WO2020137828A1 - Powder-dispersed liquid, method for producing layered product, method for producing polymer film, and method for producing coated woven fabric - Google Patents

Abstract

[Problem] To provide the following: a powder-dispersed liquid which contains a powder of a non-thermofusible polytetrafluoroethylene or a powder of a thermofusible fluoropolymer and a powder of a prescribed tetrafluoropolymer, which exhibits excellent workability without compromising the physical properties of both polymers, and which can form a molded article that exhibits strong adhesive properties; and a method for producing a layered product, a method for producing a polymer film and a method for producing a coated woven fabric using the powder-dispersed liquid. [Solution] This powder-dispersed liquid contains a powder (1) of a fluoropolymer having a unit derived from tetrafluoroethylene and an oxygen-containing polar group, a powder (21) of a non-thermofusible polytetrafluoroethylene or a powder (22) of a thermofusible fluoropolymer, and an aqueous medium.

Description

Powder dispersion, method for producing laminate, method for producing polymer film, and method for producing coated woven fabric

The present invention relates to a powder dispersion, a method for producing a laminate, a method for producing a polymer film, and a method for producing a coated woven fabric.

Fluoroolefin-based polymers such as polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene and perfluoro(alkyl vinyl ether) (PFA), copolymers of tetrafluoroethylene and hexafluoropropylene (FEP), have releasability It has excellent physical properties, such as water repellency, oil repellency, chemical resistance, weather resistance, and heat resistance, and it is utilized for various industrial applications by utilizing its physical properties.
Among them, the powder dispersion liquid in which the powder of the fluoroolefin polymer is dispersed in the solvent is useful as a coating agent because the physical properties of the fluoroolefin polymer can be imparted to the surface of the base material when it is applied to the surface of various base materials. (See Patent Documents 1 and 2).

International Publication No. 2018/016644 International Publication No. 2008/018400

Fluoroolefin-based polymers have unique properties.
It is known that non-thermofusible polytetrafluoroethylene has unique physical properties represented by fibrillarity. If a dispersion liquid obtained by mixing a powder of non-heat-melting polytetrafluoroethylene and a powder of a heat-melting fluoroolefin polymer such as PFA or FEP is used, a molded article having physical properties of both polymers can be formed. Conceivable.
However, such a dispersion has low dispersibility and is subjected to a dispersion treatment in which shear stress is applied in order to prepare a uniform dispersion, redisperse the dispersion after aging, or to further mix other components. Then, there is a problem that the non-thermofusible polytetrafluoroethylene is denatured due to, for example, becoming a fibril, and the dispersibility and moldability are lowered.

Moreover, the molded product formed from such a dispersion has a problem that mechanical strength such as crack resistance and adhesiveness are still insufficient. In particular, the crack resistance and the adhesiveness when the thickness of the molded product is increased or the molded product is stretched are still insufficient.

On the other hand, heat-fusible fluoropolymers such as modified PTFE, PFA and FEP have excellent heat resistance, chemical resistance, etc., as well as PTFE, and excellent moldability. However, the molded product is not sufficient in adhesiveness to other materials and workability (flexibility such as stretchability and bending workability), and is formed from an aqueous dispersion containing a powder of a heat-meltable fluoropolymer. The tendency is remarkable in the molded articles produced. In addition, when a component for improving adhesiveness and workability is added to such an aqueous dispersion, there are problems that the dispersion state of the dispersion is deteriorated and the fluoropolymer physical properties in the molded product are deteriorated.

The present invention includes a powder of non-heat-melting polytetrafluoroethylene or a powder of heat-melting fluoropolymer, and a powder of a predetermined tetrafluoropolymer, without impairing the physical properties of both polymers, and with excellent processability An object of the present invention is to provide a powder dispersion capable of forming a molded article exhibiting strong adhesiveness, a method for producing a laminate using the powder dispersion, a method for producing a polymer film, and a method for producing a coated woven fabric.

The present invention has the following aspects.
<1> A fluoropolymer powder (1) having a unit based on tetrafluoroethylene and an oxygen-containing polar group, and a non-heat-meltable polytetrafluoroethylene powder (21) or a heat-meltable fluoropolymer powder (22). , A powder dispersion containing an aqueous medium.
<2> The volume-based cumulative 50% diameter of the powder (1) is 0.01 to 75 μm, and the volume-based cumulative 50% diameter of the powder (21) or the powder (22) is 0.01 to 100 μm. The powder dispersion liquid according to <1> above.
<3> The ratio by mass of the content of the fluoropolymer to the content of the non-heat-meltable polytetrafluoroethylene or the content of the heat-meltable fluoropolymer is 0.4 or less, <1> Or <2> powder dispersion.
<4> The powder dispersion liquid according to any one of <1> to <3>, wherein the fluoropolymer has a melting temperature of 140 to 320° C.
<5> The powder dispersion liquid according to any one of <1> to <4>, wherein the fluoropolymer includes a unit based on the monomer having the oxygen-containing polar group.
<6> The powder dispersion liquid according to any one of the above <1> to <5>, wherein the oxygen-containing polar group is a hydroxyl group-containing group or a carbonyl group-containing group.
<7> The powder dispersion according to any one of the above <1> to <6>, wherein the non-thermofusible polytetrafluoroethylene has a fibrillation property.
<8> The heat-meltable fluoropolymer is modified polytetrafluoroethylene, a copolymer of tetrafluoroethylene and perfluoro(alkyl vinyl ether), or a copolymer of tetrafluoroethylene and hexafluoropropylene. <1> to <7 > Powder dispersion of any of
<9> The powder dispersion liquid according to any one of the above <1> to <8>, containing both the non-heat-meltable polytetrafluoroethylene powder (21) and the heat-meltable fluoropolymer powder (22).
<10> The powder dispersion liquid according to any one of the above <1> to <9>, further containing an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant.
<11> The powder dispersion liquid according to any one of <1> to <10>, further containing a fluorosurfactant, and the fluorosurfactant is fluoromonool or fluoropolyol.
<12> The powder dispersion according to any one of the above <1> to <11> is applied to the surface of a base material, and the aqueous medium is removed by heating to form a polymer layer, which is composed of the base material. A method for producing a laminate, in which a substrate layer and the polymer layer are laminated in this order to obtain a laminate.
<13> The powder dispersion according to any one of the above <1> to <11> is applied to the surface of a base material, and the aqueous medium is removed by heating to form a polymer layer, which is composed of the base material. Manufacture of a polymer film in which a base material layer and the polymer layer are laminated in this order to obtain a laminate, and the base material layer is removed from the laminate to obtain a polymer film composed of the polymer layer Method.
<14> Production of a coated woven fabric, which is obtained by impregnating a woven fabric with the powder dispersion according to any one of the above <1> to <11>, and further drying the woven fabric to obtain a woven fabric coated with a polymer layer. Method.

According to the present invention, a molded article that is excellent in state stability such as dispersibility and storage stability, is resistant to cracking, and does not impair the physical properties of the non-thermofusible polytetrafluoroethylene, and exhibits strong adhesiveness. A powder dispersion liquid capable of forming a powder, and a powder dispersion liquid having excellent state stability and capable of forming a molded article exhibiting strong adhesiveness and good processability without impairing the physical properties of the heat-meltable fluoropolymer. And are provided. Also provided are a method for producing a laminate, a method for producing a polymer film, and a method for producing a coated woven fabric using the powder dispersion.

"Powder D50" is the volume-based cumulative 50% diameter, the particle size distribution is measured by the laser diffraction/scattering method, the cumulative volume is calculated with the total volume of the group of particles as 100%, and the cumulative volume is calculated on the cumulative curve. Is the particle size at the point where is 50%.
"D90 of powder" is the volume-based cumulative 90% diameter, the particle size distribution is measured by the laser diffraction/scattering method, the cumulative volume is calculated with the total volume of the particle group as 100%, and the cumulative volume is calculated on the cumulative curve. Is the particle size at the point where is 90%.
The “unit” in a polymer may be an atomic group formed directly from a monomer by a polymerization reaction, and the polymer obtained by the polymerization reaction may be treated by a predetermined method to convert an atomic group in which a part of the structure is converted. May be Further, a unit based on the monomer A is also referred to as a monomer A unit.
The “viscosity of the powder dispersion” is a value measured with a B-type viscometer at room temperature (25° C.) under the condition of a rotation speed of 30 rpm. The measurement is repeated 3 times, and the average value of the measured values of 3 times is taken.
The "thixo ratio of the powder dispersion liquid" is a value calculated by dividing the viscosity η ₁ measured under the condition of the rotation speed of 30 rpm by the viscosity η ₂ measured under the condition of the rotation speed of 60 rpm. The measurement of each viscosity is repeated three times, and the average value of the three measured values is used.
The “melting temperature (melting point) of the polymer” is a temperature corresponding to the maximum value of the melting peak of the polymer measured by the differential scanning calorimetry (DSC) method.
"Peel strength of laminated body" means fixing a position of 50 mm from one end in the length direction of a laminated body cut out in a rectangular shape (length 100 mm, width 10 mm), pulling speed 50 mm/min, one end in the length direction. Is the maximum load (N/cm) applied when the metal foil and the resin layer are separated from each other at 90° to the laminate.
The "standard specific gravity of a polymer" is a standard specific gravity of a polymer measured according to ASTM D4895.
The “melt flow rate” is a melt mass flow rate (MFR) defined in JIS K 7210-1:2014 (corresponding international standard ISO 1133-1:2011).

