WO2024053554A1

WO2024053554A1 - Liquid composition and method for producing laminate using liquid composition

Info

Publication number: WO2024053554A1
Application number: PCT/JP2023/031818
Authority: WO
Inventors: 陽美中満; 蔵藤岡
Original assignee: Ａｇｃ株式会社
Priority date: 2022-09-09
Filing date: 2023-08-31
Publication date: 2024-03-14
Also published as: TW202428756A

Abstract

Provided is a liquid composition comprising: tetrafluoroethylene polymer particles; at least one compound selected from among compounds (1)-(3) and having no fluorine atom; and a non-aqueous solvent. Compound (1) is a silicone-modified (meth)acrylate polymer having a polyorganosiloxane group and a C6-40 monovalent hydrocarbon group. Compound (2) is a (meth)acrylate polymer having a C6-40 monovalent hydrocarbon group and at least one nitrogen atom-containing group selected from the group consisting of amino groups, ammonium groups, amide groups, and carbamate groups. Compound (3) is a carboxylic acid ester having a hydroxy group, with an amine value of 20-120 mg/KOH.

Description

Liquid composition and method for producing a laminate using the liquid composition

The present invention relates to a liquid composition containing particles of a tetrafluoroethylene polymer. Specifically, the present invention relates to a nonaqueous liquid composition containing particles of a tetrafluoroethylene polymer, and a method for producing a laminate using the liquid composition.

In recent years, tetrafluoroethylene-based polymers, which have a low dielectric constant and a low dielectric loss tangent, have been attracting attention as insulating layers for printed circuit boards of communication devices in order to respond to higher speeds and higher frequencies in communication devices. As a material for forming an insulating layer containing such a polymer, a liquid composition containing particles of a tetrafluoroethylene polymer and a nonaqueous solvent is known.
However, particles of tetrafluoroethylene polymers generally have low dispersibility in nonaqueous solvents. For the purpose of improving the dispersibility of tetrafluoroethylene polymer particles in non-aqueous solvents, Patent Documents 1 to 3 disclose methods for improving the dispersibility of tetrafluoroethylene polymer particles in a predetermined particle size, including a fluorine-based additive having a perfluoroalkyl group and a lipophilic group. Non-aqueous liquid compositions of particles of certain tetrafluoroethylene polymers have been proposed.

International Publication No. 2016/159102 JP2022-098371A Japanese Patent Application Publication No. 2020-186351

In a liquid composition containing a fluorine-based additive as in Patent Document 1 and Patent Document 2, the dispersibility of tetrafluoroethylene polymer particles is improved, but on the other hand, the liquid composition contains a coating film (polymer layer), etc. When forming a molded product, its physical properties tend to deteriorate. Specifically, such fluorine-based additives remain in the molded product and bleed out onto the surface, which tends to impair the smoothness, hydrophilicity (adhesiveness), etc. of the molded product surface. Additionally, when preparing a liquid composition, problems may occur with initial dispersibility, such as time required for dispersing the particles of the tetrafluoroethylene polymer and difficulty in obtaining a uniform liquid composition depending on the shearing conditions. there were.
The present inventors have discovered that a liquid composition containing a tetrafluoroethylene polymer, a specific (meth)acrylate polymer that does not have a fluorine atom, or a specific carboxylic acid ester that does not have a fluorine atom, and a nonaqueous solvent, It was found that it has excellent dispersion stability and is easy to handle.
In addition, molded articles such as polymer layers formed from such liquid compositions have excellent physical properties such as heat resistance and electrical properties (low coefficient of linear expansion, low dielectric constant, and low dielectric loss tangent) based on the tetrafluoroethylene polymer, It was also discovered that the surface thereof is excellent in hydrophilicity, etc., leading to the present invention.
The purpose of the present invention is to form a molded product with excellent physical properties such as heat resistance and electrical properties (low coefficient of linear expansion, low dielectric constant, and low dielectric loss tangent), as well as excellent hydrophilicity and smoothness of the surface, and a stable dispersion. The present invention provides a liquid composition containing a tetrafluoroethylene polymer that has excellent properties and handleability.

The present invention has the following aspects.
[1] Tetrafluoroethylene polymer particles,
At least one fluorine atom-free compound selected from the following compounds (1) to (3),
A liquid composition comprising a non-aqueous solvent.
Compound (1) Silicone-modified (meth)acrylate polymer having a polyorganosiloxane group and a monovalent hydrocarbon group having 6 to 40 carbon atoms Compound (2) Selected from the group consisting of an amino group, an ammonium group, an amide group, and a carbamate group A (meth)acrylate polymer having at least one nitrogen atom-containing group and a monovalent hydrocarbon group having 6 to 40 carbon atoms Compound (3) A carboxylic acid ester having an amine value of 20 to 120 mg/KOH and having a hydroxyl group
[2] Tetrafluoroethylene polymer particles, a silicone-modified (meth)acrylate polymer having a polyorganosiloxane group and a monovalent hydrocarbon group having 6 to 40 carbon atoms and no fluorine atoms, and a non-aqueous solvent A liquid composition comprising:
[3] The liquid composition of [2], wherein the tetrafluoroethylene polymer is a heat-melting tetrafluoroethylene polymer containing an oxygen-containing polar group.
[4] The liquid composition according to [2], wherein the average particle diameter of the particles of the tetrafluoroethylene polymer is 1 μm or more and less than 10 μm.
[5] The liquid composition according to [2], wherein the content of the particles of the tetrafluoroethylene polymer is 25% by mass or more.
[6] The liquid composition of [2], wherein the content of the silicone-modified (meth)acrylate polymer is 10% by mass or less.
[7] The liquid composition according to [2], wherein the content of the silicone-modified (meth)acrylate polymer is 0.01 to 0.15 as a mass ratio to the particles of the tetrafluoroethylene polymer.
[8] The liquid composition of [2], wherein the nonaqueous solvent is at least one selected from amides, ketones, and esters.
[9] The liquid composition of [1], wherein the non-aqueous solvent has a surface tension of 20 to 50 mN/m.
[10] The liquid composition of [2], wherein the monovalent hydrocarbon group possessed by the silicone-modified (meth)acrylate polymer is an alkyl group having 12 to 40 carbon atoms.
[11] The liquid composition according to [2], wherein the silicone-modified (meth)acrylate polymer is a (meth)acrylate polymer having a polysilsesquioxane structure.
[12] The liquid composition of [2], wherein the silicone-modified (meth)acrylate polymer further has a hydroxyl group.
[13] The liquid composition of [2], which has a viscosity of 3000 mPa·s or less.
[14] Furthermore, it has at least one nitrogen atom-containing group selected from the group consisting of an amino group, an ammonium group, an amide group, and a carbamate group, and a monovalent hydrocarbon group having 6 to 40 carbon atoms, and a fluorine atom. The liquid composition of [2], which contains no (meth)acrylate polymer.
[15] The liquid composition according to [14], wherein the content of the (meth)acrylate polymer is lower than the content of the silicone-modified (meth)acrylate polymer.
[16] The liquid composition according to any one of [2] to [15] is placed on the surface of a base material and heated to form a polymer layer containing the tetrafluoroethylene polymer, and the liquid composition is formed of the base material. A method for producing a laminate, comprising obtaining a laminate having a base material layer and the polymer layer in this order.
[17] Tetrafluoroethylene polymer particles, at least one nitrogen atom-containing group selected from the group consisting of an amino group, an ammonium group, an amide group, and a carbamate group, and a monovalent hydrocarbon group having 6 to 40 carbon atoms. A liquid composition comprising a (meth)acrylate-based polymer that has no fluorine atoms and a non-aqueous solvent.
[18] The liquid composition of [17], wherein the tetrafluoroethylene polymer is a heat-melting tetrafluoroethylene polymer containing an oxygen-containing polar group.
[19] The liquid composition according to [17], wherein the average particle diameter of the particles of the tetrafluoroethylene polymer is 1 μm or more and less than 10 μm.
[20] The liquid composition according to [17], wherein the content of the particles of the tetrafluoroethylene polymer is 25% by mass or more.
[21] The liquid composition according to [17], wherein the content of the (meth)acrylate polymer is 10% by mass or less.
[22] The liquid composition according to [17], wherein the content of the (meth)acrylate polymer is 0.01 to 0.15 as a mass ratio to the particles of the tetrafluoroethylene polymer.
[23] The liquid composition of [17], wherein the nonaqueous solvent is at least one polar solvent selected from amides, ketones, and esters.
[24] The liquid composition of [17], wherein the nonaqueous solvent has a surface tension of 20 to 50 mN/m.
[25] The liquid composition of [17], wherein the monovalent hydrocarbon group of the (meth)acrylate polymer is an alkyl group having 12 to 40 carbon atoms.
[26] The (meth)acrylate-based polymer has a (meth)acrylate that does not contain a nitrogen atom and at least one nitrogen atom-containing group selected from the group consisting of an amino group, an ammonium group, an amide group, and a carbamate group. The liquid composition of [17], which is a copolymer copolymerized with (meth)acrylate.
[27] The liquid composition of [17], wherein the (meth)acrylate polymer further has a hydroxyl group.
[28] The liquid composition of [17], which has a viscosity of 3000 mPa·s or less.
[29] The liquid composition of [17] further comprising a silicone-modified (meth)acrylate polymer having a polyorganosiloxane group and a monovalent hydrocarbon group having 6 to 40 carbon atoms and no fluorine atom.
[30] The liquid composition of [29], wherein the content of the silicone-modified (meth)acrylate polymer is greater than the content of the (meth)acrylate polymer.
[31] The liquid composition according to any one of [17] to [30] is placed on the surface of a base material and heated to form a polymer layer containing the tetrafluoroethylene polymer, and the liquid composition is formed of the base material. A method for producing a laminate, comprising obtaining a laminate having a base material layer and the polymer layer in this order.
[32] A liquid composition comprising particles of a tetrafluoroethylene polymer, a nonaqueous solvent, and a carboxylic acid ester having an amine value of 20 to 120 mg/KOH and having a hydroxyl group.
[33] The liquid composition of [32], wherein the tetrafluoroethylene polymer is a heat-melting tetrafluoroethylene polymer containing an oxygen-containing polar group.
[34] The liquid composition according to [32], wherein the particles of the tetrafluoroethylene polymer have an average particle diameter of 1 μm or more and less than 10 μm.
[35] The liquid composition according to [32], wherein the content of the tetrafluoroethylene polymer particles is 25% by mass or more.
[36] The liquid composition according to [32], wherein the content of the carboxylic acid ester is 10% by mass or less.
[37] The liquid composition according to [32], wherein the content of the carboxylic acid ester is 0.01 to 0.15 as a mass ratio to the particles of the tetrafluoroethylene polymer.
[38] The liquid composition of [32], wherein the nonaqueous solvent is at least one selected from amides, ketones, and esters.
[39] The liquid composition of [32], wherein the nonaqueous solvent has a surface tension of 20 to 50 mN/m.
[40] The liquid composition of [32], wherein the carboxylic acid ester has an ethyleneimine group and an oxyalkylene carbonyl group.
[41] The liquid composition of [32], wherein the carboxylic acid ester is a polymer having the ethyleneimine group in the main chain and the oxyalkylene carbonyl group in the side chain.
[42] The liquid composition of [32], wherein the carboxylic acid ester is a compound obtained by addition polymerizing ε-caprolactone to polyethyleneimine.
[43] The liquid composition of [32], which has a viscosity of 3000 mPa·s or less.
[44] The liquid composition of [32] further comprising a silicone-modified (meth)acrylate polymer having a polyorganosiloxane group and a monovalent hydrocarbon group having 6 to 40 carbon atoms and no fluorine atom.
[45] The liquid composition according to any one of [32] to [44] is placed on the surface of a base material and heated to form a polymer layer containing the tetrafluoroethylene polymer, and the liquid composition is formed of the base material. A method for producing a laminate, comprising obtaining a laminate having a base material layer and the polymer layer in this order.

