JPWO2019235439A1 - Dispersion liquid, method for manufacturing metal foil with resin, and method for manufacturing printed circuit board - Google Patents

Abstract

Provided is a dispersion liquid containing a tetrafluoroethylene polymer powder, which is excellent in dispersibility and formability of a layer (coating film) excellent in wettability, adhesiveness, thixotropy, smoothness and the like. A dispersion liquid in which the powder containing a tetrafluoroethylene polymer powder, a solvent and a dispersant is dispersed in the form of particles, and the dispersant may contain an ethereal oxygen atom as a monovalent fluorine-containing hydrocarbon. A dispersion which is a polymer having a group and at least one group selected from the group consisting of a tert-alkoxycarbonyl group, a sec-alkoxycarbonyl group, an aralkyloxycarbonyl group, a polyoxyalkylene group and an alcoholic hydroxyl group.

Description

The present invention relates to a powder dispersion containing a tetrafluoroethylene polymer powder and a specific dispersant, and a method for producing a metal foil with a resin and a printed circuit board.

Tetrafluoroethylene-based polymers such as polytetrafluoroethylene (PTFE) have excellent physical properties such as chemical resistance, water and oil repellency, heat resistance, and electrical properties, and are used in various forms such as powders, dispersions, and films. And various uses utilizing the physical characteristics are known (see Patent Documents 1 and 2).
In recent years, a tetrafluoroethylene polymer has been attracting attention as a printed circuit board material that has excellent electrical characteristics such as low dielectric constant and low dielectric loss tangent and heat resistance that can withstand solder reflow, and can handle frequencies in a high frequency band.
A metal foil with a resin having an insulating resin layer on the surface of the metal foil is used as a printed circuit board by etching the metal foil. In order to obtain a printed circuit board having excellent transmission characteristics, a tetrafluoroethylene polymer having a low relative permittivity and a dielectric loss tangent has been studied as an insulating resin layer thereof. Various materials for forming a metal leaf with a resin having a resin layer containing a tetrafluoroethylene-based polymer have been proposed.

Patent Document 1 proposes a powder dispersion in which a tetrafluoroethylene polymer powder is dispersed in a solvent. This powder dispersion has an advantage that various physical properties of the metal leaf with resin can be arbitrarily adjusted by the compounding components and an advantage that the metal leaf with resin can be formed only by applying and drying on the surface of the metal leaf.
Patent Document 3 describes PTFE powder, (meth) acrylate having a fluorine-containing block site (CH ₂ = CHC (O) OCH (CH ₃ ) O (CF ₂ ) ₆ F, etc.) and alkylene glycol mono (meth). A method for producing a copper foil with a resin from a powder dispersion containing a copolymer of acrylate (CH ₂ = CHC (O) OCH ₂ CH ₂ (OCH ₂ CH ₂ ) _{10 OH, etc.) and a solvent is described.} ..
Patent Document 4 describes a metal foil with a resin having a PTFE layer formed from a dispersion liquid in which PTFE powder is dispersed in a solvent, and a method of forming a transmission line on the metal foil to form a printed circuit board.
Patent Document 5 describes a dispersion liquid containing a PTFE powder.

International Publication No. 2018/016644 Japanese Unexamined Patent Publication No. 2018-408233 JP-A-2017-193655 Special Table 2015-509113 International Publication No. 2016/159102

Since the tetrafluoroethylene polymer has an essentially low surface tension and low interaction with other materials, the powder dispersion has low dispersibility. When a dispersant is added to the dispersion in order to improve dispersibility, the viscosity of the dispersion becomes high, and the amount of diluting component (solvent, etc.) must be increased to form a layer (coating film). May be limited, its production efficiency may be reduced, and the formulation of other additives may be limited.
In addition, the physical characteristics (wetting property, adhesiveness, smoothness, etc.) of the layer (coating film) containing the tetrafluoroethylene polymer formed from the dispersion liquid may be deteriorated. In particular, when the dispersion medium of the dispersion liquid is an organic solvent, the dispersibility and layer (coating film) formability are likely to be significantly reduced.
Further, as a mode for producing a printed circuit board, a mode in which a metal foil with a resin in which another substrate (prepreg, etc.) is laminated on the surface of a resin layer containing a tetrafluoroethylene-based polymer is laminated, or on the surface of the resin layer, etc. There is an embodiment in which the substrates (coverlay film, etc.) of the above are laminated and packaged. In these aspects, from the viewpoint of the electrical characteristics and productivity of the printed circuit board, it is necessary to firmly laminate the resin layer and the other substrate without impairing the physical properties of the metal foil and the resin layer.
However, the adhesiveness of the resin-attached copper foil of Patent Document 3 is said to be exhibited by the decomposition of the copolymer due to the desorption of the fluorine-containing block portion in the copolymer. However, in order to decompose the copolymer, the copper foil is used in a high temperature environment. It is necessary to leave it unattended (see the description of [0007], [0210], etc. in Patent Document 3). When the metal leaf with resin is left in a high temperature environment for this purpose, the metal leaf with resin deteriorates due to rust and the formation of the resin layer is hindered by the decomposition of the copolymer and the homogeneity of the resin layer deteriorates. The physical properties of the product may be impaired.

By using a specific dispersant, the present inventors can suppress these phenomena and form a resin-attached metal leaf having a fluororesin layer having excellent adhesiveness without impairing the physical properties of the resin-attached metal leaf. A dispersion was found. That is, we have found a dispersion liquid of a powder containing a tetrafluoroethylene-based polymer, which has a relatively low viscosity and has dispersibility and layer (coating film) forming property.

The present invention is the following dispersion liquid, a method for producing a metal foil with a resin, and a method for producing a printed circuit board.
[1] A dispersion in which the powder containing a tetrafluoroethylene polymer powder, a solvent and a dispersant is dispersed in the form of particles, wherein the dispersant contains a monovalent oxygen atom may be contained. A dispersion which is a polymer having a fluorine hydrocarbon group and at least one group selected from the group consisting of a tert-alkoxycarbonyl group, a sec-alkoxycarbonyl group, an aralkyloxycarbonyl group, a polyoxyalkylene group and an alcoholic hydroxyl group. liquid.

[2] The dispersion according to [1], wherein the dispersant is a polymer containing a monomer-based unit represented by the following formula (FI) and a monomer-based unit represented by the following formula (HI).
Formula ^{_{(FI) CH 2 = CR FI}} C (O) O-Q FI -Z FI
Formula (HI) CH ₂ = CR ^HI C (O) OC (-X ^1I ) ( ^{-X 2I} ) ( ^{-X 3I} )
The symbols in the formula have the following meanings.
^RFI represents a hydrogen atom, a chlorine atom or a methyl group.
^RHI represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
^QFI indicates an alkylene group or an oxyalkylene group.
Z ^FI represents a polyfluoroalkyl group or a polyfluoroalkenyl group.
For X ^1I , X ^2I and X ^3I , ^{whether X 1I} , X ^2I and X ^3I are independently alkyl or aryl groups, or X ^1I and X ^2I are hydrogen atoms and X ^3I is an aryl group, respectively. Whether X ^1I and X ^2I are independent hydrogen atoms or alkyl groups and X ^3I is an alkoxy group, or X ^1I is a hydrogen atom or alkyl group and X ^2I and X ^3I jointly form an alkylene group. , Whichever.

[3] The dispersion according to [1], wherein the dispersant is a polymer containing a unit represented by a monomer represented by the following formula (FII) and a unit based on a monomer represented by the following formula (HII). liquid.
Formula ^{_{(FII) CH 2 = CX FII}} C (O) -Q FII - (OZ FII) nII -OR FII
Equation (HII) CH ₂ = CX ^HII C (O)-(OZ ^HII ) _mII- OR ^HII
The symbols in the formula have the following meanings.
X ^FII represents a hydrogen atom or a methyl group.
Q ^FII represents a divalent linking group.
Z ^FII represents a perfluoroalkylene group.
nII represents an integer of 2 to 30.
^RFII represents a perfluoroalkyl group.
X ^HII represents a hydrogen atom or a methyl group.
Z ^HII represents an alkylene group.
mII represents an integer from 3 to 200.
^RHII represents a hydrogen atom, an alkyl group or an aryl group.

[4] The dispersant is based on a monomer-based unit represented by the following formula (FIII), an alkyl (meth) acrylate-based unit, a monomer-based unit represented by the following formula (HIII), and acrylonitrile or acrylamide. The dispersion according to [1], which is a polymer containing a unit.
Equation (FIII) CH ₂ = CX ^FIII C (O) ^{OQ FIII-} R ^FIII
Formula (HIII) CH ₂ = CX ^HIII C (O)-(OZ ^HIII ) _mIII- OR ^HIII
The symbols in the formula have the following meanings.
X ^FIII represents a hydrogen atom, a chlorine atom or a methyl group.
Q ^FIII represents an alkylene group or an oxyalkylene group.
^RFIII represents a polyfluoroalkyl group, a polyfluoroalkyl group containing an ethereal oxygen atom, or a polyfluoroalkenyl group.
X ^HIII represents a hydrogen atom or a methyl group.
Z ^HIII represents an alkylene group.
mIII represents an integer from 3 to 200.
^RHIII represents a hydrogen atom, an alkyl group or an aryl group.

[5] The dispersant contains a monomer-based unit represented by the following formula (FIV) and a monomer-based unit represented by the following formula (HIV), and has a fluorine content of 15 to 50% by mass and an oxy. The dispersion according to [1], which is a polymer having an alkylene group content of 10 to 70% by mass.
Equation (FIV) CH ₂ = CX ^FIV C (O) ^{OQ FIV-} R ^FIV
Equation (HIV) CH ₂ = CX ^HIV C (O)-(OZ ^HIV ) _mIV- OR ^HIV
The symbols in the formula have the following meanings.
X ^FIV represents a hydrogen atom, a chlorine atom or a methyl group.
Q ^FIV indicates an alkylene group or an oxyalkylene group.
R ^FIV represents a polyfluoroalkyl group, a polyfluoroalkyl group containing an ethereal oxygen atom, or a polyfluoroalkenyl group.
X ^HIV represents a hydrogen atom or a methyl group.
Z ^HIV represents an alkylene group.
mIV represents an integer from 3 to 200.
^RHIV represents an alkyl group or an aryl group.

[6] The dispersant contains a unit based on a monomer represented by the following formula (FV) and a unit based on a monomer represented by the following formula (HV), and has a fluorine content of 20 to 40% by mass and a hydroxyl value. The dispersion according to [1], wherein is a polymer of 150 to 300 mgKOH / g.
Equation (FV) CH ₂ = CX ^FV C (O) ^{OQ FV-} R ^FV
Equation (HV) CH ₂ = CX ^HV C (O) -Q ^HV- OH
The symbols in the formula have the following meanings.
X ^FV represents a hydrogen atom, a chlorine atom or a methyl group.
Q ^FV indicates an alkylene group or an oxyalkylene group.
^RFV represents a polyfluoroalkyl group, a polyfluoroalkyl group containing an ethereal oxygen atom, or a polyfluoroalkenyl group.
X ^HV represents a hydrogen atom or a methyl group.
Q ^HV indicates an alkylene group or a cycloalkylene group.

[7] The dispersion according to any one of [1] to [6], wherein the tetrafluoroethylene-based polymer contains 99.5 mol% or more of units based on tetrafluoroethylene with respect to all the units contained in the polymer. liquid.
[8] The tetrafluoroethylene-based polymer according to any one of [1] to [6], which contains more than 0.5 mol% of units based on comonomer other than tetrafluoroethylene with respect to all the units contained in the polymer. The dispersion liquid described.
[9] The tetrafluoroethylene-based polymer has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group, [1] to [8]. ] The dispersion liquid according to any one of.
[10] The dispersion liquid according to any one of [1] to [9], wherein the volume-based cumulative 50% diameter of the powder is 0.05 to 6 μm.

[11] The dispersion liquid according to any one of [1] to [10], wherein the solvent is a polar solvent.
[12] The dispersion according to any one of [1] to [11], wherein the solvent comprises one or more solvents selected from the group consisting of ketones, esters and amides.
[13] The dispersion according to any one of [1] to [12], wherein the solvent is methyl ethyl ketone, cyclohexanone, cyclopentanone, γ-butyrolactone or N-methyl-2-pyrrolidone.

[14] The dispersion liquid according to any one of [1] to [13] is applied to the surface of the metal foil, and the metal foil is heated to have a resin-attached metal having a resin layer containing the tetrafluoroethylene polymer. A method for manufacturing a metal leaf with resin to obtain a foil.
[15] A method for manufacturing a printed circuit board, wherein a metal foil with a resin is manufactured by the manufacturing method according to the above [14], and the metal foil of the metal foil with a resin is etched to form a pattern circuit.

According to the present invention, it is a powder dispersion liquid having excellent mixability, coatability and dispersibility with different kinds of resin materials (including its varnish) without impairing the physical properties of a base material such as a metal leaf. Provided is a powder dispersion liquid capable of easily forming a resin-attached metal foil or the like having a fluororesin layer having excellent adhesiveness.
The dispersion liquid of the present invention is a dispersion liquid containing a tetrafluoroethylene polymer powder, which is excellent in dispersibility and formability of a layer (coating film) such as wettability, adhesiveness, thixotropy, and smoothness. .. The layer (coating film) formed from the dispersion liquid of the present invention (hereinafter, also referred to as "layer (coating film)") is particularly excellent in wettability and adhesiveness, and is a useful resin as a material for a printed substrate. It can be suitably used for manufacturing attached metal foils and the like. The dispersion liquid of the present invention has a relatively low viscosity and is excellent in redispersibility, and the resin layer is also excellent in light transmittance and transparency.

The following terms have the following meanings.
"D50 of powder" is a volume-based cumulative 50% diameter of powder obtained by a laser diffraction / scattering method. That is, the particle size distribution of the powder is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the powder particle population as 100%, and the particle size at the point where the cumulative volume is 50% on the cumulative curve. is there. “Powder D90” is the volume-based cumulative 90% diameter of the powder obtained in the same manner.
“Polymer melt viscosity” is based on ASTM D 1238, and a polymer sample (2 g) preheated at the measurement temperature for 5 minutes using a flow tester and a 2Φ-8L die is loaded with 0.7 MPa. It is a value measured by holding it at the measurement temperature at.
The "polymer melting temperature" is the temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
"Viscosity" is a value measured using 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 for 3 times is used.
The "thixotropic ratio" is a value (η ₁ / η ₂ ) _{calculated by dividing the viscosity η 1} measured under the condition of a rotation speed of 30 rpm _{by the viscosity η 2} measured under the condition of a rotation speed of 60 rpm. ..
"Ten-point average roughness (Rz _JIS )" is a value specified in Annex JA of JIS B 0601: 2013.

The "unit" in the polymer may be an atomic group formed directly from the monomer by the polymerization reaction, and the polymer obtained by the polymerization reaction is treated by a predetermined method to convert a part of the structure. May be. A unit based on a specific monomer may be represented by adding a monomer name after the "unit". For example, a unit based on the monomer FI is also referred to as a "unit FI".
"(Meta) acrylate" is a general term for acrylate and methacrylate, and (meth) acrylamide derivative is a general term for acrylamide derivative and methacrylamide derivative.
"(Meta) acryloyloxy group" is a general term for acryloyloxy group and methylenedioxy group, and "(meth) acryloyl group" is a general term for acryloyl group and methacryloyl group.
For the "pyrolysis start temperature", a thermogravimetric analyzer (TG) and a thermogravimetric differential thermal analyzer (TG-DTA) are used, and a dispersant (10 mg) is mixed with a mixed gas (helium 90% by volume and oxygen 10% by volume). ) In an atmosphere, when the temperature is raised at a pace of 10 ° C./min, the mass reduction rate is 1% by mass / min or more.

The dispersion liquid of the present invention contains particles of a tetrafluoroethylene polymer (hereinafter, also referred to as “TFE polymer”) powder (hereinafter, also referred to as “F powder”), a solvent, and a dispersant. It is a dispersion liquid dispersed in a shape.
The dispersant is composed of a monovalent fluorine-containing hydrocarbon group which may contain an etheric oxygen atom, a tert-alkoxycarbonyl group, a sec-alkoxycarbonyl group, an aralkyloxycarbonyl group, a polyoxyalkylene group and an alcoholic hydroxyl group. A polymer having at least one group selected from the above group (polymer dispersant). The alkyl group in the one type of group may contain an unsaturated bond (double bond or triple bond) as part of the carbon atom-carbon atom bond, and forms a ring structure. May be good.

