物の 30〜70質量％、 25°Cにおける粘度が 0. lPa' s以 下であり、上記ポリオキシアルキレンアルキルエーテル系化合物（B)は、上記 PTFE 榭脂固形分 100質量部に対して 9〜20質量部であり、上記ポリテトラフルォロェチレ ン榭脂粒子 (A)を構成するポリテトラフルォロエチレン榭脂は、変性ポリテトラフルォ 口エチレン力もなる榭脂であることを特徴とする PTFE水性分散液組成物である。  [0009] The present invention relates to a polytetrafluoroethylene [PTFE] aqueous dispersion composition comprising polytetrafluoroethylene [PTFE] resin particles (A) and a polyoxyalkylene alkyl ether compound (B). The PTFE aqueous dispersion composition has a PTFE rosin solids concentration of 30 to 70% by mass of the PTFE aqueous dispersion composition and a viscosity at 25 ° C of 0.1 lPa's or less. The polyoxyalkylene alkyl ether compound (B) is 9 to 20 parts by mass with respect to 100 parts by mass of the PTFE resin solid content, and constitutes the polytetrafluoroethylene resin particles (A). The polytetrafluoroethylene resin is a PTFE aqueous dispersion composition characterized by being a resin having a modified polytetrafluoroethylene power.
[0010] 本発明は、被塗装物上に上記 PTFE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 PTFE榭脂フィルムである。 [0010] The present invention can be obtained by coating the PTFE aqueous dispersion composition on an object to be coated. PTFE resin film characterized by
本発明は、被含浸体と、上記被含浸体に上記 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ことを特徴とする PTFE榭脂含浸体である。  The present invention is a PTFE resin-impregnated body characterized by having an object to be impregnated and a film obtained by impregnating the object to be impregnated with the PTFE aqueous dispersion composition.
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 PTFE水性分散液組成物は、 PTFE榭脂粒子 (A)と、特定範囲の量のポリ ォキシアルキレンアルキルエーテル系化合物（B)とを含む水性分散液からなる組成 物であって、特定範囲の PTFE榭脂固形分濃度と、特定範囲の粘度とを有するもの である。 [0011] The PTFE aqueous dispersion composition of the present invention is a composition comprising an aqueous dispersion containing PTFE rosin particles (A) and a specific range of amounts of a polyoxyalkylene alkyl ether compound (B). It has a specific range of PTFE resin solids concentration and a specific range of viscosity.
[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榭脂から 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 V、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!、うことがあ 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 (本明細書にぉ ヽて、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、 P TFE榭脂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 or impregnated on an object to be coated, so that a film made of PTFE resin is coated on the object or the surface of the object to be impregnated. Can be formed on top. In the present specification, “V” is sometimes referred to as “substrate” as a concept that can include both the above-mentioned object to be coated and the object to be impregnated. Coating and impregnation generally involve applying the PTFE aqueous dispersion composition of the present invention onto an object to be coated or immersing the object to be coated (as a concept that can include application and immersion for the purposes of this specification). It may be referred to as “application”), and is an operation consisting of drying by heating, etc., if necessary, and then baking to a temperature above the melting point of PTFE resin.
[0013] 本発明の PTFE水性分散液組成物は、適用後の乾燥時に従来生じていたマッドクラ ック、及び、焼成後の冷却に伴う榭脂収縮により従来生じていた収縮クラックを、とも に低減することができ、また、 1回の塗装又は含浸によるクラック限界膜厚が極めて大 きぐ 1回の塗装又は含浸によっても厚膜ィ匕が可能である (厚塗り性)。  [0013] The PTFE aqueous dispersion composition of the present invention reduces both mud cracks that have conventionally occurred during drying after application, and shrinkage cracks that have conventionally occurred due to the shrinkage of the grease accompanying cooling after firing. Also, the crack limit film thickness by one coating or impregnation is extremely large. Thick film can be formed by one coating or impregnation (thick coating property).
本明細書において、上述のクラックの発生を少なくして被膜を形成することができる 性質を、「造膜性」と称することがある。  In the present specification, the property that can form a film while reducing the occurrence of the above-mentioned cracks is sometimes referred to as “film-forming property”.
[0014] 本発明の PTFE水性分散液組成物は、 PTFE榭脂粒子 (A)を含むものである。  [0014] The PTFE aqueous dispersion composition of the present invention contains PTFE rosin particles (A).
本明細書において、上記 PTFE榭脂粒子 (A)は、 PTFE榭脂からなる粒子である。 本明細書において、 PTFE榭脂は、変性ポリテトラフルォロエチレン〔変性 PTFE〕か らなる榭脂を含むものである。上記 PTFE榭脂は、変性 PTFE力もなる榭脂を含むも のであれば、テトラフルォロエチレン〔TFE〕単独重合体及び変性 PTFEカゝらなる榭 脂であってもよい。 In the present specification, the PTFE resin particles (A) are particles made of PTFE resin. In the present specification, PTFE resin includes a resin made of modified polytetrafluoroethylene [modified PTFE]. If the PTFE resin contains a resin that also has a modified PTFE power, it may be a tetrafluoroethylene [TFE] homopolymer or a modified PTFE card. Fat may be sufficient.
本発明の PTFE水性分散液組成物において、好ましくは、 PTFE榭脂粒子 (A)を構 成する上記 PTFE榭脂は、変性 PTFEカゝらなる榭脂である。 In the PTFE aqueous dispersion composition of the present invention, preferably, the PTFE resin constituting the PTFE resin particles (A) is a resin made of a modified PTFE cartridge.
本発明の PTFE水性分散液組成物は、驚くべきことに、上記 PTFE榭脂として変性 P TFEからなる榭脂を用いる場合、特に、得られる被膜の光透過性を向上させることが できる。従って、本発明の PTFE水性分散液組成物力もなる被膜を有する加工物品 は、膜構造建築物の屋根材等として好適に使用することができる。 Surprisingly, the aqueous PTFE dispersion composition of the present invention can improve the light transmittance of the resulting coating, particularly when the resin made of modified PTFE is used as the PTFE resin. Therefore, the processed article having a coating film having the composition power of the PTFE aqueous dispersion of the present invention can be suitably used as a roofing material for a membrane structure building.
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- 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。 The modified PTFE is a copolymer of TFE and a small amount of monomer copolymerizable with TFE. Examples of the trace amount of monomer include fluoroolefin, fluorinated (alkyl vinyl ether), cyclic fluorinated monomer, and perfluoroalkylethylene.
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-ルエーテル） [PMVE]、パーフルォロ（ェチルビ-ルエーテル） [PEVE] 、パーフルォロ（プロピルビュルエーテル） [PPVE]等が挙げられる。 Examples of the fluorination (alkyl butyl ether) include perfluoro (alkyl butyl ether) [PAVE], and examples of the PAVE include perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl butyl ether) [ PEVE], perfluoro (propyl butyl ether) [PPVE] and the like.
本発明の PTFE水性分散液組成物にぉ ヽて、上記 PTFE榭脂として変性 PTFEから なる榭脂を用いる場合、微量の単量体としては、 PAVE,へキサフルォロプロピレン、 クロ口トリフルォロエチレンが好ましぐ PAVEがより好ましぐ PPVEがより好ましい。 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 、。 In the PTFE aqueous dispersion composition of the present invention, in the case where a resin comprising modified PTFE is used as the PTFE resin, trace amounts of monomers include PAVE, hexafluoropropylene, black trifluoride. PP is more preferred. PVE is more preferred. The trace monomer unit derived from the above trace monomer is preferably in the range of 0.001 to 2% by mass of the entire polymer chain of the modified PTFE, and is in the range of 0.01 to 1% by mass. It is more preferable.
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の含有率は、 P TFE水性分散体を凝析、洗浄、乾燥して得られたパウダーを用いて、赤外吸収スぺ タトル測定を行って得られた値、もしくはガスクロマトグラフにより反応系内における残 存量を測定し、仕込量との関係力 消費量を算出することにより得た値である。 In the present specification, the content of the trace monomer unit derived from the trace monomer is determined by using an infrared absorption scan using a powder obtained by coagulating, washing and drying the PTFE aqueous dispersion. It is the value obtained by measuring the petal, or the value obtained by measuring the residual amount in the reaction system by gas chromatography and calculating the consumption power consumption.
本明細書にお!、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 ( O C F；) ]—で表される。 In the present specification, “monomer unit” such as the above-mentioned trace monomer unit means a part of the molecular structure of the modified PTFE and derived from the corresponding monomer. For example, the PP VE unit is a part of the molecular structure of modified PTFE, which is derived from PPVE. Yes, represented by [CF—CF (OCF;)] —.
2 3 7  2 3 7
[0016] 上記 PTFE榭脂は、数平均分子量が 2 X 104〜1 X 107であることが好ましぐ 2 X 10 5〜8 X 106であることがより好まし 、。 [0016] The PTFE resin preferably has a number average molecular weight of 2 × 10 4 to 1 × 10 7 , more preferably 2 × 10 5 to 8 × 10 6 .
上記数平均分子量が 2 X 104未満である場合、塗膜が脆くなる傾向があり、 1 X 107を 超える場合、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 2 × 10 4 , the coating film tends to be brittle, and when it exceeds 1 × 10 7 , the melt viscosity tends to be 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 measurement by the method described in “Journal of Applied Polymer Science”, Vol. 17, pages 3253-3257 (1973).
[0017] 本発明の PTFE水性分散液組成物にぉ ヽて、 PTFE榭脂粒子 (A)は、平均粒子径 力 S200〜500nmであるものが好ましい。上記平均粒子径のより好ましい下限は 300 nmであり、より好ましい上限は 400nmである。 200nm以上であると、クラック限界膜 厚が飛躍的に高まる力 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。  [0017] In the PTFE aqueous dispersion composition of the present invention, it is preferable that the PTFE resin particles (A) have an average particle diameter of S200 to 500 nm. A more preferable lower limit of the average particle diameter is 300 nm, and a more preferable upper limit is 400 nm. If it is 200 nm or more, the force that dramatically increases the crack limit film thickness exceeds 500 nm, the particles tend to settle, and the stability of the aqueous dispersion composition decreases.
本発明の PTFE水性分散液組成物は、特に、変性 PTFEでは従来一般に達成され て ヽなかった 300nm以上と!/ヽぅ大粒径を可能にしたものである。このように平均粒子 径が大きいと、 1回の適用による膜厚を厚くすることが容易なので、最終的に厚膜に する場合であっても、適用回数を低減でき、作業容易になるとともに、 TFE単独重合 体よりも従来発生しやすかつたマッドクラックを抑制することもできる。  The PTFE aqueous dispersion composition of the present invention enables a large particle size of 300 nm or more, which is not generally achieved with modified PTFE. When the average particle size is large in this way, it is easy to increase the film thickness by a single application. Therefore, even when the film is finally made thick, the number of applications can be reduced, and the work becomes easier. It can also suppress mud cracks that are more likely to occur than conventional TFE homopolymers.
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。  In the present specification, the average particle size is defined as the transmittance of 550 nm projection light with respect to the unit length of the PTF E aqueous dispersion prepared at a solid content concentration of 0.22% by mass, and the unidirectional diameter in the transmission electron micrograph. Based on the calibration curve with the average particle diameter determined by measuring the above, the transmittance was determined from the above.
[0018] 本発明の PTFE水性分散液組成物は、 PTFE榭脂固形分濃度が PTFE水性分散液 組成物の 30〜70質量0 /0であるものである。 [0018] PTFE aqueous dispersion composition of the present invention is PTFE榭脂solid concentration is 30 to 70 mass 0/0 aqueous PTFE dispersion composition.
上記 PTFE榭脂固形分濃度は、好ま U、下限が PTFE水性分散液組成物の 40質量 %、好ま 、上限が PTFE水性分散液組成物の 65質量％である。  The PTFE rosin solid content concentration is preferably U, the lower limit is 40% by mass of the PTFE aqueous dispersion composition, and the upper limit is preferably 65% by mass of the PTFE aqueous dispersion composition.