According to the present invention, a liquid composition with excellent dispersion stability and handling properties can be provided. Such a liquid composition has excellent physical properties such as heat resistance and electrical properties (low coefficient of linear expansion, low dielectric constant, and low dielectric loss tangent) based on the tetrafluoroethylene polymer, and has excellent hydrophilicity and smoothness on its surface. , molded products such as coating films (polymer layers) can be formed.

The following terms have the following meanings:
"Average particle diameter (D50)" is the volume-based cumulative 50% diameter of particles or fillers determined by laser diffraction/scattering method. That is, the particle size distribution is measured by a laser diffraction/scattering method, a cumulative curve is determined with the total volume of the particle population as 100%, and the particle diameter is the point on the cumulative curve where the cumulative volume becomes 50%.
The D50 of particles or fillers is determined by dispersing the particles in water and analyzing the particles using a laser diffraction/scattering method using a laser diffraction/scattering particle size distribution analyzer (LA-920 measuring instrument, manufactured by Horiba, Ltd.) .
"Average particle diameter (D90)" is the volume-based cumulative 90% diameter of particles, which is determined in the same manner as D50.
The specific surface area of particles or fillers is a value calculated by measuring particles by gas adsorption (constant volume method) BET multi-point method, and is determined using NOVA4200e (manufactured by Quantachrome Instruments).
"Melting temperature" is the temperature corresponding to the maximum value of the melting peak of the polymer as measured by differential scanning calorimetry (DSC).
"Glass transition point (Tg)" is a value measured by analyzing a polymer using a dynamic mechanical analysis (DMA) method.
"Viscosity" is determined by measuring the liquid composition using a B-type viscometer at 25° C. and a rotation speed of 30 rpm. Repeat the measurement three times and use the average value of the three measurements.
"Thixotropic ratio" is a value calculated by dividing the viscosity η ₁ of a liquid composition measured at a rotation speed of 30 rpm by the viscosity η ₂ measured at a rotation speed of 60 rpm. . Each viscosity measurement was repeated three times, and the average value of the three measurements was taken.
The "surface tension" of a solvent or solution is a value measured by the Wilhelmy method at 25° C. using a surface tension meter.
A "unit" in a polymer means an atomic group based on the monomer formed by polymerization of the monomer. The unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of said unit is converted into another structure by processing the polymer. Hereinafter, a unit based on monomer a will also be simply referred to as a "monomer a unit."

The liquid composition of the present invention (hereinafter also referred to as "the present composition") comprises particles (hereinafter also referred to as "F particles") of a tetrafluoroethylene polymer (hereinafter also referred to as "F polymer"). , at least one fluorine-free compound selected from the following compounds (1) to (3) (hereinafter also referred to as "non-fluorine compound"), and a non-aqueous solvent.
Compound (1): Silicone-modified (meth)acrylate polymer having a polyorganosiloxane group and a monovalent hydrocarbon group having 6 to 40 carbon atoms Compound (2): Group consisting of an amino group, an ammonium group, an amide group, and a carbamate group A (meth)acrylate polymer having at least one nitrogen atom-containing group selected from the following and a monovalent hydrocarbon group having 6 to 40 carbon atoms Compound (3): having an amine value of 20 to 120 mg/KOH and having a hydroxy group Carboxylic acid ester The present composition may contain only one type of non-fluorine compound, or may contain two or more types of non-fluorine compounds.

This composition has excellent dispersion stability and handling properties, and molded products such as coating films (polymer layers) formed from it have heat resistance, electrical properties (low linear expansion coefficient, low dielectric constant, etc.) based on the F polymer. It has excellent physical properties such as low dielectric loss tangent), and its surface has excellent hydrophilicity and smoothness.
The reason why this composition has excellent dispersion stability and handling properties is not necessarily clear, but it is thought to be as follows.

The non-fluorine compound contained in the present composition has a balanced affinity for the F polymer and the non-aqueous solvent, and tends to enhance the interaction between the two. As a result, aggregation and sedimentation of F particles in the liquid are suppressed, and liquid physical properties such as dispersion stability and viscosity of the composition are likely to be improved. In addition, since non-fluorine compounds do not have fluorine atoms, they are thought to improve the physical properties of layers such as hydrophilicity and smoothness of the surface when forming molded products such as coatings and layers.
This mechanism of action becomes more pronounced when the non-aqueous solvent constituting the composition is a specific polar solvent or when the composition contains two or more non-fluorine compounds.

The F polymer in the present invention is a polymer containing units based on tetrafluoroethylene (hereinafter also referred to as "TFE") (hereinafter also referred to as "TFE units").
The F polymer may be thermofusible or non-thermofusible. Here, the term "thermofusible polymer" means a polymer that exists at a temperature at which the melt flow rate is 1 to 1000 g/10 minutes under a load of 49N.
The melting temperature of the heat-melting F polymer is preferably 180°C or higher, more preferably 200°C or higher. The melting temperature of the F polymer is preferably 325°C or lower, more preferably 320°C or lower. In this case, a molded article such as a coating film (polymer layer) formed from the present composition tends to have excellent heat resistance.

The glass transition point of the F polymer is preferably 50°C or higher, more preferably 75°C or higher. The glass transition point of the F polymer is preferably 150°C or lower, more preferably 125°C or lower.
The fluorine content of the F polymer is preferably 70% by mass or more, more preferably 72 to 76% by mass.

F polymers include polytetrafluoroethylene (PTFE), polymers containing TFE units and units based on ethylene (ETFE), polymers containing TFE units and units based on propylene, TFE units and perfluoro(alkyl vinyl ether) (PAVE) Polymers (PFA) containing units based on (PAVE units), polymers (FEP) containing TFE units and units based on hexafluoropropylene are preferred, PFA and FEP are more preferred, and PFA is even more preferred. These polymers may further contain units based on other comonomers.
Examples of PTFE include low molecular weight PTFE and modified PTFE.
PAVE is preferably CF ₂ =CFOCF ₃ , CF ₂ =CFOCF ₂ CF ₃ and CF ₂ =CFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as "PPVE"), and PPVE is more preferred.

The F polymer preferably has an oxygen-containing polar group, more preferably a hydroxyl group-containing group or a carbonyl group-containing group, and even more preferably a carbonyl group-containing group. In this case, the present composition is more likely to exhibit the mechanism of action of the present invention, such as initial dispersibility and dispersion stability, and is likely to be excellent in dispersion stability and handleability. In addition, molded products such as coating films (polymer layers) formed from this composition have physical properties such as heat resistance, electrical properties (low coefficient of linear expansion, low dielectric constant, and low dielectric loss tangent), and hydrophilic properties of their surfaces. It tends to have excellent smoothness.
The hydroxyl group-containing group is preferably a group containing an alcoholic hydroxyl group, more preferably -CF ₂ CH ₂ OH and -C(CF ₃ ) ₂ OH.
Carbonyl group-containing groups include carboxyl group, alkoxycarbonyl group, amide group, isocyanate group, carbamate group (-OC(O)NH ₂ ), acid anhydride residue (-C(O)OC(O)-), imide Residues (-C(O)NHC(O)-, etc.) and carbonate groups (-OC(O)O-) are preferred, and acid anhydride residues are more preferred.
When the F polymer has an oxygen-containing polar group, the number of oxygen-containing polar groups in the F polymer is preferably 10 to 5,000, more preferably 100 to 3,000 per 1×10 ⁶ carbon atoms in the main chain. Note that the number of oxygen-containing polar groups in the F polymer can be quantified by the composition of the polymer or the method described in International Publication No. 2020/145133.