The polymer dispersant is a polymer different from the TFE-based polymer.
The polymer dispersant preferably has the monovalent fluorine-containing hydrocarbon group and the one type group in the side chain of the polymer, respectively.
The fluorine content of the polymer dispersant is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, and particularly preferably 25 to 45% by mass.
When the polymer dispersant has a polyoxyalkylene group, the content of the polyoxyalkylene group in the polymer dispersant is preferably 10 to 60% by mass, more preferably 20 to 50% by mass. Hereinafter, the polyoxyalkylene group content in the polymer dispersant is also referred to as “AO content”.
When the polymer dispersant has an alcoholic hydroxyl group, the hydroxyl value of the polymer dispersant is preferably 10 to 330 mgKOH / g.

The monovalent fluorine-containing hydrocarbon group is preferably a group having a polyfluoroalkyl group, a polyfluoroalkenyl group or a perfluoro (oxyalkylene) group. The monovalent fluorine hydrocarbon group preferably does not have a methylenedioxy group or an inducing group thereof (-OCH ₂ O-, -OCH (CH ₃ ) O-, etc.).
The tert- alkoxycarbonyl group is preferably a group represented by the formula ^{-C (O) OC (-X T} ) 3. 3 X ^T in the formula may be the same, or different, represent a monovalent hydrocarbon group. Also, two X ^T may form a divalent hydrocarbon group jointly.
The sec- alkoxycarbonyl group is preferably a group represented by the formula ^{-C (O) OCH (-X S} ) 2. Two X ^S in the formula may be the same, or different, represent a monovalent hydrocarbon group. Also, two X ^S may form a divalent hydrocarbon group jointly.
The aralkyloxycarbonyl group is preferably a group represented by the formula -C (O) _OCH 2 -Ar. Ar in the formula represents an aryl group.
The oxyalkylene group constituting the polyoxyalkylene group preferably has 2 to 4 carbon atoms, and particularly preferably 2. Further, the polyoxyalkylene group may be composed of two or more kinds of oxyalkylene groups. The number of oxyalkylene groups constituting the polyoxyalkylene group is preferably 2 to 200. The polyoxyalkylene group is a divalent group, but it may be a monovalent group in which a hydroxyl group is bonded to a carbon atom at one end thereof or a monovalent group is bonded. The monovalent group having a polyoxyalkylene group is a polyoxy having a monovalent group (alkoxy group, aryloxy group, etc.) or a hydroxyl group having an oxygen atom at the bond end at the terminal carbon atom of the polyoxyalkylene group. An alkylene group is preferred.

In the first suitable dispersion liquid of the present invention (hereinafter, also referred to as “dispersion liquid I”), the polymer dispersant contains a monovalent fluorine-containing hydrocarbon group, a tert-alkoxycarbonyl group, a sec-alkoxycarbonyl group, and the like. It is a dispersion liquid which is a polymer (polymer dispersant I) having at least one group selected from the group consisting of aralkyloxycarbonyl groups in a side chain.
The reason why an article (metal leaf with resin, etc.) having a layer (coating film) having excellent adhesiveness, which contains a TFE polymer and has excellent adhesiveness, can be easily produced from the dispersion liquid I without impairing its physical properties is not always clear. There is no such thing, but it can be considered as follows.
The dispersion liquid I is considered to be excellent in dispersion stability because the F powder is highly stabilized by the interaction of the polymer dispersant I with the fluorosite. Further, it is considered that the polymer dispersant I has a specific site of the side chain (the above-mentioned one group) desorbed in a low temperature atmosphere to form a hydrophilic component. Therefore, when the layer (coating film) is formed from the dispersion liquid I, specifically, when the solvent is heated and distilled off from the dispersion liquid I, such a hydrophilic component is generated, and only the dense packing of the F powder is promoted. It is also considered that it flows on the surface of the coating film and promotes the formation of a hydrophilic layer (coating film). As a result, from the dispersion liquid I, a layer (coating film) having high surface hydrophilicity and homogeneity and excellent adhesiveness can be easily formed without impairing the physical properties of the TFE polymer or the base material (metal leaf, etc.). It is considered that it was formed in.

As the polymer dispersant I, a polymer having a polyfluoroalkyl group or a polyfluoroalkenyl group and ^{a group represented by the formula -OC (-X 1I} ) ( ^{-X 2I} ) ( ^{-X 3I} ) in the side chain is preferable.
In the formula, X ^1I , X ^2I and X ^3I are ^{either X 1I} , X ^2I and X ^3I independently having an alkyl group or an aryl group, or X ^1I and X ^2I are hydrogen atoms and X ^3I is an aryl group. Or, X ^1I and X ^2I are independent hydrogen atoms or alkyl groups and X ^3I is an alkoxy group, or X ^1I is a hydrogen atom or alkyl group and X ^2I and X ^3I jointly form an alkylene group. Either form.
The ^{alkylene group in which X 2I} and X ^3I are jointly formed may be linear or branched, or may form a ring structure in the group. Further, the alkylene group may contain an unsaturated bond or a hetero atom.

As the polyfluoroalkyl group, a perfluoroalkyl group having 1 to 6 carbon atoms is preferable, and − (CF ₂ ) ₄ F and − (CF ₂ ) ₆ F are particularly preferable. As the polyfluoroalkenyl group, a perfluoroalkanoic group having 1 to 12 carbon atoms is preferable, and −OCF (CF ₃ ) C (= C (CF ₃ ) ₂ ) (CF (CF ₃ ) ₂ ) is particularly preferable.
The carbon numbers of X ^1I , X ^2I and X ^3I are preferably 1 to 16 independently of each other.
In X ^1I , X ^2I and X ^3I , ^{whether X 1I} , X ^2I and X ^3I are independently alkyl groups, X ^1I and X ^2I are hydrogen atoms and X ^3I is an aryl group, or X ^1I is It is preferably a hydrogen atom and ^{either X 2I} and X ^3I jointly form an alkylene group, and X ^1I , X ^2I and X ^3I are each independently methyl groups, X ^1I and Either X ^2I is a hydrogen atom and X ^3I is a phenyl group, or X ^1I is a hydrogen atom and X ^2I and X ^3I jointly form an hexylene group or an alkylene group having a crosslinked ring structure. Is particularly preferable.
Specific examples of the groups represented by the formulas -OC (-X ^1I ) ^{(-X 2I} ) ^{(-X 3I) include the following groups.} In the formula, * is a bond.

The polymer dispersant I includes a unit (unit FI) based on the monomer (monomer FI) represented by _{the formula CH 2} = CR ^FI C (O) O-Q ^FI- Z ^FI _{and the formula CH 2} = CR ^HI C (O). ) A polymer containing a unit (unit HI) based on a monomer (monomer HI) represented by OC (-X ^1I ) ^{(-X 2I} ) ^{(-X 3I) is preferable.}
In the formula, ^RFI represents a hydrogen atom, a chlorine atom or a methyl group.
In the formula, ^RHI represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
In the formula, ^QFI represents an alkylene group or an oxyalkylene group.
In the formula, ^ZFI represents a polyfluoroalkyl group or a polyfluoroalkenyl group.
In the formula, X ^1I , X ^2I and X ^3I have the same meanings as described above, and have the same suitable range.
It is preferable that R ^FI and R ^HI are independently hydrogen atoms or methyl groups, respectively.
The carbon number of the carbon-containing group in Q ^FI and Z ^{FI is preferably 1 to 16 independently of each other.}
Q ^FI _{is, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 O- or _-CH 2 _CH 2 _CH 2 _CH 2 is preferably O-.
The Z ^FI is preferably a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkenyl group having 1 to 12 carbon atoms, preferably − (CF ₂ ) ₄ F, − (CF ₂ ) ₆ F or −OCF (CF _3). ) C (= C (CF ₃ ) ₂ ) (CF (CF ₃ ) ₂ ) is particularly preferable.

Specific examples of the monomer FI include CH ₂ = CHC (O) OCH ₂ CH ₂ (CF ₂ ) ₄ F, CH ₂ = CClC (O) OCH ₂ CH ₂ (CF ₂ ) ₄ F, 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 = CClC (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 (= C (CF ₃ )) ₂ ) (CF (CF ₃ ) ₂ ), CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ OCF (CF ₃ ) C (= C (CF ₃ ) ₂ ) (CF (CF ₃ ) ₂ ) , CH ₂ = CHC (O) OCH ₂ CH ₂ CH ₂ CH ₂ OCF (CF ₃ ) C (= C (CF ₃ ) ₂ ) (CF (CF ₃ ) ₂ ), CH ₂ = C (CH ₃ ) C ( O) OCH ₂ CH ₂ CH ₂ CH ₂ OCF (CF ₃ ) C (= C (CF ₃ ) ₂ ) (CF (CF ₃ ) ₂ ) can be mentioned. As the monomer FI, one type may be used alone, or two or more types may be used.

Specific examples of the monomer HI include the following monomers. As the monomer HI, one type may be used alone, or two or more types may be used.

The content of the unit FI with respect to all the units contained in the polymer dispersant I is preferably 20 to 60 mol%, particularly preferably 20 to 40 mol%.
The content of the unit HI with respect to all the units contained in the polymer dispersant I is preferably 40 to 80 mol%, particularly preferably 60 to 80 mol%.
The polymer dispersant I may consist only of units based on the unit FI and the unit HI, and may further contain other units.
The fluorine content of the polymer dispersant I is preferably 10 to 45% by mass, particularly preferably 15 to 40% by mass.
The polymer dispersant I is preferably nonionic.
The mass average molecular weight of the polymer dispersant I is preferably 2000 to 80,000, particularly preferably 6000 to 20000.

The second suitable dispersion of the present invention (hereinafter, also referred to as “dispersion II”) is a polymer (polymer dispersant II) containing a unit based on a (meth) acrylate in which the polymer dispersant has a perfluoropolyether chain. It is a dispersion liquid.
The dispersion liquid II is excellent in dispersibility, and is also excellent in the formability of a layer (coating film) such as wettability, adhesiveness, thixotropic property, and smoothness. The reason is not always clear, but it can be thought of as follows.
Since the perfluoropolyether chain in the polymer dispersant II contains a fluorine atom, it has an excellent affinity with a TFE-based polymer. Since the perfluoropolyether chain contains an ethereal oxygen atom, it is considered that the molecular mobility is enhanced as compared with the perfluoroalkylene chain, and the polymer dispersant II is easily entangled with the F powder particles. On the other hand, the poly (meth) acryloyloxy moiety constituting the main polymer chain of the polymer dispersant II has high molecular mobility and excellent solvent resistance. Therefore, the dispersion liquid containing the polymer dispersant II is excellent in dispersibility, and the coating film (coating film) formed from the polymer dispersant II is excellent in physical properties (wetting property, adhesiveness, smoothness, etc.). Further, for unknown reasons, when the polymer dispersant II in which the main part of the polymer is composed of the sites having high molecular mobility is used, the viscosity of the dispersion tends to be low, and the dispersion can be used in various solvents or other solvents. It exhibits high compatibility with additives.

Polymer Dispersant II comprises a monomer-based unit having a perfluoropolyether chain and a (meth) acryloyl group.
Such a monomer is a general term for a monomer having a (meth) acryloyloxy group and a perfluoropolyether chain, and a monomer having _{a group represented by the formula CH 2} = CHC (O) NH- and a perfluoropolyether chain, and the former. Is a (meth) acrylate derivative and the latter is a (meth) acrylamide derivative. Further, such a monomer includes not only a monofunctional (meth) acrylate but also a bifunctional (meth) acrylate having (meth) acryloyloxy groups at both ends of the perfluoropolyether chain.

As such a monomer, a monomer represented by the following formula (FII) (monomer FII) is preferable. When such a monomer is selected, not only the dispersibility of the dispersion liquid is excellent, but also the physical properties such as the wettability and adhesiveness of the formed layer (coating film) are likely to be improved.
Formula ^{_{(FII) CH 2 = CX FII}} C (O) -Q FII - (OZ FII) nII -OR FII
The symbols in the formula have the following meanings.
X ^FII is a hydrogen atom or a methyl group.
Q ^FII is a divalent linking group, -OCH ₂ CF _2- , -NHC (O)-, -ONHC (O)-, -ONHC (O) NHCF _2- , -OCH ₂ CH ₂ NHC (O). It is preferably OCH ₂ CF _2- or −OCH ₂ CH ₂ NHC (O) NHCF _2-.
Z ^FII is a perfluoroalkylene group, more preferably a perfluoroalkylene group having 1 to 4 carbon atoms, and is a difluoromethylene group (-CF _2- ) or a perfluoroethylene group (-CF ₂ CF _2- ). Is particularly preferable. The Z ^FII may consist of one type of group or two or more types of groups. In the latter case, the arrangement of different types of perfluoroalkylene groups may be random or block.
nII is 2 to 30, preferably 3 to 20.
^RFII is a perfluoroalkyl group, preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably _{-CF 3} or -CF ₂ CF _3.

The monomer FII is more preferably a monomer represented by the following formula (FII1).
Equation (FII1) CH ₂ = CX ^FII C (O) -Q ^FII1- (OCF ₂ ) _nII1 · (OCF ₂ CF ₂ ) _nII2- OR ^FII1
The symbols in the formula have the following meanings.
X ^FII has the same meaning as above.
Q ^FII1 is -OCH ₂ CF _2- , -NHC (O)-, -ONHC (O)-, -OCH ₂ CH ₂ NHC (O) NHCF _2- , -OCH ₂ CH ₂ NHC (O) OCH ₂ CF ₂ − or −OCH ₂ CH ₂ NHC (O) NHCF ₂ − is indicated.
nII1 is 0 to 20, nII2 is 2 to 30, and the sum of the two is 2 to 30.
R ^{FII 1} indicates -CF ₃ or -CF ₂ CF ₃ .
Among the above-mentioned monomers, the monomer having a difluorooxymethylene group (−OCF _2- ) is also excellent in decomposability in a high temperature atmosphere, so that it is easy to improve the wettability of the surface of the layer (coating film).

The polymer dispersant II may contain only the unit FII, or may further contain units other than the unit FII.
The polymer dispersant II preferably contains a unit based on a (meth) acrylate having a polyoxyalkylene group in addition to the unit FII. In this case, as described above, the molecular mobility of the polymer dispersant II is further improved, the viscosity of the dispersion is lowered, and the compatibility with various solvents and other additives is likely to be further improved.

As the (meth) acrylate having a polyoxyalkylene group, a monomer (monomer HII) represented by the following formula (HII) is preferable. When a monomer having a chain length within the predetermined range is selected, not only the dispersibility of the dispersion liquid is excellent, but also the physical properties such as the wettability, adhesiveness, and smoothness of the layer (coating film) are likely to be improved.
Equation (HII) CH ₂ = CX ^HII C (O)-(OZ ^HII ) _mII- OR ^HII
The symbols in the formula have the following meanings.
X ^HII is a hydrogen atom or a methyl group.
Z ^HII is an alkylene group, preferably an alkylene group having 1 to 4 carbon atoms, and is an ethylene group (-CH ₂ CH _2- ), a propylene group (-CH ₂ CH (CH ₃ )-) or n-. It is particularly preferably a butylene group (-CH ₂ CH ₂ CH ₂ CH _2-). Incidentally, mII number of Z ^HII may consist one group may consist of two or more groups. In the latter case, the arrangement of dissimilar alkylene groups may be random or block.
mII is an integer from 3 to 200.
^RHII is a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and is preferably a hydrogen atom, a methyl group or a nonyl group. It is preferably a lauryl group, a stearyl group, a phenyl group, a stearylphenyl group, a laurylphenyl group or a nonylphenyl group, and particularly preferably a hydrogen atom, a methyl group or a nonylphenyl group.

Specific examples of the monomer HII include CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₄ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₉ OH. , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₂₃ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₆₆ OH, CH ₂ = C (CH ₃₎ ) C (O) (OCH ₂ CH ₂ ) ₉₀ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₁₂₀ OH, CH ₂ = CHC (O) (OCH ₂ CH ₂ ) ₄ OH , CH ₂ = CHC (O) (OCH ₂ CH ₂ ) ₈ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH (CH ₃ )) ₄ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH (CH ₃ )) ₈ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH (CH ₃ )) ₉ OH, CH ₂ = C (CH ₃ ) C (O) ) (OCH ₂ CH (CH ₃ )) ₁₃ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) _4. (OCH ₂ CH (CH ₃ )) ₃ OH, CH ₂ = C ( CH ₃ ) C (O) (OCH ₂ CH ₂ ) _10. (OCH ₂ CH ₂ CH ₂ CH ₂ ) ₅ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₄ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₉ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₂₃ OCH ₃ , CH ₂ = C (CH) ₃ ) C (O) (OCH ₂ CH ₂ ) ₆₆ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₉₀ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₁₂₀ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₃₀ O (CH ₂ ) ₁₂ H, CH ₂ = C (CH ₃ ) C (O) ( OCH ₂ CH ₂ ) ₃₀ O (CH ₂ ) ₁₈ H, CH ₂ = CHC (O) (OCH ₂ CH ₂ ) ₄ O (CH ₂ ) ₁₂ H, CH ₂ = CHC (O) (OCH) ₂ CH ₂ ) ₉ OCH ₃ , CH ₂ = CHC (O) (OCH ₂ CH (CH ₃ )) ₅ O-Phy- (CH ₂ ) ₉ H, CH ₂ = C (CH ₃ ) C (O) (OCH) ₂ CH ₂ ) ₆・ (OCH ₂ CH (CH ₃ )) ₅ O-Ph can be mentioned. In the above formula, -Phy- represents a phenylene group and Ph represents a phenyl group.