本発明の PTFE水性分散液組成物は、上記 PTFE榭脂固形分濃度が上記範囲内 にあるものなので、造膜性に優れ、容易に厚膜にすることができる。 本明細書において、上記 PTFE榭脂固形分濃度は、後述する PTFE水性分散液組 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 Since the PTFE aqueous dispersion composition of the present invention has the above-mentioned PTFE rosin solid content concentration within the above range, it is excellent in film forming property and can be easily formed into a thick film. In the present specification, the concentration of the solid content of PTFE resin is the mass of the residue obtained by drying 10 g of the PTFE aqueous dispersion composition described later at a temperature of 380 ° C. for 45 minutes. Determined as a percentage of the mass of the PTFE aqueous dispersion composition
[0019] 上記 PTFE榭脂粒子 (A)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 PTFE水 性分散体により供給することができる。 [0019] The PTFE rosin particles (A) are obtained by polymerizing TFE and the above-mentioned trace amount of monomers in the presence of an aqueous medium by a known polymerization method such as emulsion polymerization or suspension polymerization. Supplied PTFE aqueous dispersion.
上記重合は、乳化重合にて行うことが好ましい。  The polymerization is preferably performed by emulsion polymerization.
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。  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榭脂の種類及び量、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 PTFE resin used and the type of emulsifier.
[0020] 本発明の PTFE水性分散液組成物は、上記 PTFE榭脂粒子 (A)に加え、ポリオキシ アルキレンアルキルエーテル系化合物（B)をも含むものである。  [0020] The PTFE aqueous dispersion composition of the present invention contains a polyoxyalkylene alkyl ether compound (B) in addition to the PTFE rosin particles (A).
[0021] 本発明の PTFE水性分散液組成物は、基材に適用して形成した被膜を焼成する際 、該被膜中の PTFE榭脂粒子 (A)同士の間の空隙をポリオキシアルキレンアルキル エーテル系化合物（B)が埋めることとなり、適用後の乾燥に際しバインダー的作用を してクラック発生を抑制し、造膜性を向上することができるものと考えられる。また、ポ リオキシアルキレンアルキルエーテル系化合物（B)は、被膜焼成後の冷却に際して も、榭脂収縮により従来生じていた収縮クラックを何らかの作用により抑制していると 考えられる。  [0021] When the PTFE aqueous dispersion composition of the present invention is used to sinter a coating formed by applying it to a substrate, the gap between the PTFE rosin particles (A) in the coating is formed into a polyoxyalkylene alkyl ether. It is considered that the compound (B) is buried and can act as a binder during drying after application to suppress the generation of cracks and improve the film-forming property. In addition, it is considered that the polyoxyalkylene alkyl ether compound (B) suppresses shrinkage cracks that have conventionally occurred due to grease shrinkage by some action even during cooling after firing the coating.
上記ポリオキシアルキレンアルキルエーテル系化合物（B)は、上記 PTFE榭脂粒子（ A)の分散安定ィ匕にも寄与すると考えられる。  The polyoxyalkylene alkyl ether compound (B) is considered to contribute to the dispersion stability of the PTFE resin particles (A).
[0022] 上記ポリオキシアルキレンアルキルエーテル系化合物（B)としては、例えば、式 (I)： R— O— A1— H (I) [0022] Examples of the polyoxyalkylene alkyl ether compound (B) include those represented by the formula (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が好ましい。 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 、。 The polyoxyalkylene alkyl ether represented by these is preferable. As the A 1, polyoxyalkylene chain preferably having 4 to 20 amino Okishiechiren units and 0-6 O carboxymethyl propylene Unit.
[0023] 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（Π)： [0023] As the polyoxyalkylene alkyl ether, the formula (式):
C H CH (C H ) C H 0 (C H O) H (II)  C H CH (C H) C H 0 (C H O) H (II)
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 = 7-18. n is an integer from 4 to 20)
で表されるポリオキシエチレンアルキルエーテル、及び Z又は、式 (ΠΙ)：  And polyoxyethylene alkyl ether represented by Z or the formula (ΠΙ):
C H — O— A2— H (III) CH — O— A 2 — H (III)
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（ΠΙ)において、 A2は、 5〜20個のォキシエチレン単位及び 1〜2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 (ΠΙ), A 2 is preferably a polyoxyalkylene chain having 5 to 20 oxyethylene units and 1 to 2 oxypropylene units.
[0024] 上記ポリオキシアルキレンアルキルエーテル系化合物（B)としては、更に、下記式 (I V) : [0024] The polyoxyalkylene alkyl ether compound (B) further includes the following formula (IV):
R4— C H O— A3— H (IV) R 4 — CHO— A 3 — H (IV)
6 4  6 4
(式中、 R4は、炭素数 4〜12の直鎖状又は分岐鎖状のアルキル基であり、 A3は、炭 素数 8〜58のポリオキシアルキレン鎖である。 )により表されるポリオキシエチレンアル キルフエ-ルエーテル等も挙げられる。 (Wherein R 4 is a linear or branched alkyl group having 4 to 12 carbon atoms, and A 3 is a polyoxyalkylene chain having 8 to 58 carbon atoms). Examples thereof include oxyethylene alkyl ether.
上記式（IV)において、 A3は、 5〜20個のォキシエチレン単位及び 0〜 12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ぐ 5〜20個のォキシェチ レン単位及び 1〜12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よ り好ましい。 In the above formula (IV), A 3 is preferably a polyoxyalkylene chain having 5 to 20 oxyethylene units and 0 to 12 oxypropylene units, and 5 to 20 oxyshethylene units and 1 to More preferred is a polyoxyalkylene chain having 12 oxypropylene units.
[0025] 本発明の PTFE水性分散液組成物において、上記ポリオキシアルキレンアルキルェ 一テル系化合物（B)は、 PTFE榭脂固形分 100質量部に対して 12質量部を超え、 2 0質量部以下であってもよ 、し、 PTFE榭脂固形分 100質量部に対して 9〜 12質量 部であってもよい。  [0025] In the PTFE aqueous dispersion composition of the present invention, the polyoxyalkylene alkyl ether compound (B) exceeds 12 parts by mass with respect to 100 parts by mass of PTFE rosin solids, and 20 parts by mass. It may be 9 to 12 parts by mass with respect to 100 parts by mass of PTFE resin solid content.
上記ポリオキシアルキレンアルキルエーテル系化合物（B)が PTFE榭脂固形分 100 質量部に対して 9質量部未満の場合は造膜性が不十分であり、上記ポリオキシアル キレンアルキルエーテル系化合物（B)力 PTFE榭脂固形分 100質量部に対して 20 質量部を超える場合は被膜が着色するなど、 PTFE被膜としての物性が低下するこ とがある。 When the polyoxyalkylene alkyl ether compound (B) is less than 9 parts by mass relative to 100 parts by mass of the PTFE resin solid content, the film-forming property is insufficient. Kirene alkyl ether compound (B) strength When the content exceeds 20 parts by mass with respect to 100 parts by mass of the solid content of PTFE resin, the physical properties of the PTFE film may deteriorate, for example, the film may be colored.
上記ポリオキシアルキレンアルキルエーテル系化合物（B)の PTFE榭脂固形分 100 質量部に対する含有量は、好ましい下限が 12質量部、より好ましい下限が 12. 1質 量部、好ましい上限が 16質量部である。  The content of the polyoxyalkylene alkyl ether compound (B) with respect to 100 parts by mass of the PTFE rosin solid content is preferably 12 parts by mass, more preferably 12.1 parts by mass, and preferably 16 parts by mass. is there.
本明細書にぉ 、て、上記ポリオキシアルキレンアルキルエーテル系化合物（B)の量 は、上記 PTFE榭脂固形分濃度と、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水性分散体調製時の配合量も含む)とから、 PTFE榭脂固 形分 100質量部に対する質量として求めることもできるし、また、 PTFE水性分散液 組成物 10gを 100°Cの温度にて 60分間乾燥して得られた残渣をへキサンで抽出し、 その後へキサンを揮散させて得られた残渣の質量を、該乾燥前の上記 PTFE榭脂固 形分の質量に占める割合の百分率として求めることもできる。  In the present specification, the amount of the polyoxyalkylene alkyl ether compound (B) is determined based on the solid content concentration of the PTFE resin and the amount blended when preparing the PTFE aqueous dispersion composition of the present invention ( (Including the blending amount at the time of preparation of the PTFE aqueous dispersion), and can be obtained as a mass with respect to 100 parts by mass of the PTFE resin solids, or 10 g of the PTFE aqueous dispersion composition at a temperature of 100 ° C. The residue obtained by drying for 60 minutes is extracted with hexane, and then the mass of the residue obtained by volatilizing the hexane is expressed as a percentage of the mass of the PTFE resin solid before drying. You can ask for it.
[0026] 本願においてクラック限界膜厚は、アルミ板上の被膜を、実用的な加工条件である、 380°Cで 15分間焼成することにより評価した力 この場合には PTFE榭脂固形分 10 0質量部に対して上記ポリオキシアルキレンアルキルエーテル系化合物（B)が 9質量 部以上であってもクラックは発生しない。この条件でクラックが発生しなければ、実用 にあたって大きな支障はな ヽ。 [0026] In the present application, the crack limit film thickness is a force evaluated by baking a film on an aluminum plate at 380 ° C for 15 minutes, which is a practical processing condition. In this case, PTFE resin solid content 10 0 Cracks do not occur even when the polyoxyalkylene alkyl ether compound (B) is 9 parts by mass or more with respect to parts by mass. If cracks do not occur under these conditions, there will be no major problems in practical use.
一般に、本発明において、焼成時間は実用に即して短縮可能である力 PTFE水性 分散液組成物を長時間にわたって焼成する場合には、実際の熱分解量が多くなりク ラックが発生しやすくなる。該水性分散液組成物の商業的な加工においては、基材 の熱容量にもよる力 例えば、ガラスクロス含浸の場合に被膜が 380°Cの雰囲気にさ らされるのは、せいぜい 5分程度あるいはそれ以下、厨房機器へ塗装した場合に被 膜が 380°Cの雰囲気にさらされるのは 15〜20分程度である。  In general, in the present invention, the firing time can be shortened according to practical use. When a PTFE aqueous dispersion composition is fired for a long time, the actual thermal decomposition amount increases and cracks are likely to occur. . In commercial processing of the aqueous dispersion composition, the force depending on the heat capacity of the substrate. For example, in the case of glass cloth impregnation, the coating is exposed to an atmosphere of 380 ° C. for about 5 minutes or less. After that, it takes about 15 to 20 minutes for the film to be exposed to an atmosphere of 380 ° C when applied to kitchen equipment.
[0027] 上記ポリオキシアルキレンアルキルエーテル系化合物（B)は、上記ポリオキシアルキ レンアルキルエーテル系化合物（B)が上記 PTFE榭脂固形分 100質量部に対して 9 〜20質量部である場合、平均 HLBが 12以上、好ましくは 12〜 14のポリオキシアル キレンアルキルエーテル系化合物を含むものであることが好ましい。 [0028] 上記ポリオキシアルキレンアルキルエーテル系化合物（B)は、上記ポリオキシアルキ レンアルキルエーテル系化合物（B)が上記 PTFE榭脂固形分 100質量部に対して 1 2質量部を超え、 20質量部以下である場合、平均 HLBが 14以上のポリオキシアル キレンアルキルエーテル系化合物（B1)を含むものであることが好まし!/、。 [0027] When the polyoxyalkylene alkyl ether compound (B) is 9 to 20 parts by mass with respect to 100 parts by mass of the PTFE resin solid content, the polyoxyalkylene alkyl ether compound (B) is: It is preferable that the average HLB contains a polyoxyalkylene alkyl ether compound of 12 or more, preferably 12-14. [0028] In the polyoxyalkylene alkyl ether compound (B), the polyoxyalkylene alkyl ether compound (B) exceeds 12 parts by mass with respect to 100 parts by mass of the PTFE resin solid content, and 20 parts by mass. In the case where the average HLB is less than 14 parts, the polyoxyalkylene alkyl ether compound (B1) having an average HLB of 14 or more is preferred! / ,.