The oxygen-containing polar group may be contained in a unit based on a monomer in the F polymer, or may be contained in a terminal group of the main chain of the F polymer, with the former being preferred. Examples of the latter embodiment include an F polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and an F polymer obtained by subjecting the F polymer to plasma treatment or ionizing radiation treatment.

The F polymer is preferably a polymer having carbonyl group-containing groups, including TFE units and PAVE units, and includes units based on monomers having TFE units, PAVE units and carbonyl group-containing groups, and for the total units: More preferably, the polymer contains 90 to 99 mol%, 0.99 to 9.97 mol%, and 0.01 to 3 mol% of these units in this order. Specific examples of such F polymers include the polymers described in International Publication No. 2018/016644.
The monomer having a carbonyl group-containing group is preferably itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"), and more preferably NAH.

In the present invention, the D50 of the F particles is preferably 1 μm or more and less than 10 μm. The F particles may be solid particles or non-hollow particles. The F particles may be secondary particles formed from nanometer-order fine particles. The D50 of the F particles is preferably 1.0 μm or more, more preferably 1.5 μm or more. D50 of the F particles is preferably 6 μm or less, more preferably 5 μm or less. When the D50 of the F particles is below the above range, the mechanism of action of the present invention is more likely to be expressed, and the present composition with a small number of coarse particles can be easily obtained.
Furthermore, the D90 of the F particles is preferably 8 μm or less, more preferably 6 μm or less.
The specific surface area of the F particles is preferably 1 to 25 m ² /g, more preferably 6 to 15 m ² /g. When the specific surface area of the F particles is within the above range, the surfaces of the F particles are more easily wetted, the number of coarse particles is small, and the mechanism of action of the present invention is more likely to be exhibited.

The F particles are particles containing F polymer, and are preferably composed of F polymer.
More preferably, the F particles are particles of a heat-melting F polymer having an oxygen-containing polar group and having a melting temperature of 200 to 325°C. In this case, the mechanism of action of the present invention is more fully expressed, and aggregation of F particles is also more likely to be suppressed.
The F particles may contain a resin or an inorganic compound other than the F polymer, or may form a core-shell structure in which the F polymer is the core and the shell is a resin or inorganic compound other than the F polymer. A core-shell structure may be formed in which the shell is made of a resin other than F polymer or an inorganic compound is made of a core.
Here, examples of the resin other than the F polymer include aromatic polyester, polyamideimide, polyimide, and maleimide, and examples of the inorganic compound include silica and boron nitride.
One type of F particles may be used, or two or more types may be used.

The content of F particles in the present composition is preferably 25% by mass or more, more preferably 30% by mass or more. The content of F particles is preferably 75% by mass or less, more preferably 60% by mass or less.

The non-aqueous solvent in the present composition is a compound that is liquid at 25°C under atmospheric pressure, and preferably has a boiling point of 50 to 240°C. One type of non-aqueous solvent may be used, or two or more types may be used. When two types of non-aqueous solvents are used, it is preferable that the two types of non-aqueous solvents are compatible with each other.

Examples of non-aqueous solvents include hydrocarbons, amides, ketones, esters, and ethers. Hydrocarbons include hexane, octane, cyclohexane, ethylcyclohexane, benzene, ethylbenzene, toluene, xylene, cymene, mesitylene.
Amides include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy- Examples include N,N-dimethylpropanamide, N,N-diethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone.

Examples of ketones include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, and cycloheptanone.
Examples of esters include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl 3-ethoxypropionate, γ-butyrolactone, γ- One example is valerolactone.
Examples of the ether include diethylene glycol diethyl ether, anisole, ethylbenzyl ether, butylphenyl ether, and diphenyl ether.

Preferably, in the present composition, the non-aqueous solvent is selected from the group consisting of amides, ketones and esters.
The content of the nonaqueous solvent in this composition is preferably 30% by mass or more, more preferably 40% by mass or more. The content of the non-aqueous solvent is preferably 70% by mass or less, more preferably 60% by mass or less.

Furthermore, the surface tension of the non-aqueous solvent is preferably 20 to 50 mN/m. For example, the surface tension of N-methyl-2-pyrrolidone is 41 mN/m, and the surface tension of cyclohexanone is 35.2 mN/m. It is thought that when a non-aqueous solvent whose surface tension is within the above range is used, the dispersion stability of the F particles is excellent and the mechanism of action of the present invention is more likely to be expressed.

A preferred embodiment of the present composition includes F particles, a silicone-modified (meth)acrylate polymer having a polyorganosiloxane group, a monovalent hydrocarbon group having 6 to 40 carbon atoms, and no fluorine atom ( Embodiment (1) includes a silicone-modified (meth)acrylate polymer (hereinafter also referred to as "silicone-modified (meth)acrylate polymer") and a non-aqueous solvent. In other words, embodiment (1) is an embodiment in which the non-fluorine compound is compound (1).
The present composition, which is aspect (1) (hereinafter also referred to as "the present composition (1)"), has excellent dispersion stability and handling properties, and is suitable for molded products such as coating films (polymer layers) formed from it. has excellent physical properties such as heat resistance and electrical properties (low coefficient of linear expansion, low dielectric constant, and low dielectric loss tangent) based on the F polymer, and also has excellent hydrophilicity and smoothness of its surface.
The reason why this composition (1) has excellent dispersion stability and handling properties is not necessarily clear, but it is thought to be as follows.

The silicone-modified (meth)acrylate polymer contained in the present composition (1) has a high affinity for F particles due to its polyorganosiloxane moiety, and particularly tends to improve the wettability of F particles. In addition, due to the presence of monovalent hydrocarbon groups having 6 to 40 carbon atoms, it has an affinity for non-aqueous solvents, and these properties are balanced by the rigid (meth)acrylic chains that make up the polymer chain. It is thought that there are. Therefore, this composition has excellent liquid physical properties such as dispersion stability and handling properties of F particles, and since the silicone-modified (meth)acrylate polymer does not have fluorine atoms, it can be used in molded products such as coatings and layers. It is thought that in forming the layer, the physical properties of the layer such as hydrophilicity and smoothness of the surface are improved.
This mechanism of action becomes more pronounced when the non-aqueous solvent constituting the present composition (1) is a specific polar solvent or when the present composition (1) further contains the compound (2). .

The monovalent hydrocarbon group having 6 to 40 carbon atoms contained in the silicone-modified (meth)acrylate polymer constituting the present composition (1) includes an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and the following formula (1). )
-C(Q ¹ )(Q ² )(Q ³ )(1)
[In formula (1), Q ¹ , Q ² ^and Q ³ are each independently an alkyl group or an aryl group, or ^{Q 1} ^and ^{Q 2} ^are hydrogen atoms, and Q ³ is an aryl group, Q ¹ and Q ² are each independently a hydrogen atom or an alkyl group and Q ³ is an alkoxy group, or Q ¹ is a hydrogen atom or an alkyl group and Q ² and Q ³ are together to form a linear or branched alkylene group which may have a ring structure. ] Examples include groups represented by the following. These groups may have a substituent. Note that the alkylene group in formula (1) may contain an unsaturated bond or a hetero atom.
Examples of monovalent hydrocarbon groups include cyclohexyl group, t-butylcyclohexyl group, benzyl group, norbornyl group, dicyclopentadienyl group, adamantyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group. group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group.
Among them, it is preferable that the monovalent hydrocarbon group is an alkyl group having 12 to 40 carbon atoms, and dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group are more preferable. preferable.

The polyorganosiloxane group possessed by the silicone-modified (meth)acrylate polymer constituting the present composition (1) is preferably derived from a (meth)acrylate unit having a polyorganosiloxane group.
Examples of such (meth)acrylates include (meth)acrylates having polyorganosiloxane groups obtained by reacting 3-(trialkoxysilyl)propyl (meth)acrylate with alkoxysilane or phenoxysilane.

Examples of silicone-modified (meth)acrylate-based polymers include (meth)acrylate-based polymers having a polysilsesquioxane (dehydrated polycondensate of a hydrolyzate of a silane compound having three hydrolyzable functional groups) structure. Examples of such polymers include ladder-type polysilsesquioxane in which a silicon-containing group is introduced at the end of a ladder skeleton, which is described in JP-A No. 2013-155231.

The silicone-modified (meth)acrylate polymer preferably further has a hydroxyl group from the viewpoint of further improving the hydrophilicity of the surface of a molded product formed from the present composition. The hydroxyl group may be present in the main chain or in the side chain of the silicone-modified (meth)acrylate polymer.
A silicone-modified acrylate polymer having a monovalent hydrocarbon group having 6 to 40 carbon atoms and a polyorganosiloxane group, preferably in a side chain or a graft chain, and further having a hydroxyl group, is preferred from the viewpoint of bulk and hydrophilicity. , is preferable for further inclusion in the present composition.
Commercially available silicone-modified (meth)acrylate polymers can be used, such as "SQ100" and "SQ200" (both trade names) manufactured by Tokushiki Co., Ltd. and "Charine" series manufactured by Nissin Chemical Industry Co., Ltd., and the like.