Among the above, as the monomer HII, a monomer represented by the following formula (HII1) or a monomer represented by the following formula (HII2) is preferable.
Equation (HII1) CH ₂ = CX ^HII C (O)-(OZ ^HII ) _mII1- OH
Equation (HII2) CH ₂ = CX ^HII C (O)-(OZ ^HII ) _mII2- OR ^HII1
The symbols in the formula have the following meanings.
X ^HII and Z ^HII have the same meanings as described above, respectively.
mII1 is 3 to 30.
mII2 is 20 to 150.
^RHII1 represents a methyl group or a phenyl group.

The fluorine content of the polymer dispersant II is preferably 20 to 50% by mass. Since the lower limit of the fluorine content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the fluorine content is within the above range, the affinity of the dispersant for each component of the dispersant is balanced, and in addition to the dispersibility of the dispersion liquid, the formability of the layer (coating film) is likely to be improved. For example, the layer (coating film) is characterized by high wettability and excellent adhesiveness. The fluorine content of Polymer Dispersant II can be calculated from the type of monomer used for its synthesis and the amount charged.

When the polymer dispersant II contains a unit based on a (meth) acrylate having a polyoxyalkylene group, the content (AO content) of the polyoxyalkylene group of the polymer dispersant II is preferably 10 to 60% by mass. Since the lower limit of the AO content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the AO content is within the above range, the affinity of the polymer dispersant II for each of the TFE polymer and the solvent is balanced, and in addition to the dispersibility of the dispersion liquid, the formability of the layer (coating film) is formed. Is easy to improve. Specifically, in the layer (coating film), the physical characteristics of the TFE polymer itself are likely to be expressed as they are. The AO content can be calculated from the type of monomer used for its synthesis and the amount charged.
Further, if the polymer dispersant II having the fluorine content and the AO content in the above range is used, the viscosity of the dispersion liquid tends to decrease.

The amount of the unit FII with respect to all the units contained in the polymer dispersant II is preferably 10 to 100 mol%, more preferably 20 to 70 mol%.
The amount of the unit based on the unit HII with respect to all the units contained in the polymer dispersant II is preferably 0 to 90 mol%, more preferably 30 to 80 mol%.
The total amount of the unit FII and the unit HII with respect to all the units contained in the polymer dispersant II is preferably 90 to 100 mol%.
The polymer dispersant II is preferably nonionic.
The weight average molecular weight of the polymer dispersant II is preferably 2000 to 80,000, particularly preferably 6000 to 20000.

In the third suitable dispersion liquid of the present invention (hereinafter, also referred to as “dispersion liquid III”), the polymer dispersant is a unit based on an acrylate-based monomer having a monovalent fluorine-containing hydrocarbon group and a monovalent hydrocarbon. A dispersion liquid which is a polymer (polymer dispersant III) containing a unit based on a (meth) acrylate having a group, a unit based on a (meth) acrylate having a polyoxyalkylene group, and a unit based on a monomer having a nitrogen-containing group. Is.

The dispersion liquid III is excellent in dispersibility, and is also excellent in the formability of a layer (coating film) such as wettability, adhesiveness, thixotropic property, and smoothness. The reason is not always clear, but it can be considered as follows.
Since the polymer dispersant III contains a unit based on an acrylate-based monomer having a monovalent fluorine-containing hydrocarbon group, it has a high affinity with a TFE-based polymer, and thus can be highly adhered to powder particles. Further, the polymer dispersant III contains a highly hydrophilic (highly polar) unit based on a (meth) acrylate having a polyoxyalkylene group and a unit based on a monomer having a nitrogen-containing group, and thus has an affinity with a solvent. Highly sex. Therefore, the dispersion liquid III is excellent in the dispersibility of the F powder.
In particular, the polymer dispersant III also contains units based on (meth) acrylates that are highly hydrophobic (low polarity) and have monovalent hydrocarbon groups, so that electrical interactions between the highly polar groups occur. Is alleviated, and it is considered that the original function of the polar group (high affinity with the solvent) is effectively expressed. Further, it is considered that the polymer dispersant III has increased molecular mobility as the glass transition temperature decreases due to the presence of a unit based on a monomer having a nitrogen-containing group, and is easily entangled with powder particles. From this point of view, the dispersion liquid III has very high dispersibility.
In addition, in the polymer dispersant III, the monovalent hydrocarbon group and the nitrogen-containing group are easily separated from the polymer chain during heating, and are easily decomposed by the generation of radicals. Therefore, it is considered that the polymer dispersant III is unlikely to remain in the layer (coating film). Therefore, the layer (coating film) is excellent in wettability, adhesiveness, thixotropic property, smoothness and the like. The thermal decomposition start temperature of the polymer dispersant III can be adjusted by the content of each unit, and is preferably 250 ° C. or lower, more preferably 200 ° C. or lower.

The acrylate-based monomer having a monovalent fluorine-containing hydrocarbon group includes a polymerizable group such as a (meth) acryloyloxy group and an α-chloroacryloyloxy group, and a polyfluoroalkyl group having a polyfluoroalkyl group and an etheric oxygen atom. , A generic term for monomers having a monovalent fluorine-containing hydrocarbon group such as a polyfluoroalkenyl group.
As the monomer, a monomer represented by the following formula (FIII) (monomer FIII) is preferable. When a monomer having a fluorine-containing group having a relatively short chain length is selected, not only the dispersibility of the dispersion liquid is excellent, but also the physical properties such as the wettability and adhesiveness of the layer (coating film) are likely to be improved.
Equation (FIII) CH ₂ = CX ^FIII C (O) ^{OQ FIII-} R ^FIII
The symbols in the formula have the following meanings.
X ^FIII is a hydrogen atom, a chlorine atom or a methyl group.
Q ^FIII is an alkylene group or an oxyalkylene group, and is preferably an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 2 to 4 carbon atoms. However, when ^RFIII is a polyfluoroalkyl group having 1 to 6 carbon atoms or a polyfluoroalkyl group having 3 to 6 carbon atoms containing an ether oxygen atom, ^QFIII is a methylene group (-CH _2- ) or It is preferably an ethylene group (−CH ₂ CH _2−). When ^RFIII is a polyfluoroalkenyl group having 4 to 12 carbon atoms, ^QFIII is an oxyethylene group (-CH ₂ CH ₂ O-) or an oxybutylene group (-CH ₂ CH ₂ CH ₂ CH _2). O-) is preferable.
^RFIII is a polyfluoroalkyl group, a polyfluoroalkyl group containing an ether oxygen atom, or a polyfluoroalkenyl group, and has a polyfluoroalkyl group having 1 to 6 carbon atoms and a carbon number of 3 to 6 including an ether oxygen atom. It is preferably a polyfluoroalkyl group or a polyfluoroalkenyl group having 4 to 12 carbon atoms, preferably − (CF ₂ ) ₄ F, − (CF ₂ ) ₆ F, −CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ , −. CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) C (= C (CF ₃ ) ₂ ) (CF (CF ₃ ) ₂ ) or -C (CF ₃ ) C (= C (CF (CF) CF ₃ ) ₂ ) ₂ ) is more preferable,-(CF ₂ ) ₄ F,-(CF ₂ ) ₆ F, -CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ or -CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ is particularly preferable. Above all, from the viewpoint of further excellent physical properties (wetting property, adhesiveness, smoothness, etc.) of the layer (coating film), ^{RF III} is further preferably − (CF ₂ ) ₄ F or − (CF ₂ ) ₆ F. Preferably, − (CF ₂ ) ₆ F is most preferred. In particular, a monomer having a linear polyfluoroalkyl group is suitable because it can be obtained at a relatively low cost.

Specific examples of the monomer FIII include CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ (CF ₂ ) ₆ 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 ) ₄ F, CH ₂ = CClC (O) OCH ₂ CH ₂ (CF ₂ ) ₄ F, CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ CH ₂ CH ₂ OCF (CF ₃ ) C (= C (CF ₃ ) ₂ ) (CF (CF ₃ ) ₂ ), CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ CH ₂ CH ₂ OC (CF ₃ ) C (= C (CF (CF ₃ ) ₂ ) ₂ ) can be mentioned.

The (meth) acrylate having a monovalent hydrocarbon group (hereinafter, also referred to as “monomer HCIII”) is a (meth) acryloyloxy group and a monovalent hydrocarbon such as an alkyl group, an alkenyl group, an aryl group, and an aralkyl group. It is a general term for monomers having a group. The alkyl group may be linear, branched, or cyclic.
The monovalent hydrocarbon group in the monomer HCIII includes a cycloalkyl group having 6 to 10 carbon atoms, a bridging cyclic alkyl group having 9 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkyl having 6 to 30 carbon atoms. Groups are preferred.
From the viewpoint of obtaining a dispersion having better dispersibility of the dispersion, the monovalent hydrocarbon group is more preferably an alkyl group having 6 to 30 carbon atoms, and further preferably an alkyl group having 10 to 20 carbon atoms. preferable. In this case, physical properties such as thixotropic properties of the layer (coating film) are more likely to be improved.
From the viewpoint of further enhancing the wettability and adhesiveness of the surface of the layer (coating film), the monovalent hydrocarbon group is a crosslinked cyclic alkyl group having 9 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms. More preferably, it is an isobornyl group or a benzyl group.

Specific examples of the monomer HCIII include CH ₂ = C (CH ₃ ) C (O) O (CH ₂ ) ₁₂ H, CH ₂ = CHC (O) O (CH ₂ ) ₁₂ H, CH ₂ = C (CH _3). ) C (O) O (CH ₂ ) ₁₆ H, CH ₂ = CHC (O) O (CH ₂ ) ₁₆ H, CH ₂ = C (CH ₃ ) C (O) O (CH ₂ ) ₁₈ H, CH ₂ = CHC (O) O (CH ₂ ) ₁₈ H, CH ₂ = C (CH ₃ ) C (O) O (CH ₂ ) ₂₀ H, CH ₂ = CHC (O) O (CH ₂ ) ₂₀ H, CH ₂ = CHC (O) OCH _2- Ph, CH ₂ = C (CH ₃ ) C (O) OCH _2- Ph, CH ₂ = CHC (O) OCH <Nb, CH ₂ = C (CH ₃ ) C (O) OCH <Nb can be mentioned. In the above formula, -Ph represents a phenyl group and -CH <Nb represents an isobornyl group.

The (meth) acrylate having a polyoxyalkylene group is a monomer having a (meth) acryloyloxy group and a polyoxyalkylene group.
As such a monomer, a monomer represented by the following formula (HIII) (monomer HIII) is preferable. When a monomer having a chain length within the predetermined range is selected, not only the dispersibility of the dispersion liquid is excellent, but also the physical properties such as the wettability, adhesiveness, and smoothness of the layer (coating film) are likely to be improved.
Formula (HIII) CH ₂ = CX ^HIII C (O)-(OZ ^HIII ) _mIII- OR ^HIII
The symbols in the formula have the following meanings.
X ^HIII is a hydrogen atom or a methyl group.
Z ^HIII is an alkylene group, preferably an alkylene group having 1 to 4 carbon atoms, and is an ethylene group (-CH ₂ CH _2- ), a propylene group (-CH ₂ CH (CH ₃ )-) or n-. It is particularly preferably a butylene group (-CH ₂ CH ₂ CH ₂ CH _2-). In addition, Z ^HIII may consist of one kind of group or may consist of two or more kinds of groups. In the latter case, the arrangement of dissimilar alkylene groups may be random or block.
The mIII is 3 to 200, preferably 6 to 100, more preferably 9 to 70, and even more preferably 12 to 40 from the viewpoint of particularly excellent wettability and smoothness of the layer (coating film).
^RHIII is a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and a methyl group, a nonyl group, a lauryl group, and the like. It is preferably a stearyl group, a phenyl group, a stearylphenyl group, a laurylphenyl group or a nonylphenyl group, and particularly preferably a methyl group.

As the monomer, a monomer represented by the following formula (HIII1) and a monomer represented by the following formula (HIII2) are more preferable depending on the terminal of the polyoxyalkylene group.
Formula (HIII1) CH ₂ = CX ^HIII C (O)-(OZ ^HIII ) _mIII1- OH
Formula (HIII2) CH ₂ = CX ^HIII C (O)-(OZ ^HIII ) _mIII2- OR ^HIII2
The symbols in the formula have the following meanings.
X ^HIII and Z ^HIII have the same meanings as described above, respectively.
mIII1 is 3 to 40, preferably 6 to 20.
mIII2 is 10 to 100, and 20 to 75 is particularly preferable.
R ^HIII2 represents a methyl group or a phenyl group.

Specific examples of the monomer include CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₄ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₉ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₂₃ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₆₆ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₉₀ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₁₂₀ OH, CH ₂ = CHC (O) (OCH ₂ CH ₂ ) ₄ OH, CH ₂ = CHC (O) (OCH ₂ CH ₂ ) ₈ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH (CH ₃ )) ₄ OH, CH ₂ = C (CH ₃ ) C ( O) (OCH ₂ CH (CH ₃ )) ₈ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH (CH ₃ )) ₉ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH (CH ₃ )) ₁₃ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) _4. (OCH ₂ CH (CH ₃ )) ₃ OH, CH ₂ = C (CH) ₃ ) C (O) (OCH ₂ CH ₂ ) _10. (OCH ₂ CH ₂ CH ₂ CH ₂ ) ₅ OH, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₄ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₉ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₂₃ OCH ₃ , CH ₂ = C (CH ₃₎ ) C (O) (OCH ₂ CH ₂ ) ₆₆ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₉₀ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) ( OCH ₂ CH ₂ ) ₁₂₀ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₃₀ O (CH ₂ ) ₁₂ H, CH ₂ = C (CH ₃ ) C (O) (OCH) ₂ CH ₂ ) ₃₀ O (CH ₂ ) ₁₈ H, CH ₂ = CHC (O) (OCH ₂ CH ₂ ) ₄ O (CH ₂ ) ₁₂ H, CH ₂ = CHC (O) (OCH ₂₎ CH ₂ ) ₉ OCH ₃ , CH ₂ = CHC (O) (OCH ₂ CH (CH ₃ )) ₅ O-Phy- (CH ₂ ) ₉ H, CH ₂ = C (CH ₃ ) C (O) (OCH ₂₎ CH ₂ ) ₆・ (OCH ₂ CH (CH ₃ )) ₅ O-Ph can be mentioned. In the above formula, -Phy- represents a phenylene group and Ph represents a phenyl group.

The monomer having a nitrogen-containing group (hereinafter, also referred to as “monomer NIII”) includes a polymerizable group such as a vinyl group, a vinyloxy group, a (meth) acryloyl group, and a (meth) acryloyloxy group, and a cyano group and an amino group. , A generic term for monomers having a nitrogen-containing group such as an amide group and an imidazole group.
As the monomer NIII, acrylonitrile or acrylamide is preferable, and acrylonitrile is more preferable. When such a monomer is selected, not only the dispersibility of the dispersion liquid is excellent, but also the physical properties such as the wettability and adhesiveness of the layer (coating film) are likely to be improved.
In particular, when the polymer dispersant III has the above nitrogen-containing group, the molecular mobility of the polymer dispersant III is enhanced and the fluidity of the polymer dispersant III in the dispersion is also enhanced, so that the polymer dispersant III is easily entangled with the powder particles. Not only that, the thixotropy of the dispersion is also improved. Therefore, in this case, the dispersibility of the dispersion liquid and the formability of the layer (coating film) are further improved.

The fluorine content of the polymer dispersant III is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, still more preferably 25 to 45% by mass. Since the lower limit of the fluorine content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the fluorine content is within the above range, the affinity of the polymer dispersant III for each component of the polymer dispersant III is balanced, and in addition to the dispersibility of the dispersion liquid, the formability of the layer (coating film) is improved. Easy to improve. For example, the layer (coating film) is characterized by high wettability and excellent smoothness and adhesiveness. The fluorine content of Polymer Dispersant III can be calculated from the type of monomer used for its synthesis and the amount charged.
The content of the polyoxyalkylene group (AO content) of the polymer dispersant III is preferably 10 to 60% by mass, more preferably 20 to 50% by mass. Since the lower limit of the AO content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the AO content is within the above range, the affinity of the polymer dispersant for each of the TFE polymer and the solvent is balanced, and in addition to the dispersibility of the dispersion liquid, the layer (coating film) formability is improved. Easy to do. Specifically, in the layer (coating film), the physical characteristics of the TFE polymer itself are likely to be expressed as they are. The AO content of the polymer dispersant III can be calculated from the type of monomer used for its synthesis and the amount charged thereof.
The amount of the unit based on the unit FIII with respect to all the units contained in the polymer dispersant III is preferably 30 to 60 mol%, more preferably 40 to 50 mol%.
The amount of the unit HCIII with respect to all the units contained in the polymer dispersant III is preferably 5 to 30 mol%, more preferably 10 to 20 mol%.
The amount of the unit AOIII with respect to all the units contained in the polymer dispersant III is preferably 5 to 30 mol%, more preferably 10 to 20 mol%.
The amount of the unit NIII with respect to all the units contained in the polymer dispersant III is preferably 10 to 40 mol%, more preferably 15 to 30 mol%.
When the amount of each unit with respect to all the units contained in the polymer dispersant III is within the above range, the dispersibility of the dispersion liquid is further improved, and various physical properties of the layer (coating film) are exhibited in a well-balanced manner. In addition, the thermal decomposition start temperature of the polymer dispersant III is further lowered.

