Aqueous dispersions and their manufacturing methods

Abstract

The present invention provides an aqueous dispersion containing tetrafluoroethylene polymer particles, which has excellent dispersion stability and can form a molded body with excellent electrical properties such as low dielectric loss factor and low transmission loss, or excellent flexibility such as flexural strength, UV absorption, adhesion and tightness to resin films such as polyimide films. The aqueous dispersion of the present invention comprises tetrafluoroethylene polymer particles, an aromatic amide resin with an acid value of 20-100 mg / KOH, and water, and has a pH value of 5-10.

Description

Technical field

[0001] The present invention relates to an aqueous dispersion comprising tetrafluoroethylene polymer particles and a specific aromatic imide resin, and a method for producing the aqueous dispersion.

Prior technology

[0002] Tetrafluoroethylene-based polymers such as polytetrafluoroethylene (PTFE) have excellent physical properties such as electrical properties, water and oil repellency, chemical resistance, and heat resistance, and are used in various industrial applications (Patent Document 1) . A dispersion containing tetrafluoroethylene-based polymer particles is known as a coating agent for imparting the above-mentioned physical properties to the surface of a substrate. In particular, in recent years, dispersions containing tetrafluoroethylene-based polymer particles have attracted attention as materials with excellent electrical properties such as low dielectric constant and low dielectric loss factor that form the dielectric layer of printed circuit boards corresponding to high-band frequencies. .

[0003] From the viewpoint of operability, it is preferable to make the above-mentioned dispersion liquid an aqueous system. Patent Document 2 discloses a laminate formed by applying an aqueous dispersion of a fluororesin to one or both sides of a resin film and heating it. Patent Document 3 discloses a composition comprising an aqueous polyimide precursor, a fluororesin, and water, and these are uniformly mixed. Prior Art Documents Patent Documents

[0004] Patent Document 1: Japanese Patent Application Publication No. 2019-218484 Patent Document 2: Japanese Patent Application Publication No. 09-157418 Patent Document 3: Japanese Patent Application Publication No. 2016-20488

Content of invention

[0005] [the problem to be solved by the invention]

[0006] However, the dispersion state of an aqueous dispersion of a tetrafluoroethylene-based polymer is generally inferior to that of a non-aqueous dispersion. Therefore, during the coating and firing of the base material, the filling property of the tetrafluoroethylene polymer particles becomes loose, and the compactness of the formed polymer layer tends to cause problems. Specifically, if the polymer layer is formed on a base material such as a resin film by a continuous production process such as roll to roll, cracks or pinholes are likely to occur in the polymer layer. According to the research of the inventors of the present invention, these tendencies become remarkable when the aqueous dispersion liquid of the prior art document is used.

[0007] The inventors of the present invention have conducted intensive research and found that the dispersion of a dispersion liquid containing tetrafluoroethylene polymer particles, a specific aromatic imide resin, and water, and setting the pH value to a specific range Excellent stability. In addition, it was found that the molded article obtained from the dispersion liquid is relatively dense, has excellent low dielectric loss factor and low linear expansion coefficient, and has flexibility such as flex resistance, UV (Ultraviolet, ultraviolet) absorption, and polyamide The adhesion and adhesion of plastic films such as amine films are improved. The object of the present invention is to provide an aqueous dispersion that is excellent in dispersion stability, and the resulting molded product has flexibility such as flex resistance, UV absorption, adhesion to resin films such as polyimide films, Excellent adhesion. [Technical means to solve the problem]