This composition (1) may further contain compound (2).
When compound (2) is further contained, its content is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the liquid composition.
Further, when compound (2) is further contained, the content is preferably 0.01 to 0.15 as a mass ratio to the F particles contained in the present composition. is preferably smaller than the content of the silicone-modified (meth)acrylate polymer (compound (1)).

A preferred embodiment of the present composition includes F particles, at least one nitrogen atom-containing group selected from the group consisting of an amino group, an ammonium group, an amide group, and a carbamate group, and a monovalent group having 6 to 40 carbon atoms. Embodiment (2) comprising a (meth)acrylate polymer having a hydrocarbon group and no fluorine atom (hereinafter also referred to as "nitrogen-containing atom group-containing (meth)acrylate polymer") and a non-aqueous solvent can be mentioned. In other words, embodiment (2) is an embodiment in which the non-fluorine compound is compound (2).
The present composition, which is aspect (2) (hereinafter also referred to as "the present composition (2)"), has excellent dispersion stability and handling properties, and is suitable for molded products such as coating films (polymer layers) formed from it. has excellent physical properties such as heat resistance and electrical properties (low coefficient of linear expansion, low dielectric constant, and low dielectric loss tangent) based on the F polymer, and also has excellent hydrophilicity and smoothness of its surface.
The reason why the present composition (2) has excellent dispersion stability and handling properties is not necessarily clear, but it is thought to be as follows.

The nitrogen-containing group-containing (meth)acrylate polymer contained in the present composition (2) not only has a high affinity for the nitrogen-containing group with respect to non-aqueous solvents, but also has rigidity that constitutes the polymer chain. The monovalent hydrocarbon group having 6 to 40 carbon atoms held in the (meth)acrylic chain acts as a steric hindrance, easily suppressing aggregation and sedimentation of F particles, and improving the dispersibility of F particles in this composition. is estimated to be increasing. Therefore, this composition (2) has excellent liquid properties such as dispersion stability and handleability, and since the (meth)acrylate polymer containing nitrogen-containing atom groups does not have fluorine atoms, it is possible to form coating films, layers, etc. It is thought that this improves the layer properties such as hydrophilicity and smoothness of the surface during the formation of the product.
This mechanism of action becomes even more remarkable when the non-aqueous solvent constituting the present composition (2) is a specific polar solvent or when the present composition (2) further contains the compound (1). .

The nitrogen-containing atom group-containing (meth)acrylate polymer contained in the present composition (2) is selected from the group consisting of (meth)acrylates that do not contain nitrogen atoms, amino groups, ammonium groups, amide groups, and carbamate groups. Preferably, it is a copolymer obtained by copolymerizing a (meth)acrylate having at least one nitrogen atom-containing group (hereinafter also referred to as "nitrogen atom-containing (meth)acrylate").

(Meth)acrylate that does not contain a nitrogen atom is expressed by the following formula (2)
CH ₂ =C(R ¹ )-CO-O-A ¹ ...(2)
(In formula (2), R ¹ represents a hydrogen atom or a methyl group, and A ¹ represents a monovalent hydrocarbon group).
The above-mentioned monovalent hydrocarbon group may have a substituent, and the group may contain an unsaturated bond or a heteroatom. Examples of monovalent hydrocarbon groups include alkyl groups having 1 to 40 carbon atoms, alkenyl groups having 2 to 40 carbon atoms, hydroxyalkyl groups having 2 to 4 carbon atoms, and alkylmonoalkylene containing alkyl groups having 1 to 18 carbon atoms. Glycol group, alkyl polyalkylene glycol group containing an alkyl group having 1 to 18 carbon atoms, alkenyl monoalkylene glycol group containing an alkenyl group having 2 to 18 carbon atoms, or poly substituted with an alkenyl group having 2 to 18 carbon atoms Examples include alkylene glycol groups, and alkyl groups having 12 to 40 carbon atoms are preferred.

Examples of the compound represented by formula (2) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. ) acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, octadecyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate ) acrylate, allyl (meth)acrylate, crotyl (meth)acrylate, oleyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methoxydiethylene glycol Examples include (meth)acrylate, methoxypropylene glycol (meth)acrylate, n-butoxyethylene glycol (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and trioxyethylenenonylphenol (meth)acrylate.

The nitrogen atom-containing (meth)acrylate described above is represented by the following formula (3)
CH ₂ =C(R ² )-CO-O-C _n H _2n -A ² ...(3)
^[ In formula (3), R ² represents a hydrogen atom or a methyl group, n represents an integer of 2 to 8, and A ² represents an amino group (R 4 ) represented by -N(R ⁴ )(R ⁵ ) , R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 ^to ⁶ carbon atoms ⁾ , ^an ammonium ^group (R ⁶ , R ⁷ and R ⁸ each independently have an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, an alkoxyalkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aralkyl group, or a substituent. (X ^- represents a halide ion or an anionic residue of an acid), an amide group represented by -NHC(O)(R ⁹ ) (R ⁹ is a carbon number of 1 to 10) ), or a carbamate group represented by -NHC(O)-OR ¹⁰ (R ¹⁰ represents an organic group having 1 to 10 carbon atoms)]. .

Examples of the alkyl group having 1 to 6 carbon atoms each independently represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ include methyl group, ethyl group, propyl group, butyl group, heptyl group, and hexyl group. Can be mentioned. These groups may have a substituent.
Examples of the hydroxyalkyl group having 2 to 6 carbon atoms each independently represented by R ⁶ , R ⁷ and R ⁸ include hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxyheptyl group, and hydroxyhexyl group, Examples of the alkoxyalkyl group having 1 to 4 carbon atoms include methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxymethyl group, ethoxyethyl group, and propoxymethyl group, and examples of the cycloalkyl group include cyclopropyl group. , cyclobutyl group, cyclopentyl group, and cyclohexyl group, and examples of the aralkyl group include benzyl group and ethylphenyl group.
The above groups may have a substituent.
Examples of the organic group having 1 to 10 carbon atoms represented by R ⁹ and R ¹⁰ include the groups exemplified above as the groups represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ .
The alkylene group represented by -C _n H _2n - may have a hydroxyl group on any carbon atom thereof.
Examples of the halide ions represented by X ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , and F ⁻ , and examples of acid anion residues include HSO ₄ ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , PO ₄ ^{3 -} , HPO ₄ ^3- , H ₂ PO ₄ ^- , C ₆ H ₆ SO ₃ ^- , and OH ^- .

Examples of the compound represented by formula (3) include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, Nt-butylaminoethyl (meth)acrylate, N, N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate, N-propylaminoethyl (meth)acrylate, N-butylaminoethyl (meth)acrylate; 2-hydroxy-3-(meth)acrylate; ) acryloxypropyltrimethylammonium chloride, 2-hydroxy-3-(meth)acryloxypropyltriethanolammonium chloride, 2-hydroxy-3-(meth)acryloxypropyldimethylbenzyl ammonium chloride, 2-hydroxy-3-(meth)acryloxypropyltrimethylammonium chloride, ) acryloxypropyldimethylphenylammonium chloride, (meth)acryloxyethyltrimethylammonium chloride, and (meth)acrylamidopropyltrimethylammonium chloride.

The nitrogen-containing (meth)acrylate polymer contains the above-described nitrogen-free (meth)acrylate, the above-described nitrogen-containing (meth)acrylate, and a terminal (meth)acryloyl group-containing macromonomer. It may also be a polymerized copolymer.
This terminal (meth)acryloyl group-containing macromonomer has the following formula (4)
CH ₂ =C(R ³ )-CO-O-A ³ ...(4)
[In formula (4), R ³ represents a hydrogen atom or a methyl group, and A ³ represents any one of a polyalkyl (meth)acrylate group, a polyalkenyl (meth)acrylate group, a polyester group, or a polystyrene group. ] It is preferable that it is at least one type of compound represented by the following.
Commercially available products can also be used as the terminal (meth)acryloyl group-containing macromonomer. For example, macromonomer AA-6 (trade name, polymethyl methacrylate containing a terminal methacryloyl group, number average molecular weight (Mn) 6000), both manufactured by Toagosei Co., Ltd., and macromonomer AW-6S (trade name, polyisobutyl containing a terminal methacryloyl group) methacrylate, Mn6000), macromonomer AB-6 (trade name, polybutyl acrylate containing a terminal methacryloyl group, Mn6000), and macromonomer AS-6 (trade name, polystyrene containing a terminal methacryloyl group, Mn6000).

The nitrogen-containing (meth)acrylate polymer contains, for example, 10 to 85 parts by mass of (meth)acrylate that does not contain nitrogen atoms, 10 to 60 parts by mass of nitrogen-containing (meth)acrylate, and optionally A copolymer having a number average molecular weight (Mn) of 4,000 to 100,000 is preferably copolymerized with 5 to 30 parts by mass of a macromonomer containing a terminal (meth)acryloyl group. When Mn is within the above range, the above-mentioned mechanism of action is more fully expressed, and aggregation of F particles is also more likely to be suppressed. Furthermore, molded products such as coating films (polymer layers) formed from the composition tend to have excellent surface hydrophilicity and smoothness. Such copolymers may be random copolymers, block copolymers, or graft copolymers.