The polymer dispersant III may consist of only the above-mentioned four types of units, and may further contain additional units other than the above-mentioned four types of units as long as the effects of the present invention are not impaired. The monomer forming the additional unit is not particularly limited.
The total amount of the above-mentioned four units with respect to all the units contained in the polymer dispersant III is preferably 90 to 100 mol%, particularly preferably 99 to 100 mol%. That is, the polymer dispersant III is preferably a polymer consisting substantially of only the above-mentioned four types of units.
The polymer dispersant III is preferably nonionic.
The weight average molecular weight of the polymer dispersant III is preferably 2000 to 80,000, more preferably 6000 to 20000.

Preferable specific examples of the polymer dispersant III include a monomer-based unit represented by the following formula (FIII1), a monomer-based unit represented by the following formula (HCIII1), a unit HIII1 or a unit HIII2, and acrylonitrile. A quaternary polymer consisting of a unit based on.
Equation (FIII1) CH ₂ = CX ^FIII1 C (O) O-CH ₂ CH _2- R ^FIII1
Formula (HCIII1) CH ₂ = CX ^HCIII1 C (O) ^{OR HCIII1}
The symbols in the formula have the following meanings.
X ^FIII1 is a hydrogen atom or a methyl group.
R ^{FIII 1} is − (CF ₂ ) ₄ F or − (CF ₂ ) ₆ F.
X ^HCIII1 is a hydrogen atom or a methyl group.
R ^HCIII1 is an alkyl group having 6 to 30 carbon atoms, and preferably a linear alkyl group having 6 to 30 carbon atoms.
The amounts of the units based on the unit FIII1, the unit HCIII1, the unit HIII1 or the unit HIII2, and the acrylonitrile with respect to all the units contained in the quaternary polymer are 30 to 60 mol%, 5 to 30 mol%, and 5 to 30 in this order. Mol%, 10-40 mol%.

In the fourth suitable dispersion of the present invention (hereinafter, also referred to as "dispersion IV"), the polymer dispersant has a unit based on a fluoroacrylate-based monomer and a one-ended sealed polyoxyalkylene group (meth). A dispersion which is a polymer (polymer dispersant IV) containing an acrylate-based unit.
The fluorine content of the polymer dispersant IV is 10 to 50% by mass, and the content of the polyoxyalkylene group (AO content) of the polymer dispersant IV is 10 to 60% by mass.
The dispersion liquid IV is excellent in dispersibility, and is also excellent in layer (coating film) forming property such as wettability, adhesiveness, thixotropic property, and smoothness. The reason is that the polymer dispersant IV has a fluorine-containing moiety and a polyoxyalkylene group in which a terminal hydroxyl group is capped, and the AO content and the fluorine content of each are adjusted to the above-mentioned predetermined ranges. There are some points.
The AO content and the fluorine content in the polymer dispersant IV are in a trade-off relationship, and it is not easy to adjust the AO content and the fluorine content to balance the affinity for the TFE polymer and the organic solvent. Absent. That is, the fluorine content of the polymer dispersant IV is the structure of the fluoroacrylate-based monomer and its content, and the AO content of the polymer dispersant IV is the structure of the (meth) acrylate having a one-ended sealed polyoxyalkylene group and its content. It depends on the content. For example, if the former monomer having a high fluorine content is selected and the content is increased, a polymer dispersant having a high fluorine content can be prepared. However, while such a polymer dispersant improves the affinity with the TFE-based polymer, its AO content is relatively low, so that the affinity with the organic solvent is considered to be low. As a result, it is considered that the dispersibility itself of the dispersion liquid containing the dispersant is lowered.
As a result of diligent studies, the present inventors can select the structures and contents of both monomers and adjust the fluorine content and AO content of the polymer dispersant IV within the above-mentioned predetermined ranges to obtain the dispersion liquid. First, we found that the dispersibility was improved. Further, if the former monomer and the latter monomer having the terminal hydroxyl group capped are selected respectively and the fluorine content and the AO content of the polymer dispersant IV are adjusted within the above-mentioned predetermined ranges, the layer (coating film) is formed. ) Was found to be excellent in physical properties, and the present invention was completed.

The fluoroacrylate-based monomer includes a (meth) acryloyloxy group or an α-chloroacryloyloxy group, and a fluorine-containing organic group such as a polyfluoroalkyl group, a polyfluoroalkyl group having an ethereal oxygen atom, and a polyfluoroalkenyl group. It is a general term for the monomers having.
As the fluoroacrylate-based monomer, a monomer represented by the following formula (FIV) (monomer FIV) is preferable. When such a monomer is selected, not only the dispersibility of the dispersion liquid is excellent, but also the physical properties such as the wettability, adhesiveness, and smoothness of the layer (coating film) are likely to be improved.
Equation (FIV) CH ₂ = CX ^FIV C (O) ^{OQ FIV-} R ^FIV
The symbols in the formula have the following meanings.
X ^FIV is a hydrogen atom, a chlorine atom or a methyl group.
Q ^FIV is an alkylene group or an oxyalkylene group, and is preferably an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 2 to 4 carbon atoms. However, when R ^FIV is a polyfluoroalkyl group having 1 to 6 carbon atoms or a polyfluoroalkyl group having 3 to 6 carbon atoms containing an ether oxygen atom, Q ^FIV is a methylene group (-CH _2- ). Alternatively, it is preferably an ethylene group (-CH ₂ CH _2-). When R ^FIV is a polyfluoroalkenyl group having 4 to 12 carbon atoms, Q ^FIV is an oxyethylene group (-CH ₂ CH ₂ O-) or an oxybutylene group (-CH ₂ CH ₂ CH ₂ CH). ₂ O−) is preferable.
R ^FIV is a polyfluoroalkyl group, a polyfluoroalkyl group containing an ether oxygen atom, or a polyfluoroalkenyl group, and has a polyfluoroalkyl group having 1 to 6 carbon atoms and a carbon number of 3 to 6 including an ether oxygen atom. It is preferably a polyfluoroalkyl group or a polyfluoroalkenyl group having 4 to 12 carbon atoms, preferably − (CF ₂ ) ₄ F, − (CF ₂ ) ₆ F, −CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ , −. CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) C (= C (CF ₃ ) ₂ ) (CF (CF ₃ ) ₂ ) or -C (CF ₃ ) C (= C (CF (CF) CF ₃ ) ₂ ) ₂ ) is more preferable,-(CF ₂ ) ₄ F,-(CF ₂ ) ₆ F, -CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ or -CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ is particularly preferable. Above all, from the viewpoint of further excellent physical properties (wetting property, adhesiveness, smoothness, etc.) of the layer (coating film), the R ^FIV is further preferably − (CF ₂ ) ₄ F or − (CF ₂ ) ₆ F. Preferably, − (CF ₂ ) ₆ F is most preferable.

Specific examples of fluoroacrylate-based monomers include CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ (CF ₂ ) ₆ 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 ) ₄ F, CH ₂ = CClC (O) OCH ₂ CH ₂ (CF ₂ ) ₄ F, CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ CH ₂ CH ₂ OCF (CF ₃ ) (C (= C (CF ₃ ) ₂ ) (CF (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 ) can be mentioned.

The (meth) acrylate having a one-terminal sealed polyoxyalkylene group includes a (meth) acryloyloxy group and a hydrocarbon group bonded to the terminal carbon atom of the polyoxyalkylene group and the polyoxyalkylene group via an oxygen atom. It is a general term for monomers having.
As the (meth) acrylate having a one-ended sealed polyoxyalkylene group, a monomer (monomer HIV) represented by the following formula (HIV) is preferable. When a monomer having a chain length in a predetermined range in which the terminal hydroxyl group is capped is selected, not only the dispersibility of the dispersion liquid is excellent, but also the physical properties such as wettability, adhesiveness, and smoothness of the layer (coating film) are further improved. Easy to do.
Equation (HIV) CH ₂ = CX ^HIV C (O)-(OZ ^HIV ) _mIV- OR ^HIV
The symbols in the formula have the following meanings.
X ^HIV is a hydrogen atom or a methyl group.
Z ^HIV is an alkylene group, preferably an alkylene group having 1 to 4 carbon atoms, and is an ethylene group (-CH ₂ CH _2- ), a propylene group (-CH ₂ CH (CH ₃ )-) or n-. It is particularly preferably a butylene group (-CH ₂ CH ₂ CH ₂ CH _2-). The mIV Z ^HIV may be composed of one type of group or two or more types of groups. In the latter case, the arrangement of dissimilar alkylene groups may be random or block.
The mIV is 3 to 200, preferably 6 to 100, more preferably 9 to 70, and particularly preferably 12 to 40 from the viewpoint of particularly excellent wettability and smoothness of the layer (coating film).
^RHIV is an alkyl group or an aryl group, preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and is preferably a methyl group, a nonyl group, a lauryl group, a stearyl group, a phenyl group, and the like. It is more preferably a stearylphenyl group, a laurylphenyl group or a nonylphenyl group, and particularly preferably a methyl group.

Specific examples of the monomer include CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₄ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₉ OCH. ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₂₃ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₆₆ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₉₀ OCH ₃ , CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₁₂₀ OCH ₃ , CH ₂ = C (CH ₃ ) C ( O) (OCH ₂ CH ₂ ) ₃₀ O (CH ₂ ) ₁₂ H, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₃₀ O (CH ₂ ) ₁₈ H, CH ₂ = CHC (O) ) (OCH ₂ CH ₂ ) ₄ O (CH ₂ ) ₁₂ H, CH ₂ = CHC (O) (OCH ₂ CH ₂ ) ₉ OCH ₃ , CH ₂ = CHC (O) (OCH ₂ CH (CH ₃ )) ₅ O-Phy- (CH ₂ ) ₉ H, CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₆ · (OCH ₂ CH (CH ₃ )) ₅ O-Ph can be mentioned. In the above formula, -Phy- represents a phenylene group and Ph represents a phenyl group.

The fluorine content of the polymer dispersant IV is 10 to 50% by mass, preferably 20 to 40% by mass. Since the lower limit of the fluorine content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the fluorine content is in the above range, the affinity of the polymer dispersant IV for each component is balanced, and in addition to the dispersibility of the dispersion liquid, the layer (coating film) formability is likely to be improved. For example, the layer (coating film) has high wettability and is characterized by excellent smoothness and adhesiveness. The fluorine content of the polymer dispersant IV can be calculated from the type of monomer used for its synthesis and the amount charged.
The AO content of the polymer dispersant IV is 20 to 70% by mass, preferably 20 to 50% by mass, and particularly preferably 25 to 45% by mass. Since the lower limit of the AO content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the AO content is within the above range, the affinity of the polymer dispersant IV for each of the TFE polymer and the organic solvent is balanced, and in addition to the dispersibility of the dispersion liquid, the layer (coating film) formability thereof. Is easy to improve. Specifically, the coating film obtained from the dispersion liquid IV tends to express the physical characteristics of the TFE polymer itself as it is. The AO content of the polymer dispersant IV can be calculated from the type of monomer used for its synthesis and the amount charged thereof.
The amount of the unit FIV with respect to all the units contained in the polymer dispersant IV is preferably 60 to 90 mol%, particularly preferably 70 to 90 mol%.
The amount of unit HIV with respect to all units contained in the polymer dispersant IV is preferably 10 to 40 mol%, particularly preferably 10 to 30 mol%.
The polymer dispersant IV may consist of only the above-mentioned two types of units, and may further contain additional units other than the above-mentioned two types of units as long as the effects of the present invention are not impaired. The monomer forming the additional unit is not particularly limited.
The total amount of the above two units with respect to all the units contained in the polymer dispersant IV is preferably 90 to 100 mol%, particularly preferably 99 to 100 mol%. That is, the polymer dispersant IV is preferably a polymer consisting substantially of only the above-mentioned two types.
The polymer dispersant IV is preferably nonionic.
The mass average molecular weight of the polymer dispersant IV is preferably 2000 to 80,000, particularly preferably 6000 to 20000.

Preferable specific examples of the polymer dispersant IV include a unit based on the monomer (monomer FIV1) represented by the following formula (FIV1) and a unit based on the monomer (monomer HIV1) represented by the following formula (HIV1). Examples thereof include polymers having a fluorine content of 20 to 40% by mass and an AO content of 20 to 50% by mass.
Equation (FIV1) CH ₂ = CX ^FIV1 C (O) O-CH ₂ CH _2- R ^FIV1
Equation (HIV1) CH ₂ = CX ^HIV1 C (O)-(OCH ₂ CH ₂ ) _{mIV1- OCH 3}
X ^FIV1 is a hydrogen atom or a methyl group.
R ^{FIV 1} is − (CF ₂ ) ₄ F or − (CF ₂ ) ₆ F.
X ^HIV1 is a hydrogen atom or a methyl group.
The mIV1 is 9 to 70, preferably 12 to 40.
The amount of the unit FIV1 with respect to all the units contained in the polymer is 60 to 90 mol%, preferably 70 to 90 mol%.
The amount of the unit HIV1 with respect to all the units contained in the polymer is 10 to 40 mol%, preferably 10 to 30 mol%.
The total amount of the unit FIV1 and the unit HIV1 with respect to all the units contained in the polymer is 90 to 100 mol%, preferably 100 mol%.

In the fifth preferred dispersion of the present invention (hereinafter, also referred to as "dispersion V"), the polymer dispersant is a unit based on a fluoromonomer having a fluoroalkyl group or a fluoroalkenyl group, and a hydroxyalkyl group or hydroxycyclo. A dispersion which is a polymer dispersant (polymer dispersant V) containing a unit based on a (meth) acrylate having an alkyl group. The fluorine content of the polymer dispersant V is 15 to 45% by mass, and the hydroxyl value of the polymer dispersant V is 100 to 330 mgKOH / g.
The dispersion liquid V is excellent in dispersibility, and is also excellent in the formability of a layer (coating film) such as wettability, adhesiveness, thixotropic property, and smoothness. The reason is that the polymer dispersant V has a fluorine-containing moiety and a hydroxyl group, and each of the hydroxyl value and the fluorine content is adjusted within the above-mentioned predetermined ranges.
The hydroxyl value and fluorine content of the polymer dispersant V are in a trade-off relationship, and it is not easy to adjust the hydroxyl value and the fluorine content to balance the affinity for the TFE polymer and the solvent. That is, the fluorine content of the polymer dispersant V is due to the structure and content of the fluoromonomer, and the hydroxyl value of the polymer dispersant V is due to the structure and content of the (meth) acrylate. For example, if a fluoromonomer having a high fluorine content is selected and the content is increased, a polymer dispersant having a high fluorine content can be prepared. However, while such a polymer dispersant improves the affinity with the TFE-based polymer, its hydroxyl value is relatively low, so that the affinity with the solvent is considered to be low. As a result, it is considered that the dispersibility of the dispersion liquid containing the polymer dispersant is lowered.
The present inventors have attempted to study the structure of the fluoromonomer and the structure of the (meth) acrylate. As a result, when a predetermined fluoromonomer and a predetermined (meth) acrylate having a molecular weight smaller than that of the hydroxyl group are selected and the fluorine content and the hydroxyl value are adjusted within the above-mentioned predetermined ranges, the dispersion liquid is used. The present invention was completed by discovering that the dispersibility of the layer (coating film) formed from the dispersion liquid is excellent and the physical properties of the layer (coating film) are excellent.