The powder dispersion liquid (present dispersion liquid) of the present invention is a powder (1) of a polymer having a unit based on tetrafluoroethylene (TFE) (TFE unit) and an oxygen-containing polar group (hereinafter, also referred to as “F polymer”). And a powder (22) of non-heat-melting polytetrafluoroethylene (hereinafter also referred to as “non-heat-melting PTFE”) or a heat-melting fluoropolymer (hereinafter also referred to as “M polymer”) (22). ) And an aqueous medium.
It can be said that the present dispersion liquid is a dispersion liquid in which the powder (1) and the powder (21) or the powder (22) are dispersed in the form of particles in an aqueous medium containing water as a main component.
The F polymer, non-thermofusible PTFE and M polymer are different polymers.
A molded article (including a molding site such as a polymer layer. The same applies hereinafter) formed from this dispersion liquid is used for individual fluoropolymers such as fibrillarity of non-heat-meltable PTFE and processability of heat-meltable fluoropolymer. It exhibits strong adhesiveness and crack resistance while having the unique physical properties of the polymer.

The reason is not always clear, but it is considered as follows.
In the present dispersion liquid containing the powder (21), both the non-thermofusible PTFE and the F polymer are polymers containing TFE units, and they easily interact with each other and are easily fused and bonded. Further, since the F polymer has an oxygen-containing polar group, it has high stability in an aqueous medium and interacts with the non-thermomelting PTFE to improve the dispersion stability of the powder. Conceivable. As a result, both powders are stabilized and uniformly dispersed in the aqueous medium, and this dispersion is considered to have excellent state stability.
Further, it is considered that in forming a molded article, the F polymer having an oxygen-containing polar group not only exhibits adhesiveness but also promotes interaction between the polymers, for example, formation of a matrix. It is considered that this interaction forms a state in which the respective polymer chains are likely to be uniformly entangled. As a result, it is considered that a molded article excellent in adhesiveness and crack resistance could be formed from the dispersion liquid without impairing the properties of the non-thermofusible PTFE.

On the other hand, even in the present dispersion liquid containing the powder (22), both the M polymer and the F polymer are polymers having a fluorine atom, and it is easy for them to interact with each other and fuse and bond. Further, since the F polymer has an oxygen-containing polar group, it has a high stability in an aqueous medium, and it is considered that the F polymer also interacts with the M polymer to improve the dispersion stability of the powder. As a result, both powders are stabilized and uniformly dispersed in the aqueous medium, and this dispersion is considered to have excellent state stability.
Further, it is considered that in forming a molded article, the F polymer having an oxygen-containing polar group not only exhibits adhesiveness but also promotes interaction between the polymers, for example, formation of a matrix. It is considered that this interaction forms a state in which the respective polymer chains are likely to be uniformly entangled. As a result, it is considered that a molded article having excellent adhesiveness and processability could be formed from the dispersion without impairing the properties of the M polymer.

The powder (1) in the present invention is a powder containing an F polymer, and is preferably a powder composed of an F polymer. The content of the F polymer in the powder (1) is preferably 80% by mass or more, and particularly preferably 100% by mass.
The D50 of the powder (1) is preferably 0.01 to 75 μm, more preferably 0.05 to 6 μm, and further preferably 0.1 to 4 μm. Preferable embodiments of D50 of the powder (1) include a mode of 0.1 μm or more and less than 1 μm and a mode of 1 μm or more and 4 μm or less.
D90 of the powder (1) is preferably 8 μm or less, more preferably 6 μm or less. D90 of the powder (1) is preferably 0.1 μm or more, more preferably 0.3 μm or more. Preferable aspects of D90 of the powder (1) include an aspect of 0.3 μm or more and less than 2 μm and an aspect of 2 μm or more and 6 μm or less.
In this case, it is easy to further improve the dispersion stability of this dispersion and the physical properties of the molded product. For example, if the D50 of the powder (1) is 0.1 μm or more and less than 1 μm, the dispersibility is more excellent, and a molded product having excellent mechanical strength such as stretching characteristics is easily obtained. When the D50 of the powder (1) is 1 μm or more and 4 μm or less, it is easy to obtain a molded product having excellent crack resistance.

The oxygen-containing polar group contained in the F polymer of the present invention may be contained in a unit based on a monomer having an oxygen-containing polar group, may be contained in a polymer end group, and may be surface-treated (radiation treatment, electron beam treatment). Treatment, corona treatment, plasma treatment, etc.), and the former is preferable. Further, the oxygen-containing polar group of the F polymer may be a group prepared by modifying a polymer having a group capable of forming an oxygen-containing polar group. The oxygen-containing polar group contained in the polymer end group can be obtained by adjusting the components (polymerization initiator, chain transfer agent, etc.) used in the polymerization of the polymer.
The oxygen-containing polar group is a polar atomic group containing an oxygen atom. However, the oxygen-containing polar group does not include the ester bond itself and the ether bond itself, but includes an atomic group containing these bonds as a characteristic group.

The oxygen-containing polar group is preferably at least one group selected from the group consisting of a hydroxyl group-containing group, a carbonyl group-containing group, an acetal group and an oxycycloalkane group, more preferably a hydroxyl group-containing group or a carbonyl group-containing group, and -CF ₂ CH ₂ OH, —C(CF ₃ ) ₂ OH, 1,2-glycol group (—CH(OH)CH ₂ OH), —CF ₂ C(O)OH, >CFC(O)OH, carboxamide group (-C(O)NH _2, etc.), acid anhydride residue (-C(O)OC(O)-), imide residue (-C(O)NHC(O)-, etc.), dicarboxylic acid residue (—CH(C(O)OH)CH ₂ C(O)OH and the like) or carbonate group (—OC(O)O—) is more preferable.
The oxycycloalkane group is preferably an epoxy group or an oxetanyl group.
Further, from the viewpoint of not easily impairing the adhesiveness of the molded article, crack resistance and physical properties of the polymer, the oxygen-containing polar group is a polar group and a cyclic group or its ring-opening group, a cyclic acid anhydride residue, Cyclic imide residues, cyclic carbonate groups, cyclic acetal groups, 1,2-dicarboxylic acid residues or 1,2-glycol groups are particularly preferred, and cyclic acid anhydride residues are most preferred.

The F polymer includes a TFE unit and a unit based on hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (hereinafter also referred to as “PAVE”) or fluoroalkyl ethylene (hereinafter also referred to as “FAE”) (hereinafter, referred to as “FAE”). A polymer containing a “PAE unit”) and a unit based on a monomer having an oxygen-containing polar group (hereinafter, also referred to as “polar unit”) is preferable.
The proportion of TFE units is preferably 50 to 99 mol%, more preferably 90 to 99 mol%, based on all units constituting the F polymer.
The PAE unit is preferably a unit based on PAVE or a unit based on HFP, and more preferably a unit based on PAVE. Two or more types of PAE units may be used.
The proportion of PAE units is preferably 0.5 to 9.97 mol% based on all units constituting the F polymer.

The _{PAVE, CF 2 = CFOCF 3 (} PMVE), CF 2 = CFOCF 2 CF 3, CF 2 = CFOCF 2 CF 2 CF 3 (PPVE), CF 2 = CFOCF 2 CF 2 CF 2 CF 3, CF 2 = CFO _{(CF 2) 8} F can be mentioned, PMVE or PPVE is preferred.
The _{FAE, CH 2 = CH (CF} 2) 2 F (PFEE), CH 2 = CH (CF 2) 3 F, CH 2 = CH (CF 2) 4 F (PFBE), CH 2 = CF (CF 2 _{) 3 H, CH 2 = CF} (CF 2) 4 H can be mentioned, PFEE or PFBE is preferred.