The nitrogen-containing atom group-containing (meth)acrylate polymer preferably has a hydroxyl group from the viewpoint of further improving the hydrophilicity of the surface of a molded product formed from the present composition. The hydroxyl group may be present in the main chain or side chain of the (meth)acrylate polymer, and may be present at the terminal, in the polymer block, or in the graft chain. good. Examples of the (meth)acrylate polymer having a hydroxyl group include a compound represented by formula (2) in which A ¹ is a hydroxyalkyl group or a (mono/poly)alkylene glycol group, or a compound represented by formula (3). A compound in which any carbon atom of the alkylene group represented by -C _n H _2n - has a hydroxyl group, or any one of R ⁶ , R ⁷ , and R ⁸ in A ² is a hydroxyalkyl group. Examples include copolymers.

When the nitrogen-containing atom group-containing (meth)acrylate polymer is a polymer having an amino group or an ammonium group, the amine value thereof is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, and still more preferably 100 mgKOH/g or less. preferable. Moreover, the amine value is preferably 10 mgKOH/g or more.
As the (meth)acrylate polymer, commercially available products can be used, such as "DOPA-15B", "DOPA-15BHFS", "DOPA-17HF", "DOPA-22", "DOPA-35" manufactured by Kyoeisha Kagakusha. ” (both are product names).

This composition (2) may further contain compound (1).
When compound (1) is further contained, its content is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of composition (2).
Further, when compound (1) is further contained, the content thereof is preferably 0.01 to 0.15 as a mass ratio to the F particles contained in the present composition.
Furthermore, it is preferable that the content of compound (1) in the present composition (2) is greater than the content of compound (2).

A preferred embodiment of the present composition includes F particles, a nonaqueous solvent, and a carboxylic acid ester having an amine value of 20 to 120 mg/KOH and having a hydroxyl group (hereinafter also referred to as "carboxylic acid ester"). Embodiment (3) includes the following. In other words, embodiment (3) is an embodiment in which the compound having no fluorine atom is compound (3).
The present composition of aspect (3) (hereinafter also referred to as "present composition (3)") has excellent initial dispersibility and dispersion stability, and is excellent in handleability. Molded products such as coating films (polymer layers) formed from the present composition (3) have excellent heat resistance and electrical properties (low coefficient of linear expansion, low dielectric constant, low dielectric loss tangent), etc. based on the tetrafluoroethylene polymer. It has excellent physical properties, and its surface has excellent hydrophilicity and smoothness.

The carboxylic acid ester contained in the present composition (3) has an amine value of 20 to 120 mg/KOH and has a hydroxy group. The amine value of the carboxylic acid ester is preferably 100 mgKOH/g or less. Moreover, the amine value is preferably 25 mgKOH/g or more.
Further, the acid value of the carboxylic acid ester is preferably 5 to 20 mg/KOH, more preferably 5 to 15 mg/KOH.
The amine value is a value calculated by potentiometric titration using a 0.1N aqueous hydrochloric acid solution and converted into an equivalent amount of potassium hydroxide. The acid value can be measured by potentiometric titration according to JIS K 0070.

The carboxylic acid ester preferably has an ethyleneimine group and an oxyalkylenecarbonyl group, and is preferably a polymer having an ethyleneimine group in its main chain and an oxyalkylenecarbonyl group in its side chain. The oxyalkylene carbonyl group is preferably a group formed by ring opening of a lactone such as ε-caprolactone, γ-valerolactone, δ-valerolactone, 4-methyl-δ-valerolactone, etc. A group formed by ring polymerization is more preferable. Such an oxyalkylene carbonyl group can have a hydroxy group at its terminal by ring opening of the lactone.

The carboxylic acid ester contained in the present composition (3) has a hydroxy group, and is thought to contribute to improving the hydrophilicity of the surface of a molded product formed from the present composition. The hydroxyl group may be present in the main chain or side chain of the carboxylic acid ester polymer, and may be present at the terminal or in the polymer chain.

A carboxylic acid ester having a hydroxy group can be produced by a known method. Examples include compounds obtained by reacting polyethyleneimine with polyester, which are described in JP-A-54-37082, JP-A-61-174,939, and the like.
Among these, the carboxylic acid ester is preferably a polymer whose main chain is polyethyleneimine and whose side chain contains at least polycaprolactone. In other words, it is more preferable that the carboxylic acid ester is a compound obtained by addition polymerizing ε-caprolactone to polyethyleneimine.
When the carboxylic acid ester is a polymer as described above in which the hydrophobic part, which is the alkylene moiety of each of the polyethyleneimine group and the oxyalkylene carbonyl group, and the hydrophilic part, which is the amino group and the hydroxy group, are arranged in a balanced manner, It is presumed that the interaction between the F particles and the carboxylic acid ester that adsorbs them in a well-balanced manner is likely to occur, and aggregation and sedimentation between the F particles can be suppressed, making it easier to improve the dispersibility of the F particles in the present composition. Therefore, it is believed that this composition has improved initial dispersibility and dispersion stability, and also improves layer properties such as surface hydrophilicity and smoothness when forming molded products such as coatings and layers. It will be done.
This mechanism of action becomes even more pronounced when the composition (3) further contains the compound (1).

The weight average molecular weight (Mw) of the polymer carboxylic acid ester is preferably in the range of 2,000 to 20,000. Further, the molecular weight distribution of such a polymer is preferably 2 or less. When Mw is within the above range, the above-mentioned mechanism of action is more fully expressed and aggregation of F particles is also more likely to be suppressed. Furthermore, molded products such as coating films (polymer layers) formed from the composition tend to have excellent surface hydrophilicity and smoothness.

Commercially available products can also be used as such carboxylic acid esters. For example, it can be selected from compounds in the "DISPER" series (manufactured by BYK) such as "DISPERBYK107" and "DISPERBYK108", the "Sols Bars" series (manufactured by Lubrizol), and the "Ajisper" series (manufactured by Ajinomoto Fine Techno).

This composition (3) may further contain compound (1).
When compound (1) is further contained, its content is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the liquid composition.
Further, when compound (1) is further contained, the content thereof is preferably 0.01 to 0.15 as a mass ratio to the F particles contained in composition (3).
Further, it is preferable that the content of the silicone-modified (meth)acrylate polymer (compound (1)) in the present composition (3) is greater than the content of the carboxylic acid ester contained in the present composition (3).

The content of the non-fluorine compound in the composition is preferably 10% by mass or less based on the total mass of the composition.
Further, the content of the non-fluorine compound is preferably 0.01 to 0.15, more preferably 0.03 to 0.12, as a mass ratio to the F particles contained in the present composition.

The viscosity of the present composition is preferably 3000 mPa·s or less, more preferably 2000 mPa·s or less. The viscosity of this composition part is preferably 10 mPa·s or more, more preferably 25 mPa·s or more. In this case, the present composition has excellent coating properties and is easy to form into a molded article such as a coating film (polymer layer) having an arbitrary thickness. Further, the present composition having a viscosity within this range tends to exhibit the physical properties of the F polymer to a high degree in a molded article formed from the composition.
The thixotropic ratio of the present composition is preferably 1.0 to 2.5. In this case, the present composition has excellent coating properties and homogeneity, and can easily produce denser molded products.

The composition may further contain a nonionic surfactant. In this case, it becomes easier to adjust the surface tension of the nonaqueous solvent to the above range. Examples of the nonionic surfactant include glycol surfactants, acetylene surfactants, and silicone surfactants different from compound (1). One type of nonionic surfactant may be used, or two or more types may be used.
When the present composition further contains a nonionic surfactant, the content thereof is preferably in the range of 1 to 15% by mass, and 3 to 10% by mass, based on the F particles in the composition. The range is more preferred.

The composition may further contain an inorganic filler. In this case, a molded article such as a coating film (polymer layer) formed from the present composition tends to have excellent electrical properties and low linear expansion.
The shape of the inorganic filler may be spherical, needle-like (fibrous), or plate-like, and specifically, spherical, scale-like, layered, leaf-like, apricot-like, columnar, cock-comb-like, etc. It may be axial, leaf-like, mica-like, block-like, flat-plate-like, wedge-like, rosette-like, mesh-like, or prismatic.
Examples of inorganic fillers include quartz powder, silica, wollastonite, talc, silicon compounds such as silicon nitride, silicon carbide, and mica; nitrogen compounds such as boron nitride and aluminum nitride; aluminum oxide, zinc oxide, titanium oxide, and cerium oxide. , metal oxides such as beryllium oxide, magnesium oxide, nickel oxide, vanadium oxide, copper oxide, iron oxide, silver oxide; carbon fibers; carbon allotropes such as graphite, graphene, carbon nanotubes; metals such as silver and copper; It will be done.
One type of inorganic filler may be used, or two or more types may be used in combination.
The D50 of the inorganic filler is preferably 0.1 to 50 μm.
The surface of the inorganic filler may be surface-treated with a silane coupling agent.
When the present composition contains an inorganic filler, the content of the inorganic filler in the present composition is preferably 1 to 25% by mass.

The composition may further contain other resins different from the F polymer. Such other resin may be contained in the present composition as non-hollow particles, or may be contained dissolved or dispersed in the non-aqueous solvent constituting the present composition.
Other resins include polyester resins such as liquid crystalline aromatic polyesters, polyimide resins, polyamideimide resins, epoxy resins, maleimide resins, urethane resins, polyphenylene ether resins, polyphenylene oxide resins, and polyphenylene sulfide resins.
As the other resin, aromatic polymers are preferred, and at least one aromatic imide polymer selected from the group consisting of aromatic polyimide, aromatic polyamic acid, aromatic polyamideimide, and precursors of aromatic polyamideimide is more preferred. preferable.
When the present composition further contains other resins, the content of the other resins relative to the F particles is preferably 1 to 25% by mass.