[0008] The present invention has the following aspects. <1> An aqueous dispersion comprising tetrafluoroethylene polymer particles, an aromatic imide resin having an acid value of 20-100 mg / KOH, and water, and having a pH of 5-10. <2> The aqueous dispersion according to <1>, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer having an oxygen-containing polar group including a perfluoro(alkyl vinyl ether)-based unit. <3> The aqueous dispersion according to <1> or <2>, wherein the tetrafluoroethylene-based polymer particles include non-heat-fusible tetrafluoroethylene-based polymer particles and heat-fusible tetrafluoroethylene-based polymer particles. <4> The aqueous dispersion according to any one of <1> to <3>, wherein the aromatic imide-based resin is a water-soluble aromatic polyimide precursor or a water-soluble aromatic polyimide Imine precursors. <5> The aqueous dispersion according to any one of <1> to <4>, which further contains an inorganic filler. <6> The aqueous dispersion according to any one of <1> to <5>, which further contains a nonionic surfactant. <7> The aqueous dispersion according to any one of <1> to <6>, further comprising one selected from the group consisting of polyvinyl alcohol-based polymers, polyvinylpyrrolidone-based polymers, and polysaccharides. At least one nonionic polymer. <8> The aqueous dispersion according to any one of <1> to <7>, which contains amine or ammonia. <9> The aqueous dispersion according to any one of <1> to <8>, wherein the ratio of the mass of the aromatic imide resin to the mass of the tetrafluoroethylene polymer particles is 0.001 to 0.1 scope. <10> The aqueous dispersion according to any one of <1> to <9>, wherein the total content of the particles and the aromatic imide-based resin in the aqueous dispersion is relative to the total mass of the aqueous dispersion 20% by mass or more. <11> The aqueous dispersion according to any one of <1> to <10>, which has a viscosity of 50 to 3000 mPa·s. <12> The aqueous dispersion according to any one of <1> to <11>, which is used to form a polymer layer containing a tetrafluoroethylene-based polymer by applying to at least one surface of a resin film and heating. <13> The aqueous dispersion according to any one of <1> to <12>, wherein the resin constituting the resin film is a polyimide-based resin. <14> A method for producing an aqueous dispersion, which is the method for producing an aqueous dispersion according to any one of <1> to <13>, comprising the above-mentioned tetrafluoroethylene-based polymer particles, the above-mentioned aromatic acyl The composition of the amine resin and water is kneaded to obtain a kneaded product, and the kneaded product is mixed with water to obtain the above-mentioned aqueous dispersion. <15> A layered product, which is formed by applying the aqueous dispersion according to any one of <1> to <13> to both surfaces of the resin film and heating to form the above-mentioned layer containing a tetrafluoroethylene polymer. The polymer layer has the above-mentioned polymer layer on both sides of the substrate layer including the above-mentioned resin film. [Effect of Invention]

[0009] According to the present invention, an aqueous dispersion of a tetrafluoroethylene-based polymer having excellent dispersion stability and a method for producing the aqueous dispersion can be provided. The aqueous dispersion of the present invention can form a molded article having excellent physical properties such as low dielectric loss factor and low transmission loss, etc., and flexibility such as flex resistance, UV absorbability, and polymeric properties. Excellent adhesion and adhesion of resin films such as imide films. Therefore, the aqueous dispersion of the present invention can be used, for example, as a constituent material of a printed circuit board.

Implementation

[0010] The following terms have the following meanings. "Average particle diameter (D50)" is the volume-based cumulative 50% diameter of the object (particles and fillers) obtained by the laser diffraction-scattering method. That is, it measures the particle size distribution by the laser diffraction-scattering method, sets the total volume of the clusters of objects (particles and fillers) as 100% to obtain the cumulative curve, and the cumulative volume on the cumulative curve is 50%. The particle size of the point. The D50 of the object (particles and fillers) is obtained by dispersing the objects (particles and fillers) in water and using a laser diffraction-scattering particle size distribution measuring device (manufactured by Horiba, LA-920 measuring device) The laser diffraction-scattering method is analyzed and obtained. The "melting temperature" is the temperature corresponding to the maximum value of the melting peak of the polymer measured by differential scanning calorimetry (DSC) method. "Viscosity" is obtained by measuring the object (dispersion and kneaded product) using a B-type viscometer at 25°C and 30 rpm. The measurement was repeated 3 times, and the average value of the 3 measurements was used. "Thixotropic ratio" is the viscosity η1 measured by the object (dispersion and kneading) at a rotation speed of 30 rpm divided by the object (dispersion and kneading) at a rotation speed of 60 rpm The value calculated from the viscosity η2 measured under the conditions. The measurement of each viscosity was repeated 3 times, and the average value of the 3 measurements was adopted. "HLB (Hydrophile Lipophile Balance, hydrophilic / oil ratio) value of polyoxyalkylene-modified polydimethylsiloxane" is the value calculated by Griffin's formula, which is the polyoxyalkylene group in the molecule The value obtained by dividing the molecular weight of the part by the molecular weight of the organopolysiloxane was multiplied by 20 to obtain it. "Static surface tension" is obtained by Wilhelmy method using an automatic surface tensiometer CBVP-Z type (manufactured by Kyowa Interface Science Co., Ltd.) using a 0.1% by mass aqueous solution of polyoxyalkylene-modified polydimethylsiloxane out. "Dynamic surface tension" refers to the dynamic surface tension of a 0.1% by mass aqueous solution of polyoxyalkylene-modified polydimethylsiloxane at 25°C at a bubble generation period of 6 Hz by the maximum bubble pressure method. Under the environment of 25°C, the sensor of the dynamic surface tensiometer SITA t60 manufactured by Yinghong Seiki Co., Ltd. was immersed in the aqueous solution, and the polyoxyalkylene modified at a ratio of 0.1 mass % was modified by the maximum bubble pressure method. The value obtained by measuring the dynamic surface tension of the aqueous solution of polydimethylsiloxane. The measurement was carried out by setting the bubble generation period of the aqueous solution to 6 Hz. The "unit" in a polymer means an atomic group based on the above-mentioned monomer formed by polymerization of the monomer. The unit may be a unit directly formed by a polymerization reaction, or may be a unit obtained by converting a part of the above unit into another structure by treating a polymer. Hereinafter, the unit based on monomer a is simply described as "monomer a unit".