As the fluoromonomer, a monomer having a polymerizable group such as a (meth) acryloyloxy group or an α-chloro-acryloyloxy group and a fluoroalkyl group or a fluoroalkenyl group is preferable.
As the fluoromonomer, a monomer represented by the following formula (FV) (monomer FV) is more preferable. When an acrylate-based monomer having a relatively short chain length of the fluorine-containing portion is selected, not only the dispersibility of the dispersion is excellent, but also the physical properties such as the wettability and adhesiveness of the F layer are likely to be improved.
Equation (FV) CH ₂ = CX ^FV C (O) ^{OQ FV-} R ^FV
The symbols in the formula have the following meanings.
X ^FV is a hydrogen atom, a chlorine atom or a methyl group.
Q ^FV is an alkylene group or an oxyalkylene group, and is preferably an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 2 to 4 carbon atoms. However, when the ^RFV is a polyfluoroalkyl group having 1 to 6 carbon atoms or a polyfluoroalkyl group having 3 to 6 carbon atoms containing an ether oxygen atom, the Q ^FV is a methylene group (-CH _2- ). Alternatively, it is preferably an ethylene group (-CH ₂ CH _2-). ^Further, when ^{R FV} is polyfluoroalkenyl group having 4 to 12 carbon ^{atoms, Q FV} oxyethylene group _(-CH 2 _CH 2 O-) or oxybutylene group _{(-CH 2} CH 2 _CH 2 CH ₂ O−) is preferable.
^RFV is a polyfluoroalkyl group, a polyfluoroalkyl group containing an ether oxygen atom, or a polyfluoroalkenyl group, and has a polyfluoroalkyl group having 1 to 6 carbon atoms and a carbon number of 3 to 6 including an ether oxygen atom. It is preferably a polyfluoroalkyl group or a polyfluoroalkenyl group having 4 to 12 carbon atoms, preferably − (CF ₂ ) ₄ F, − (CF ₂ ) ₆ F, −CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ , −. CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) C (= C (CF ₃ ) ₂ ) (CF (CF ₃ ) ₂ ) or -C (CF ₃ ) C (= C (CF (CF) CF ₃ ) ₂ ) ₂ ) is more preferable,-(CF ₂ ) ₄ F,-(CF ₂ ) ₆ F, -CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ or -CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ is particularly preferable. Among them, the physical properties of the layer (coating film) (wettability, adhesiveness, smoothness, etc.) from the viewpoint of further ^{excellent, R FV} is, - _{(CF 2) 4} F or - _{(CF 2) 6} It is further an F Preferably, − (CF ₂ ) ₆ F is most preferable. In particular, a monomer having a linear polyfluoroalkyl group is suitable because it can be obtained at a relatively low cost.

Specific examples of the fluoromonomer include CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ (CF ₂ ) ₆ 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 ) ₄ F, CH ₂ = CClC (O) OCH ₂ CH ₂ (CF ₂ ) ₄ F, CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ CH ₂ CH ₂ OCF (CF ₃ ) C (= C (CF ₃ ) ₂ ) (CF (CF ₃ ) ₂ ), CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ CH ₂ CH ₂ OC (CF ₃ ) C (= C (CF (CF ₃ ) ₂ ) ₂ ) can be mentioned.

The (meth) acrylate having a hydroxyalkyl group or a hydroxycycloalkyl group is a general term for compounds having a (meth) acryloyloxy group and a hydroxyalkyl group or a hydroxycycloalkyl group. The hydroxyalkyl group may be linear or branched. Further, the cyclic structure of the hydroxycycloalkyl group may be a monocyclic structure or a bridged ring structure.

As the (meth) acrylate, a monomer (monomer HV) represented by the following formula (HV) is preferable. Such a monomer has a small molecular weight as compared with the content of the hydroxyl group, and if the fluorine content and the hydroxyl value of the polymer dispersant V are adjusted within a predetermined range, the dispersibility of the dispersion liquid and the wettability of the layer (coating film) can be adjusted. , It is easy to improve physical properties such as adhesiveness.
Equation (HV) CH ₂ = CX ^HV C (O) O-Q ^HV- OH
The symbols in the formula have the following meanings.
X ^HV is a hydrogen atom or a methyl group.
Q ^HV is an alkylene group or a cycloalkylene group, preferably an alkylene group having 2 to 12 carbon atoms or a cycloalkylene group having 4 to 12 carbon atoms, and particularly preferably an alkylene group having 2 to 6 carbon atoms. preferable.
Specific examples of the (meth) acrylate include CH ₂ = CHC (O) OCH ₂ CH ₂ OH, CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ OH, CH ₂ = CHC (O) OCH. ₂ CH ₂ CH ₂ CH ₂ OH, CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ CH ₂ CH ₂ OH, CH ₂ = CHC (O) OCH _2- Cy-CH ₂ OH, CH ₂ = C (CH ₃ ) C (O) OCH _2- Cy-CH ₂ OH, CH ₂ = CHC (O) O-Cy-OH, CH ₂ = C (CH ₃ ) C (O) O-Cy-OH, CH ₂ = CHC (O) OCH ₂ CH ₂ CH ₂ CH ₂ OH, CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ CH ₂ CH ₂ OH. In the formula, -Cy- represents a 1,4-cyclohexylene group.

The fluorine content of the polymer dispersant V is 15 to 45% by mass, preferably 20 to 40% by mass. Since the lower limit of the fluorine content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the fluorine content is in the above range, the affinity of the dispersant for each component of the dispersant is balanced, and in addition to the dispersibility of the dispersion liquid, the formability of the layer (coating film) is likely to be improved. For example, the layer (coating film) is characterized by high wettability and excellent adhesiveness. The fluorine content of the polymer dispersion V can be calculated from the type of monomer used for its synthesis and the amount charged thereof.
The hydroxyl value of the polymer dispersant V is 100 to 330 mgKOH / g, preferably 150 to 300 mgKOH / g. Since the lower limit of the hydroxyl value is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the hydroxyl value is within the above range, the affinity of the polymer dispersant V for each of the TFE polymer and the solvent is balanced, and in addition to the dispersibility of the dispersion liquid, the layer (coating film) formability is improved. Easy to do. Specifically, the F layer tends to express the physical characteristics of the TFE polymer itself as it is. The hydroxyl value of the polymer dispersant V can be calculated from the type of monomer used for its synthesis and the amount charged thereof.
The amount of the unit FV with respect to all the units contained in the polymer dispersant V is preferably 5 to 40 mol%, particularly preferably 10 to 25 mol%.
The amount of the unit HV with respect to all the units contained in the polymer dispersant V is preferably 60 to 95 mol%, particularly preferably 75 to 90 mol%.
The polymer dispersant V may consist of only the unit FV and the unit HV, and may further contain additional units other than the unit FV and the unit HV as long as the effects of the present invention are not impaired. The monomer forming the additional unit is not particularly limited.
The total amount of the unit FV and the unit HV with respect to all the units contained in the polymer dispersant V is preferably 90 to 100 mol%, particularly preferably 99 to 100 mol%. That is, the polymer dispersant V is preferably a polymer consisting substantially only of the unit FV and the unit HV.
The polymer dispersant V is preferably nonionic.
The weight average molecular weight of the polymer dispersant V is preferably 2000 to 80,000, particularly preferably 6000 to 20000.

Specific examples of the polymer dispersant V include a unit based on the monomer (monomer FV1) represented by the following formula (FV1) and a unit based on the monomer (monomer FV1) represented by the following formula (HV1), and fluorine. Examples thereof include polymers having a content of 20 to 40% by mass and a hydroxyl value of 150 to 300 mgKOH / g.
Equation (FV1) CH ₂ = CX ^FV1 C (O) O-CH ₂ CH _2- R ^FV1
Equation (HV1) CH ₂ = CX ^HV1 C (O) -Q ^HV1- OH
X ^FV1 is a hydrogen atom or a methyl group.
R ^{FV 1} is − (CF ₂ ) ₄ F or − (CF ₂ ) ₆ F.
X ^HV1 is a hydrogen atom or a methyl group.
Q ^HV1 is an alkylene group having 2 to 6 carbon atoms.
The amount of the unit FV1 with respect to all the units contained in the polymer dispersant V of the above specific example is 5 to 40 mol%, preferably 10 to 25 mol%.
The amount of the unit HV1 with respect to all the units contained in the polymer dispersant V of the above specific example is 60 to 95 mol%, preferably 75 to 90 mol%.
The total amount of the unit FV1 and the unit HV1 with respect to all the units contained in the polymer dispersant V of the above specific example is 90 to 100 mol%, preferably 100 mol%.

The TFE-based polymer in the present invention is a polymer containing a unit (TFE unit) based on tetrafluoroethylene (TFE). The TFE-based polymer may be a homopolymer of TFE, or may be a copolymer of TFE and another monomer copolymerizable with TFE (hereinafter, also referred to as a comonomer). The TFE-based polymer preferably contains 90 to 100 mol% of TFE units with respect to all the units contained in the polymer.
Examples of TFE-based polymers include polytetrafluoroethylene (PTFE), TFE and ethylene copolymer (ETFE), TFE and propylene copolymer, TFE and perfluoro (alkyl vinyl ether) (PAVE) copolymer (PFA), and TFE and hexafluoropropylene. Examples include a copolymer of (HFP) (FEP), a copolymer of TFE and chlorotrifluoroethylene.
Melting temperature of the TFE-based polymer is preferably ^{1 × 10 2 ~1 × 10 6} Pa · s at 380 ° C., preferably ^{1 × 10 2 ~1 × 10 6} Pa · s at 340 ° C., 1 × 10 at 300 ° C. ² to 1 × 10 ⁶ Pa · s is preferable.

Preferable embodiments of TFE-based polymers include low molecular weight PTFE. The low molecular weight PTFE may be PTFE in which only the shell portion satisfies the above-mentioned melt viscosity in the core-shell structure composed of the core portion and the shell portion.
As low molecular weight PTFE, PTFE 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). (See No. 2018/026017, etc.), and PTFE (Japanese Patent Laid-Open No. 2009-1745, International) obtained by reducing the molecular weight by using a chain transfer agent when polymerizing TFE to produce PTFE. (See Publication No. 2010/114033, etc.).
The low molecular weight PTFE may be a polymer obtained by polymerizing TFE alone or a copolymer obtained by copolymerizing TFE and a comonomer (International Publication No. 2009/20187). See issue etc.). The TFE unit is preferably 99.5 mol% or more, more preferably 99.8 mol% or more, still more preferably 99.9 mol% or more, based on all the units contained in the polymer. When the TFE unit is in the above range, the PTFE physical properties can be maintained. Examples of the comonomer include fluoromonomers described later, and HFP, PAVE or FAE are preferable.

Examples of the PTFE having a core-shell structure include PTFE described in JP-A-2005-527652, International Publication No. 2016/170918, and the like. In order to keep the melt viscosity of the shell portion within the above range, a method of reducing the molecular weight of the shell portion by using a chain transfer agent (see Japanese Patent Application Laid-Open No. 2015-232082, etc.), and TFE during the production of the shell portion. And the method of copolymerizing the comonomer with the above-mentioned comonomer (see Japanese Patent Application Laid-Open No. 09-087334) and the like.
In the latter case, the amount of comonomer used is preferably 0.001 to 0.05 mol% with respect to TFE. Further, not only the shell portion but also the core portion may be produced by copolymerization. In this case as well, the amount of comonomer used is preferably 0.001 to 0.05 mol% with respect to TFE.
The standard specific gravity of low molecular weight PTFE is preferably 2.14 to 2.22, more preferably 2.16 to 2.20. The standard density can be measured according to ASTM D4895-04.

A preferred embodiment of the TFE-based polymer is a copolymer of TFE and a comonomer, which is a fluoropolymer containing more than 0.5 mol% of units based on the comonomer with respect to all the units contained in the copolymer (hereinafter, "polymer F"). Also referred to as.). The melting point of the polymer F is preferably 240 ° C. or higher and lower than 330 ° C., more preferably 260 to 320 ° C., and particularly preferably 295 to 310 ° C. In this case, the heat resistance of the polymer and the melt moldability are balanced. Examples of the polymer F include ETFE, FEP, PFA and the like. As the polymer F, PFA and FEP are more preferable, and PFA is particularly preferable, from the viewpoint of electrical characteristics (relative permittivity, dielectric loss tangent) and heat resistance.

The TFE-based polymer has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group (hereinafter, "functional group") because of its excellent adhesiveness. A TFE-based polymer having ()) is preferable. The functional group may be imparted by plasma treatment or the like.
The functional group may be contained in a unit in the TFE-based polymer, or may be contained in the terminal group of the main chain of the polymer. Examples of the latter polymer include polymers having a functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like.
As the polymer F, a polymer containing a unit having a functional group and a TFE unit is preferable. Further, the polymer F in this case preferably contains other units (PAVE unit, HFP unit, etc., which will be described later).

As the functional group, a carbonyl group-containing group is preferable from the viewpoint of adhesiveness between the layer (coating film) and the metal foil. Examples of the carbonyl group-containing group include a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride residue (-C (O) O (O) C-), a fatty acid residue and the like, and include a carboxy group and a fatty acid residue. Acid anhydride residues are preferred.
As the unit having a functional group, a unit based on a monomer having a functional group is preferable, a unit based on a monomer having a carbonyl group-containing group, a unit based on a monomer having a hydroxy group, a unit based on a monomer having an epoxy group and an isocyanate group. A unit based on a monomer having a carbonyl group is more preferable, and a unit based on a monomer having a carbonyl group-containing group is particularly preferable.
As the monomer having a carbonyl group-containing group, a cyclic monomer having an acid anhydride residue, a monomer having a carboxy group, a vinyl ester and a (meth) acrylate are preferable, and a cyclic monomer having an acid anhydride residue is particularly preferable.
As the cyclic monomer, itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (also known as hymic anhydride, hereinafter also referred to as “NAH”) and maleic anhydride are preferable.

As the unit having a functional group and other units other than the TFE unit, HFP unit, PAVE unit and FAE unit are preferable.
As PAVE, CF ₂ = CFOCF ₃ , 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, and the like, PPVE is preferred.
As FAE, CH ₂ = CH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F, CH ₂ = CH (CF ₂ ) ₄ F, CH ₂ = CF (CF ₂ ) ₃ H, CH ₂ = CF (CF ₂ ) ₄ H and the like, and CH ₂ = CH (CF ₂ ) ₄ F and CH ₂ = CH (CF ₂ ) ₂ F are preferable.
As the polymer F, a polymer containing a unit having a functional group, a TFE unit, a PAVE unit or an HFP unit is preferable. Specific examples of such polymer F include the polymer (X) described in International Publication No. 2018/16644.

The ratio of TFE units in the polymer F is preferably 90 to 99 mol% of all the units constituting the polymer F.
The ratio of PAVE units or HFP units in the polymer F is preferably 0.5 to 9.97 mol% of all the units constituting the polymer F.
The ratio of the units having a functional group in the polymer F is preferably 0.01 to 3 mol% of all the units constituting the polymer F.

The F powder in the present invention contains a TFE-based polymer. The F powder may contain components other than the TFE-based polymer as long as the effects of the present invention are not impaired, but it is preferable that the F-powder contains the TFE-based polymer as the main component. The content of the TFE polymer in the F powder is preferably 80% by mass or more, and particularly preferably 100% by mass. Other resins that can be contained in the F powder include aromatic polyesters, polyamideimides, thermoplastic polyimides, polyphenylene ethers, and polyphenylene oxides.

The D50 of the F powder is preferably 0.05 to 6 μm, preferably 0.1 to 3 μm, and particularly preferably 0.2 to 3.0 μm. In this range, the fluidity and dispersibility of the F powder become good, and the electrical characteristics (low dielectric constant, etc.) and heat resistance of the TFE polymer are most likely to be exhibited.
The D90 of the F powder is preferably 8 μm or less, more preferably 6 μm or less, and particularly preferably 5 μm or less. The D90 of the F powder is preferably 0.3 μm or more, and particularly preferably 0.8 μm or more. In this range, the fluidity and dispersibility of the F powder become good, and the electrical characteristics (low dielectric constant, etc.) and heat resistance of the layer (coating film) are most likely to be exhibited.
The sparse filling bulk density of the F powder is preferably 0.05 g / mL or more, and particularly preferably 0.08 to 0.5 g / mL.
The densely packed bulk density of the F powder is preferably 0.05 g / mL or more, and particularly preferably 0.1 to 0.8 g / mL.
The method for producing the F powder is not particularly limited, and the methods described in [0065] to [0069] of International Publication No. 2016/017801 can be adopted. As the F powder, if the desired powder is commercially available, it may be used.