本発明の PTFE水性分散液組成物は、上記ポリオキシアルキレンアルキルエーテル 系化合物（B)が上記 PTFE榭脂固形分 100質量部に対して 12質量部を超え、 20質 量部以下であり、且つ、上記ポリオキシアルキレンアルキルエーテル系化合物（B)と して上記ポリオキシアルキレンアルキルエーテル系化合物（B1)を含む場合、特に優 れた造膜性を示す。  In the PTFE aqueous dispersion composition of the present invention, the polyoxyalkylene alkyl ether compound (B) is more than 12 parts by mass and less than 20 parts by mass with respect to 100 parts by mass of the PTFE resin solid content, and When the polyoxyalkylene alkyl ether compound (B) includes the polyoxyalkylene alkyl ether compound (B1), the film-forming property is particularly excellent.
本明細書において、平均 HLBは、 Griffinの式に基づき算出した値である。  In this specification, the average HLB is a value calculated based on the Griffin equation.
[0029] 上記ポリオキシアルキレンアルキルエーテル系化合物（B1)は、上記ポリオキシアル キレンアルキルエーテル系化合物（B)が上記 PTFE榭脂固形分 100質量部に対し て 12質量部を超え、 20質量部以下である場合、ポリオキシアルキレンアルキルエー テル系化合物（B)の 1〜99質量％であることが好ましい。 [0029] In the polyoxyalkylene alkyl ether compound (B1), the polyoxyalkylene alkyl ether compound (B) is more than 12 parts by mass and less than 20 parts by mass with respect to 100 parts by mass of the PTFE resin solid content. In some cases, it is preferably 1 to 99% by mass of the polyoxyalkylene alkyl ether compound (B).
上記ポリオキシアルキレンアルキルエーテル系化合物（B1)の含有量は、上記ポリオ キシアルキレンアルキルエーテル系化合物（B)が上記 PTFE榭脂固形分 100質量 部に対して 12質量部を超え、 20質量部以下である場合、より好ましい下限がポリオ キシアルキレンアルキルエーテル系化合物（B)の 10質量％、更に好ましい下限が 2 0質量％であり、より好ましい上限が 95質量％、更に好ましい上限が 90質量％である 本発明の PTFE水性分散液組成物は、上記範囲内の量の上記ポリオキシアルキレ ンアルキルエーテル系化合物（B1)を有する場合、適度な粘度を有することとなり、 更に造膜性に優れたものとなる。  The content of the polyoxyalkylene alkyl ether compound (B1) is such that the polyoxyalkylene alkyl ether compound (B) exceeds 12 parts by mass and 20 parts by mass or less based on 100 parts by mass of the PTFE resin solid content. In this case, a more preferable lower limit is 10% by mass of the polyoxyalkylene alkyl ether compound (B), a further preferable lower limit is 20% by mass, a more preferable upper limit is 95% by mass, and a further preferable upper limit is 90% by mass. When the PTFE aqueous dispersion composition of the present invention has the polyoxyalkylene alkyl ether compound (B1) in an amount within the above range, it has an appropriate viscosity, and further has excellent film-forming properties. It will be a thing.
[0030] 上記ポリオキシアルキレンアルキルエーテル系化合物（B)は、上記ポリオキシアルキ レンアルキルエーテル系化合物（B)が上記 PTFE榭脂固形分 100質量部に対して 9 〜 12質量部である場合、平均 HLBが 12以上、 14未満のポリオキシアルキレンアル キルエーテル系化合物（B2)を含むものであることが好まし 、。 [0030] When the polyoxyalkylene alkyl ether compound (B) is 9 to 12 parts by mass with respect to 100 parts by mass of the PTFE resin solid content, the polyoxyalkylene alkyl ether compound (B) is: It is preferred that the polyoxyalkylene alkyl ether compound (B2) has an average HLB of 12 or more and less than 14.
本発明の PTFE水性分散液組成物は、上記ポリオキシアルキレンアルキルエーテル 系化合物（B)が上記 PTFE榭脂固形分 100質量部に対して 9〜 12質量部であり、且 つ、上記ポリオキシアルキレンアルキルエーテル系化合物（B)として上記ポリオキシ アルキレンアルキルエーテル系化合物（B2)を含む場合、特に優れた造膜性を示す 上記ポリオキシアルキレンアルキルエーテル系化合物（B2)としては、造膜性の点で 、平均 HLBが 12. 5〜13. 7であるものが好ましい。 The aqueous PTFE dispersion composition of the present invention comprises the above polyoxyalkylene alkyl ether. Compound (B) is 9 to 12 parts by mass with respect to 100 parts by mass of the PTFE resin solid content, and the polyoxyalkylene alkyl ether compound (B2) is used as the polyoxyalkylene alkyl ether compound (B). ), The polyoxyalkylene alkyl ether compound (B2) exhibiting particularly excellent film-forming properties is preferably those having an average HLB of 12.5 to 13.7 in terms of film-forming properties.
[0031] 上記ポリオキシアルキレンアルキルエーテル系化合物（B2)は、上記ポリオキシアル キレンアルキルエーテル系化合物（B)が上記 PTFE榭脂固形分 100質量部に対し て 9〜 12質量部である場合、ポリオキシアルキレンアルキルエーテル系化合物（B) の 1〜99質量％であることが好ましい。 [0031] The polyoxyalkylene alkyl ether compound (B2) is a polyoxyalkylene alkyl ether compound (B2) when the polyoxyalkylene alkyl ether compound (B) is 9 to 12 parts by mass with respect to 100 parts by mass of the PTFE resin solid content. It is preferably 1 to 99% by mass of the alkylene alkyl ether compound (B).
上記ポリオキシアルキレンアルキルエーテル系化合物（B2)の含有量は、上記ポリオ キシアルキレンアルキルエーテル系化合物（B)が上記 PTFE榭脂固形分 100質量 部に対して 9〜 12質量部である場合、より好ましい下限がポリオキシアルキレンアル キルエーテル系化合物（B)の 10質量％、更に好ましい下限が 20質量％であり、より 好ましい上限が 95質量％、更に好ましい上限が 90質量％である。  The content of the polyoxyalkylene alkyl ether compound (B2) is more when the polyoxyalkylene alkyl ether compound (B) is 9 to 12 parts by mass with respect to 100 parts by mass of the PTFE resin solid content. A preferable lower limit is 10% by mass of the polyoxyalkylene alkyl ether compound (B), a further preferable lower limit is 20% by mass, a more preferable upper limit is 95% by mass, and a further preferable upper limit is 90% by mass.
本発明の PTFE水性分散液組成物は、上記範囲内の量の上記ポリオキシアルキレ ンアルキルエーテル系化合物（B2)を有する場合、適度な粘度を有することとなり、 更に造膜性に優れたものとなる。  When the PTFE aqueous dispersion composition of the present invention has the polyoxyalkylene alkyl ether compound (B2) in an amount within the above range, it has an appropriate viscosity, and further has excellent film-forming properties. It becomes.
[0032] 本発明の PTFE水性分散液組成物は、また、微量のフッ素系界面活性剤ゃシリコー ン系界面活性剤等を添加することにより、その表面張力を適当な値に調整することが できる。これらの界面活性剤の添加量は微量であるために、 PTFE水性分散液組成 物の粘度を大きく変化させることはない。  [0032] The PTFE aqueous dispersion composition of the present invention can be adjusted to an appropriate value for the surface tension by adding a trace amount of a fluorosurfactant, a silicone surfactant, or the like. . Since the addition amount of these surfactants is very small, the viscosity of the aqueous PTFE dispersion composition does not change greatly.
[0033] 本発明の PTFE水性分散液組成物は、更に、造膜改良剤（C)をも含むものであって ちょい。  [0033] The aqueous PTFE dispersion composition of the present invention further contains a film-forming improver (C).
本明細書において、上記「造膜改良剤 (C)」は、これを配合することにより、配合しな V、ものに比べ、造膜性を向上し得るものであればよ!、。  In the present specification, the “film-formation improver (C)” may be any compound that can improve the film-formability by blending it with V.
上記造膜改良剤 (C)は、本発明の PTFE水性分散液組成物を基材に適用して得ら れる被膜において、ポリオキシアルキレンアルキルエーテル系化合物（B)が PTFE 榭脂粒子同士の間の間隙を充填することを補充して、造膜性を向上するものと考えら れる。 In the film obtained by applying the aqueous PTFE dispersion composition of the present invention to a base material, the film-forming modifier (C) is a polyoxyalkylene alkyl ether compound (B) in which PTFE It is considered that the film forming property is improved by supplementing the filling of the gaps between the resin particles.
[0034] 本発明の PTFE水性分散液組成物は、特に、 PTFE榭脂として変性 PTFEカゝらなる 榭脂を用いるため、 TFE単独重合体よりもクラックを発生しやすいので、造膜改良剤 (C)をも含むものであることが好ましい。本発明の PTFE水性分散液組成物は、また 、ポリオキシアルキレンアルキルエーテル系化合物（B)力 PTFE榭脂固形分 100質 量部に対して 9〜20質量部であるため、クラック発生抑止力向上の点で、造膜改良 剤（C)をも含むものであることが好ま 、。  [0034] Since the PTFE aqueous dispersion composition of the present invention uses, in particular, a resin made of a modified PTFE resin as the PTFE resin, cracks are more likely to occur than a TFE homopolymer. C) is also preferably included. The PTFE aqueous dispersion composition of the present invention also has a polyoxyalkylene alkyl ether compound (B) strength. Since it is 9 to 20 parts by mass with respect to 100 parts by mass of the solid content of PTFE resin, the crack generation inhibiting power is improved. In view of this, it is preferable that the film-forming improver (C) is included.
本発明の PTFE水性分散液組成物において、造膜改良剤 (C)は、用いる造膜改良 剤（C)の種類にもよるが、 PTFE榭脂固形分 100質量部に対して 10質量部以下で あることが好ましぐ上記範囲内であれば 0. 1質量部以上であることが好ましぐ 1質 量部以上であることがより好まし 、。  In the PTFE aqueous dispersion composition of the present invention, the film-forming improver (C) depends on the type of film-forming improver (C) to be used, but it is 10 parts by mass or less with respect to 100 parts by mass of PTFE oil solid content. If it is in the above-mentioned range, it is more preferable that it is 0.1 part by mass or more, and it is more preferable that it is 1 part by mass or more.
[0035] 本発明において、上記造膜改良剤 (C)としては特に限定されないが、アクリル榭脂、 シリコーン系界面活性剤、 380°Cでの分解残渣が 5%以上である非イオン性界面活 性剤、乾燥遅延剤、フッ素系界面活性剤等が挙げられ、アクリル榭脂、シリコーン系 界面活性剤、 380°Cでの分解残渣が 5%以上である非イオン性界面活性剤及び Z 又は乾燥遅延剤であることが好まし 、。 [0035] In the present invention, the film-forming improver (C) is not particularly limited, but is a nonionic surfactant having an acrylic resin, a silicone-based surfactant, and a decomposition residue at 5% or more at 380 ° C. Such as acrylic resin, silicone surfactant, nonionic surfactant having a decomposition residue of 5% or more at 380 ° C and Z or dry. Preferred to be a retarder.
本明細書において、上記「アクリル榭脂、シリコーン系界面活性剤、 380°Cでの分解 残渣が 5%以上である非イオン性界面活性剤及び Z又は乾燥遅延剤」とは、これら 4 種類のうち、 1種又は 2種以上を用いることができることを意味する。  In the present specification, the above-mentioned “acrylic resin, silicone surfactant, nonionic surfactant having a decomposition residue at 5% or more at 380 ° C. and Z or drying retarder” refers to these four types. Of these, one or two or more can be used.