The present composition may further contain a viscosity modifier from the viewpoint of adjusting its viscosity and thixotropic ratio.

The present composition further contains an antifoaming agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a coloring agent, a conductive agent, a mold release agent, and a flame retardant. It may contain additives such as.

This composition is obtained by mixing F particles, a non-fluorine compound, a non-aqueous solvent, a nonionic surfactant, an inorganic filler, other resins, additives, and the like.
This composition may be obtained by mixing the F particles, the non-fluorine compound, and the non-aqueous solvent all at once, or may be obtained by mixing them separately one after another, or by preparing a masterbatch of these in advance and mixing it with the remaining The ingredients may be mixed. There is no particular restriction on the order of mixing, and the mixing method may be all at once or divided into multiple batches.

For example, the present composition can be obtained by dispersing F particles in advance in a part of a non-aqueous solvent, then adding and mixing a non-fluorine compound, and adding the resulting mixture to the remaining non-aqueous solvent. It is preferable from the viewpoint of improving dispersibility.
When the above-mentioned non-fluorine compound is further mixed, it may be added as it is or as a solution in the above-mentioned non-aqueous solvent. In addition, when further mixing the above-mentioned nonionic surfactant, inorganic filler, other resin, additives, etc. as necessary, even if they are mixed at the time of mixing the F particles and the non-aqueous solvent, the mixture may be mixed with the non-aqueous solvent. They may be mixed when added to the solvent.

Mixing devices for obtaining the present composition include stirring devices equipped with blades such as Henschel mixer, pressure kneader, Banbury mixer, and planetary mixer, ball mill, attritor, basket mill, sand mill, sand grinder, dyno mill, Grinding equipment equipped with media such as Dispermat, SC mill, spike mill, and agitator mill, microfluidizer, nanomizer, ultimizer, ultrasonic homogenizer, resolver, disperser, high-speed impeller, thin-film rotating high-speed mixer, rotation-revolution stirrer and a dispersion device equipped with other mechanisms such as a V-type mixer.

The dielectric constant of a molded article formed from the present composition is preferably 2.4 or less, more preferably 2.2 or less. Moreover, it is preferable that the dielectric constant is more than 1.0. The dielectric loss tangent of the molded product is preferably 0.0022 or less, more preferably 0.0020 or less. Moreover, it is preferable that the dielectric loss tangent is more than 0.0010. The thermal conductivity of the molded product is preferably 1 W/m·K or more, more preferably 3 W/m·K or more.

If this composition is subjected to a molding method such as extrusion into a sheet, a molded article such as a sheet containing the F polymer can be formed. The sheet obtained by extrusion may be further subjected to press molding, calendar molding, etc. and then cast. Preferably, the sheet is further heated to remove the non-aqueous solvent and sinter the F polymer.

The thickness of the sheet formed from the present composition is preferably 1 to 1000 μm.
Suitable ranges of the dielectric constant, dielectric loss tangent, and thermal conductivity of the sheet are the same as the ranges of the dielectric constant, dielectric loss tangent, and thermal conductivity of the molded article, respectively. Note that the thermal conductivity of the sheet means the thermal conductivity in the in-plane direction of the sheet.
The coefficient of linear expansion of the sheet is preferably 250 ppm/°C or less, more preferably 220 ppm/°C or less. The lower limit of the linear expansion coefficient of the sheet is 30 ppm/°C. Note that the linear expansion coefficient means a value obtained by measuring the linear expansion coefficient of a test piece in the range of 25° C. or higher and 260° C. or lower according to the measurement method specified in JIS C 6471:1995.

A laminate can be formed by laminating such sheets on a base material. Examples of the method for manufacturing the laminate include a method of extrusion molding the present composition onto the base material, a method of thermocompression bonding the sheet and the base material, and the like.
As a base material, metal substrates such as metal foils of copper, nickel, aluminum, titanium, alloys thereof, etc.; polyimide, polyamide, polyetheramide, polyphenylene sulfide, polyallyletherketone, polyamideimide, liquid crystalline polyester, tetrafluorocarbon Examples include films of heat-resistant resin such as ethylene-based polymer; prepreg substrates (precursor of fiber-reinforced resin substrates); ceramic substrates such as silicon carbide, aluminum nitride, and silicon nitride; and glass substrates.

Examples of the shape of the base material include a planar shape, a curved shape, and an uneven shape. Further, the shape of the base material may be any of foil, plate, film, and fiber.
The ten-point average roughness of the surface of the base material is preferably 0.01 to 0.05 μm.
The surface of the base material may be surface-treated with a silane coupling agent or may be plasma-treated. Such silane coupling agents include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, -A silane coupling agent having a functional group such as isocyanatepropyltriethoxysilane is preferred.
The peel strength between the sheet and the base material is preferably 10 to 100 N/cm.

In addition, if this composition is placed on the surface of a base material and heated to form a polymer layer containing F polymer (hereinafter also referred to as "F layer"), it is possible to form a polymer layer containing F polymer (hereinafter also referred to as "F layer"). A laminate having the layers in this order is obtained.
The F layer is preferably formed by placing the present composition on the surface of the base material, heating to remove the nonaqueous solvent, and further heating to bake the F polymer. By separating the base material from such a laminate, a sheet containing the F polymer can be obtained.
Examples of the base material include those similar to those that can be laminated with the sheet described above, and preferred embodiments thereof are also the same.

Methods for disposing the composition include a coating method, a droplet discharge method, and a dipping method, with roll coating, knife coating, bar coating, die coating, and spraying being preferred.
Heating during removal of the nonaqueous solvent is preferably carried out at 100 to 200° C. for 0.1 to 30 minutes. In this heating, the non-aqueous solvent does not need to be completely removed, but may be removed to the extent that the layer formed by packing the F particles can maintain a self-supporting film. Further, during heating, air may be blown to promote removal of the non-aqueous solvent by air drying.

Heating during firing of the F polymer is preferably carried out at a temperature equal to or higher than the melting temperature of the F polymer, more preferably at 360 to 400° C. for 0.1 to 30 minutes.
Examples of heating devices for each heating include an oven and a ventilation drying oven. The heat source in the device may be a contact heat source (hot air, hot plate, etc.) or a non-contact heat source (infrared rays, etc.).
Moreover, each heating may be performed under normal pressure or under reduced pressure.
Further, the atmosphere in each heating may be an air atmosphere or an inert gas (helium gas, neon gas, argon gas, nitrogen gas, etc.) atmosphere.

The F layer is formed through the steps of arranging the composition and heating it. These steps may be performed once or may be repeated two or more times. For example, the present composition may be placed on the surface of the base material and heated to form an F layer, and then the present composition may be placed on the surface of the F layer and heated to form a second F layer. . Further, at the stage where the present composition is placed on the surface of the base material and heated to remove the non-aqueous solvent, the present composition may be further placed on the surface and heated to form the F layer.
The composition may be placed on only one surface of the substrate, or on both sides of the substrate. In the former case, a laminate is obtained that has a base layer and an F layer on one surface of the base layer, and in the latter case, a laminate is obtained that has a base layer and an F layer on both surfaces of the base layer. A laminate is obtained.
The thickness of the F layer varies depending on the use of the laminate, but is preferably in the range of 1 to 1000 μm.

Preferred specific examples of the laminate include a metal foil and a metal clad laminate having an F layer on at least one surface of the metal foil, a polyimide film and a multilayer film having an F layer on both surfaces of the polyimide film. can be mentioned.
The preferred ranges of the thickness, dielectric constant, dielectric loss tangent, thermal conductivity, coefficient of linear expansion, and peel strength between the F layer and the base material layer of the F layer are the thickness, The preferred ranges are the same as the dielectric constant, dielectric loss tangent, thermal conductivity, coefficient of linear expansion, and peel strength between the sheet and the base material.

This composition is useful as a material for imparting insulation, heat resistance, corrosion resistance, chemical resistance, water resistance, impact resistance, and thermal conductivity.
Specifically, the present composition is used in printed wiring boards, thermal interface materials, power module substrates, coils used in power devices such as motors, in-vehicle engines, heat exchangers, vials, syringes, Ampules, medical wires, secondary batteries such as lithium ion batteries, primary batteries such as lithium batteries, radical batteries, solar cells, fuel cells, lithium ion capacitors, hybrid capacitors, capacitors, capacitors (aluminum electrolytic capacitors, tantalum electrolytic capacitors, etc.) ), electrochromic devices, electrochemical switching devices, electrode binders, electrode separators, and electrodes (positive and negative electrodes).
The composition is also useful as an adhesive for bonding parts together. Specifically, this composition can be used for adhesion of ceramic parts, adhesion of metal parts, adhesion of electronic parts such as IC chips, resistors, and capacitors on substrates of semiconductor elements and module parts, adhesion of circuit boards and heat sinks, and adhesion of LEDs. Can be used to bond chips to substrates.