The polar unit is preferably a unit based on a monomer having an acid anhydride residue, a carbonate group, a cyclic acetal group, a 1,2-dicarboxylic acid residue, a 1,2-diol residue, or a 1,3-diol residue. A unit based on a monomer having a cyclic acid anhydride residue or a cyclic carbonate group is more preferable, and a unit based on a monomer having a cyclic acid anhydride residue is further preferable. The polarity unit may be one type or two or more types.
Examples of the monomer having a cyclic acid anhydride residue include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (also called hymic acid anhydride; hereinafter also referred to as “NAH”) or maleic anhydride. Acids are preferred and NAH is more preferred.
The proportion of the polar unit is preferably 0.01 to 3 mol% based on all units constituting the F polymer.

In addition, the F polymer in this case may further include a unit other than the TFE unit, the PAE unit, and the polar unit (hereinafter, also referred to as “other unit”). The other unit may be one type or two or more types.
Examples of monomers forming other units include ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride (VDF), and chlorotrifluoroethylene (CTFE). Other units are preferably ethylene, VDF or CTFE, more preferably ethylene.
The proportion of the other units in the F polymer is preferably 0 to 50 mol% and more preferably 0 to 40 mol% based on all the units constituting the F polymer.

The melting temperature of the F polymer is preferably 140 to 320°C, more preferably 200 to 320°C, and even more preferably 260 to 320°C. In this case, the fusion bondability between the F polymer and the non-thermofusible PTFE is balanced, the adhesiveness and crack resistance of the molded product are further improved, and the physical properties of the non-thermofusible PTFE are not easily impaired.

This dispersion liquid contains powder (21) or powder (22), may contain only powder (21), may contain only powder (22), and may contain powder (21) and powder (22). Both may be included.
The powder (21) is a powder containing non-heat-melting PTFE, and is preferably a powder containing non-heat-melting PTFE. The content of the non-thermofusible PTFE in the powder (21) is preferably 80% by mass or more, more preferably 100% by mass. In this specification, the components (surfactant etc.) used in the production of the non-heat-melting PTFE are not included in the components other than the non-heat-melting PTFE.
The powder (22) in the present invention is a powder containing M polymer, and is preferably a powder composed of M polymer. 80 mass% or more is preferable and, as for content of F polymer in powder (22), 100 mass% is more preferable.

The D50 of the powder (21) is preferably 0.01 to 100 μm, more preferably 0.1 to 10 μm. A preferred embodiment of D50 of the powder (21) is an embodiment of 0.1 to 1 μm.
The D90 of the powder (21) is preferably 200 μm or less, more preferably 20 μm or less. D90 of the powder (21) is preferably 0.1 μm or more, more preferably 0.2 μm or more. A specific preferred embodiment of D90 of the powder (21) is an embodiment having a particle size of 0.1 to 2 μm.
In this case, the dispersibility of the powder (1) and the interaction between the powders are good, and the physical properties of the present dispersion and the molded product are likely to be further improved.

As a preferred embodiment of the relationship between the D50 of the powder (1) and the D50 of the powder (21), the D50 of the powder (1) is 0.1 μm or more and less than 1 μm or 1 μm or more and 4 μm or less, and the D50 of the powder (21) is A mode in which D50 is 0.1 μm or more and 1 μm or less can be mentioned. In the former embodiment, the dispersibility of the present dispersion is excellent, and a molded product having excellent mechanical strength such as stretching properties is easily obtained. In the latter embodiment, it is easy to obtain a molded article having excellent crack resistance.

The D50 of the powder (22) is preferably 0.01 to 100 μm, more preferably 0.1 to 10 μm. A preferred embodiment of D50 of the powder (22) is an embodiment of 0.1 to 1 μm.
The D90 of the powder (22) is preferably 200 μm or less, more preferably 20 μm or less. D90 of the powder (22) is preferably 0.1 μm or more, more preferably 0.2 μm or more. A preferred embodiment of D90 of the powder (22) is an embodiment having a particle size of 0.1 to 2 μm. In this case, the dispersibility of the powder (22) and the interaction with the powder (1) are good, and the adhesiveness of the molded article, crack resistance and physical properties of the M polymer are likely to be improved.

As a preferred aspect of the relationship between D50 of powder (1) and D50 of powder (22), D50 of powder (1) is 0.1 μm or more and less than 1 μm or D50 is 1 μm or more and 4 μm or less, and powder (22) And D50 of 0.1 μm or more and 1 μm or less. In the former embodiment, the dispersibility of the present dispersion is excellent, and a molded product having excellent mechanical strength such as stretching properties is easily obtained. In the latter embodiment, it is easy to obtain a molded article having excellent crack resistance.

Non-heat-melting PTFE is polytetrafluoroethylene (PTFE), and in addition to a homopolymer of TFE, a so-called modified PTFE, which is a copolymer of a very small amount of comonomer (PAVE, HFP, FAE, etc.) and TFE, is also available. Included.
As described above, the molded product obtained from the present dispersion not only exhibits strong adhesiveness and crack resistance, but also has a fibrous surface physical property and its porosity originally possessed by the non-heat-melting PTFE molded product. Hard to be damaged.
The proportion of TFE units in the non-thermofusible PTFE is preferably 99.5 mol% or more, more preferably 99.9 mol% or more, based on all units.

The non-thermofusible PTFE is preferably a polymer obtained by emulsion polymerization of TFE in water. The non-heat-meltable PTFE powder is a powder in which a polymer obtained by emulsion-polymerizing TFE in water is dispersed as particles in water. When using such powder, the powder dispersed in water may be used as it is, or the powder may be recovered from water and used.
Non-heat-melting PTFE is widely available as a powder or a dispersion thereof.
The non-thermofusible PTFE preferably has a fibrillation property. If it has a fibrillation property, a porous film can be easily produced by a stretching process. The non-thermofusible PTFE having fibrillarity means PTFE that allows unextruded polymer powder to be paste extruded. That is, it means PTFE having strength or elongation in the molded product obtained by paste extrusion.

The number average molecular weight of the non-thermofusible PTFE is preferably 300,000 to 300,000,000, more preferably 500,000 to 25,000,000.
The standard specific gravity, which is an index of the average molecular weight of the non-thermofusible PTFE, is preferably 2.14 to 2.22, more preferably 2.15 to 2.21.
The melt viscosity of the non-heat-melting PTFE at 380° C. is preferably 1×10 ⁹ Pa·s or more. The upper limit of the melt viscosity is usually 1×10 ¹⁰ Pa·s.
When at least one of the number average molecular weight, the standard specific gravity and the melt viscosity of the non-thermofusible PTFE is in the above range, the fibrillability of the non-thermofusible PTFE is better and the molding excellent in mechanical properties and the like. Goods can be formed. Further, in this case, the state stability of the present dispersion is more likely to be improved.

The M polymer is a polymer containing a unit based on a fluoroolefin different from the F polymer (hereinafter, also referred to as “F unit”), and a polymer containing the F unit and having no oxygen-containing polar group is preferable.
The proportion of F units in the M polymer is preferably 50.0 mol% or more, more preferably 99.5 mol% or more, still more preferably 99.9 mol% or more, based on all units.
The fluoroolefin in the M polymer is preferably TFE or VDF, and more preferably TFE. Two or more kinds of fluoroolefins may be used.

The M polymer is preferably a copolymer of TFE and PAVE (PFA), a copolymer of TFE and HFP (FEP), a copolymer of TFE and ethylene (ETFE), a homopolymer of VDF (PVDF) or a low molecular weight PTFE, and a low molecular weight PTFE. More preferred is molecular weight PTFE.
In addition to the homopolymer of TFE, low-molecular-weight PTFE also includes so-called modified PTFE, which is a copolymer of an extremely small amount of comonomer (PAVE, HFP, FAE, etc.) and TFE. The PFA may also contain units based on monomers other than TFE and PAVE. The same applies to the other copolymers (FEP, ETFE, PVDF) described above.
One of the preferable embodiments of the M polymer is low molecular weight PTFE or modified PTFE.