The solvent in the present invention is a dispersion medium, which is a liquid inert solvent (compound) at 25 ° C. that does not react with F powder, has a boiling point lower than that of the components other than the solvent contained in the powder dispersion, and is heated. It is preferable that the solvent can be volatilized and removed by such means.
The solvent may be a polar solvent or a non-polar solvent. The polar solvent may be protic or aprotic. Further, the polar solvent may be an aqueous solvent or a non-aqueous solvent.
As the solvent, a non-aqueous polar solvent is preferable.
As the solvent, one type may be used alone, or two or more types may be used in combination.
The solvent is a solvent that does not volatilize instantaneously, and is preferably a solvent having a boiling point of 80 to 275 ° C., particularly preferably a solvent having a boiling point of 125 to 250 ° C. In this range, when the dispersion liquid applied to the surface of the metal foil is kept at a predetermined temperature, the volatilization of the solvent and the partial decomposition and flow of the dispersant proceed effectively, and the dispersant segregates the surface. Cheap

Specific examples of the solvent include water, methanol, ethanol, 1-propanol (boiling point: 97 ° C.), 2-propanol (boiling point: 82 ° C.), 1-butanol (boiling point: 117 ° C.), 1-methoxy-2-propanol. (Boiling point: 119 ° C.), N, N-dimethylformamide, N, N-dimethylacetamide, methyl ethyl ketone, N-methyl-2-pyrrolidone (boiling point: 202 ° C.), γ-butyrolactone (boiling point: 204 ° C.), cyclohexanone (boiling point) 156 ° C), cyclopentanone (boiling point: 131 ° C), dimethyl sulfoxide, diethyl ether, dioxane, ethyl lactate, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, ethylene glycol monoisopropyl ether, Examples thereof include cellosolve (methyl cellosolve, ethyl cellosolve, etc.).
As the solvent, an organic solvent is preferable from the viewpoint that the liquid physical properties (viscosity, thixotropy, etc.) of the dispersion liquid can be more easily adjusted, and from the viewpoint of further improving the dispersion stability of the dispersion liquid, amide, alcohol, sulfoxide, etc. Esters, ketones, aromatic hydrocarbons or glycol ethers are preferred, esters, ketones and amides are more preferred, methyl ethyl ketone, N-methyl-2-pyrrolidone, γ-butyrolactone, cyclohexanone and cyclopentanone are particularly preferred, methyl ethyl ketone, cyclohexanone and N-Methyl-2-pyrrolidone is more preferred.
As the solvent of the dispersion liquid IV of the present invention, an organic solvent is preferable, amide, alcohol, sulfoxide, ester, ketone and glycol ether are more preferable, ketone and amide are particularly preferable, and methyl ethyl ketone, cyclohexanone and N-methyl-2 are particularly preferable. -Pyrrolidone is more preferred.

The proportion of the TFE-based polymer in the dispersion liquid of the present invention is preferably 5 to 60% by mass, more preferably 30 to 50% by mass, and particularly preferably 35 to 45% by mass. In this range, it is easy to form a layer (coating film) having excellent electrical characteristics and mechanical strength.
The proportion of the dispersant in the dispersion liquid of the present invention is preferably 0.1 to 30% by mass, more preferably 1 to 30% by mass, particularly preferably 3 to 15% by mass, and even more preferably 5 to 10 parts by mass. In this range, the physical properties (uniformity, hydrophilicity, wettability, adhesiveness, etc.) of the layer (coating film) are more likely to be improved.
The proportion of the solvent in the dispersion liquid of the present invention is preferably 15 to 65% by mass, more preferably 25 to 60% by mass, and particularly preferably 25 to 50 parts by mass. In this range, the coatability of the dispersion liquid is excellent, and the appearance of the layer (coating film) is unlikely to deteriorate.

The dispersion liquid of the present invention may contain materials other than the F powder, the dispersant and the solvent as long as the effects of the present invention are not impaired. Other materials may or may not be dissolved in the dispersion.
The other material may be a non-curable resin or a curable resin.
Examples of the non-curable resin include thermosetting resins and non-meltable resins. Examples of the heat-meltable resin include thermoplastic polyimides and the like. Examples of the non-meltable resin include a cured product of a curable resin.
Examples of the curable resin include polymers or oligomers having a reactive group. Examples of the reactive group include a carbonyl group-containing group, a hydroxy group, an amino group and an epoxy group.
Examples of the curable resin include epoxy resin, thermosetting polyimide, polyamic acid which is a polyimide precursor, thermosetting acrylic resin, phenol resin, thermosetting polyester resin, thermosetting polyolefin resin, modified polyphenylene ether resin, and polyfunctionality. Examples thereof include cyanate ester resin, polyfunctional maleimide-cyanic acid ester resin, polyfunctional maleimide resin, vinyl ester resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, and melamine-urea cocondensation resin.

Specific examples of the epoxy resin include naphthalene type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, and aliphatic chain epoxy resin. Examples thereof include cresol novolac type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, aralkyl type epoxy resin, and biphenol type epoxy resin.
Examples of the bismaleimide resin include the resin composition (BT resin) described in JP-A-7-70315 and the resin described in International Publication No. 2013/0083667.
Examples of the diamine and polyvalent carboxylic acid dianhydride forming the polyamic acid include [0020] of Japanese Patent No. 5766125, [0019] of Japanese Patent No. 5766125, and [0055] and [0055] of Japanese Patent Application Laid-Open No. 2012-145676. 0057] and the like.

Examples of the thermosetting resin include thermoplastic resins such as thermoplastic polyimide and thermosetting cured products of curable resins.
Examples of the thermoplastic resin include polyester resin, polyolefin resin, styrene resin, polycarbonate, thermoplastic polyimide, polyarylate, polysulfone, polyarylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylensulfide, polyaryletherketone, and the like. Examples thereof include polyamideimide, liquid crystal polyester, and polyphenylene ether, and thermoplastic polyimide, liquid crystal polyester, and polyphenylene ether are preferable.
Other materials include thixo-imparting agents, defoaming agents, inorganic fillers, reactive alkoxysilanes, dehydrating agents, plasticizers, weather-resistant agents, antioxidants, heat stabilizers, lubricants, antistatic agents, and whitening agents. Agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, flame retardants and the like can also be mentioned.

The viscosity of the dispersion liquid of the present invention is preferably 50 to 10000 mPa · s, more preferably 70 to 5000 mPa · s, further preferably 100 to 3000 mPa · s, and particularly preferably 150 to 1000 mPa · s. In this case, the dispersion stability and coatability of the dispersion liquid are excellent, and a layer (coating film) can be easily formed.
Further, the viscosity of the dispersion liquid of the present invention may be preferably 100 to 10000 mPa · s. In that case, 130 to 7000 mPa · s is more preferable, 150 to 5000 mPa · s is further preferable, and 170 to 3000 mPa · s is particularly preferable. In this case, the stability and coatability of the dispersion are further excellent, and a more uniform layer (coating film) can be easily formed.
Further, the viscosity of the dispersion liquid of the present invention may be preferably 50 to 3000 mPa · s. In that case, 70 to 1500 mPa · s is more preferable, 80 to 1000 mPa · s is further preferable, and 100 to 500 mPa · s is particularly preferable. In this case, the coatability of the dispersion liquid is excellent when a varnish is formed with another resin material.

The thixotropy of the dispersion liquid of the present invention is preferably 1.0 to 2.2. In this case, the dispersibility of the dispersion liquid and the coatability are excellent, and a layer (coating film) can be easily formed.
The thixotropy of the dispersion liquid of the present invention is preferably 1.4 to 2.2, more preferably 1.45 to 2.10, and even more preferably 1.5 to 2.0. In this case, the dispersibility of the dispersion liquid and the coatability are excellent, and a more uniform layer (coating film) can be formed.
Further, the thixotropy ratio of the present invention may be preferably 1.0 to 1.5. In that case, 1.05 to 1.45 is more preferable, 1.1 to 1.4 is further preferable, and 1.1 to 1.3 is particularly preferable. In this case, the mixing property of different resin materials with the varnish is further excellent.
The viscosity of the dispersion liquid II of the present invention can be less than 100 mPa · s, preferably 1 to 75 mPa · s, and more preferably 10 to 50 mPa · s. Since the dispersion liquid having such a viscosity is not too viscous, it is easy to handle and has excellent compatibility with varnishes of different resin materials. Further, since the viscosity of the dispersion liquid can be adjusted in an arbitrary range by using a viscosity modifier or the like, the range of options for the method of supplying the dispersion liquid to the surface of the base material when forming the layer (coating film) is wide. spread.
The thixotropy of the dispersion liquid II of the present invention is preferably 1.0 to 2.2, more preferably 1.4 to 2.2, and even more preferably 1.5 to 2.0.

The dispersion liquid of the present invention can form a resin layer containing a TFE-based polymer (hereinafter, also referred to as “F layer”). It is preferable to form an F layer on the surface of the base material from the dispersion liquid of the present invention.
When forming the F layer, it is preferable that the dispersion liquid of the present invention is applied to the surface of the base material to form a wet film, and then the wet film is heated to distill off the solvent to form the F layer.

As the base material, a metal foil is preferable.
Examples of the material of the metal foil include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, titanium alloy and the like.
Examples of the metal foil include rolled copper foil and electrolytic copper foil. A rust preventive layer (oxide film such as chromate), a heat resistant layer, or the like may be formed on the surface of the metal foil.
The ten-point average roughness of the surface of the metal foil is preferably 0.2 to 1.5 μm. In this case, the adhesiveness with the F layer tends to be good.
The thickness of the metal foil is preferably 1 to 40 μm, particularly preferably 2 to 20 μm.
The surface of the metal foil may be treated with a silane coupling agent, the entire surface of the metal foil may be treated with a silane coupling agent, and a part of the surface of the metal foil may be treated with a silane coupling agent. It may have been done.

The present invention provides a method for producing a resin-attached metal foil having an F layer by applying the dispersion liquid of the present invention to the surface of the metal foil and heating the metal foil.
The metal leaf with resin in the present invention has an F layer on at least one surface of the metal leaf. That is, the metal foil with resin may have an F layer on only one side of the metal foil, or may have an F layer on both sides of the metal foil.

The warpage rate of the metal leaf with resin is preferably 25% or less, and particularly preferably 7% or less. In this case, the handleability when processing the metal foil with resin into a printed circuit board and the transmission characteristics of the obtained printed circuit board are excellent.
The warpage rate of the metal leaf with resin is measured by cutting out a 180 mm square test piece from the metal leaf with resin and measuring the test piece according to JIS C 6471: 1995 (corresponding international standard IEC 249-1: 1982). It is a value measured according to.
The dimensional change rate of the metal foil with resin is preferably ± 1% or less, and particularly preferably ± 0.2% or less. In this case, it is easy to process the metal foil with resin into a printed circuit board and further multi-layer it.
For the dimensional change rate of the metal leaf with resin, cut out the metal leaf with resin at a size of 150 mm square, make holes at the four corners using a 0.3 mm drill, measure the position of the holes with a coordinate measuring device, and attach the resin. It can be calculated from the difference in the positions of the holes before and after etching when the metal foil of the metal foil is removed by etching, dried at 130 ° C. for 30 minutes, and the positions of the holes formed at the four corners are measured by a three-dimensional measuring device.
The water contact angle on the surface of the F layer is preferably 70 to 100 °, particularly preferably 70 to 90 °. In this case, the adhesiveness between the F layer and other base materials is more excellent. When the above range is not more than the lower limit, the electrical characteristics (low dielectric loss and low dielectric constant) when the metal foil with resin is processed into a printed circuit board are more excellent.

The thickness of the F layer is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 5 μm or more. The thickness of the F layer is preferably 50 μm or less, preferably 15 μm or less, and particularly preferably less than 10 μm. In this range, it is easy to balance the electrical characteristics when the resin-attached metal foil is processed into a printed circuit board and the suppression of warpage of the resin-attached metal foil. When the resin-attached metal foil has F layers on both sides of the metal foil, the composition and thickness of each F layer are preferably the same from the viewpoint of suppressing warpage of the resin-attached metal foil.
The relative permittivity of the F layer is preferably 2.0 to 3.5, more preferably 2.0 to 3.0. In this case, a metal foil with a resin can be suitably used for a printed circuit board or the like that requires a low dielectric constant.
Ra on the surface of the F layer is less than the thickness of the F layer, preferably 2.2 to 8 μm. In this range, it is easy to balance the adhesiveness and processability of the resin-attached metal leaf.

The coating method may be any method as long as a stable wet film composed of a powder dispersion is formed on the surface of the metal foil after coating, and is a spray method, a roll coating method, a spin coating method, a gravure coating method, or a micro gravure coating method. , Gravure offset method, knife coating method, kiss coating method, bar coating method, die coating method, fountain Mayer bar method, slot die coating method and the like.

When heating the metal foil after applying the powder dispersion, it is preferable to keep the metal foil in a low temperature region and distill off the solvent. The temperature in the low temperature region is preferably 80 ° C. or higher and lower than 180 ° C., more preferably 100 to 175 ° C., and particularly preferably 120 ° C. to 170 ° C. As described above, since the dispersant contained in the dispersion liquid of the present invention can form a hydrophilic component even in this low temperature region, a resin having an F layer having excellent adhesiveness without impairing the physical properties of the metal foil and the F layer. Attached metal foil can be formed. The temperature at which it is held in the low temperature region indicates the temperature of the atmosphere.
The holding of the low temperature region may be carried out in one step, or may be carried out in two or more steps at different temperatures.
Examples of the method of holding in the low temperature region include a method using an oven, a method using a ventilation drying furnace, a method of irradiating heat rays such as infrared rays, and the like.
The atmosphere for holding the low temperature region may be any of normal pressure and reduced pressure. The atmosphere in the holding is any of an oxidizing gas (oxygen gas, etc.) atmosphere, a reducing gas (hydrogen gas, etc.) atmosphere, and an inert gas (helium gas, neon gas, argon gas, nitrogen gas, etc.) atmosphere. It may be.
The atmosphere for holding is preferably an atmosphere containing oxygen gas from the viewpoint of promoting oxidative decomposition of the dispersant and further improving the adhesiveness of the F layer.
The oxygen gas concentration (volume basis) in an atmosphere containing oxygen gas ^{is preferably 1 × 10 2 to} 3 × 10 ⁵ ppm, and particularly preferably ^{0.5 × 10 3} to 1 × 10 ^{4 ppm.} In this range, it is easy to balance the oxidative decomposition of the dispersant and the suppression of the oxidation of the metal foil.
The holding time in the low temperature region is preferably 0.1 to 10 minutes, particularly preferably 0.5 to 5 minutes.

In the method for producing a metal foil with a resin of the present invention, a TFE polymer is further fired in a temperature region above the holding temperature in a low temperature region (hereinafter, also referred to as a “firing region”), and F It is preferable to form a layer. The temperature of the firing region indicates the temperature of the atmosphere.
In the present invention, it is considered that the fusion of the TFE polymer proceeds in a state where the F powder is densely packed and the hydrophilic component derived from the dispersant is effectively surface segregated, and as a result, the F with excellent adhesiveness is obtained. Layers are formed. If the powder dispersion contains a thermosetting resin, an F layer composed of a mixture of the TFE polymer and the soluble resin is formed, and if the powder dispersion contains the thermosetting resin, the TFE polymer and the thermosetting resin are formed. An F layer composed of the cured product of is formed.

Examples of the firing method include a method using an oven, a method using a ventilation drying furnace, a method of irradiating heat rays such as infrared rays, and the like. In order to improve the smoothness of the surface of the F layer, pressure may be applied with a heating plate, a heating roll, or the like. As a heating method, a method of irradiating far infrared rays is preferable because it can be fired in a short time and the far infrared ray furnace is relatively compact. As a heating method, infrared heating and hot air heating may be combined.
The effective wavelength band of far infrared rays is preferably 2 to 20 μm, more preferably 3 to 7 μm, from the viewpoint of promoting homogeneous fusion of the TFE polymer.
The atmosphere in firing may be either under normal pressure or under reduced pressure. The atmosphere is any of an oxidizing gas (oxygen gas, etc.) atmosphere, a reducing gas (hydrogen gas, etc.) atmosphere, and an inert gas (helium gas, neon gas, argon gas, nitrogen gas, etc.) atmosphere. It may be preferable to use a reducing gas atmosphere or an inert gas atmosphere from the viewpoint of suppressing oxidative deterioration of each of the metal foil and the formed F layer.
The atmosphere in firing is preferably a gas atmosphere composed of an inert gas and having a low oxygen gas concentration, and preferably a gas atmosphere composed of nitrogen gas and having an oxygen gas concentration (volume basis) of less than 500 ppm. The oxygen gas concentration (volume basis) is particularly preferably 300 ppm or less. The oxygen gas concentration (volume basis) is usually 1 ppm or more. In this range, further oxidative decomposition of the dispersant is suppressed, and the hydrophilicity of the F layer is likely to be improved.
The temperature of the firing region is preferably 250 ° C. to 400 ° C. or lower, and particularly preferably 300 to 380 ° C.
The time for holding in the firing region is preferably 30 seconds to 5 minutes, particularly preferably 1 to 2 minutes.
When the F layer in the resin-attached metal foil is a conventional insulating material (a cured product of a thermosetting resin such as polyimide), long-term heating is required to cure the thermosetting resin. On the other hand, in the present invention, the F layer can be formed by heating for a short time by fusing the TFE polymer. Further, when the powder dispersion liquid contains a thermosetting resin, the firing temperature can be lowered. As described above, the manufacturing method of the present invention is a method in which the heat load on the metal leaf when forming the F layer on the resin-attached metal leaf is small, and the damage to the metal leaf is small.