Molded products such as sheets and laminates formed from the present composition are useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry products, heat dissipation parts, and the like.
Specifically, electric wire coating materials (aircraft wires, etc.), enameled wire coating materials used in motors of electric vehicles, electrical insulation tape, oil drilling insulation tape, oil transportation hoses, hydrogen tanks, printed circuit boards, etc. materials, separation membranes (precision filtration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc.), electrode binders or electrode coating materials (for lithium secondary batteries, fuel cells, etc.) , copy rolls, furniture, automobile dashboards, covers for home appliances, etc., sliding parts (load bearings, yaw bearings, sliding shafts, valves, bearings, bushes, seals, thrust washers, wear rings, pistons, slide switches, gears, cams, belt conveyors, food conveyor belts, etc.), tension ropes, wear pads, wear strips, tube lamps, test sockets, wafer guides, centrifugal pump wear parts, chemical and water supply pumps, tools (shovels, files, cutters, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, racket guts, dies, toilet bowls, container coverings, mounted heat dissipation boards for power devices, heat dissipation materials for wireless communication devices, transistors, thyristors, rectifiers, transformers. , power MOS FETs, CPUs, heat dissipation fins, metal heat dissipation plates, blades for wind turbines, wind power generation equipment, aircraft, etc., casings for computers and displays, electronic device materials, interior and exterior of automobiles, processing machines that perform heat treatment under low oxygen conditions. It is useful as a sealing material for vacuum ovens, plasma processing equipment, etc., heat dissipation parts in processing units such as sputtering and various dry etching equipment, and electromagnetic shielding.

Molded products such as sheets and laminates formed from the present composition are useful as electronic board materials such as flexible printed wiring boards and rigid printed wiring boards, protective films and heat dissipation boards, particularly as heat dissipation boards for automobiles.

Although the present composition and the method for manufacturing a laminate having a polymer layer formed from the present composition have been described above, the present invention is not limited to the configuration of the embodiments described above. For example, in the composition of the above embodiment, any other composition may be added, or any composition that exhibits the same function may be substituted for the present composition. In addition, the method for manufacturing a laminate having a polymer layer formed from the present composition may additionally include any other configuration in the configuration of the above embodiment, or any other configuration that exhibits the same function. It may be replaced with the configuration.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.
1. Preparation of each component [F polymer]
F particle 1: Contains 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE units, NAH units, and PPVE units in this order, and carbonyl group-containing groups per 1 × 10 ⁶ main chain carbon atoms. Particles of tetrafluoroethylene polymer (melting temperature: 300°C) having 1000 particles (D50: 2.0 μm, specific surface area: 7 m ² /g)
[Dispersant that is a non-fluorine compound]
Polymer 11: has a ladder-like polyorganosiloxane group derived from _CH2 =CH( _CH3 )C(O)O( _CH2 ) _3SiO ( _CH3 ) ₃ , and the monovalent hydrocarbon group is an octadecyl group. A silicone-modified (meth)acrylate polymer having no fluorine atom and having an octadecyl methacrylate unit Polymer 21: having -N(CH ₃ ) ₃ ⁺ Cl ^- (ammonium group) as a nitrogen atom-containing group, 1 A fluorine-free (meth)acrylate polymer having an octadecyl methacrylate unit whose valent hydrocarbon group is an octadecyl group (amine value: 13)
Polymer 22: has -N(CH ₃ ) ₃ ⁺ Cl ^- (ammonium group) as a nitrogen atom-containing group, has an octadecyl group as a monovalent hydrocarbon group, has an octadecyl methacrylate unit, does not have a fluorine atom ( meth)acrylate polymer (amine value: 120)
Carboxylic acid ester 1: Carboxylic acid ester having a hydroxy group, having an ethyleneimine group in the main chain and an oxyalkylene carbonyl group in the side chain (amine value: 71 mgKOH/g)
Carboxylic acid ester 2: (meth)acrylate polymer having an ethyleneimine group in the main chain, an oxyalkylene carbonyl group in the side chain, and a carboxylic acid ester having a hydroxy group (amine value: 144 mgKOH/g)
[Dispersant that is not a non-fluorine compound]
Polymer E: has a polyorganosiloxane group derived from _CH2 =CH( _CH3 )C(O)O( _CH2 ) _3SiO ( _CH3 ) ₃ , and the monovalent hydrocarbon group is a methyl group, Silicone-modified (meth)acrylate polymer without fluorine atoms, having methyl methacrylate units Polymer O: having octadecyl methacrylate units, having no polyorganosiloxane groups and whose monovalent hydrocarbon group is an octadecyl group, and having fluorine atoms Atom-free (meth)acrylate polymer Polymer F: A (meth)acrylate polymer containing a fluorine atom and having a (meth)acrylate unit having a perfluoroalkyl group and an alkyl (meth)acrylate unit Polymer N1: Nitrogen atom A (meth)acrylate-based polymer having no fluorine atom and having an octadecyl methacrylate unit whose monovalent hydrocarbon group is an octadecyl group Polymer N2: -N(CH ₃ ) as a nitrogen atom-containing group ₃ ⁺ Cl ⁻ (ammonium group), the monovalent hydrocarbon group is a methyl group, a methyl methacrylate unit, a fluorine-free (meth)acrylate polymer (amine value: 30)
Surfactant 1: Fluorine surfactant (manufactured by Neos, trade name "Ftergent 610FM")
[Non-aqueous solvent]
NMP: N-methylpyrrolidone Tol: toluene

2-1. Production example of liquid composition [Example 1-1]
F particles 1, polymer 11, polymer 21, and NMP were placed in a pot, and zirconia balls were placed in the pot. Thereafter, the pot was rolled at 150 rpm for 1 hour, containing F particles 1 (30 parts by mass), polymer 11 (2.5 parts by mass), polymer 21 (0.5 parts by mass) and NMP (67 parts by mass). Liquid composition 11 (viscosity: 30 mPa·s) was obtained.

[Example 1-2]
A liquid composition containing F particles 1 (30 parts by mass), polymer 11 (2.5 parts by mass) and NMP (67.5 parts by mass) in the same manner as in Example 1-1 except that polymer 21 was not added. I got 12.
[Example 1-3]
F particles 1 (30 parts by mass), polymer 11 (2.5 parts by mass), polymer 21 (0.5 parts by mass) and Tol were prepared in the same manner as in Example 1-1 except that Tol was used instead of NMP. A liquid composition 13 containing (67 parts by mass) was obtained.
[Example 1-4]
F particles 1 (30 parts by mass), polymer O (2.5 parts by mass) and NMP (67 parts by mass) were prepared in the same manner as in Example 1-1 except that polymer O was used instead of polymer 11 and polymer 21 was not added. .5 parts by mass) was obtained.

[Example 1-5]
F particles 1 (30 parts by mass), polymer E (2.5 parts by mass) and NMP (67 parts by mass) were prepared in the same manner as in Example 1-1 except that polymer E was used instead of polymer 11 and polymer 21 was not added. .5 parts by mass) was obtained.
[Example 1-6]
F particles 1 (30 parts by mass), polymer F (0.5 parts by mass) and NMP (69 parts by mass) were prepared in the same manner as in Example 1-1 except that polymer F was used instead of polymer 11 and polymer 21 was not added. .5 parts by mass) was obtained.

3-1. Evaluation 3-1-1. Dispersibility of Liquid Composition The dispersibility of each of the liquid compositions obtained in Examples 1-1 to 1-6 above was visually observed and evaluated using the following criteria.
[Dispersibility]
A: No aggregation or sedimentation of F particles 1 is observed, and it is well dispersed. B: It is viscous and has a tendency to agglomerate, but it is dispersed. C: It becomes a slurry, and some gelation is also observed, and it is not dispersed.

3-2. Production of Laminate and Evaluation of Layer Physical Properties A laminate was produced using each of the liquid compositions 11 to 13 and 16 that had good dispersibility, and the formed polymer layer was evaluated. Specifically, each liquid composition is applied to one surface of copper foil to form a coating layer using a roll-to-roll process, and then placed in a ventilation drying oven (furnace temperature: 150°C) for 3 minutes. The non-aqueous solvent was removed to form a dry membrane. Next, the base material on which the dry film was formed was passed through a far-infrared furnace (furnace temperature of 300 °C near the entrance and exit of the furnace, furnace temperature of 360 °C near the center) for 5 minutes to melt and bake the F particles 1. A laminate having a polymer layer (thickness: 25 μm) on the surface of copper foil was obtained.
The water contact angle of the surface of the obtained polymer layer was measured and evaluated based on the following criteria.
[Layer properties]
A: Water contact angle is less than 75° B: Water contact angle is 75° to 120° C: Water contact angle is more than 120° The above evaluation results are summarized in Table 1.

2-2. Production example of liquid composition [Example 2-1]
F particles 1, polymer 21, polymer 11, and NMP were placed in a pot, and zirconia balls were placed in the pot. Thereafter, the pot was rolled at 150 rpm for 1 hour to contain F particles 1 (30 parts by mass), polymer 21 (0.5 parts by mass), polymer 11 (2.5 parts by mass) and NMP (67 parts by mass). Liquid composition 21 (viscosity: 30 mPa·s) was obtained.

[Example 2-2]
A liquid composition containing F particles 1 (30 parts by mass), polymer 21 (0.5 parts by mass) and NMP (69.5 parts by mass) in the same manner as in Example 2-1 except that polymer 11 was not added. I got 22.
[Example 2-3]
F particles 1 (30 parts by mass), polymer 21 (0.5 parts by mass), polymer 11 (2.5 parts by mass) and Tol were prepared in the same manner as in Example 2-1 except that Tol was used instead of NMP. A liquid composition 23 containing (67 parts by mass) was obtained.
[Example 2-4]
F particle 1 (30 parts by mass), polymer 22 (0.5 parts by mass), polymer 11 (2.5 parts by mass) in the same manner as Example 2-1 except that polymer 22 was used instead of polymer 21. A liquid composition 24 containing NMP (67 parts by mass) was obtained.