In this case, the melt viscosity of the M polymer at 380° C. is preferably 1×10 ² to 1×10 ⁶ Pa·s, more preferably 1×10 ³ to 1×10 ⁶ Pa·s.
In this case, the melting temperature of the polymer is preferably 321 to 340°C, more preferably 325 to 335°C.
In this case, the melt flow rate of the polymer is preferably 1 to 10 g/10 minutes, more preferably 1 to 5 g/10 minutes.
When at least one of the melt viscosity, melt flow rate and melt temperature of the low molecular weight PTFE or modified PTFE is within the above range, a molded article excellent in physical properties of these PTFEs (workability, mechanical strength, etc.) can be formed. Moreover, in this case, the interaction between the powder (22) and the powder (1) in the main dispersion is improved, and the state stability of the main dispersion is more likely to be improved.

Low-molecular-weight PTFE is obtained by irradiating high-molecular-weight PTFE (melt viscosity is about 1×10 ⁹ to 1×10 ¹⁰ Pa·s) with radiation (International Publication No. 2018/026012, International Publication No. 2018). /026017, etc.), and PTFE obtained by polymerizing TFE to prepare PTFE to prepare a PTFE (JP-A-2009-1745, WO 2010/ 114033, JP-A-2005-232082, etc.).

A preferred specific example of the low molecular weight PTFE is PTFE having a number average molecular weight (Mn) of 200,000 or less calculated based on the following formula (1).
Mn=2.1×10 ¹⁰ ×ΔHc ^−5.16 (1)
In the formula (1), ΔHc represents the heat of crystallization (cal/g) of the PTFE measured by the differential scanning calorimetry.
The Mn of this low molecular weight PTFE is preferably 10 or less, more preferably 50,000 or less. The Mn of this low molecular weight PTFE is preferably 10,000 or more.

Moreover, PFA or FEP is mentioned as one of the suitable aspects of M polymer.
In this case, the melt viscosity of the M polymer at 380° C. is preferably 1×10 ² to 1×10 ⁴ Pa·s, more preferably 1×10 ² to 1×10 ³ Pa·s.
In this case, the melt flow rate of the M polymer is preferably 5 to 30 g/10 minutes, more preferably 5 to 20 g/10 minutes.
In this case, the melting temperature of the M polymer is preferably 260 to 320°C, more preferably 280 to 310°C.
If at least one of the melt viscosity, the melt flow rate and the melt temperature of PFA or FEP is within the above range, excellent molded products can be formed due to the physical properties of PFA or FEP (workability, mechanical strength, etc.). Not only that, the state stability of the dispersion is more likely to be improved.

The M polymer is preferably a polymer obtained by emulsion-polymerizing a fluoroolefin in water. The M polymer powder is a powder in which a polymer obtained by emulsion-polymerizing a fluoroolefin in water is dispersed as particles in water. When using such powder, the powder dispersed in water may be used as it is, or the powder may be recovered from water and used.
The M polymer may be modified by surface treatment (radiation treatment, electron beam treatment, corona treatment, plasma treatment, etc.). Examples of such surface treatment methods include the methods described in International Publication No. 2018/026012 and International Publication No. 2018/026017.
As the M polymer, a commercially available product is widely available as a powder or a dispersion liquid thereof.

The present dispersion may contain only non-thermofusible PTFE, may contain only M polymer, and may contain both non-heat-meltable PTFE and M polymer. Each polymer is preferably contained as a powder.
When this dispersion contains both non-heat-melting PTFE and M polymer, D50 of the non-heat-melting PTFE powder (powder (21)) is preferably 0.1 to 1 μm, and its D90 is 0.1 to 2 μm. Is preferred. In this case, the D50 of the M polymer powder (powder (22)) is preferably 0.1 to 1 μm, and the D90 thereof is preferably 0.1 to 2 μm.

In this case, the mass ratio of the content of the F polymer to the content of the non-thermofusible PTFE or the content of the M polymer in this dispersion is preferably 0.4 or less, more preferably 0.15 or less. In this case, the interaction between the powders is good, the state stability of the present dispersion is further improved, and the adhesiveness, crack resistance and physical properties between the polymers can be easily balanced.
In this case, the total content of the non-thermofusible PTFE and the M polymer is preferably 20 to 70% by mass, more preferably 30 to 60% by mass.

The present dispersion liquid preferably contains a dispersant from the viewpoint of improving the dispersibility of each powder and improving the moldability thereof. The components used for producing the polymer (for example, the surfactant used for emulsion-polymerizing the fluoroolefin) do not correspond to the dispersant in the present invention.

The dispersant is preferably a compound having a hydrophobic site and a hydrophilic site, and examples thereof include an acetylene-based surfactant, a silicone-based surfactant, and a fluorine-based surfactant. These dispersants are preferably nonionic.
The dispersant is preferably fluoroalcohol, more preferably fluoromonool or fluoropolyol.
The fluorine content of fluoromonool is preferably 10 to 50% by mass, more preferably 10 to 45% by mass, and further preferably 15 to 40% by mass.
The fluoromonool is preferably nonionic.
The hydroxyl value of fluoromonool is preferably 40 to 100 mgKOH/g, more preferably 50 to 100 mgKOH/g, and further preferably 60 to 100 mgKOH/g.

The fluoromonool is preferably a compound represented by the following formula (a).
Formula _{^{(a): R a - (}} OQ a) ma -OH
The symbols in the formulas have the following meanings.
R ^a represents a polyfluoroalkyl group or a polyfluoroalkyl group containing an etheric oxygen atom, and is —CH ₂ (CF ₂ ) ₄ F, —CH ₂ (CF ₂ ) ₆ F, —CH ₂ CH ₂ (CF ₂ ) ₄ F, —CH ₂ CH ₂ (CF ₂ ) ₆ F, —CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ , —CH ₂ CF(CF ₃ )CF ₂ OCF ₂ CF ₂ CF ₃ , —CH _{2 CF (CF 3) OCF 2 CF} (CF 3) OCF 3, or _{-CH 2 CF 2 CHFO (CF 2} ) 3 OCF 3 are preferred.
Q ^a represents an alkylene group having 1 to 4 carbon atoms, and is preferably an ethylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ₂ CH(CH ₃ )—). Q ^a may be composed of two or more kinds of groups. When it is composed of two or more kinds of groups, the groups may be arranged randomly or in a block.
ma represents an integer of 0 to 20, preferably an integer of 4 to 10.
The hydroxyl group of fluoromonool is preferably a secondary hydroxyl group or a tertiary hydroxyl group, and particularly preferably a secondary hydroxyl group.

Specific examples of the fluoromonool include F(CF ₂ ) ₆ CH ₂ (OCH ₂ CH ₂ ) ₇ OCH ₂ CH(CH ₃ )OH, F(CF ₂ ) ₆ CH ₂ (OCH ₂ CH ₂ ) ₁₂ OCH _{2 CH (CH 3) OH, F} (CF 2) 6 CH 2 CH 2 (OCH 2 CH 2) 7 OCH 2 CH (CH 3) OH, F (CF 2) 6 CH 2 CH 2 (OCH 2 CH 2) 12 _{OCH 2 CH (CH 3) OH} , F (CF 2) 4 CH 2 CH 2 (OCH 2 CH 2) 7 OCH 2 CH (CH 3) OH and the like.
Such fluoromonool can be obtained as a commercially available product ("Aluroma Co.,""FluowetN083","FluowetN050", etc.).

The fluorine content of the fluoropolyol is preferably 10 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass.
The fluoropolyol is preferably nonionic.
The hydroxyl value of the fluoropolyol is preferably 10 to 35 mgKOH/g, more preferably 10 to 30 mgKOH/g, still more preferably 10 to 25 mgKOH/g.
The weight average molecular weight of the fluoropolyol is preferably 2,000 to 80,000, more preferably 6,000 to 20,000.
The fluoropolyol is preferably a fluoropolyol containing units based on fluoro(meth)acrylate. In addition, "(meth)acrylate" is a general term for acrylate and methacrylate.

The fluoro(meth)acrylate is preferably a monomer represented by the following formula (f).
Formula (f): CH ₂ =CX ^f C(O)O-Q ^f- R ^f
The symbols in the formulas have the following meanings.
X ^f represents a hydrogen atom, a chlorine atom or a methyl group.
Q ^f represents an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 2 to 4 carbon atoms.
R ^f represents a polyfluoroalkyl group having 1 to 6 carbon atoms, a polyfluoroalkyl group having 3 to 6 carbon atoms containing an etheric oxygen atom, or a polyfluoroalkenyl group having 4 to 12 carbon atoms, and —CF(CF ₃ )(C(CF(CF ₃ ) ₂ )(=C(CF ₃ ) ₂ )), —C(CF ₃ )═C(CF(CF ₃ ) ₂ ) ₂ , —(CF ₂ ) ₄ F or −( CF ₂ ) ₆ F is preferred.