[0011] The aqueous dispersion of the present invention (hereinafter, also referred to as "this dispersion") comprises tetrafluoroethylene polymer (hereinafter, also referred to as "F polymer") particles (hereinafter, also referred to as "F particle") ”), an aromatic imide-based resin with an acid value of 20-100 mg / KOH (hereinafter also referred to as “imide-based resin P”), and water, with a pH of 5-10.

[0012] The dispersion liquid has excellent dispersion stability. In addition, the molded article (baked article) formed from this dispersion liquid has excellent physical properties based on tetrafluoroethylene-based polymers such as electrical properties, excellent surface smoothness, and flexibility such as flex resistance, UV absorption, and polyamide Adhesiveness and adhesion of resin films such as imide films are also excellent. The reason why the dispersion stability of the present dispersion liquid is improved is not necessarily clear, but it can be estimated as follows, for example. It is considered that since the imide resin P in the present invention has a specific acid value, it is easy to interact with F particles and water, and it not only functions as a dispersant for F particles in this dispersion, but also acts as a dispersant for this dispersion. The viscosity modifier plays a role in improving the dispersion stability of the dispersion. Moreover, this dispersion liquid has a pH value within a specific range, not only to enhance this effect, but also to increase the reactivity of the imide-based resin P when this dispersion liquid is further heated to form a molded product. As a result, it is considered that the interaction between the imide-based resin P and the F polymer or the substrate is improved, and the flexibility, adhesiveness, and adhesion (adhesive ability) of the obtained molded product are improved. As a result, it is considered that this dispersion liquid has excellent dispersion stability, and it is possible to form a molded product with excellent electrical properties, flex resistance, UV absorption, etc. from this dispersion liquid by a continuous production process such as roll-to-roll.

[0013] The F polymer in the dispersion is a polymer comprising tetrafluoroethylene (TFE)-based units (TFE units). One type of F polymer may be used, or two or more types may be used. The F polymers may be thermally fusible or non-thermally fusible, but at least one of the F polymers is preferably thermally fusible. In this case, the molded article formed from this dispersion liquid tends to be excellent in flexibility, adhesiveness and adhesion to resin films such as polyimide films. Furthermore, the hot melt property means that under the condition of a load of 49 N, at a temperature higher than the melting temperature of the polymer by 20°C or more, there is a melt flow rate at a temperature of 0.1 to 1000 g / 10 minutes. polymer. When the polymer F is thermally fusible, the melting temperature is preferably from 200 to 320°C, more preferably from 260 to 320°C. In this case, the heat resistance of the molded article formed from this dispersion liquid tends to become excellent.

[0014] The content of fluorine atoms in the F polymer is preferably at least 70% by mass, more preferably 70 to 76% by mass. The dispersion liquid is particularly easy to improve the water dispersibility of the F polymer particles with higher fluorine atom content through the above-mentioned action mechanism. The glass transition point of polymer F is preferably from 75 to 125°C, more preferably from 80 to 100°C.

[0015] As the F polymer, for example: polytetrafluoroethylene (PTFE), polymer (ETFE) comprising TFE units and ethylene-based units, comprising TFE units and based on perfluoro (alkyl vinyl ether) ( PAVE) units (PAVE units) (PFA), polymers comprising TFE units and hexafluoropropylene (HFP)-based units (FEP). Each of ETFE, PFA and FEP may further comprise other units as well. As PAVE, CF2=CFOCF3, CF2=CFOCF2CF3 and CF2=CFOCF2CF2CF3 (PPVE) are preferable, and PPVE is more preferable. The F polymer is preferably PFA or FEP, more preferably PFA.