[Example 2-5]
F particles 1 (30 parts by mass), polymer N1 (0.5 parts by mass) and NMP (69 parts by mass) were prepared in the same manner as in Example 2-1 except that polymer N1 was used instead of polymer 21 and polymer 11 was not added. .5 parts by mass) was obtained.
[Example 2-6]
F particles 1 (30 parts by mass), polymer N2 (0.5 parts by mass) and NMP (69 parts by mass) were prepared in the same manner as in Example 2-1 except that polymer N2 was used instead of polymer 21 and polymer 11 was not added. .5 parts by mass) was obtained.
[Example 2-7]
F particles 1 (30 parts by mass), polymer F (0.5 parts by mass) and NMP (69 parts by mass) were prepared in the same manner as in Example 2-1 except that polymer F was used instead of polymer 21 and polymer 11 was not added. .5 parts by mass) was obtained.

3-2. Evaluation 3-2-1. Dispersibility of Liquid Composition The dispersibility of each of the liquid compositions obtained in Examples 2-1 to 2-7 above was visually observed and evaluated using the following criteria.
[Dispersibility]
A: No agglomeration or sedimentation of F particles 1 is observed, and it is well dispersed. B: It is viscous and tends to aggregate, but it is dispersed. C: It becomes a slurry, and some gelation is also observed, and it is not dispersed.

3-2-2. Production of laminates and evaluation of layer physical properties Laminates were produced using each of the liquid compositions 21 to 24 and 27, which had good dispersibility, and the formed polymer layers were evaluated. Specifically, each liquid composition is applied to one surface of copper foil to form a coating layer using a roll-to-roll process, and then placed in a ventilation drying oven (furnace temperature: 150°C) for 3 minutes. The non-aqueous solvent was removed to form a dry membrane. Next, the base material on which the dry film was formed was passed through a far-infrared furnace (furnace temperature of 300 °C near the entrance and exit of the furnace, furnace temperature of 360 °C near the center) for 5 minutes to melt and bake the F particles 1. A laminate having a polymer layer (thickness: 25 μm) on the surface of copper foil was obtained.
The water contact angle of the surface of the obtained polymer layer was measured and evaluated based on the following criteria.
[Layer properties]
A: Water contact angle is less than 75° B: Water contact angle is 75° to 120° C: Water contact angle is more than 120° The above evaluation results are summarized in Table 2.

2-3. Production example of liquid composition [Example 3-1]
F particles 1, carboxylic acid ester 1, polymer 11, and NMP were placed in a pot, and zirconia balls were placed in the pot. Thereafter, the pot was rolled at 150 rpm for 1 hour, and F particles 1 (30 parts by mass), carboxylic acid ester 1 (0.5 parts by mass), polymer 11 (2.5 parts by mass), and NMP (67 parts by mass) A liquid composition 31 (viscosity: 30 mPa·s) containing the following was obtained.

[Example 3-2]
A liquid containing F particles 1 (30 parts by mass), carboxylic acid ester 1 (0.5 parts by mass) and NMP (69.5 parts by mass) was prepared in the same manner as in Example 3-1 except that polymer 11 was not added. Composition 32 was obtained.
[Example 3-3]
F particles 1 (30 parts by mass), carboxylic acid ester 1 (0.5 parts by mass), and polymer 1 (2.5 parts by mass) were prepared in the same manner as in Example 3-1 except that Tol was used instead of NMP. A liquid composition 33 containing Tol (67 parts by mass) was obtained.

[Example 3-4]
F particles 1 (30 parts by mass), carboxylic ester 2 (0.5 parts by mass), polymer 11 ( A liquid composition 34 containing NMP (2.5 parts by mass) and NMP (67 parts by mass) was obtained.
[Example 3-5]
F particles 1 (30 parts by mass) and surfactant 1 (0.5 parts by mass) were prepared in the same manner as in Example 3-1 except that surfactant 1 was used instead of carboxylic acid ester 1 and polymer 11. A liquid composition 35 containing NMP (69.5 parts by mass) was obtained.

3-3. Evaluation 3-3-1. Initial dispersibility Each component was added to a beaker equipped with a rotor at a composition ratio corresponding to each of the liquid compositions of Examples 3-1 to 3-5 above and stirred. The state after the start of stirring was visually observed, and the initial dispersibility was evaluated based on the following criteria.
[Initial dispersibility]
A: F particles are quickly and uniformly dispersed in the liquid B: F particles are quickly dispersed in the liquid, but uniform dispersion takes time

3-3-2. Dispersion Stability of Liquid Compositions Each of the liquid compositions obtained in Examples 3-1 to 3-5 above was allowed to stand for a long period of time, and its dispersion stability was visually observed and evaluated using the following criteria.
[Dispersion stability]
A: No agglomeration or sedimentation of F particles 1 is observed, and the particles are well dispersed. B: Agglomeration and sedimentation are observed, but they can be easily redispersed. C: Formed into a slurry, with some gelation observed and not dispersed.

3-3-3. Production of Laminate and Evaluation of Layer Physical Properties Laminates were produced using each of Liquid Compositions 31 to 35, and the formed polymer layers were evaluated. Specifically, each liquid composition is applied to one surface of copper foil to form a coating layer using a roll-to-roll process, and then placed in a ventilation drying oven (furnace temperature: 150°C) for 3 minutes. The non-aqueous solvent was removed to form a dry membrane. Next, the base material on which the dry film was formed was passed through a far-infrared furnace (furnace temperature 300°C near the entrance and exit of the furnace, furnace temperature 360°C near the center) for 5 minutes to melt and bake the F particles 1. A laminate having a polymer layer (thickness: 25 μm) on the surface of copper foil was obtained.
The water contact angle of the surface of the obtained polymer layer was measured and evaluated based on the following criteria.
[Layer properties]
A: Water contact angle is less than 75° B: Water contact angle is 75° to 120° C: Water contact angle is more than 120° The above evaluation results are summarized in Table 3.

The liquid composition of the present invention has excellent initial dispersibility and dispersion stability, and is easy to handle. Further, it is possible to form molded products such as coating films (polymer layers) that exhibit the physical properties of the F polymer to a high degree and have excellent surface hydrophilicity.
In addition, the specifications and patents of Japanese Patent Application No. 2022-143825, Japanese Patent Application No. 2022-143826, filed on September 9, 2022, and Japanese Patent Application No. 2022-178270, filed on November 7, 2022. The entire contents of the claims and abstract are hereby incorporated by reference as a disclosure of this invention.

Claims

Tetrafluoroethylene polymer particles,
At least one fluorine atom-free compound selected from the following compounds (1) to (3),
A liquid composition comprising a non-aqueous solvent.
Compound (1) Silicone-modified (meth)acrylate polymer having a polyorganosiloxane group and a monovalent hydrocarbon group having 6 to 40 carbon atoms Compound (2) Selected from the group consisting of an amino group, an ammonium group, an amide group, and a carbamate group A (meth)acrylate polymer having at least one nitrogen atom-containing group and a monovalent hydrocarbon group having 6 to 40 carbon atoms Compound (3) A carboxylic acid ester having an amine value of 20 to 120 mg/KOH and having a hydroxyl group
The liquid composition according to claim 1, wherein the at least one fluorine atom-free compound is the silicone-modified (meth)acrylate polymer (compound (1)).
The liquid composition according to claim 2, wherein the tetrafluoroethylene polymer is a heat-melting tetrafluoroethylene polymer containing an oxygen-containing polar group.
The liquid composition according to claim 2, wherein the average particle diameter of the particles of the tetrafluoroethylene polymer is 1 μm or more and less than 10 μm.
The liquid composition according to claim 2, wherein the content of the particles of the tetrafluoroethylene polymer is 25% by mass or more.
The liquid composition according to claim 2, wherein the content of the silicone-modified (meth)acrylate polymer is 0.01 to 0.15 as a mass ratio to the particles of the tetrafluoroethylene polymer.
The liquid composition according to claim 2, wherein the nonaqueous solvent is at least one selected from amides, ketones, and esters.
The liquid composition according to claim 2, which has a viscosity of 3000 mPa·s or less.
The liquid composition according to claim 1, wherein the at least one fluorine atom-free compound is the (meth)acrylate polymer (compound (2)).
The liquid composition according to claim 9, wherein the content of the (meth)acrylate polymer is 0.01 to 0.15 as a mass ratio to the particles of the tetrafluoroethylene polymer.
The liquid composition according to claim 9, which has a viscosity of 3000 mPa·s or less.
The liquid composition according to claim 1, wherein the at least one fluorine atom-free compound is the carboxylic acid ester (compound (3)).
The liquid composition according to claim 12, wherein the content of the carboxylic acid ester is 0.01 to 0.15 as a mass ratio to the particles of the tetrafluoroethylene polymer.
The liquid composition according to claim 12, which has a viscosity of 3000 mPa·s or less.
The liquid composition according to any one of claims 1 to 14 is placed on the surface of a base material and heated to form a polymer layer containing the tetrafluoroethylene polymer, and the base material made of the base material is A method for manufacturing a laminate, comprising obtaining a laminate having a material layer and the polymer layer in this order.