Specific examples of the fluoro(meth)acrylate include CH ₂ ═CHC(O)OCH ₂ CH ₂ (CF ₂ ) ₄ F and CH ₂ ═C(CH ₃ )C(O)OCH ₂ CH ₂ (CF ₂ ) _{4. F, CH 2 = CHC (O} ) OCH 2 CH 2 (CF 2) 6 F, CH 2 = C (CH 3) C (O) OCH 2 CH 2 (CF 2) 6 F, CH 2 = CHC (O) _{OCH 2 CH 2 OCF (CF 3} ) (C (CF (CF 3) 2) (= C (CF 3) 2)), CH 2 = C (CH 3) C (O) OCH 2 CH 2 OC (CF 3 _{) = C (CF (CF 3} ) 2) 2, CH 2 = CHC (O) OCH 2 CH 2 CH 2 CH 2 OCF (CF 3) (C (CF (CF 3) 2) (= C (CF 3) _{2)), CH 2 = C} (CH 3) C (O) OCH 2 CH 2 CH 2 CH 2 OC (CF 3) = C (CF (CF 3) 2) 2 and the like.

Preferable specific examples of the fluoropolyol include copolymers of the monomer represented by the above formula (f) and the monomer represented by the following formula (o).
Formula (o): CH ₂ =CX ^o C(O)-(OZ ^o ) _mo —OH
The symbols in the formulas have the following meanings.
X ^o represents a hydrogen atom or a methyl group.
Z ^o represents an alkylene group having 1 to 4 carbon atoms, and an ethylene group (—CH ₂ CH ₂ —) is preferable.
mo is an integer of 1 to 200, preferably an integer of 4 to 30.
In addition, Z ^o may be composed of two or more kinds of groups. In this case, the arrangement of different alkylene groups may be random or block.
When the compound represented by the formula (o) is used, not only the dispersibility of the present dispersion is excellent, but also the physical properties such as wettability and adhesiveness of the molded product are likely to be improved.

Specific examples of the monomer represented by the formula (o) include CH ₂ ═CHCOO(CH ₂ CH ₂ O) ₈ OH, CH ₂ ═CHCOO(CH ₂ CH ₂ O) ₁₀ OH, CH ₂ ═CHCOO(CH _{2 CH 2 O) 12 OH, CH} 2 = CHCOOCH 2 CH 2 CH 2 CH 2 O (CH 2 CH 2 O) 8 OH, CH 2 = CHCOOCH 2 CH 2 CH 2 CH 2 O (CH 2 CH 2 O) 10 OH , CH ₂ =CHCOOCH ₂ CH ₂ CH ₂ CH ₂ O(CH ₂ CH ₂ O) ₁₂ OH, CH ₂ =C(CH ₃ )COO(CH ₂ CH(CH ₃ )O) ₈ OH, CH ₂ =C( _{CH 3) COO (CH 2 CH} (CH 3) O) 12 OH, CH 2 = C (CH 3) COO (CH 2 CH (CH 3) O) 16 OH, CH 2 = C (CH 3) COOCH 2 CH _{2 CH 2 CH 2 O (CH} 2 CH (CH 3) O) 8 OH, CH 2 = C (CH 3) COOCH 2 CH 2 CH 2 CH 2 O (CH 2 CH (CH 3) O) 12 OH, CH _{2 = C (CH 3) COOCH} 2 CH 2 CH 2 CH 2 O (CH 2 CH (CH 3) O) 16 OH and the like.

The fluoropolyol may be composed only of a unit based on the monomer represented by the formula (f) and a unit based on the monomer represented by the formula (o), and may further include another unit. ..
The content of the unit based on the monomer represented by the formula (f) with respect to all units contained in the fluoropolyol is preferably 60 to 90 mol%, more preferably 70 to 90 mol%.
The content of the unit based on the monomer represented by the formula (o) with respect to all units contained in the fluoropolyol is preferably 10 to 40 mol%, more preferably 10 to 30 mol%.
The total content of the unit based on the monomer represented by the formula (f) and the monomer represented by the formula (o) is preferably 90 to 100 mol %, based on all units contained in the fluoropolyol. Mol% is more preferred.
The proportion of fluoroalcohol in this dispersion is preferably 10% by mass or less, more preferably 1% by mass or less, and further preferably 0.01% by mass or less. The lower limit of the above ratio is usually more than 0%.

The aqueous medium in the present invention is a dispersion medium of the present dispersion liquid and contains water as a main component.
The aqueous medium may consist only of water, or may consist of water and a water-soluble compound.
However, the water-soluble compound is preferably a compound which is liquid at 25° C. and does not react with each polymer or has extremely poor reactivity and can be easily removed by heating or the like. The aqueous medium preferably contains water in an amount of 95% by mass or more, more preferably contains 99% by mass or more of water, and further preferably contains 100% by mass of water.
The proportion of the aqueous medium in this dispersion is preferably 15 to 65% by mass, more preferably 25 to 50% by mass. Within this range, the dispersibility of the present dispersion is excellent, and the resulting molded article is less likely to have a poor appearance.

The dispersion may contain F polymer, non-thermofusible PTFE or M polymer, and other materials other than the aqueous medium. Other materials include thixotropic agents, fillers, defoamers, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, colorants, conductive agents. , Release agents, surface treatment agents, viscosity modifiers, flame retardants. Other materials may or may not dissolve in the dispersion.

As other materials, thermosetting resins (epoxy resin, thermosetting polyimide resin, polyimide precursor (polyamic acid), acrylic resin, phenol resin, which are resins other than F polymer, non-thermofusible PTFE or M polymer. , Polyester resin, polyolefin resin, modified polyphenylene ether resin, bismaleimide resin, polyfunctional cyanate ester resin, polyfunctional maleimide-cyanate ester resin, polyfunctional maleimide resin, vinyl ester resin, urea resin, diallyl phthalate resin, melanin Resin, guanamine resin, melamine-urea co-condensation resin, etc., heat-melting resin (polyester resin, polyolefin resin, styrene resin, polycarbonate, thermoplastic polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic poly) Etheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, liquid crystalline polyester, polyphenylene ether, etc.), reactive alkoxysilane, carbon black, inorganic filler (glass microspheres, ceramic microspheres, etc., hollow inorganic microspheres) ) Is mentioned.

The viscosity of this dispersion is preferably from 1 to 1000 mPa·s, more preferably from 5 to 500 mPa·s, even more preferably from 10 to 200 mPa·s.
The thixo ratio of this dispersion is preferably 0.8 to 2.2.
In this case, it is easy to balance the dispersibility of the present dispersion and the coatability.

This dispersion can be produced by mixing the powder (1) with the powder (21) or the powder (22). Specifically, it is preferable that the dispersion liquid (p1) containing the powder (1) and the aqueous medium and the dispersion liquid (p2) containing the powder (21) or the powder (22) and the aqueous medium are mixed and produced. ..
The dispersion liquid (p1) and the dispersion liquid (p2) are preferably mixed in a state where the respective dispersion liquids are well dispersed. For example, when solid content is observed to be precipitated in the dispersion liquid (p1), the dispersion liquid (p1) is subjected to a dispersion treatment using a homodisper immediately before mixing, and further subjected to a dispersion treatment using a homogenizer to obtain a dispersion state. Is preferably improved. Particularly, when the dispersion liquid (p1) stored at 0 to 40° C. is used, it is preferable to perform the dispersion treatment.
The aqueous medium (dispersion medium) in the dispersion liquid (p1) and the dispersion liquid (p2) is preferably water.

This dispersion is excellent in dispersion stability and storage stability, and also excellent in handling property. This dispersion can form a molded article having excellent crack resistance and strong adhesiveness without impairing the physical properties of the non-thermofusible PTFE or M polymer.
The present dispersion is applied to the surface of a base material and heated to form a polymer layer containing an F polymer and a non-thermofusible PTFE or M polymer. It is possible to manufacture a laminated body in which and are laminated in this order.
The ranges of the F polymer, the powder (1), the non-heat-melting PTFE, the M polymer, the powder (21), the powder (22), and the aqueous medium in this laminate, including the preferred embodiments thereof, in the present dispersion liquid Same as the definition. Further, the polymer layer may be formed on at least one surface of the base material layer, the polymer layer may be formed only on one surface of the base material layer, or the polymer layer may be formed on both surfaces of the base material layer. ..