[0036] 上記アクリル榭脂を構成するアクリルポリマーとしては、特に限定されないが、メタタリ レート系単量体を重合して得られる重合体が好まし 、。 [0036] The acrylic polymer constituting the acrylic resin is not particularly limited, but a polymer obtained by polymerizing a methacrylate monomer is preferred.
上記メタタリレート系単量体としては、例えば、メチルメタタリレート、ェチルメタクリレー ト、プロピルメタタリレート、ジメチルプロピルメタタリレート、ブチルメタタリレート、ペン チルメタタリレート等が挙げられる。  Examples of the metatalylate monomer include methyl metatalylate, ethyl methacrylate, propyl methacrylate, dimethylpropyl methacrylate, butyl methacrylate, and pentyl methacrylate.
上記アクリル榭脂は、水性分散体に調製して使用することが好ま 、。  It is preferable to prepare and use the above acrylic resin in an aqueous dispersion.
上記アクリル榭脂は、単独重合体であっても安定な水性分散体に調製することがで きるが、安定な水性分散体を容易に調製し易い点で、カルボキシル基又はヒドロキシ ル基を有する単量体を適宜共単量体とする重合体であることが好ま 、。上記アタリ ル榭脂を水性分散体に調製して使用する場合、更に安定性を高めるために、必要に 応じて、該水性分散体に非イオン性界面活性剤を添加してもよ ヽ。 The acrylic resin can be prepared as a stable aqueous dispersion even if it is a homopolymer. However, in view of easy preparation of a stable aqueous dispersion, It is preferred that the polymer is a polymer having a monomer having a ru group as appropriate as a comonomer. When preparing and using the above talyl resin in an aqueous dispersion, a nonionic surfactant may be added to the aqueous dispersion as necessary in order to further enhance the stability.
上記アクリル榭脂は、得られる水性分散液組成物の造膜性の点で、 300〜320°Cの 温度範囲で加熱前の約 25〜50質量％残存し、 330〜345°Cの温度範囲で加熱前 の 10〜 20質量％残存するものが好ましい。  In terms of film-forming properties of the resulting aqueous dispersion composition, the above-mentioned acrylic resin remains in a temperature range of 300 to 320 ° C, approximately 25 to 50% by mass before heating, and a temperature range of 330 to 345 ° C. It is preferable that 10 to 20% by mass before heating remains.
[0037] 本発明の PTFE水性分散液組成物は、上記造膜改良剤 (C)としてアクリル榭脂を使 用する場合、アクリル榭脂は PTFE榭脂固形分 100質量部に対して 10質量部以下 であることが好ましい。 [0037] In the PTFE aqueous dispersion composition of the present invention, when acrylic resin is used as the film-forming improver (C), the acrylic resin is 10 parts by mass with respect to 100 parts by mass of PTFE resin solids. It is preferable that
PTFE榭脂固形分 100質量部に対する上記アクリル榭脂のより好ましい上限は 8質 量部であり、下限は特に限定されないが、上記アクリル榭脂を配合することによる効 果を得る点で、好ま 、下限は 1質量部である。  A more preferable upper limit of the above-mentioned acrylic resin relative to 100 parts by mass of PTFE resin is 8 parts by mass, and the lower limit is not particularly limited, but is preferable in that it obtains an effect by blending the above-mentioned acrylic resin. The lower limit is 1 part by mass.
[0038] 上記シリコーン系界面活性剤としては、例えば、下記一般式： [0038] Examples of the silicone surfactant include the following general formula:
R1 SiO -（SiR1 O) -R 1 SiO-(SiR 1 O)-
3 2 n (SiR o) SiR1 3 2 n (SiR o) SiR 1
m 3  m 3
(式中、 nは、 0〜20の整数を表し、 mは、 0〜20の整数を表し、 n+m> lである。 R1 は、同一又は異なって、炭素数 1〜30のアルキル基、炭素数 6〜30のァリール基、 炭素数 1〜30のアルコキシル基、炭素数 6〜30のァリールォキシ基、又は、水素原 子を表す。 R2は、式— R3— (C H O) (In the formula, n represents an integer of 0 to 20, m represents an integer of 0 to 20, and n + m> l. R 1 may be the same or different and has 1 to 30 carbon atoms. Group, an aryl group having 6 to 30 carbon atoms, an alkoxyl group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a hydrogen atom R 2 is a formula —R 3 — (CHO)
2 4 q一（C H O) —Y  2 4 q (C H O) —Y
3 6 r で表される置換基を表す。 R 3 represents a substituent represented by r. R
3は、炭素数 1〜30のアルキレン基を表し、 Yは、炭素数 1〜30のアルキル基を表す 。 q及び rは、同一又は異なって、 0〜20の整数を表し、 q+r> lである。 ) により表されるものが挙げられる。製造者によっては、このような一般式を有する化合 物を変性シリコーンオイルとして販売して 、るが、本願ではシリコーン系界面活性剤と して扱うこととする。 3 represents an alkylene group having 1 to 30 carbon atoms, and Y represents an alkyl group having 1 to 30 carbon atoms. q and r are the same or different and represent an integer of 0 to 20, and q + r> l. ). Depending on the manufacturer, a compound having such a general formula is sold as a modified silicone oil, but in this application, it is treated as a silicone surfactant.
[0039] 本発明の PTFE水性分散液組成物は、上記造膜改良剤 (C)としてシリコーン系界面 活性剤を使用する場合、シリコーン系界面活性剤は、 PTFE榭脂固形分 100質量部 に対して 10質量部以下であることが好まし 、。  [0039] In the PTFE aqueous dispersion composition of the present invention, when a silicone-based surfactant is used as the film-forming improver (C), the silicone-based surfactant is used with respect to 100 parts by mass of the solid content of PTFE resin. It is preferable that the amount is 10 parts by mass or less.
PTFE榭脂固形分 100質量部に対する上記シリコーン系界面活性剤のより好ましい 上限は 5質量部であり、下限は特に限定されないが、シリコーン系界面活性剤を配合 することによる効果を得る点で、好ましい下限は 0. 1質量部である。 More preferably, the upper limit of the silicone-based surfactant is 100 parts by weight based on PTFE rosin solid content, and the lower limit is not particularly limited. A preferable lower limit is 0.1 part by mass in terms of obtaining the effect of the above.
[0040] 上記 380°Cでの分解残渣が 5%以上である非イオン性界面活性剤としては、例えば 、種々のポリオキシエチレン誘導体等が挙げられる。 [0040] Examples of the nonionic surfactant whose decomposition residue at 380 ° C is 5% or more include various polyoxyethylene derivatives.
本明細書において、「380°Cでの分解残渣が 5%以上である」とは、 380°Cにて少な くとも 10分間加熱した後の残渣が、該加熱前の 5質量％以上であることを意味する。 本発明の PTFE水性分散液組成物は、上記造膜改良剤 (C)として 380°Cでの分解 残渣が 5%以上である非イオン性界面活性剤を使用する場合、上記非イオン性界面 活性剤は、 PTFE榭脂固形分 100質量部に対して 10質量部以下であることが好まし い。  In this specification, “the decomposition residue at 380 ° C. is 5% or more” means that the residue after heating at 380 ° C. for at least 10 minutes is 5% by mass or more before the heating. Means that. The PTFE aqueous dispersion composition of the present invention uses the nonionic surfactant when the nonionic surfactant whose decomposition residue at 380 ° C is 5% or more is used as the film-forming improver (C). The agent is preferably 10 parts by mass or less with respect to 100 parts by mass of the solid content of PTFE resin.
PTFE榭脂固形分 100質量部に対する上記 380°Cでの分解残渣が 5%以上である 非イオン性界面活性剤のより好ましい上限は 5質量部であり、下限は特に限定されな Vヽが、 380°Cでの分解残渣が 5%以上である非イオン性界面活性剤を配合すること による効果を得る点で、好ましい下限は 0. 1質量部である。  The decomposition residue at 380 ° C is 5% or more with respect to 100 parts by mass of PTFE resin solid content. A more preferable upper limit of the nonionic surfactant is 5 parts by mass, and the lower limit is not particularly limited. A preferable lower limit is 0.1 part by mass in that an effect is obtained by adding a nonionic surfactant whose decomposition residue at 380 ° C is 5% or more.
[0041] 上記乾燥遅延剤としては、当業者に通常「乾燥遅延剤」と認識されているものであれ ばよぐ例えば、 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。 [0041] Examples of the drying retardant include those having a boiling point of about 200 to 300 ° C, as long as they are normally recognized by those skilled in the art as "drying retardants". As such a solvent, a water-soluble solvent is preferable.
上記水溶性溶剤としては、グリセリン、ジエチレングリコールモノェチルエーテル（ェ チルカルビトール）、ジエチレングリコールモノブチルエーテル（ブチルカルビトール） 、トリエチレングリコール、エチレングリコール、 1, 3 プロパンジオール、 1, 3 ブタ ンジオール、 1, 4 ブタンジオール、 1, 5 ペンタンジオール、 2 ブテン 1, 4 ジオール、 2 ェチルー 2 ヒドロキシメチルー 1, 3 プロパンジオール等が好まし い。  Examples of the water-soluble solvent include glycerin, diethylene glycol monoethyl ether (ethyl carbitol), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol, ethylene glycol, 1,3 propanediol, 1,3 butanediol, 1 1,4-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, 2-ethyl-2-hydroxymethyl-1,3-propanediol and the like are preferred.
上記乾燥遅延剤は、本発明の PTFE水性分散液組成物を基材に適用して得られる 被膜から、乾燥や加熱により水、ポリオキシアルキレンアルキルエーテル系化合物（B )等を低減又は除去した後にお 、ても、該被膜中に残存して PTFE榭脂粒子同士の 間の間隙を埋める作用をすることにより、造膜性を向上するものと考えられる。  The drying retardant is obtained by reducing or removing water, polyoxyalkylene alkyl ether compound (B), etc. by drying or heating from a coating obtained by applying the PTFE aqueous dispersion composition of the present invention to a substrate. However, it is considered that the film-forming property is improved by remaining in the coating and acting to fill the gaps between the PTFE resin particles.
[0042] 本発明の PTFE水性分散液組成物は、上記造膜改良剤 (C)として乾燥遅延剤を使 用する場合、乾燥遅延剤は、その種類に応じて、適宜、配合量を設定することができ る力 PTFE榭脂固形分 100質量部に対して 10質量部以下であることが好ましい。 乾燥遅延剤のうち、ジエチレングリコールモノアルキルエーテルは、アクリル榭脂を溶 解する働きを有するので、アクリル榭脂と併用することにより造膜性を一層向上させる ことが可能となる。 [0042] When the PTFE aqueous dispersion composition of the present invention uses a drying retarder as the film-forming modifier (C), the amount of the drying retarder is appropriately set according to the type of the drying retarder. It is possible The strength is preferably 10 parts by mass or less with respect to 100 parts by mass of the solid content of PTFE resin. Among the drying retardants, diethylene glycol monoalkyl ether has a function of dissolving acrylic resin, so that the film forming property can be further improved by using it together with acrylic resin.
[0043] 本発明の PTFE水性分散液組成物は、上記造膜改良剤 (C)として、なかでも、アタリ ル榭脂、シリコーン系界面活性剤又は 380°Cでの分解残渣が 5%以上である非ィォ ン性界面活性剤を含むことが好ましぐアクリル榭脂を含むことがより好ましい。  [0043] The PTFE aqueous dispersion composition of the present invention has, as the film-forming improver (C), an allyl resin, a silicone-based surfactant, or a decomposition residue at 380 ° C of 5% or more. It is more preferable to include an acrylic resin which preferably includes a certain nonionic surfactant.
本発明において造膜改良剤 (C)として用いるアクリル榭脂は、本発明の PTFE水性 分散液組成物を塗布乾燥したのち焼成する際、 PTFE榭脂粒子 (A)へのバインダー 効果を維持しながら徐々に分解するので、収縮クラックの発生を効果的に防止するこ とがでさる。  The acrylic resin used as the film-forming modifier (C) in the present invention maintains the binder effect on the PTFE resin particles (A) when the PTFE aqueous dispersion composition of the present invention is applied and dried and then fired. Since it gradually decomposes, the occurrence of shrinkage cracks can be effectively prevented.