In the metal leaf with resin in the present invention, the surface of the F layer may be surface-treated in order to control the linear expansion of the F layer and further improve the adhesiveness of the F layer.
Surface treatment methods for the surface of the F layer include annealing treatment, corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, UV ozone treatment, excimer treatment, chemical etching, silane coupling treatment, and fine roughening treatment. Can be mentioned.
The temperature in the annealing treatment is preferably 80 to 190 ° C, particularly preferably 120 to 180 ° C.
The pressure in the annealing treatment is preferably 0.001 to 0.030 MPa, particularly preferably 0.005 to 0.015 MPa.
The annealing treatment time is preferably 10 to 300 minutes, particularly preferably 30 to 120 minutes.
Examples of the plasma irradiation device in plasma processing include a high frequency induction method, a capacitively coupled electrode method, a corona discharge electrode-plasma jet method, a parallel plate type, a remote plasma type, an atmospheric pressure plasma type, and an ICP type high density plasma type. ..
Examples of the gas used for the plasma treatment include oxygen gas, nitrogen gas, rare gas (argon and the like), hydrogen gas, ammonia gas and the like, and rare gas or nitrogen gas is preferable. Specific examples of the gas used for the plasma treatment include argon gas, a mixed gas of hydrogen gas and nitrogen gas, and a mixed gas of hydrogen gas, nitrogen gas and argon gas.
As the atmosphere in the plasma treatment, an atmosphere having a volume fraction of rare gas or nitrogen gas of 70% by volume or more is preferable, and an atmosphere of 100% by volume is particularly preferable. In this range, Ra on the surface of the F layer is adjusted to 2.0 μm or less, and fine irregularities are easily formed on the surface of the F layer.

Since the surface of the F layer of the metal leaf with resin obtained in the present invention is highly hydrophilic and has excellent adhesiveness, it can be easily and firmly laminated with another substrate.
Examples of other substrates include a heat-resistant resin film, a prepreg which is a precursor of a fiber-reinforced resin plate, a laminate having a heat-resistant resin film layer, and a laminate having a prepreg layer.
The heat-resistant resin means a polymer compound having a melting temperature of 280 ° C. or higher, or a polymer compound having a maximum continuous use temperature of 121 ° C. or higher as defined by JIS C 4003: 2010 (IEC 60085: 2007). ..
The prepreg is a sheet-like substrate in which a base material (toe, woven fabric, etc.) of reinforcing fibers (glass fibers, carbon fibers, etc.) is impregnated with a thermosetting resin or a thermoplastic resin.
The heat-resistant resin film is a film containing one or more of heat-resistant resins, and may be a single-layer film or a multilayer film.
Examples of the heat-resistant resin include polyimide, polyarylate, polysulfone, polyarylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, and liquid crystal polyester.

Examples of the method of laminating another base material on the surface of the F layer of the metal foil with resin in the present invention include a method of heat-pressing the metal foil with resin and another substrate.
When the other substrate is a prepreg, the press temperature is preferably equal to or lower than the melting point of the TFE polymer, more preferably 120 to 300 ° C, and particularly preferably 160 to 220 ° C. In this range, the F layer and the prepreg can be firmly adhered while suppressing the thermal deterioration of the prepreg.
When the substrate is a heat-resistant resin film, the press temperature is preferably 310 to 400 ° C. In this range, the F layer and the heat-resistant resin film can be firmly adhered to each other while suppressing thermal deterioration of the heat-resistant resin film.
The hot press is preferably performed in a reduced pressure atmosphere, and particularly preferably at a vacuum degree of 20 kPa or less. In this range, air bubbles can be suppressed from being mixed into the interfaces of the F layer, the substrate, and the metal foil in the laminated body, and deterioration due to oxidation can be suppressed.
Further, during hot pressing, it is preferable to raise the temperature after reaching the degree of vacuum. If the temperature is raised before reaching the degree of vacuum, the F layer is crimped in a softened state, that is, in a state of having a certain degree of fluidity and adhesion, which causes air bubbles.
The pressure in the hot press is preferably 0.2 MPa or more. The upper limit of the pressure is preferably 10 MPa or less. In this range, the F layer and the substrate can be firmly adhered to each other while suppressing damage to the substrate.

The metal leaf with resin and the laminate thereof in the present invention can be used for manufacturing a printed circuit board as a flexible copper-clad laminate or a rigid copper-clad laminate.
For example, a method of processing a metal foil of a metal leaf with resin in the present invention into a conductor circuit (pattern circuit) having a predetermined pattern by etching or the like, or an electrolytic plating method (semi-additive method (SAP method)) of metal leaf with resin in the present invention. ), Modified semi-additive method (MSAP method), etc.), the printed substrate can be manufactured from the metal leaf with resin in the present invention by using the method of processing into a pattern circuit.
In the production of the printed circuit board, after forming the pattern circuit, an interlayer insulating film may be formed on the pattern circuit, and a conductor circuit may be further formed on the interlayer insulating film. The interlayer insulating film can be formed, for example, by the powder dispersion liquid in the present invention.
In the production of the printed circuit board, a solder resist may be laminated on the pattern circuit. The solder resist can be formed, for example, by the powder dispersion liquid in the present invention.
In the production of the printed circuit board, the coverlay film may be laminated on the pattern circuit.

Although the dispersion liquid of the present invention has been described above, the present invention is not limited to the configuration of the above-described embodiment.
For example, the dispersion liquid of the present invention may have any other configuration added to the above-described embodiment, or may be replaced with any configuration exhibiting the same function.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
The materials used are shown below.
[F powder]
Powder 1: Copolymer (melting point: 300 ° C.) powder (D50: 1.7 μm, D90) containing 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE unit, NAH unit, and PPVE unit in this order. : 3.8 μm, sparsely packed bulk density: 0.269 g / mL, densely packed bulk density: 0.315 g / mL).
Powder 2: Powder of substantially TFE homopolymer (melt viscosity at 380 ° C.: 1.4 × 10 ⁴ ) containing 99.5 mol% or more of TFE units (D50: 0.3 μm, D90: 0.6 μm,) ..
The physical characteristics of the polymer and the powder were measured according to the following methods.

<Melting viscosity of polymer>
In accordance with ASTM D 1238, using a flow tester and a 2Φ-8L die, a polymer sample (2 g) that had been preheated at the measurement temperature for 5 minutes was held at the measurement temperature under a load of 0.7 MPa. It was measured.
<Polymer melting temperature>
Using a differential scanning calorimeter (DSC-7020 manufactured by Seiko Instruments Inc.), the temperature of the TFE polymer was raised at a rate of 10 ° C./min for measurement.
<Powder D50 and D90>
Using a laser diffraction / scattering type particle size distribution measuring device (LA-920 measuring device manufactured by HORIBA, Ltd.), the powder was dispersed in water for measurement.

[Dispersant]
Dispersant 11: Copolymer of monomer F ¹ , monomer H ¹ , monomer H ² and monomer R ¹ (nonionic property).
Dispersant 12: Copolymer of monomer O ¹ and monomer AO ¹ (nonionic).
Dispersant 13: Copolymer of monomer F ¹ and monomer R ¹ (nonionic).
Dispersant 14: Copolymer of monomer F ¹ and monomer AO ¹ (nonionic).
Dispersant 15: Copolymer of monomer F ¹ , monomer H ¹ and monomer R ¹ (nonionic).
Dispersant 21: a monomer ^{F 2} units, a monomer AO ² units, 45 mol% in this order, 55 mol% containing polymer.
Dispersant 22: A polymer containing ¹ unit of ^{monomer F and 2} units of monomer AO in an order of 38 mol% and 62 mol%.
Dispersant 23: Ring-opening adduct of hexafluoropropylene oxide.

Dispersant 31: ^{A quaternary polymer containing 1} unit of ^{monomer F, 3} units of ^{monomer R, 31} units of monomer AO, and acrylonitrile units in this order of 48 mol%, 16 mol%, 14 mol%, and 22 mol%.
Dispersant 32: ^{A quaternary polymer containing 1} unit of ^{monomer F, 3} units of ^{monomer R, 32} units of monomer AO, and acrylonitrile units in this order of 50 mol%, 15 mol%, 15 mol%, and 20 mol%.
Dispersant 33: A ^{ternary polymer containing 1 unit of monomer F, 3} units of monomer R, ^{and 32} units of monomer AO in this order of 55 mol%, 23 mol%, and 22 mol%.
Dispersant 41: A polymer containing ¹ unit of ^{monomer F and 41} units of monomer AO in an order of 81 mol% and 19 mol% (fluororesin content: 35% by mass, AO content: 34% by mass).
Dispersant 42: A polymer containing ¹ unit of ^{monomer F and 42} units of monomer AO in an order of 68 mol% and 32 mol% (fluorine content: 13% by mass, AO content: 74% by mass).
Dispersant 43: A polymer containing ¹ unit of ^{monomer F and 41} units of monomer AO in an order of 56 mol% and 44 mol% (fluorine content: 19% by mass, AO content: 60% by mass).
Dispersant 44: A polymer containing ¹ unit of ^{monomer F and 41} units of monomer AO in an order of 42 mol% and 58 mol% (fluorine content: 12% by mass, AO content: 70% by mass).
Dispersant 45: A polymer containing ¹ unit of ^{monomer F and 43} units of monomer AO in an order of 76 mol% and 24 mol% (fluorine content: 12% by mass, AO content: 78% by mass).
Dispersant 51: A polymer containing ¹ unit of ^{monomer F and 5} units of monomer AO in an order of 16 mol% and 84 mol% (fluororesin content: 22% by mass, hydroxyl value: 263 mgKOH / g).
Dispersant 52: A polymer containing ¹ unit of ^{monomer F and 5} units of monomer AO in an order of 8 mol% and 92 mol% (fluororesin content: 13% by mass, hydroxyl value: 333 mgKOH / g).
Dispersant 53: A polymer containing ¹ unit of ^{monomer F and 5} units of monomer AO in this order of 55 mol% and 45 mol% (fluororesin content: 46% by mass, hydroxyl value: 85 mgKOH / g).

The monomers used are shown below.
Monomer F ¹ : CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ (CF ₂ ) ₆ F
Monomer F ² : CH ₂ = C (CH ₃ ) C (O) OCH ₂ CF ₂ (OCF ₂ ) _a · (OCF ₂ CF ₂ ) _b OCF ₃ (a and b are natural numbers, respectively, and their sum is 20.)
Monomer O ¹ : CH ₂ = C (CH ₃ ) C (O) OCH (CH ₃ ) O (CF ₂ ) ₆ F
Monomer H ¹ : CH ₂ = C (CH ₃ ) C (O) OCH _2- Ph (in the formula, "Ph" is a phenyl group)
Monomer H ² : CH ₂ = C (CH ₃ ) C (O) OCH <Nb (In the formula, "CH <Nb" indicates an isobornyl group)
Monomer R ¹ : CH ₂ = CHC (O) O (CH ₂ ) ₁₇ CH ₃
Monomer R ³ : CH ₂ = C (CH ₃ ) C (O) O (CH ₂ ) ₁₂ H
Monomer AO ¹ : CH ₂ = CHC (O) (OCH ₂ CH ₂ ) ₁₁ OH
Monomer AO ² : CH ₂ = CHC (O) (OCH ₂ CH ₂ ) ₉ OH
Monomer AO ³¹ : CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₃₅ OCH ₃
Monomer AO ³² : CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₉ OH
Monomer AO ⁴¹ : CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₂₃ OCH ₃
Monomer AO ⁴² : CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₆₆ OCH ₃
Monomer AO ⁴³ : CH ₂ = C (CH ₃ ) C (O) (OCH ₂ CH ₂ ) ₁₂₀ OCH ₃
Monomer AO ⁵ : CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ OH
_{The number of (OCH 2} CH ₂ ) units in each monomer AO is an average value.

[Metal leaf]
Copper foil 1: A low-roughened copper foil (thickness 12 μm, surface ten-point average roughness 0.6 μm).
[solvent]
CHN: Cyclohexanone MEK: Methylethylketone NMP: N-Methyl-2-pyrrolidone

[Example 1] Production / evaluation example of dispersion liquid I 1. Preparation of Dispersion Liquid The dispersion liquid 11 was prepared by mixing 30 parts by mass of powder 1, 6 parts by mass of a solution containing 25% by mass of dispersant 11, and 64 parts by mass of CHN.
In the dispersion liquid 11 that had been allowed to stand for one month, the powder that had settled in the form of a hard cake could be easily loosened, and the dispersion liquid 11 was excellent in redispersibility.
The viscosity (25 ° C.) of the dispersion liquid 11 measured at the rotation speeds of 6 rpm, 30 rpm, and 60 rpm was 773 mPa · s, 197 mPa · s, and 109 mPa · s in this order. The viscosities (25 ° C.) of the dispersion prepared using MEK instead of CHN measured at 6 rpm, 30 rpm, and 60 rpm are 1427 mPa · s, 328 mPa · s, and 176 mPa · s in this order. Met.

Dispersions 12 to 16 were obtained in the same manner as in the preparation example of the dispersion 11 except that the types of the F powder and the dispersant were changed. The results are summarized in Table 1.

2. Manufacture and evaluation of copper foil with resin A dispersion liquid 11 is applied to the surface of the copper foil 1 using a die coater, and the copper foil 1 is ventilated and dried (atmospheric temperature: 170 ° C., atmospheric gas: nitrogen gas with an oxygen gas concentration of 8000 ppm). ), Hold for 1 minute, pass through a far infrared furnace (temperature: 340 ° C., gas: nitrogen gas with an oxygen gas concentration of less than 100 ppm) for 1 minute, and contain the polymer 1 on the surface of the copper foil 1. A copper foil 11 with a resin having an F layer (thickness 5 μm) was produced.
The resin-attached copper foils 11 to 16 were produced in the same manner as the resin-attached copper foil 11 except that the type of the dispersion liquid and the conditions of the ventilation drying furnace (atmospheric temperature, oxygen gas concentration of the atmospheric gas) were changed.
The water contact angle of the F layer, the smoothness of the F layer, and the color tone of the metal foil of each resin-attached copper foil were evaluated according to the following criteria.

<Smoothness of F layer>
The light-irradiated F layer was visually observed from diagonally above and evaluated according to the following criteria.
◯: The pattern is not confirmed.
Δ: No striped pattern is confirmed, but a yuzu skin pattern is confirmed.
X: A striped pattern is confirmed.
<Water contact angle of F layer>
When pure water (about 2 μL) is placed on the surface of the F layer of the metal leaf with resin at 25 ° C, the angle between the water droplets and the surface of the F layer is measured by a contact angle meter (CA-X manufactured by Kyowa Interface Science Co., Ltd.). It was measured using a mold) and evaluated according to the following criteria.
◯: The water contact angle is 90 ° or less.
X: The water contact angle is more than 90 °.
<Metal leaf color tone>
◯: The surface of the metal leaf does not discolor before and after the production of the metal leaf with resin.
X: The surface of the metal foil turns bronze before and after the production of the metal foil with resin.
The results of the above manufacturing and evaluation are summarized in Table 2. In the resin-attached copper foil 11, no yellowing was confirmed in the F layer, and the F layer was also excellent in transparency.

3. 3. Manufacture and evaluation of laminate The surface of the F layer of the resin-attached copper foil 12 was subjected to vacuum plasma treatment. The treatment conditions were output: 4.5 kW, introduction gas: argon gas, introduction gas flow rate: 50 cm ³ / min, pressure: 50 mTorr (6.7 Pa), and treatment time: 2 minutes.
FR-4 (manufactured by Hitachi Kasei Co., Ltd., GEA-67N 0.2t (HAN), reinforcing fiber: glass fiber, matrix resin: epoxy resin, thickness) on the surface of the F layer of the treated copper foil 12 with resin as a prepreg. : 0.2 mm) was layered and vacuum heat pressed for 60 minutes under pressurized conditions of 185 ° C. and 3.0 MPa to produce the laminated body 11.
Laminates 12 to 13 were manufactured in the same manner except that the copper foil with resin was changed. The peel strength of each laminate was evaluated according to the following criteria.

<Peeling strength of laminated body>
The position of 50 mm from one end in the length direction of the laminated body cut out in a rectangular shape (length 100 mm, width 10 mm) is fixed, and the tensile speed is 50 mm / min, 90 ° from one end in the length direction to the laminated body. The maximum load applied when the metal foil and the F layer were peeled off was measured as the peeling strength (N / cm). The results are summarized in Table 3.