The coating method for the surface of the base material includes a spray method, a roll coating method, a spin coating method, a gravure coating method, a micro gravure coating method, a gravure offset method, a knife coating method, a kiss coating method, a bar coating method, a die coating method, a fountain. Examples include the Mayer bar method and the slot die coating method.
The polymer layer may be formed by heating, and it is preferable to heat the base material to a temperature at which the aqueous medium volatilizes (temperature range of 100 to 300° C.), and the base material at a temperature range (100 to 300° C.) at which the aqueous medium volatilizes. More preferably, the base material is heated to a temperature range (300 to 400° C.) in which the non-heat-melting PTFE is fired.
That is, it is preferable that the polymer layer in the case of using the present dispersion liquid containing non-heat-melting PTFE contains the F polymer and is a polymer layer obtained by baking the non-heat-melting PTFE. In this case, the non-thermofusible PTFE may be partially calcined or completely calcined.
In addition, the polymer layer in the case of using the present dispersion liquid containing the M polymer is preferably a polymer layer containing the F polymer and the M polymer being melt-processed. In this case, the M polymer may be partially melt processed or may be completely melt processed.

Examples of the method for heating the base material include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating heat rays (infrared rays).
The atmosphere for heating the base material may be either under normal pressure or under reduced pressure. The atmosphere in the holding is any of an oxidizing gas (oxygen gas etc.), a reducing gas (hydrogen gas etc.) and an inert gas (helium gas, neon gas, argon gas, nitrogen gas etc.). It may be.
The heating time of the substrate is usually 0.5 to 30 minutes.
The thickness of the polymer layer is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 10 μm or less. The thickness of the polymer layer is preferably 0.1 μm or more, particularly preferably 4 μm or more. Within this range, a polymer layer having excellent crack resistance can be easily formed without impairing the physical properties of the non-heat-melting PTFE or M polymer.

In the laminate, the base material layer and the polymer layer are firmly adhered. The peel strength between the base material layer and the polymer layer is preferably 10 N/cm or more, and particularly preferably 15 N/cm or more. The upper limit of the peel strength is usually 100 N/cm.
The material of the base material may be any of metals such as copper, aluminum, iron, nickel, zinc, alloys thereof, glass, resin, silicon and ceramics.
The shape of the base material may be any of a plane shape, a curved surface shape, an uneven shape, and may be a foil shape, a plate shape, a film shape, or a fibrous shape.
Specific examples of the laminate include a metal foil with a polymer layer, a metal foil as a base material, and a metal foil with a polymer layer, which has a metal foil layer and a polymer layer in this order. An adhesive layer may be separately provided between the metal foil layer and the polymer layer, but since the polymer layer has excellent adhesiveness, the adhesive layer may not be provided.

As a preferable aspect of the metal foil, a copper foil such as a rolled copper foil or an electrolytic copper foil can be mentioned. The thickness of the metal foil in the laminate is preferably 3 to 18 μm, and the thickness of the polymer layer is preferably 1 to 50 μm.
The laminated body can be used as a printed wiring board having a polymer layer as an electrically insulating layer by forming a pattern circuit on the copper foil layer.

As a specific example of the laminate, a substrate is a polyimide film, a laminate film having a polymer layer formed from the present dispersion liquid on at least one surface of a polyimide layer formed of the polyimide film, and more specifically. Specifically, a laminated film having a polymer layer formed from the present dispersion liquid on both surfaces of the polyimide layer can be mentioned.
An adhesive layer may be separately provided between the polyimide layer and the polymer layer, but since the polymer layer formed from the present dispersion has excellent adhesiveness, the adhesive layer may not be provided.

A preferred embodiment of the polyimide film is 2,2′,3,3′- or 3,3′,4,4′-biphenyltetracarboxylic dianhydride (3,3′,4,4′-benzophenonetetra). Carboxylic acid dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, etc.) as a main component, and a polymer film of a component mainly containing paraphenylenediamine Can be mentioned. A specific example of the polyimide film is Optical Type AF (manufactured by Kaneka North America).
Such a polyimide film is useful as an insulating coating. The basis weight is preferably 23.5 g/m ² or less, and the loop stiffness value is preferably 0.45 g/cm or more.
The thickness of the polymer layer in the laminated film is preferably 1 to 200 μm, more preferably 5 to 20 μm. The thickness of the polyimide layer (polyimide film) is preferably 5 to 150 μm.

Such a laminated film has excellent electric insulation, abrasion resistance, hydrolysis resistance, etc., and can be used as a packaging material for electric insulation tape, electric cables or electric wires, for aerospace or electric vehicles, and electric wires. It can be used particularly preferably as a material or a cable material.

Since the laminate of the present invention has a polymer layer containing an F polymer and having excellent adhesiveness, it is possible to produce a composite laminate by laminating another material on the polymer layer of the laminate.
When the surface of the polymer layer of the laminate and the second base material are pressure-bonded to each other, the first base material layer (the original base material layer of the laminate), the polymer layer, and the second base material are formed. A second laminate of the second base material is laminated in this order to obtain a composite laminate.

The material of the second base material may be any of metals such as copper, aluminum, iron, nickel, zinc, alloys thereof, glass, resin, silicon and ceramics.
The shape of the second base material is not particularly limited, and may be any of a flat shape, a curved surface shape, an uneven shape, a foil shape, a plate shape, a film shape, and a fibrous shape.
Specific examples of the second base material include a heat resistant resin base material and a prepreg which is a precursor of a fiber reinforced resin plate.
A prepreg is a sheet-like base material obtained by impregnating a base material (tow, woven fabric, etc.) of reinforcing fibers (glass fiber, carbon fiber, etc.) with a resin (thermosetting resin, thermoplastic resin, etc. described above). ..
The heat resistant resin substrate is preferably a film containing a heat resistant resin, and may be a single layer or a multilayer.
Examples of the heat resistant resin include polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamide imide, liquid crystalline polyester, PTFE and the like.

As a method for pressure-bonding the surface of the polymer layer of the laminate and the second base material, a thermocompression bonding method can be mentioned.
When the second base material is a prepreg, the pressure bonding temperature is preferably 160 to 220°C.
When the second substrate is a heat resistant resin substrate, the pressure bonding temperature is preferably 300 to 400°C.
The thermocompression bonding is preferably performed in a reduced pressure atmosphere, and particularly preferably performed in a vacuum degree of 20 kPa or less. Within this range, it is possible to prevent bubbles from entering the respective interfaces in the composite laminated body and suppress deterioration due to oxidation. Moreover, it is preferable that the temperature of the thermocompression bonding be raised after reaching the vacuum degree.
The pressure in thermocompression bonding is preferably 0.2 to 10 MPa.

If the liquid layer forming material for forming the second polymer layer is applied to the surface of the polymer layer of the laminate to form the second polymer layer, the first base material layer, the polymer layer and the second A polymer laminate obtained by laminating the polymer layer of 1 above in this order is obtained.
The liquid layer forming material is not particularly limited, and the present dispersion liquid may be used.
The method for forming the second polymer layer is also not particularly limited and can be appropriately determined depending on the properties of the liquid layer forming material used. For example, when the layer forming material is the present dispersion liquid, the second polymer layer can be formed under the same conditions as the method for forming the polymer layer in the laminate. That is, when the layer forming material is the present dispersion liquid, the polymer layer can be formed into multiple layers to easily form a thicker polymer layer.

Specific examples of the composite laminate obtained by the production method include the present dispersion liquid and the composite laminate obtained by using the dispersion liquid containing the F polymer as a liquid layer forming material. Since the second polymer layer is formed on the polymer layer showing strong adhesion, a composite laminate having high peel strength can be obtained even by using the latter main dispersion.
According to the laminate of the present invention, it can be said that a polymer layer having excellent crack resistance without deteriorating the physical properties of each polymer is formed. By removing the base material layer from the laminate, a polymer film containing each polymer uniformly can be obtained.
In the polymer film containing non-heat-melting PTFE, it is preferable that the non-heat-melting PTFE containing F polymer is a polymer film subjected to a baking treatment. In this case, the non-thermofusible PTFE may be partially calcined or completely calcined.
In the polymer film containing the M polymer, the M polymer containing the F polymer is preferably a polymer film that has been subjected to a baking treatment. In this case, the M polymer may be partially calcined or completely calcined.