[0044] 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!/、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、乾燥剤、増粘剤、レべリング剤、ハジキ防止剤などが挙げられる。  [0044] The PTFE aqueous dispersion composition of the present invention can be blended with 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 agents, thickeners, leveling agents, repellency inhibitors, and the like.
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、シリコーンオイル等が挙げられる。  Examples of the antifoaming agent include toluene, xylene, non-polar solvents such as hydrocarbons having 9 to 11 carbon atoms, and silicone oil.
上記乾燥剤としては、例えば、酸ィ匕コバルト等が挙げられる。  Examples of the desiccant include acid cobalt.
上記増粘剤としては、例えば、メチルセルロース、ポリビュルアルコール、カルボキシ ル化ビュルポリマー等が挙げられる。  Examples of the thickener include methyl cellulose, polybulal alcohol, carboxylated bulle polymer, and the like.
[0045] 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 のである。 [0045] The PTFE aqueous dispersion composition of the present invention has a viscosity at 25 ° C of 0.1 Pa's or less.
本発明の PTFE水性分散液組成物は、上記粘度が 0. 06Pa' s以下であることがより 好ましぐまた上記範囲内であれば、 0. OlPa' s以上であってもよい。  The PTFE aqueous dispersion composition of the present invention preferably has a viscosity of 0.06 Pa's or less, and may be 0.0 OlPa's or more as long as it is within the above range.
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 K6893に準拠して、 25°Cの温度にて測定したものである。 [0046] 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、ポリオキシアルキレンアルキルエーテル系 化合物（B)、並びに、必要に応じ、造膜改良剤（C)及び他の添加剤を添加し、混合 すること〖こより調製することができる。 In the present specification, the viscosity is measured at a temperature of 25 ° C. according to JIS K6893 using a B-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.). [0046] 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 polyoxyalkylene alkyl ether compound (B), and as necessary, Depending on the situation, the film-forming improver (C) and other additives can be added and mixed.
上記調製において、ポリオキシアルキレンアルキルエーテル系化合物（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、 PT FE水性分散体の調製後に追加して、 目的とする粘度に調整することが好ましい。 上記攪拌、添加及び混合の各操作の条件は、使用する組成物の種類や量により適 宜設定することができる力 5〜30°Cの温度にて行うことが好ましい。  In the above preparation, the polyoxyalkylene alkyl ether compound (B) can be added when preparing an aqueous PTFE dispersion, and has been conventionally used, for example, for concentrating an aqueous dispersion that is a polymerization product. Although it may be added as a dispersant, it is usually preferable to add after the preparation of the PTFE aqueous dispersion to adjust to the target viscosity. The conditions for the above-mentioned stirring, addition and mixing operations are preferably performed at a force of 5 to 30 ° C., which can be appropriately set according to the type and amount of the composition to be used.
[0047] 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、上述のように耐ク ラック性、厚塗り性を向上するほか、 1回の適用によるクラック限界膜厚を極めて大き くすることができ、 1回の適用によるクラック限界膜厚は、特に、 PTFE榭脂粒子 (A)と して変性 PTFEカゝらなる榭脂を用いる場合、従来 2 m程度までしか達成されなかつ たのに対し、本発明によれば、例えば 20 m程度以上とすることもできる。  [0047] Since the PTFE aqueous dispersion composition of the present invention has the above-described configuration, it improves the crack resistance and thick coatability as described above, and also has an extremely large crack limit film thickness by one application. The crack limit film thickness by one application can be achieved only up to about 2 m in the past, especially when using a PTFE resin particle (A) as a modified PTFE resin. On the other hand, according to the present invention, for example, it can be about 20 m or more.
本明細書において、上記クラック限界膜厚は、 20cm X 10cm X l. 5mmのアルミ板 上に PTFE水性分散液組成物（5ml)を滴下し、コーティングアプリケーター（安田精 機社製)を用い、膜厚が O /z mを超え、 200 m以下の間で連続的に変化するよう塗 布し、 100°Cで 10分間乾燥した後に 380°Cで 15分間焼成した際、クラックの発生し な 、最大膜厚を測定したものである。  In this specification, the crack limit film thickness is determined by dropping a PTFE aqueous dispersion composition (5 ml) on an aluminum plate of 20 cm × 10 cm × l. 5 mm and using a coating applicator (manufactured by Yasuda Seiki Co., Ltd.). When the coating thickness is greater than O / zm and continuously changes between 200 m and below, when dried at 100 ° C for 10 minutes and then baked at 380 ° C for 15 minutes, no cracks occur. The film thickness was measured.
[0048] 一般に、変性 PTFEは TFE単独重合体よりも透明性に優れた被膜を与えることがで きるが、本発明の PTFE水性分散液組成物は、 PTFE榭脂として変性 PTFE力ゝらな る榭脂を用いる場合、クラック限界膜厚が極めて大きいにも関わらず、光透過性が高 く且つ厚膜の被膜を得ることができる。  [0048] In general, modified PTFE can provide a coating with better transparency than a TFE homopolymer, but the aqueous PTFE dispersion composition of the present invention has a modified PTFE strength as a PTFE resin. When the resin is used, it is possible to obtain a thick film with high light transmittance despite the extremely large crack limit film thickness.
[0049] 本発明の PTFE榭脂フィルムは、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ものである。  [0049] The PTFE resin film of the present invention is obtained by coating the above-mentioned PTFE aqueous dispersion composition of the present invention on an object to be coated.
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、各種耐熱榭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。 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.
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〖こより行うことができる。  The coating can usually be performed by applying the PTFE aqueous dispersion composition of the present invention, drying, and then firing.
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 aqueous PTFE dispersion composition of the present invention may be directly applied to a substrate, but in order to improve the adhesion to the substrate, a primer layer may be provided and formed as an overcoat layer.
[0050] 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。  [0050] 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、使用するポリオキシアルキレンアルキルエーテル系化合物（B)、造膜 改良剤（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 80〜150°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 polyoxyalkylene alkyl ether compound (B), film-forming improver (C), etc. to be used, but it is room temperature to 150 ° C, preferably 80 to 150 °. It is preferably performed at a temperature of C for 5 to 20 minutes.
上記焼成は、一般に、使用する PTFE榭脂の溶融温度以上、通常、 340〜415°Cの 温度下で、 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 しい。  In general, the firing can be performed for 5 to 60 minutes at a temperature equal to or higher than the melting temperature of the PTFE resin to be used, usually 340 to 415 ° C, and is performed at 360 to 400 ° C for 10 to 30 minutes. That power S is preferable.
本発明の PTFE榭脂フィルムは、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 the coated product via a primer layer or the like.
[0051] 本発明の PTFE榭脂フィルムは、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、約 5〜： LOO μ m、好ましくは、約 10〜： LOO μ mの厚さ を有する。 [0051] Since the PTFE resin film of the present invention is formed by coating the PTFE aqueous dispersion composition of the present invention described above, it is usually about 5 to: LOO μm, preferably about 10 to: It has a thickness of LOO μm.
本発明の PTFE榭脂フィルムは、被塗装物が焼成時に実質的に劣化しな 、ものであ れば特に限定することなく得ることができるものであるので、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、アイ口 ン底板、製氷トレー、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 (特に半導体工業用）、铸型等の被覆材とすることができる。  Since 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, it can be obtained, for example, metal cooking utensils, bearings, valves, etc. , Electric wire, metal foil, boiler, pipe, ship bottom, oven lining, iron bottom plate, ice tray, snow shovel, plow, chute, conveyor, roll, mold, die, saw, file, cutting tool, knife, Scissors, hoppers, other industrial containers (especially for the semiconductor industry), and scissors can be used.
本発明の PTFE榭脂フィルムは、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。 [0052] 本発明の PTFE榭脂含浸体は、被含浸体と、上記被含浸体に上述の本発明の PTF E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ものである。 In particular, the PTFE resin film of the present invention can be suitably used as a coating material for high-frequency printed circuit boards, conveyor belts, packings and the like. [0052] The PTFE resin-impregnated body of the present invention has 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.
[0053] 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。  [0053] The impregnated body is not particularly limited, and examples thereof include a fiber base material, a woven fabric and a non-woven fabric.
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 (ケプラー繊維等）が挙げられる。上記織布 '不織布としては、例えば、膜構造建 築物の屋根材 (テント膜)等が挙げられる。該屋根材として光透過性が求められる場 合、 PTFE榭脂として変性 PTFEカゝらなる榭脂を用いることが好ま 、。  The fiber substrate is not particularly limited, and examples thereof include glass fiber, carbon fiber, and aramid fiber (Kepler fiber, etc.). Examples of the woven fabric'nonwoven fabric include a roof material (tent membrane) of a membrane structure building. When light transmission is required as the roofing material, it is preferable to use a modified PTFE resin as the PTFE resin.
上記含浸は、公知の方法にて行うことができる。  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が、通常、約 5〜： LOO μ m、好ましくは、約 10〜： LOO μ 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, it usually depends on the shape and thickness of the substrate, but is usually about 5 to: LOO μm, preferably About 10 ~: having a thickness of LOO μm.
発明の効果  The invention's effect
[0054] 本発明の PTFE水性分散液組成物は、上述の構成カゝらなるものであるので、厚膜で あるにもかかわらずクラックが生じないコーティング用糸且成物として好適に使用するこ とがでさる。  [0054] Since the PTFE aqueous dispersion composition of the present invention has the above-mentioned constitution, it can be suitably used as a coating yarn and composition that does not cause cracks despite being a thick film. Togashi.
本発明の PTFE榭脂フィルムは、上述の構成からなるものであるので、クラック等の欠 陥がなぐ厚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 thick film free from defects such as cracks.
本発明の PTFE榭脂含浸体は、上述の構成カゝらなるものであるので、クラック等の欠 陥がなぐ厚膜の被膜とすることも可能である。  Since the PTFE resin impregnated body of the present invention has the above-mentioned constitution, it can be a thick film without cracks and the like.
また、本発明の PTFE水性分散液組成物は、変性 PTFEからなる榭脂を含む場合、 得られる被膜は高 、光透過性を有するものである。  In addition, when the aqueous PTFE dispersion composition of the present invention contains a resin made of modified PTFE, the resulting coating is highly light transmissive.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0055] 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い。 [0055] 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.
[0056] 各実施例、比較例で行った測定は、以下の方法により行った。 [0056] Measurements performed in each example and comparative example were performed by the following methods.
(1)パーフルォロ（プロピルビュルエーテル） [PPVE]共単量体単位量  (1) Perfluoro (propyl butyl ether) [PPVE] comonomer unit amount
PTFE水性分散液を凝析、洗浄、乾燥して得られたパウダーを用いて、赤外吸収ス ベクトルバンドの 995cm の吸光度と 2360cm の吸光度との比に 0. 95を乗じて 得られる値を PPVE共単量体単位量とした。 Using the powder obtained by coagulating, washing and drying the PTFE aqueous dispersion, The value obtained by multiplying the ratio of the absorbance of the vector band at 995 cm to the absorbance at 2360 cm by 0.95 was taken as the PPVE comonomer unit amount.
(2)平均粒径  (2) Average particle size
榭脂固形分濃度を 0. 22質量％に調製した 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。 Average determined by measuring the transmittance of 550 nm projection light with respect to the unit length of PTFE aqueous dispersion adjusted to 0.22% by mass of the solid content of rosin and the directional direction diameter in the transmission electron micrograph Based on the calibration curve with the particle diameter, it was determined from the transmittance.
(3) PTFE榭脂固形分濃度  (3) PTFE oil solids concentration
PTFE水性分散体 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水性分散体の質量に占める割合の百分率として求めた。 The mass of the residue obtained by drying 10 g of the PTFE aqueous dispersion at a temperature of 380 ° C. for 45 minutes was determined as a percentage of the mass of the PTFE aqueous dispersion before the drying.