4. Example of film production 4 parts by mass of a solution containing 25% by mass of dispersant 11, 8 parts by mass of a solution containing 25% by mass of dispersant 14, and 58 parts by mass of NMP are mixed, and 30 parts by mass of powder 1 is further added. The dispersion was mixed to prepare a dispersion liquid 17. A resin-attached copper foil is produced in the same manner as in the above-mentioned production example of the resin-attached copper foil 11 except that the dispersion liquid 17 is used instead of the dispersion liquid 11, and the copper foil is further removed by etching to form an F layer. I got a film. The total light transmittance of the film was 96%, the diffusion transmittance was 1.6%, and the haze value was 1.7%. In addition, no yellowing was confirmed on the film, and the film was excellent in transparency.

5. Example of preparation / evaluation of dispersion liquid 4 parts by mass of a solution containing 25% by mass of a dispersant 15, 8 parts by mass of a solution containing 25% by mass of a dispersant 14, and 58 parts by mass of NMP are mixed, and 30 parts of powder 1 is further mixed. The dispersion liquid 18 was prepared by mixing parts by mass. In the dispersion liquid 18 that had been allowed to stand for one month, the powder that had settled in the form of a hard cake could be easily loosened, and the dispersion liquid 18 was excellent in redispersibility.

[Example 2] Production / evaluation example of dispersion liquid II 1. Preparation of Dispersion Liquid A dispersion liquid 21 was prepared by mixing 40 parts by mass of powder 1 with a solution containing 55 parts by mass of NMP and 5 parts by mass of dispersant 21.
Dispersions 22 to 23 were obtained in the same manner as in the above-mentioned preparation conditions for the dispersion 21 except that the type of the dispersant was changed. The results are summarized in Table 4.

2. Evaluation of dispersion 2-1. Viscosity The viscosity of the dispersion is determined by repeating the measurement of the dispersion three times at room temperature (25 ° C) at a rotation speed of 30 rpm using a B-type viscometer, and the average value of the measured values for the three measurements. And said.
2-2. Dispersibility The dispersion state of the dispersion was visually confirmed and evaluated according to the following criteria.
[Evaluation criteria]
〇: It settled, but it redispersed when lightly stirred.
Δ: Redispersed when agitated with shearing.
X: No redispersion was applied even after shearing.

2-3. Smoothness First, a dispersion liquid is applied to the surface of the copper foil 1 using a die coater, passed through a ventilation drying furnace (atmospheric temperature: 120 ° C.) and held for 1 minute, and further placed in a far-infrared ray furnace (temperature: 340 ° C.). The copper foil was held for 3 minutes to obtain a copper foil with a resin having an F layer (thickness 5 μm) of polymer 1 on the surface of the copper foil. In this way, copper foils 21 to 23 with resin were obtained for each of the dispersion liquids 21 to 23. The surface of the F layer of the copper foil with resin was visually observed and evaluated according to the following criteria.
[Evaluation criteria]
〇: No yuzu pattern was observed on the surface of the F layer.
X: A citron pattern was observed on the surface of the F layer.

なお、ＮＭＰに代えて、ＮＭＰ又はＣＨＮをそれぞれ用いる以外は、上記と同様にして分散液を調製すると、上記と同等の結果を示す。The evaluation results of the above dispersions are shown in Table 5 below.

When the dispersion is prepared in the same manner as above except that NMP or CHN is used instead of NMP, the same result as above is obtained.

[Example 3] Production / evaluation example of dispersion liquid III 1. Preparation of Dispersion Liquid A dispersion liquid 31 was prepared by mixing 5 parts by mass of the dispersant 31 and 45 parts by mass of powder 1 with 50 parts by mass of NMP.
Dispersions 32 to 33 were obtained in the same manner as in the above-mentioned preparation conditions for the dispersion 31 except that the type of the dispersant was changed. The results are summarized in Table 6.

2. Evaluation of dispersion 2-1. Dispersibility of dispersion liquid The dispersion state of the dispersion liquid was visually confirmed and evaluated according to the following criteria.
[Evaluation criteria]
〇: It settled, but it redispersed when lightly stirred.
Δ: Redispersed when agitated with shearing.
X: No redispersion was applied even after shearing.

2-2. Wetting property of F layer A dispersion liquid is applied to the surface of the copper foil 1 using a die coater, and the F layer (thickness) of the F polymer is applied to the surface of the copper foil 1 in the same manner as in the production example of the resin-attached copper foil of Example 2. A copper foil with a resin having a size of 5 μm) was obtained. In this way, copper foils 31 to 33 with resin were obtained for each of the dispersion liquids 31 to 33.
After that, when pure water (about 2 μL) was placed on the surface of the F layer of the metal foil with resin at 25 ° C, the angle formed by the water droplets and the surface of the F layer was measured by a contact angle meter (CA manufactured by Kyowa Interface Science Co., Ltd.). -X type) was used for measurement and evaluation was performed according to the following criteria.
[Evaluation criteria]
◯: The water contact angle is 80 ° or less.
X: The water contact angle is more than 80 °.

2-3. Adhesiveness First, the surface of the F layer of the resin-attached copper foil obtained above was subjected to vacuum plasma treatment under the same conditions as in Example 1. Next, FR-4 was superposed as a prepreg on the surface of the F layer of the treated copper foil with resin, and vacuum heat pressed under the same conditions as in Example 1 to obtain a laminate. Then, the peel strength of the laminated body was measured and evaluated according to the following criteria.
[Evaluation criteria]
〇: The peel strength is 5 N / cm or more.
X: The peel strength is less than 5 N / cm.

The above evaluation results are shown in Table 7 below.

[Example 4] Production / evaluation example of dispersion liquid IV 1. Preparation of Dispersion Liquid 64 parts by mass of NMP and 3 parts by mass of dispersant 41 were mixed, and 33 parts by mass of powder 1 was further mixed to prepare a dispersion liquid 41.
Dispersions 42 to 45 were obtained in the same manner as in the above-mentioned preparation conditions for the dispersion 41 except that the type of the dispersant was changed. The dispersibility of the dispersion was evaluated according to the following criteria.

<Dispersibility of dispersion>
The dispersed state of the dispersion was visually confirmed and evaluated according to the following criteria.
〇: It settled, but it redispersed when lightly stirred.
Δ: Redispersed when agitated with shearing.
X: No redispersion was applied even after shearing.

なお、分散液４１におけるＮＭＰのかわりに、ＭＥＫ又はＣＨＮをそれぞれ用いる以外は同様にして調製した分散液は、分散液４１と同等の分散性を示した。The results are summarized in Table 8.

The dispersion prepared in the same manner except that MEK or CHN was used instead of NMP in the dispersion 41 showed the same dispersibility as the dispersion 41.

2. Example of production / evaluation of copper foil with resin A dispersion liquid 41 is applied to the surface of the copper foil 1 using a die coater, and the polymer 1 is applied to the surface of the copper foil 1 in the same manner as in the production example of the copper foil with resin in Example 2. A copper foil 41 with a resin having an F layer (thickness of 5 μm) was obtained. Further, the copper foils 42 and 43 with resin were manufactured in the same manner except that the dispersion liquids 42 and 43 were used instead of the dispersion liquid 41.
The smoothness of the F layer in the resin-attached copper foil was evaluated under the same conditions as in Example 2. The results are summarized in Table 9.

3. 3. Example of Manufacture / Evaluation of Laminated Body The surface of the F layer of the resin-attached copper foil 41 was subjected to vacuum plasma treatment under the same conditions as in Example 1. FR-4 was superposed as a prepreg on the surface of the F layer of the treated copper foil 41 with resin, and vacuum heat pressed under the same conditions as in Example 1 to obtain a laminate. As a result of measuring the peel strength of the laminated body in the same manner as in Example 1, it was 8 N / cm.

[Example 5] Production / evaluation example of dispersion liquid V 1. Preparation of Dispersion Liquid 35 parts by mass of MEK and 5 parts by mass of dispersant 51 were mixed, and 60 parts by mass of powder 1 was further mixed to prepare a dispersion liquid 51.
Dispersions 52 to 53 were obtained in the same manner as in the preparation conditions of the dispersion 51 except that the type of the dispersant was changed. The dispersibility of the dispersion was evaluated according to the following criteria.
<Dispersibility of dispersion>
The dispersed state of the dispersion was visually confirmed and evaluated according to the following criteria.
〇: It settled, but it redispersed when lightly stirred.
X: No redispersion was applied even after shearing.
The results are summarized in Table 10.

2. Example of manufacturing a copper foil with resin and a laminate A dispersion liquid 51 is applied to the surface of the copper foil 1 using a die coater, and a polymer is applied to the surface of the copper foil 1 in the same manner as in the example of manufacturing the resin-attached copper foil of Example 2. A copper foil 51 with a resin having an F layer (thickness 5 μm) of 1 was obtained.
The surface of the F layer of the resin-attached copper foil 51 was subjected to vacuum plasma treatment under the same conditions as in Example 1. FR-4 was superposed as a prepreg on the surface of the F layer of the treated copper foil 51 with resin, and vacuum heat pressed under the same conditions as in Example 1 to obtain a laminated body 51. As a result of measuring the peel strength of the laminated body 51 in the same manner as in Example 1, it was 6 N / cm.

The dispersion liquid of the present invention can easily form a fluororesin layer containing a fluoropolymer and having excellent adhesiveness, and films, fiber-reinforced films, prepregs, metal laminates, printed circuit boards and the like can be used as antenna parts, printed circuit boards, aircraft. It can be used as a material for parts for automobiles, automobile parts, sports equipment, food industry supplies, saws, sliding bearings, etc.
Japanese patent application No. 2018-108740 filed on June 06, 2018, Japanese patent application No. 2018-173420 filed on September 18, 2018, Japanese patent filed on October 30, 2018. Applications 2018-203957, Japanese Patent Application 2018-2030959 filed on October 30, 2018, Japanese Patent Application 2018-209241 filed on November 06, 2018 and filed on November 21, 2018. The entire contents of the specification, the scope of patent claims, and the abstract of Japanese Patent Application No. 2018-218321 have been cited herein and are incorporated as disclosure of the specification of the present invention.

Claims (15)

A dispersion liquid in which the powder containing a tetrafluoroethylene polymer powder, a solvent and a dispersant is dispersed in the form of particles, and the dispersant may contain an ethereal oxygen atom as a monovalent fluorine-containing hydrocarbon. A dispersion which is a polymer having a group and at least one group selected from the group consisting of a tert-alkoxycarbonyl group, a sec-alkoxycarbonyl group, an aralkyloxycarbonyl group, a polyoxyalkylene group and an alcoholic hydroxyl group. The dispersion according to claim 1, wherein the dispersant is a polymer containing a monomer-based unit represented by the following formula (FI) and a monomer-based unit represented by the following formula (HI).
Formula ^{_{(FI) CH 2 = CR FI}} C (O) O-Q FI -Z FI
Formula (HI) CH ₂ = CR ^HI C (O) OC (-X ^1I ) ( ^{-X 2I} ) ( ^{-X 3I} )
The symbols in the formula have the following meanings.
^RFI represents a hydrogen atom, a chlorine atom or a methyl group.
^RHI represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
^QFI indicates an alkylene group or an oxyalkylene group.
Z ^FI represents a polyfluoroalkyl group or a polyfluoroalkenyl group.
For X ^1I , X ^2I and X ^3I , ^{whether X 1I} , X ^2I and X ^3I are independently alkyl or aryl groups, or X ^1I and X ^2I are hydrogen atoms and X ^3I is an aryl group, respectively. Whether X ^1I and X ^2I are independent hydrogen atoms or alkyl groups and X ^3I is an alkoxy group, or X ^1I is a hydrogen atom or alkyl group and X ^2I and X ^3I jointly form an alkylene group. , Whichever. The dispersion according to claim 1, wherein the dispersant is a polymer containing a unit represented by a monomer represented by the following formula (FII) and a unit based on a monomer represented by the following formula (HII).
Formula ^{_{(FII) CH 2 = CX FII}} C (O) -Q FII - (OZ FII) nII -OR FII
Equation (HII) CH ₂ = CX ^HII C (O)-(OZ ^HII ) _mII- OR ^HII
The symbols in the formula have the following meanings.
X ^FII represents a hydrogen atom or a methyl group.
Q ^FII represents a divalent linking group.
Z ^FII represents a perfluoroalkylene group.
nII represents an integer of 2 to 30.
^RFII represents a perfluoroalkyl group.
X ^HII represents a hydrogen atom or a methyl group.
Z ^HII represents an alkylene group.
mII represents an integer from 3 to 200.
^RHII represents a hydrogen atom, an alkyl group or an aryl group. The dispersant has a monomer-based unit represented by the following formula (FIII), an alkyl (meth) acrylate-based unit, a monomer-based unit represented by the following formula (HIII), and an acrylonitrile or acrylamide-based unit. The dispersion according to claim 1, which is a polymer containing the mixture.
Equation (FIII) CH ₂ = CX ^FIII C (O) ^{OQ FIII-} R ^FIII
Formula (HIII) CH ₂ = CX ^HIII C (O)-(OZ ^HIII ) _mIII- OR ^HIII
The symbols in the formula have the following meanings.
X ^FIII represents a hydrogen atom, a chlorine atom or a methyl group.
Q ^FIII represents an alkylene group or an oxyalkylene group.
^RFIII represents a polyfluoroalkyl group, a polyfluoroalkyl group containing an ethereal oxygen atom, or a polyfluoroalkenyl group.
X ^HIII represents a hydrogen atom or a methyl group.
Z ^HIII represents an alkylene group.
mIII represents an integer from 3 to 200.
^RHIII represents a hydrogen atom, an alkyl group or an aryl group. The dispersant contains a monomer-based unit represented by the following formula (FIV) and a monomer-based unit represented by the following formula (HIV), and has a fluorine content of 15 to 50% by mass and a polyoxyalkylene group. The dispersion according to claim 1, which is a polymer having a content of 10 to 70% by mass.
Equation (FIV) CH ₂ = CX ^FIV C (O) ^{OQ FIV-} R ^FIV
Equation (HIV) CH ₂ = CX ^HIV C (O)-(OZ ^HIV ) _mIV- OR ^HIV
The symbols in the formula have the following meanings.
X ^FIV represents a hydrogen atom, a chlorine atom or a methyl group.
Q ^FIV indicates an alkylene group or an oxyalkylene group.
R ^FIV represents a polyfluoroalkyl group, a polyfluoroalkyl group containing an ethereal oxygen atom, or a polyfluoroalkenyl group.
X ^HIV represents a hydrogen atom or a methyl group.
Z ^HIV represents an alkylene group.
mIV represents an integer from 3 to 200.
^RHIV represents an alkyl group or an aryl group. The dispersant contains a unit based on a monomer represented by the following formula (FV) and a unit based on a monomer represented by the following formula (HV), and has a fluorine content of 20 to 40% by mass and a hydroxyl value of 150 to 150. The dispersion according to claim 1, which is a polymer of 300 mgKOH / g.
Equation (FV) CH ₂ = CX ^FV C (O) ^{OQ FV-} R ^FV
Equation (HV) CH ₂ = CX ^HV C (O) -Q ^HV- OH
The symbols in the formula have the following meanings.
X ^FV represents a hydrogen atom, a chlorine atom or a methyl group.
Q ^FV indicates an alkylene group or an oxyalkylene group.
^RFV represents a polyfluoroalkyl group, a polyfluoroalkyl group containing an ethereal oxygen atom, or a polyfluoroalkenyl group.
X ^HV represents a hydrogen atom or a methyl group.
Q ^HV indicates an alkylene group or a cycloalkylene group. The dispersion according to any one of claims 1 to 6, wherein the tetrafluoroethylene-based polymer contains 99.5 mol% or more of units based on tetrafluoroethylene with respect to all the units contained in the polymer. The dispersion according to any one of claims 1 to 6, wherein the tetrafluoroethylene-based polymer contains more than 0.5 mol% of units based on a comonomer other than tetrafluoroethylene with respect to all the units contained in the polymer. liquid. Any one of claims 1 to 8, wherein the tetrafluoroethylene-based polymer has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group. The dispersion according to the section. The dispersion liquid according to any one of claims 1 to 9, wherein the volume-based cumulative 50% diameter of the powder is 0.05 to 6 μm. The dispersion liquid according to any one of claims 1 to 10, wherein the solvent is a polar solvent. The dispersion according to any one of claims 1 to 11, wherein the solvent comprises one or more solvents selected from the group consisting of ketones, esters and amides. The dispersion according to any one of claims 1 to 12, wherein the solvent is methyl ethyl ketone, cyclohexanone, cyclopentanone, γ-butyrolactone or N-methyl-2-pyrrolidone. The dispersion liquid according to any one of claims 1 to 13 is applied to the surface of the metal foil, and the metal foil is heated to obtain a resin-attached metal foil having a resin layer containing the tetrafluoroethylene-based polymer. A method for manufacturing metal leaf with resin. A method for manufacturing a printed circuit board, wherein the metal foil with resin is manufactured by the manufacturing method according to claim 14, and the metal foil of the metal foil with resin is etched to form a pattern circuit.