Examples of the method of removing the base material layer from the laminate include a method of peeling and removing the base material layer from the laminate, and a method of dissolving and removing the base material layer from the laminate. For example, when the base material layer is made of copper foil, the base material layer is dissolved and removed by contacting the base material layer side surface of the laminate with an etching solution such as hydrochloric acid, and the polymer layer A polymer film composed solely can be easily obtained.
The range of the polymer in the polymer film is the same as the definition in the present dispersion liquid, including the preferable embodiments thereof.
The thickness of the polymer film is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 10 μm or less. The thickness of the polymer film is preferably 1 μm or more, more preferably 4 μm or more. In this range, the polymer film is more excellent in adhesiveness and crack resistance without impairing the physical properties of each polymer.

By impregnating a woven fabric with the dispersion liquid and further drying the woven fabric, a coated woven fabric which is a woven fabric coated with a polymer layer is obtained.
The woven cloth is a heat resistant woven cloth that is resistant to drying, and is preferably a glass fiber woven cloth, a carbon fiber woven cloth, an aramid fiber woven cloth or a metal fiber woven cloth, more preferably a glass fiber woven cloth or a carbon fiber woven cloth, and an electric cloth. From the viewpoint of insulating properties, a plain woven glass fiber woven fabric composed of E glass yarn for electrical insulation defined by JIS R 3410:2006 is more preferable. The woven fabric may be treated with a silane coupling agent from the viewpoint of enhancing the close contact adhesiveness with the polymer layer.
The total content of the F polymer and the non-thermofusible PTFE or M polymer in the coated woven fabric is preferably 30 to 80% by mass.

Examples of the method of impregnating the woven fabric with the present dispersion include a method of immersing the woven fabric in the present dispersion, and a method of applying the present dispersion to the woven fabric. The number of times of immersion in the former method and the number of times of application in the latter method may each be once or twice or more. Since the present dispersion liquid containing an F polymer having excellent adhesion to other materials is used, a coated woven fabric having a high polymer content, in which the woven fabric and the polymer are firmly adhered at least at the number of times of dipping or application, can be obtained. To be
The method for drying the woven fabric can be appropriately determined depending on the type of the aqueous medium contained in the present dispersion liquid. For example, when the aqueous medium is composed of only water, the woven fabric is subjected to ventilation drying in an atmosphere of 80 to 120°C. The method of passing through a furnace is mentioned.
The polymer may be fired when the woven fabric is dried. The method of firing the polymer can be appropriately determined depending on the type of each polymer, and examples thereof include a method of passing the woven fabric through a ventilation drying furnace in an atmosphere of 300 to 400° C. The woven fabric may be dried and the polymer may be fired in one step.

Since the polymer layer contains the F polymer, the obtained coated woven fabric is excellent in properties such as high adhesion and adhesion between the polymer layer and the woven fabric, high surface smoothness, and little distortion. A laminate obtained by thermocompression bonding such a coated woven fabric and a metal foil has high peel strength and is less likely to warp, and therefore can be suitably used as a printed circuit board material.
Alternatively, the present dispersion containing a woven fabric may be applied to the surface of a substrate and dried by heating to form a coated woven fabric layer containing an F polymer and non-heat-melting PTFE or M polymer and a woven fabric. Good. This makes it possible to manufacture a laminate in which the base material layer composed of the base material and the coated woven fabric layer are laminated in this order. The mode is not particularly limited, and if the main dispersion liquid containing a woven cloth is applied to a part of the inner wall surface of a molded product such as a tank, pipe, or container, and the molded product is heated while rotating, the inner wall of the molded product A coated woven fabric layer can be formed on the entire surface. INDUSTRIAL APPLICABILITY The method for producing a coated woven fabric of the present invention is also useful as a method for lining the inner wall surface of molded articles such as tanks, pipes and containers.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
Various measuring methods are shown below.
<D50 and D90 of powder>
The powder was dispersed in water and measured using a laser diffraction/scattering type particle size distribution measuring device (“LA-920 measuring device” manufactured by Horiba Ltd.).
<Storage stability of powder dispersion>
After the powder dispersion was left at 25° C. for 1 week, the state was visually confirmed and evaluated according to the following evaluation criteria.
◯: No sediment is confirmed.
Δ: A sediment is confirmed, but it is redispersed when shaken by hand.
X: A sediment was confirmed, and it was not redispersed only by shaking by hand.

<Crack resistance of polymer layer>
Apply the powder dispersion on the surface of a stainless steel plate (thickness: 0.5 mm) with a vinyl tape attached to one edge, slide the rod along the edge, and then at 100°C for 3 minutes. It was dried three times and further heated at 340° C. for 10 minutes. As a result, a polymer layer having an inclined thickness was formed on the surface of the stainless steel plate due to the thickness of the vinyl tape attached to the edges. This stainless steel plate was visually confirmed, and the thickness of the polymer layer at the tip of the crack line generation part (the part where the polymer layer was thinnest) was measured using MINTEST3000 (manufactured by Electro Physik), and the following evaluation criteria were used. evaluated.
◯: The thickness of the polymer layer at the tip where cracks occur is 10 μm or more.
Δ: The thickness of the polymer layer at the tip where cracks occur is 5 μm or more and less than 10 μm.
X: The thickness of the polymer layer at the tip where cracks occur is less than 5 μm.

<Peel strength of laminate>
The position of 50 mm from one end in the length direction of the laminate cut out in a rectangular shape (length: 100 mm, width: 10 mm) was fixed, the pulling speed was 50 mm/min, and 90° from one end in the length direction to the laminate. Then, the maximum load applied when the metal foil layer and the polymer layer were peeled off was measured as the peeling strength (N/cm) and evaluated according to the following evaluation criteria.
Good: Peel strength is 10 N/cm or more.
X: Peel strength is less than 10 N/cm.

The materials used are shown below.
[Polymer and its powder]
F polymer 1: copolymer containing TFE-based unit, NAH-based unit and PPVE-based unit in the order of 97.9 mol%, 0.1 mol% and 2.0 mol% (melting point: 300° C.)
Polymer A1: A copolymer containing 98.0 mol% and 2.0 mol% of units based on TFE and units based on PPVE, in this order, having no oxygen-containing polar group (melting point: 305° C.).
P polymer 1: non-heat-melting PTFE having a fibrillation property, containing 99.9 mol% or more of units based on TFE (standard specific gravity: 2.18, melt viscosity at 380° C.: 3.0×10 ⁹ Pa·s)
M polymer 1: Thermomeltable modified PTFE (melt viscosity at 380° C.: 1×10 ⁶ Pa·s) containing 99.5 mol% or more of TFE-based units and a very small amount of PFBE-based units

F powder 11: F polymer 1 powder (D50: 1.7 μm, D90: 3.8 μm)
F powder 12: powder of F polymer 1 (D50: 0.3 μm, D90: 1.8 μm) [This F powder 12 was obtained by subjecting F powder 11 to a wet jet mill. ]
Powder A1: Polymer A1 powder (D50: 0.3 μm, D90: 1.5 μm)
P powder 1: P polymer 1 powder (D50: 0.3 μm) [This P powder 1 is available as an aqueous dispersion of P powder 1. ]
M powder 1: powder of M polymer 1 (D50: 0.3 μm) [This M powder 1 is available as an aqueous dispersion of M powder 1]. ]

[Dispersant]
_{FM1: F (CF 2) 6} CH 2 (OCH 2 CH 2) 7 OCH 2 CH (CH 3) OH ( fluorine content: 34 wt%, hydroxyl value: 78 mgKOH / g)
_{FP1: CH 2 = C (CH} 3) C (O) OCH 2 CH 2 (CF 2) units based on ₆ F and _{CH 2 = C (CH 3)} C (O) (OCH 2 CH 2) based on 23 OH Copolymer containing units (fluorine content: 35% by mass, hydroxyl value: 19 mgKOH/g)

[Example 1] Production Example of Powder Dispersion [Example 1-1] Production Example of Dispersion 1 Dispersion containing 30 parts by mass of F powder 12, 5 parts by mass of FM1 and 65 parts by mass of water, and P powder 1. Was mixed with an aqueous dispersion containing 50% by mass. Thereby, the respective powders are dispersed in water, and the powder dispersion liquid 1 (F polymer 1 containing 90 mass% of P polymer 1 and 10 mass% of F polymer 1 relative to the total of P polymer 1 and F polymer 1). Content/P polymer 1 content: 0.11).
[Example 1-2 to Example 1-9] Production Examples of Powder Dispersions 2 to 9 Powder Dispersions 2 to 9 were prepared in the same manner as in Example 1-1, except that the type of powder and the type of dispersant were changed. Got Table 1 below shows the type of each powder dispersion and the evaluation results of its storage stability.