(4) PTFE水性分散液組成物におけるポリオキシアルキレンアルキルエーテル系化 合物 (B)濃度 (4) Polyoxyalkylene alkyl ether compound in PTFE aqueous dispersion composition (B) Concentration
上記（3)により求めた PTFE榭脂固形分濃度と、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水性分散体調製時の配合量も含む)とから、 PT FE榭脂固形分 100質量部に対する質量として求めた。 From the PTFE rosin solid concentration determined in (3) above and the amount to be blended when preparing the PTFE aqueous dispersion composition of the present invention (including the blending amount at the time of preparing the PTFE aqueous dispersion), PT FE It calculated | required as a mass with respect to 100 mass parts of resin solid content.
なお、（3)、（4)以外の組成物濃度は、添加する際の質量力も換算した値である。In addition, the composition concentrations other than (3) and (4) are values in which mass force at the time of addition is also converted.
(5)粘度 (5) Viscosity
B型回転粘度計 (東京計器社製)を用い、 JIS K6893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 K6893.
(6)クラック限界膜厚  (6) Crack limit film thickness
20cm X 10cm X 1. 5mmのアルミ板上に PTFE水性分散液組成物（5ml)を滴下し 、コーティングアプリケーター (安田精機社製)を用いて、膜厚が O /z mを超え、 200 μ m以下の間で連続的に変化するよう 1回塗布し、 100°Cで 10分間乾燥した後に 38 0°Cで 15分間焼成した。膜厚の厚い部分にはクラックが発生するが、クラックが発生 しな 、最大膜厚をクラック限界膜厚とした。  Drop the PTFE aqueous dispersion composition (5 ml) on a 20 cm X 10 cm X 1.5 mm aluminum plate, and use a coating applicator (manufactured by Yasuda Seiki Co., Ltd.). The coating was applied once so as to continuously change between and dried at 100 ° C. for 10 minutes and then baked at 380 ° C. for 15 minutes. Although cracks occurred in the thick part, the maximum film thickness was defined as the crack limit film thickness.
調製例 1 Preparation Example 1
乳化重合により平均粒径 273nm、ポリマー濃度 [P. C.、 PTFE榭脂固形分に相当 ] 30. 7質量0 /0、パーフルォロ（プロピルビュルエーテル） [PPVE]単位が PTFEの 0 . 12質量％である PTFE水性分散体 12000gを得た。 得られた PTFE水性分散体を、ポリオキシエチレンアルキルエーテル（商品名 TDS — 80、第一工業製薬社製;平均 HLB= 13)を用いて 5040gに濃縮し、 P. C. 71. 2 質量％、ポリオキシエチレンアルキルエーテル濃度 [N. C. ]が PTFE榭脂固形分の 2. 9質量％である PTFE水性分散液濃縮品 Aを調製した。 The average particle diameter of 273nm by emulsion polymerization, PTFE polymer concentration [PC, corresponding to the PTFE榭脂solids] 30.7 mass 0/0, the Pafuruoro (propyl Bulle ether) [PPVE] units is zero. 12 mass% of PTFE 12000 g of an aqueous dispersion was obtained. The obtained PTFE aqueous dispersion was concentrated to 5040 g using polyoxyethylene alkyl ether (trade name TDS-80, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; average HLB = 13), and PC 71.2% by mass, polyoxy A PTFE aqueous dispersion concentrate A having an ethylene alkyl ether concentration [NC] of 2.9% by mass of PTFE rosin solids was prepared.
[0058] 調製例 2 [0058] Preparation Example 2
乳化重合により平均粒径 354nm、 P. C. 34. 6質量％、 PPVE単位が PTFEの 0. 1 3質量％である PTFE水性分散体 12000gを得た。  By emulsion polymerization, 12000 g of an aqueous PTFE dispersion having an average particle size of 354 nm, P. C. 34.6% by mass, and PPVE units of 0.13% by mass of PTFE was obtained.
これを TDS— 80により 4968gに濃縮し、 P. C. 73. 6質量0 /0、 N. C.力 SPTFE樹月旨 固形分の 1. 9質量％である PTFE水性分散液濃縮品 Bを調製した。 This was concentrated to 4968g by the TDS- 80, to prepare a PC 73. 6 wt 0/0, NC force SPTFE Kitsuki PTFE aqueous dispersion concentrated product B is 1.9% by weight of the fact solids.
[0059] 調製例 3 [0059] Preparation Example 3
乳化重合により平均粒径 342nm、 P. C. 30. 8質量％のPTFE水性分散体 (TFE 単独重合体水性分散体) 12000gを得た。  By emulsion polymerization, 12000 g of an aqueous PTFE dispersion (TFE homopolymer aqueous dispersion) having an average particle diameter of 342 nm and P. C. 30.8% by mass was obtained.
これを TDS— 80により 4992gに濃縮し、 P. C. 71. 8質量0 /0、 N. C.力 SPTFE樹月旨 固形分の 2. 7質量％である PTFE水性分散液濃縮品 Cを調製した。 This was concentrated to 4992g by the TDS- 80, to prepare a PTFE aqueous dispersion concentrated product C is 2.7% by weight of the PC 71. 8 mass 0/0, NC force SPTFE Kitsuki fact solids.
[0060] 実施例 1 [0060] Example 1
PTFE水性分散液濃縮品 A 300gに、 TDS— 80 6. 6gとポリオキシエチレンアル キルエーテル (商品名 TDS— 120、第一工業製薬社製;平均 HLB= 14. 5) 15. Og と純水 81. 4gを添加して、 P. C. 53質量％、 N. C.力 PTFE榭脂固形分の 13質量 %、平均 HLBが 14以上のポリオキシエチレンアルキルエーテル系化合物の全ポリオ キシエチレンアルキルエーテル系化合物に対する割合 (以下、「（Bl) Z (B)」と 、う。 )が 54質量％である PTFE水性分散液組成物を得た。  PTFE aqueous dispersion concentrate A 300g, TDS-806.6g and polyoxyethylene alkyl ether (trade name TDS-120, Daiichi Kogyo Seiyaku Co., Ltd .; average HLB = 14.5) 15. Og and pure water 81.4g added, 53% by mass of PC, 13% by mass of NC force PTFE resin solids, ratio of polyoxyethylene alkyl ether compounds with an average HLB of 14 or more to the total polyoxyethylene alkyl ether compounds ( Hereinafter, a PTFE aqueous dispersion composition in which “(Bl) Z (B)” and “)” were 54 mass% was obtained.
得られた PTFE水性分散液組成物は、粘度が 2. 05 X 10"2Pa- s,クラック限界膜厚 力 SlO /z mであった。 The obtained PTFE aqueous dispersion composition had a viscosity of 2.05 X 10 " 2 Pa-s and a crack limit film thickness force SlO / zm.
[0061] 実施例 2 [0061] Example 2
PTFE水'性分散液濃縮品 A 300gに、 TDS— 80 6. 6gと TDS— 120 15. Og, アクリル榭脂水性分散体（日本触媒社製、固形分濃度 40質量％) 16. Og及び純水 6 5. 4gを添加して、 P. C. 53%、 N. C.力 SPTFE榭脂固形分の 13質量0 /0、アクリル 榭脂が PTFE榭脂固形分の 3質量％、（Bl)Z(B) = 54質量％である PTFE水性分 散液組成物を得た。 PTFE aqueous dispersion concentrate A 300 g, TDS- 80 6.6 g and TDS- 120 15. Og, acrylic resin aqueous dispersion (manufactured by Nippon Shokubai Co., Ltd., solid content concentration 40 mass%) 16. Og and pure water 6 5. 4g was added, PC 53%, NC force SPTFE榭脂13 mass 0/0 of solids, 3% by weight of acrylic榭脂is PTFE榭脂solids, (Bl) Z (B) = PTFE water content of 54% by mass A spray composition was obtained.
得られた PTFE水性分散液組成物は、粘度が 5. 80 X 10"2Pa- s,クラック限界膜厚 力 ΐ4 ;ζ πιであった。 The obtained PTFE aqueous dispersion composition had a viscosity of 5.80 × 10 ” 2 Pa-s, crack limit film thickness force ΐ4; ζ πι.
[0062] 実施例 3 [0062] Example 3
PTFE水性分散液濃縮品 A 300gに、 TDS— 120 21. 6g、アクリル榭脂水性分 散体（日本触媒社製、固形分濃度 40質量％) 16. Og、ェチルカルビトール（日本触 媒社製、沸点 202°C) 8. Og、純水 57. 4gを添カ卩して、 P. C. 53質量％、 N. C.が P TFE榭脂固形分の 13質量％、アクリル榭脂が PTFE榭脂固形分の 3質量％、ェチ ルカルビトールがアクリル榭脂水性分散体の 50質量％、（Bl)Z(B) = 78質量％の PTFE水性分散液組成物を得た。  PTFE aqueous dispersion concentrate A 300 g, TDS-120 21.6 g, acrylic resin aqueous dispersion (Nihon Shokubai Co., Ltd., solid concentration 40% by mass) 16. Og, ethyl carbitol (Nippon Shokubai Co., Ltd.) (Boiling point: 202 ° C) 8. Og, 57.4g of pure water added, PC 53% by mass, NC is 13% by mass of PTFE resin solids, Acrylic resin is PTFE resin solids Thus, a PTFE aqueous dispersion composition was obtained in which 3% by mass of ethyl carbitol was 50% by mass of the aqueous dispersion of acrylic resin and (Bl) Z (B) = 78% by mass.
得られた PTFE水性分散液組成物は、粘度が 4. 80 X 10"2Pa- s,クラック限界膜厚 が 20 /z mであった。 The obtained PTFE aqueous dispersion composition had a viscosity of 4.80 × 10 ” 2 Pa-s and a crack limit film thickness of 20 / zm.
[0063] 実施例 4 [0063] Example 4
PTFE水性分散液濃縮品 A 300gに、 TDS— 120 19. 4g、アクリル榭脂水性分 散体（日本触媒社製、固形分濃度 40質量％) 16. Og、ェマルゲン A— 60 (花王社製 、ポリオキシエチレン誘導体） 2. lg、ェチルカルビトール 4. Og及び純水 61. 4gを添 加して、 P. C. 53質量％、 N. C.力 SPTFE榭脂固形分の 13質量％、アクリル榭脂が PTFE榭脂固形分の 3質量％、ェマルゲン A— 60が PTFE榭脂固形分の 1質量％、 ェチルカルビトールがアクリル榭脂水性分散体の 25質量％、（Bl)Z(B) = 78質量 %の PTFE水性分散液組成物を得た。  PTFE aqueous dispersion concentrate A 300 g, TDS-120 19.4 g, acrylic resin aqueous dispersion (Nippon Shokubai Co., Ltd., solid concentration 40% by mass) 16. Og, Emargen A-60 (manufactured by Kao Corporation) Polyoxyethylene derivatives) 2. lg, ethyl carbitol 4. Og and 61.4 g of pure water are added, 53% by weight of PC, 13% by weight of NC SPTFE resin solids, acrylic resin is PTFE Emulgen A-60 is 1% by mass of PTFE resin solids, Ethylcarbitol is 25% by mass of an aqueous acrylic resin dispersion, (Bl) Z (B) = 78% % PTFE aqueous dispersion composition was obtained.
得られた PTFE水性分散液組成物は、粘度が 3. 55 X 10"2Pa- s,クラック限界膜厚 が 20 /z mであった。 The obtained PTFE aqueous dispersion composition had a viscosity of 3.55 × 10 ” 2 Pa-s and a crack limit film thickness of 20 / zm.
[0064] 実施例 5 [0064] Example 5
PTFE水性分散液濃縮品 A 300gに、 TDS— 120 21. 6g、アクリル榭脂水性分 散体（日本触媒社製、固形分濃度 40質量％) 16. 0g、ェチルカルビトール 8. 0g、グ リセリン 2. lg及び純水 55. 2gを添カ卩して、 P. C. 53質量0 /0、 N. C.力 PTFE榭脂 固形分の 13質量％、アクリル榭脂が PTFE榭脂固形分の 3質量％、ェチルカルビト ールがアクリル榭脂水性分散体の 50質量％、グリセリンが PTFE榭脂固形分の 1質 量％、（Bl)Z(B) =78質量％の PTFE水性分散液組成物を得た。 PTFE aqueous dispersion concentrate A 300 g, TDS-120 21.6 g, acrylic resin aqueous dispersion (Nippon Shokubai Co., Ltd., solid content 40% by mass) 16.0 g, ethyl carbitol 8.0 g, g glycerin 2. lg and pure water 55. 2 g of添Ka卩, PC 53 mass 0/0, NC force 13 mass% of PTFE榭脂solids, 3% by weight of acrylic榭脂is PTFE榭脂solids, Ethylcarbitol is 50% by mass of the aqueous dispersion of acrylic resin, and glycerin is a part of the solid content of PTFE resin. A PTFE aqueous dispersion composition having an amount of% and (Bl) Z (B) = 78% by mass was obtained.
得られた PTFE水性分散液組成物は、粘度が 5.70X10"2Pa-s,クラック限界膜厚 力 ΐ8;ζπιであった。 The obtained PTFE aqueous dispersion composition had a viscosity of 5.70 × 10 ” 2 Pa-s, a crack limit film thickness force of 8; ζπι.
[0065] 実施例 6 [0065] Example 6
PTFE水性分散液濃縮品 A 300gに、 TDS— 120 21.6g、シルウエット L— 77( 日本ュ-カー社製、シリコーン系界面活性剤） 2. Ig及び純水 79.3gを添加して、 P . C.53質量％、N. C.が PTFE榭脂固形分の 13質量％、シリコーン系界面活性剤 が PTFE榭脂固形分の 1質量％、（Bl)Z(B)
Figure imgf000022_0001
PTFE aqueous dispersion concentrate A 300 g, TDS-120 21.6 g, Silwet L-77 (manufactured by Nippon Carker, silicone surfactant) 2. Add Ig and 79.3 g of pure water, .53% by mass, NC is 13% by mass of PTFE resin solids, Silicone surfactant is 1% by mass of PTFE resin solids, (Bl) Z (B)
Figure imgf000022_0001
成物を得た。  A composition was obtained.
得られた PTFE水性分散液組成物は、粘度が 5.70X10"2Pa-s,クラック限界膜厚 力 ΐ2;ζπιであった。 The obtained PTFE aqueous dispersion composition had a viscosity of 5.70 × 10 ” 2 Pa-s, crack limit film thickness force ΐ2; ζπι.
[0066] 実施例 7 [0066] Example 7
PTFE水性分散液濃縮品 A 300gに、 TDS— 120 21.6g、 KF— 618 (信越ィ匕学 工業社製、シリコーン系界面活性剤） 2. lg、純水 79.3gを添加して、 P. C.53質量 %、 N. C.が PTFE榭脂固形分の 13質量％、シリコーン系界面活性剤が PTFE榭 脂固形分の 1質量％、（Bl)Z(B) =
Figure imgf000022_0002
PTFE aqueous dispersion concentrate A 300g, TDS-120 21.6g, KF-618 (Shin-Etsu Chemical Co., Ltd., silicone surfactant) 2.lg, 79.3g of pure water was added, and PC53 mass% , NC is 13% by mass of PTFE resin solids, Silicone surfactant is 1% by mass of PTFE resin solids, (Bl) Z (B) =
Figure imgf000022_0002
得られた PTFE水性分散液組成物は、粘度は 4.40X10"2Pa-s,クラック限界膜厚 は 12 /zmであった。 The resulting PTFE aqueous dispersion composition had a viscosity of 4.40 × 10 ” 2 Pa-s and a crack limit film thickness of 12 / zm.
[0067] 実施例 8 [0067] Example 8
PTFE水性分散液濃縮品 A 300gに、 TDS— 80 6.6g、 TDS— 120 15. Og、グ リセリン 2. Ig及び純水 79.3gを添カ卩して、 P. C.53質量％、 N. C.が PTFE榭脂 固形分の 13質量％、グリセリンが PTFE榭脂固形分の 1質量％、（Bl)Z(B) =54 質量％の PTFE水性分散液組成物を得た。  PTFE aqueous dispersion concentrate A 300g, TDS-80 6.6g, TDS-120 15. Og, glycerin 2. Ig and pure water 79.3g are added, and PC53 mass%, NC is PTFE oil A PTFE aqueous dispersion composition having a solid content of 13% by mass, glycerin of 1% by mass of PTFE rosin solids, and (Bl) Z (B) = 54% by mass was obtained.
得られた PTFE水性分散液組成物は、粘度が 4.90X10"2Pa-s,クラック限界膜厚 力 mであった。 The obtained PTFE aqueous dispersion composition had a viscosity of 4.90 × 10 ” 2 Pa-s and a crack limit film thickness force m.
[0068] 実施例 9 [0068] Example 9
PTFE水性分散液濃縮品 A 300gに、 TDS— 80 6.6g、 TDS— 120 15. Og、ト ジエチレングジ =3—ノレ 2. lg<¾び! ¾水 79.3gを添カロして、 P. C.53 量0 /0、 N. C. PTFE榭脂固形分の 13質量％、トリエチレングリコールが PTFE榭脂固形分の 1質 量％、（Bl)Z(B) = 54質量％の PTFE水性分散液組成物を得た。 PTFE aqueous dispersion concentrate A 300 g, TDS- 80 6.6 g, TDS- 120 15. Og, Todiethylene gaze = 3— Nore 2. l g < ¾ and ¾ water 79.3 g added, PC53 amount 0 / 0 , NC A PTFE aqueous dispersion composition having a solid content of 13% by weight of PTFE rosin, 1% by weight of triethylene glycol and 1% by weight of the solid content of PTFE mortar, (Bl) Z (B) = 54% by weight was obtained.
得られた PTFE水性分散液組成物は、粘度が 5. 70 X 10"2Pa- s,クラック限界膜厚 力 SlO /z mであった。 The obtained PTFE aqueous dispersion composition had a viscosity of 5.70 × 10 ” 2 Pa-s and a crack limit film thickness force SlO / zm.
[0069] 実施例 10 [0069] Example 10
PTFE水性分散液濃縮品 B 300gに、 TDS— 120 24. 5g、アクリル榭脂水性分散 体（日本触媒社製、固形分濃度 40%) 16. 6g、ェチルカルビトール 8. 3g及び純水 6 7. 3gを添カ卩して、 P. C. 53質量0 /0、 N. C.力 SPTFE榭脂固形分の 13質量0 /0、ァク リル樹脂が PTFE榭脂固形分の 3質量％、ェチルカルビトールがアクリル榭脂水性分 散体の 50質量％、 (Bl) / (B)
Figure imgf000023_0001
PTFE aqueous dispersion concentrate B 300 g, TDS-120 24.5 g, acrylic resin aqueous dispersion (manufactured by Nippon Shokubai Co., Ltd., solid concentration 40%) 16. 6 g, ethyl carbitol 8.3 g and pure water 6 7.添Ka卩the 3 g, PC 53 mass 0/0, NC force SPTFE榭脂solids of 13 weight 0/0, 3 wt% of § click Lil resin PTFE榭脂solids, E chill carbitol Is 50% by mass of the aqueous dispersion of acrylic resin, (Bl) / (B)
Figure imgf000023_0001
得られた PTFE水性分散液組成物は、粘度が 4. 95 X 10"2Pa- s,クラック限界膜厚 が 29 /z mであった。 The obtained PTFE aqueous dispersion composition had a viscosity of 4.95 × 10 ” 2 Pa-s and a crack limit film thickness of 29 / zm.
実施例 11  Example 11
PTFE水性分散液濃縮品 A 300g〖こ、 TDS— 80 13. Ogと純水 90. Ogを添加して 、 P. C. 53質量％、N. C.が PTFE榭脂固形分の 9質量％、（Bl)Z(B) =0質量％ の PTFE水性分散液を得た。得られた水性分散液組成物は、粘度が 1. 80 X 10"2P a' s、クラック限界膜厚は 5 μ mであった。 PTFE aqueous dispersion concentrate A 300g coconut, TDS-80 13. Add Og and pure water 90.Og, PC 53% by mass, NC is 9% by mass of PTFE oil solids, (Bl) Z ( B) A 0% by mass PTFE aqueous dispersion was obtained. The obtained aqueous dispersion composition had a viscosity of 1.80 × 10 ” 2 Pa ′s and a crack limit film thickness of 5 μm.
[0070] 実施例 12 [0070] Example 12
PTFE水性分散液濃縮品 A 300gに、 TDS— 80 19. 4gと純水 83. 6gを添加して 、 P. C. 53質量％、N. C.力 SPTFE榭脂固形分の 12質量％、（B1)Z(B) =0質量 %の PTFE水性分散液組成物を得た。  PTFE aqueous dispersion concentrate A 300g, TDS-80 19.4g and pure water 83.6g are added, PC 53 mass%, NC force SPTFE oil solid content 12 mass%, (B1) Z (B ) = 0 mass% PTFE aqueous dispersion composition was obtained.
得られた水性分散液組成物は、粘度が 7. 45 X 10_2Pa' s、クラック限界膜厚が 5 mであった。 The obtained aqueous dispersion composition had a viscosity of 7.45 × 10_2 Pa's and a crack limit film thickness of 5 m.
[0071] 実施例 13 [0071] Example 13
PTFE水性分散液濃縮品 A 300gに、 TDS— 80 6. 6g、TDS— 120 12. 8g及 び純水 83. 6gを添加して、 P. C. 53質量％、N. C.力 SPTFE榭脂固形分の 12質量 %、（Bl)Z(B) =
Figure imgf000023_0002
PTFE aqueous dispersion concentrate A 300 g, TDS- 80 6.6 g, TDS-120 12.8 g and pure water 83.6 g are added, PC 53 mass%, NC force 12 mass of SPTFE oil solid content %, (Bl) Z (B) =
Figure imgf000023_0002
得られた水性分散液組成物は、粘度が 2. 00 X 10_2Pa' s、クラック限界膜厚が 8 mであった。 The resulting aqueous dispersion composition has a viscosity of 2.00 X 10 _2 Pa's and a crack limit film thickness of 8 m.
[0072] 比較例 1 [0072] Comparative Example 1
PTFE水性分散液濃縮品 C 300gに、 TDS— 80 7. lg、TDS— 120 12.9gと 純水 86.4gを添加して、 P. C.53質量％、 N. C.が PTFE榭脂固形分の 12質量％ 、（Bl)Z(B) =
Figure imgf000024_0001
Concentrated PTFE aqueous dispersion C 300 g, TDS- 80 7. lg, TDS-120 12.9 g and pure water 86.4 g are added, PC 53 mass%, NC is 12 mass% PTFE oil solid content, (Bl ) Z (B) =
Figure imgf000024_0001
得られた水性分散液組成物は、粘度が 2.00X10"2Pa-s,クラック限界膜厚が 29 μ mであった。 The obtained aqueous dispersion composition had a viscosity of 2.00 × 10 ” 2 Pa-s and a crack limit film thickness of 29 μm.
[0073] 比較例 2 [0073] Comparative Example 2
PTFE水'性分散液濃縮品 A 300gに、 TDS— 80 6.6g, TDS -120 15. Ogと 純水 532.7gを添カ卩して、 P. C.25質量0 /0、 N. C.力 SPTFE榭脂固形分の 13質量 %、（Bl)Z(B) =
Figure imgf000024_0002
The PTFE aqueous' dispersion liquid concentrate products A 300g, TDS- 80 6.6g, TDS -120 and 15. Og of pure water 532.7g The添Ka卩, the PC25 mass 0/0, NC force SPTFE榭脂solids 13% by mass, (Bl) Z (B) =
Figure imgf000024_0002
得られた水性分散液組成物は、粘度が 0.60X10"2Pa-s,クラック限界膜厚が 1 μ mであった。 The resulting aqueous dispersion composition had a viscosity of 0.60 × 10 ” 2 Pa-s and a crack limit film thickness of 1 μm.