[Example 2] Production Example of Laminated Body [Example 2-1] Production Example of Laminated Body 1 The powder dispersion liquid 1 was applied to the surface of a copper foil and dried at 100°C for 10 minutes, and then under an inert gas atmosphere at 340°C. After firing for 10 minutes, it was gradually cooled. Thereby, a laminate (with a polymer layer) having a copper foil layer formed of a copper foil and a polymer layer (thickness: 5 μm) containing P polymer 1 and F polymer 1 formed on the surface of the copper foil layer Copper foil) 1 was obtained.
[Example 2-2 to Examples 2 to 9] Production Examples of Laminates 2 to 9 Laminates 2 to 9 were produced in the same manner as in Example 2-1 except that the type of powder dispersion was changed.
The evaluation results of the crack resistance of the powder dispersions 1 to 4 and 9 and the evaluation results of the peel strength of the laminates 1 to 9 are summarized in Table 2 below.

[Example 3] Production Example of Polymer Membrane [Example 3-1] Production Example of Polymer Membrane 3 The powder dispersion 3 was applied onto the surface of a copper foil and dried at 100°C for 10 minutes, and then under an inert gas atmosphere at 340°C. After firing for 10 minutes, it was gradually cooled. Thereby, a laminate having a copper foil layer composed of a copper foil and a polymer layer containing P polymer 1 and F polymer 1 formed on the surface of the copper foil layer was obtained. The operations of coating, drying and firing the powder dispersion liquid 3 on the surface of the polymer layer of this laminate were repeated under the same conditions. This increased the thickness of the polymer layer to 30 μm. Then, the copper foil layer of the laminate was removed with hydrochloric acid to obtain a polymer film 3 containing P polymer 1 and F polymer 1.
[Example 3-2] Production Example of Polymer Membrane 4 and Polymer Membranes 7 to 9 The polymer membrane 4 was powder-dispersed from the powder dispersion 4 in the same manner as in Example 3-1, except that the type of powder dispersion was changed. A polymer film 7 was obtained from the liquid 7, a polymer film 8 was obtained from the powder dispersion liquid 8, and a polymer film 9 was obtained from the powder dispersion liquid 9.

Each of the polymer film 3, the polymer film 4, and the polymer film 9 was a porous film, and the rupture strength when subjected to the stretching treatment was the polymer film 3, the polymer film 4, and the polymer film 9 in descending order. ..
Further, the polymer film was subjected to a stretching treatment (stretching ratio: 200%) to obtain a polymer film 3 to a stretched film 3, a polymer film 4 to a stretched film 4, and a polymer film 9 to a stretched film 9. Each of the stretched membranes is a porous membrane, and when the open states are compared, the pore size distribution is in the order of the stretched membrane 3, the stretched membrane 4, and the stretched membrane 9 from the ascending order, and the dense porous membrane in this order. Had formed.
The breaking strengths when the polymer film 7, the polymer film 8 and the polymer film 9 were subjected to the stretching treatment were the polymer film 7, the polymer film 8 and the polymer film 9 in descending order. As a result of subjecting each thin film to the repeated bending test, the number of times until the thin film was cut was the polymer film 7, the polymer film 8, and the polymer film 9 in order from the largest.

[Example 4] Production Example of Polymer Film (Part 2)
Dispersion liquid containing 30 parts by mass of F powder 12, 5 parts by mass of FM1, and 65 parts by mass of water, water dispersion liquid containing 50 mass% of M powder 1 and water dispersion liquid containing 50 mass% of P powder 1. And mixed. As a result, the respective powders are dispersed in water, and 10% by mass of the M polymer 1, 10% by mass of the F polymer 1 and 10% by mass of the P polymer 1 with respect to the total of the M polymer 1, the F polymer 1 and the P polymer 1. A powder dispersion containing 80% by mass (content of F polymer 1/content of M polymer 1: 1.0) was obtained.
This powder dispersion was applied on the surface of a copper foil, dried at 100° C. for 10 minutes, baked at 340° C. for 10 minutes in an inert gas atmosphere, and then gradually cooled. This obtained the laminated body which has the copper foil layer comprised with copper foil, and the polymer layer formed in the surface of the copper foil layer. The operations of coating, drying and firing the powder dispersion on the surface of the polymer layer of this laminate were repeated under the same conditions. This increased the thickness of the polymer layer to 30 μm. Then, the copper foil layer of the laminate was removed with hydrochloric acid to obtain a polymer film containing M polymer 1, F polymer 1 and P polymer 1. When this polymer membrane was subjected to a stretching treatment (stretching ratio: 200%), a dense porous membrane with a small pore size distribution was obtained.

This dispersion can be used for the production of molded products such as films, impregnated products (prepregs, etc.), laminates (metal laminates such as copper foil with resin), mold release properties, electrical properties, water/oil repellency, resistance It can be used to manufacture molded products for applications requiring chemical resistance, weather resistance, heat resistance, slipperiness, wear resistance, etc. Molded products obtained from this dispersion are useful as antenna parts, printed circuit boards, aircraft parts, automotive parts, sports equipment, food industry products, paints, cosmetics, and the like. Electric wires, etc.), electrical insulation tape, oil drilling insulation tape, printed circuit board materials, separation membranes (microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc.), Electrode binders (for lithium secondary batteries, fuel cells, etc.), covers for copy rolls, furniture, automobile dashboards, home appliances, etc., sliding members (load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors) , Food conveying belts, etc.), tools (shovels, files, cuts, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, dies, toilet bowls, container coating materials.

Claims (14)

1. Fluoropolymer powder (1) having a unit based on tetrafluoroethylene and an oxygen-containing polar group (1), non-heat-meltable polytetrafluoroethylene powder (21) or heat-meltable fluoropolymer powder (22), and aqueous medium Powder dispersion containing and.
2. The volume-based cumulative 50% diameter of the powder (1) is 0.01 to 75 μm, and the volume-based cumulative 50% diameter of the powder (21) or the powder (22) is 0.01 to 100 μm. The powder dispersion liquid according to claim 1.
3. The mass ratio of the content of the fluoropolymer to the content of the non-heat-meltable polytetrafluoroethylene or the content of the heat-meltable fluoropolymer is 0.4 or less. Powder dispersion.
4. The powder dispersion liquid according to any one of claims 1 to 3, wherein a melting temperature of the fluoropolymer is 140 to 320°C.
5. The powder dispersion liquid according to any one of claims 1 to 4, wherein the fluoropolymer includes units based on the monomer having the oxygen-containing polar group.
6. The powder dispersion liquid according to any one of claims 1 to 5, wherein the oxygen-containing polar group is a hydroxyl group-containing group or a carbonyl group-containing group.
7. The powder dispersion liquid according to any one of claims 1 to 6, wherein the non-thermofusible polytetrafluoroethylene has a fibrillation property.
8. The heat-meltable fluoropolymer is a modified polytetrafluoroethylene, a copolymer of tetrafluoroethylene and perfluoro(alkyl vinyl ether), or a copolymer of tetrafluoroethylene and hexafluoropropylene. The powder dispersion described in.
9. The powder dispersion liquid according to any one of claims 1 to 8, comprising both the non-heat-meltable polytetrafluoroethylene powder (21) and the heat-meltable fluoropolymer powder (22).
10. The powder dispersion liquid according to any one of claims 1 to 9, further containing an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant.
11. The powder dispersion liquid according to any one of claims 1 to 10, further comprising a fluorosurfactant, and the fluorosurfactant is fluoromonool or fluoropolyol.
12. A substrate comprising the powder dispersion according to any one of claims 1 to 11 which is applied to the surface of a substrate and which is heated to remove the aqueous medium to form a polymer layer, the substrate being the substrate. A method for producing a laminate, in which a layer and the polymer layer are laminated in this order to obtain a laminate.
13. A substrate comprising the powder dispersion according to any one of claims 1 to 11 which is applied to the surface of a substrate and which is heated to remove the aqueous medium to form a polymer layer, the substrate being the substrate. A method for producing a polymer film, comprising: obtaining a laminate in which a layer and the polymer layer are laminated in this order, and removing the base material layer from the laminate to obtain a polymer film including the polymer layer.
14. A method for producing a coated woven fabric, wherein a woven fabric is impregnated with the powder dispersion according to any one of claims 1 to 11, and the woven fabric is dried to obtain a woven fabric coated with a polymer layer.