[0074] 比較例 3 [0074] Comparative Example 3
PTFE水'性分散液濃縮品 A 300gに、 TDS— 80 16.6g, TDS- 120 5. Ogと 純水 81.4gを添加して、 P. C.53質量％、 N. C.が PTFE榭脂固形分の 13質量％ 、（Bl)Z(B) =
Figure imgf000024_0003
PTFE aqueous dispersion concentrate A 300g, TDS-80 16.6g, TDS-120 5. Og and pure water 81.4g are added, PC53 mass%, NC is 13 mass% PTFE oil solid content, (Bl) Z (B) =
Figure imgf000024_0003
得られた水性分散液組成物は、粘度が 13.90X10"2Pa-s,クラック限界膜厚が 6 μ mであった。 The resulting aqueous dispersion composition had a viscosity of 13.90 × 10 ” 2 Pa-s and a crack limit film thickness of 6 μm.
[0075] 比較例 4 [0075] Comparative Example 4
PTFE水'性分散液濃縮品 A 300gに、 TDS— 80 6.6g, TDS -120 34.2gと 純水 62.2gを添カ卩して、 P. C.53質量％、 N. C.が PTFE榭脂固形分の 22質量％ 、（Bl)Z(B) =
Figure imgf000024_0004
PTFE aqueous dispersion concentrate A 300g, TDS-80 6.6g, TDS-120 34.2g and 62.2g of pure water are added, PC 53% by mass, NC is 22% by mass of PTFE oil solid content , (Bl) Z (B) =
Figure imgf000024_0004
得られた水性分散液組成物は、粘度が 15.05X10"2Pa-s,クラック限界膜厚が 5 μ mであった。 The resulting aqueous dispersion composition had a viscosity of 15.05 × 10 ” 2 Pa-s and a crack limit film thickness of 5 μm.
[0076] 比較例 5 [0076] Comparative Example 5
PTFE水性分散液濃縮品 C 300gに、 TDS— 80 7. lg、TDS— 120 15. lg、ァ クリル樹脂水性分散体（日本触媒社製、固形分濃度 40質量％) 16.2g、ェチルカル ビトール 8. lg及び純水 60. Ogを添加して、 P. C. 53質量0 /0、 N. C.力 PTFE榭脂 固形分の 13質量％、アクリル榭脂が PTFE榭脂固形分の 3質量％、ェチルカルビト ールがアクリル榭脂水性分散体の 50質量％、（Bl)Z(B) =
Figure imgf000025_0001
PTFE aqueous dispersion concentrate C 300g, TDS-80 7.lg, TDS-120 15.lg, acrylic resin aqueous dispersion (Nippon Shokubai Co., Ltd., solid content concentration 40% by mass) 16.2g, Ethylcal Bitoru 8. added lg and pure water 60. Og, PC 53 mass 0/0, NC force 13 mass% of PTFE榭脂solids, 3% by weight of acrylic榭脂is PTFE榭脂solids, Echirukarubito chromatography Is 50% by weight of the aqueous dispersion of acrylic resin, (Bl) Z (B) =
Figure imgf000025_0001
性分散液組成物を得た。  An aqueous dispersion composition was obtained.
得られた水性分散液組成物は、粘度が 3. 05 X 10"2Pa- s,クラック限界膜厚が 41 μ mであった。 The obtained aqueous dispersion composition had a viscosity of 3.05 X 10 " 2 Pa-s and a crack limit film thickness of 41 µm.
[0077] 比較例 6 [0077] Comparative Example 6
PTFE水性分散液濃縮品 A 300gに、 TDS— 80 8. 8gと純水 94. 2gを添カ卩して、 P. C. 53質量％、N. C.が PTFE榭脂固形分の 7質量％、（Bl)Z(B) =0質量％ の PTFE水性分散液を得た。  PTFE aqueous dispersion concentrated product A 300g, TDS-808.8g and pure water 94.2g added, 53% PC by weight, NC 7% by weight PTFE solids, (Bl) Z (B) A PTFE aqueous dispersion with 0 mass% was obtained.
得られた水性分散液組成物は、粘度が 1. 55 X 10"2Pa- s,クラック限界膜厚は 2 mであった。 The obtained aqueous dispersion composition had a viscosity of 1.55 × 10 ” 2 Pa-s and a crack limit film thickness of 2 m.
[0078] 試験例 [0078] Test example
実施例 3から得られた PTFE水性分散液組成物、並びに、比較例 1及び比較例 5か ら得られた水性分散液組成物を、アルミ板（20cm X 15cmX l. 5mm)上に膜厚 10 〜20 mになるよう塗布し、 100°Cにて 10分間乾燥したのち、 380°Cにて 15分間焼 成して得られた被膜を剥がし取り、直読ヘイズメーター (東洋精機製作所製)を用い て膜厚 15 mの箇所の全光線透過率とヘイズ値を測定した。  The PTFE aqueous dispersion composition obtained from Example 3 and the aqueous dispersion compositions obtained from Comparative Example 1 and Comparative Example 5 were coated on an aluminum plate (20 cm × 15 cm × l.5 mm) with a film thickness of 10 Apply to ~ 20 m, dry at 100 ° C for 10 minutes, peel off the film obtained by baking at 380 ° C for 15 minutes, and use a direct reading haze meter (Toyo Seiki Seisakusho) Then, the total light transmittance and haze value of the portion having a film thickness of 15 m were measured.
全光線透過率は光の透過する割合を示し、値が大き ヽほど光透過性に優れることを 意味する。  The total light transmittance indicates the light transmission ratio, and the larger the value, the better the light transmittance.
ヘイズ値は透過光のうち拡散した光の割合を示し、値が小さ 、ほど透明性に優れる ことを意味する。  The haze value indicates the ratio of diffused light in the transmitted light, and the smaller the value, the better the transparency.
実施例 3、比較例 1及び比較例 5で得られる被膜の全光線透過率とヘイズ値を表 1に 示す。  Table 1 shows the total light transmittance and haze value of the coatings obtained in Example 3, Comparative Example 1 and Comparative Example 5.
[0079] [表 1] 全光線透過率 ヘイズ値 [0079] [Table 1] Total light transmittance Haze value
実施例 3 9 4 . 9 % 8 . 0 % 比較例 1 9 2 . 5 % 2 3 . 7 % 比較例 5 9 3 . 5 % 1 9 . 4 %  Example 3 9 4 .9% 8.0% Comparative Example 1 9 2.5% 2 3.7% Comparative Example 5 9 3 .5% 1 9 .4%
[0080] 実施例 3では PPVE変性 PTFEを用いているのに対し、比較例 1及び比較例 5では P TFE単独重合体 (Homo系の PTFE)を用いて!/、る。変性 PTFE力 なる榭脂を含む 被膜の方が光透過性に優れ、また拡散光の割合が低いために透明性に優れること が分かる。 In Example 3, PPVE-modified PTFE is used, while in Comparative Examples 1 and 5, PTFE homopolymer (Homo PTFE) is used! It can be seen that the coating containing the modified PTFE-strengthened resin is superior in light transmission, and has a low ratio of diffused light, and thus excellent in transparency.
産業上の利用可能性  Industrial applicability
[0081] 本発明の PTFE水性分散液組成物は、上述の構成力もなるものであるので、厚膜と することが容易であるにもかかわらずクラックが生じないコーティング用糸且成物として 好適に使用することができる。 [0081] Since the PTFE aqueous dispersion composition of the present invention also has the above-mentioned constitutional power, it is suitable as a coating yarn and composition that does not cause cracks despite being easy to form a thick film. Can be used.
本発明の PTFE榭脂フィルムは、上述の構成からなるものであるので、クラック等の欠 陥がなぐ厚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 thick film free from defects such as cracks.
本発明の PTFE榭脂含浸体は、上述の構成カゝらなるものであるので、クラック等の欠 陥がなぐ厚膜の被膜とすることも可能である。  Since the PTFE resin impregnated body of the present invention has the above-mentioned constitution, it can be a thick film without cracks and the like.
また、本発明の PTFE水性分散液組成物は、変性 PTFEからなる榭脂を含む場合、 得られる被膜は高 、光透過性を有するものである。  In addition, when the aqueous PTFE dispersion composition of the present invention contains a resin made of modified PTFE, the resulting coating is highly light transmissive.

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榭脂粒子 (A)とポリオキシアルキレンアルキルエーテル系 化合物（B)とを含むポリテトラフルォロエチレン水性分散液組成物であって、 前記ポリテトラフルォロエチレン水性分散液組成物は、ポリテトラフルォロエチレン榭 脂固形分濃度が前記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 %、 25°Cにおける粘度が 0. lPa' s以下であり、  [1] A polytetrafluoroethylene aqueous dispersion composition comprising polytetrafluoroethylene resin particles (A) and a polyoxyalkylene alkyl ether compound (B), the polytetrafluoroethylene aqueous dispersion composition comprising: The ethylene aqueous dispersion composition has a polytetrafluoroethylene resin solid content concentration of 30 to 70% by mass of the polytetrafluoroethylene aqueous dispersion composition, and a viscosity at 25 ° C of 0.1 lPa's. And
前記ポリオキシアルキレンアルキルエーテル系化合物（B)は、前記ポリテトラフルォロ エチレン榭脂固形分 100質量部に対して 9〜20質量部であり、  The polyoxyalkylene alkyl ether compound (B) is 9 to 20 parts by mass with respect to 100 parts by mass of the polytetrafluoroethylene resin solid content,
前記ポリテトラフルォロエチレン榭脂粒子 (A)を構成するポリテトラフルォロエチレン 榭脂は、変性ポリテトラフルォロエチレン力もなる榭脂である  The polytetrafluoroethylene resin constituting the polytetrafluoroethylene resin particles (A) is a resin having a modified polytetrafluoroethylene power.
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] 更に、造膜改良剤（C)をも含むものである請求項 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。 [2] The aqueous polytetrafluoroethylene dispersion composition according to claim 1, further comprising a film-forming improver (C).
[3] 造膜改良剤 (C)は、アクリル榭脂、シリコーン系界面活性剤、 380°Cでの分解残渣が [3] The film-forming improver (C) is composed of acrylic resin, silicone surfactant, and decomposition residue at 380 ° C.
5%以上である非イオン性界面活性剤及び Z又は乾燥遅延剤である請求項 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。 The aqueous polytetrafluoroethylene dispersion composition according to claim 2, which is a nonionic surfactant and Z or a drying retardant that is 5% or more.
[4] 造膜改良剤 (C)は、ポリテトラフルォロエチレン榭脂固形分 100質量部に対して 10 質量部以下である請求項 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] The aqueous polytetrafluoroethylene dispersion according to claim 2 or 3, wherein the film-forming modifier (C) is 10 parts by mass or less with respect to 100 parts by mass of the polytetrafluoroethylene resin solid content. Composition.
[5] ポリテトラフルォロエチレン榭脂粒子 (A)は、平均粒子径が 200〜500nmである請 求項 1、 2、 3又は 4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] The polytetrafluoroethylene aqueous dispersion composition according to claim 1, 2, 3 or 4, wherein the polytetrafluoroethylene resin particles (A) have an average particle diameter of 200 to 500 nm.
[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榭脂フィルム。  A polytetrafluoroethylene resin film characterized by that.
[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榭脂含浸体。  A polytetrafluoroethylene resin impregnated body characterized by the above.
PCT/JP2005/017643 2004-09-27 2005-09-26 Aqueous polytetrafluoroethylene dispersion composition, poly- tetrafluoroethylene resin film, and products impregnated with polytetrafluoroethylene resin WO2006035726A1 (en)

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