[0016] It is preferred that at least one of the F polymers has an oxygen-containing polar group. In this case, since the affinity of F polymer, imide resin P, and water improves, this dispersion liquid is easy to disperse and is excellent in stability. Also, in this case, it is considered that when the dispersion liquid is fired, the F polymer reacts with the imide resin P to form a crosslink, and as a result, the fired product (polymer layer, etc.) obtained from the dispersion liquid Physical properties such as electrical characteristics, surface smoothness, adhesion and adhesion to resin films such as polyimide films are more excellent. The oxygen-containing polar group may be included in the unit of the F polymer, or may be included in the terminal group of the main chain of the F polymer. As the latter aspect, for example, F polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., obtained by plasma treatment or ionizing radiation treatment of F polymer F polymers with oxygen-containing polar groups. The oxygen-containing polar group is preferably a hydroxyl-containing group, a carbonyl-containing group, and a phosphonyl-containing group, and is more preferably a hydroxyl-containing group or a carbonyl-containing group from the viewpoint of dispersion stability of the dispersion. , and more preferably a carbonyl-containing group.

[0017] The hydroxyl-containing group is preferably a group containing an alcoholic hydroxyl group, more preferably -CF2CH2OH, -C(CF3)2OH and 1,2-ethylene glycol (-CH(OH)CH2OH). The carbonyl-containing group is a group containing a carbonyl group (>C(O)), preferably a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH2) , anhydride residues (-C(O)OC(O)-), imide residues (-C(O)NHC(O)-, etc.) and carbonate groups (-OC(O)O-), more An acid anhydride residue is preferred. When the F polymer has a carbonyl-containing group, the number of carbonyl-containing groups in the F polymer is preferably 10 to 5,000 per 1×106 main chain carbons, more preferably 100 to 3,000 , and more preferably 800 to 1500 pieces. Furthermore, the number of carbonyl-containing groups in the F polymer can be quantified by the composition of the polymer or the method described in International Publication No. 2020 / 145133.

[0018] As the F polymer, it is preferably a polymer with an oxygen-containing polar group comprising a TFE unit and a PAVE unit, more preferably a unit comprising a TFE unit, a PAVE unit, and a monomer based on an oxygen-containing polar group More preferably, it is a polymer comprising 90-99 mol%, 0.5-9.97 mol%, and 0.01-3 mol% of these units sequentially relative to all units. Also, the monomer having an oxygen-containing polar group is preferably itaconic anhydride, citraconic anhydride, or 5-northene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"). Specific examples of the polymer include polymers described in International Publication No. 2018 / 16644. These F polymers are not only excellent in the dispersion stability of the particles, but also tend to be denser and more uniformly distributed in molded products (polymer layers, etc.) obtained from this dispersion. Furthermore, micro-spherulites are easily formed in the molded product, and the adhesiveness with other components tends to be high. As a result, it becomes easier to obtain a molded article excellent in various physical properties such as electrical characteristics.

[0019] As the non-thermofusible F polymer, non-thermofusible PTFE can be exemplified. The number average molecular weight of the non-thermofusible PTFE is preferably 1 million to 100 million. In addition, the number average molecular weight of non-heat-fusible PTFE is the value calculated based on following formula (1). Mn=2.1×1010×ΔHc-5.16・・・ (1) In formula (1), Mn represents the number average molecular weight of non-thermal fusibility PTFE, and ΔHc represents the non-thermal fusibility measured by differential scanning calorimetry The heat of crystallization of PTFE (cal / g). When the number average molecular weight is within this range, the F polymer is less likely to be fibrillated, and the dispersion stability of the present dispersion is likely to be excellent.

[0020] In this dispersion, the D50 of the F particles is preferably 0.1-25 μm. The D50 of the F particles is preferably 20 μm or less, more preferably 10 μm or less, further preferably 8 μm or less. The D50 of the F particles is preferably at least 0.1 μm, more preferably at least 1 μm, and still more preferably at least 2 μm. In this range of D50, the fluidity and dispersibility of F particles tend to become better.

[0021] In terms of the dispersion stability of the dispersion, the bulk density of the F particles is preferably 0.15 g / m2 or more, more preferably 0.20 g / m2 or more. The bulk density of F particles is preferably not more than 0.50 g / m2, more preferably not more than 0.35 g / m2. Also, the specific surface area of ​​the F particles is preferably 1 to 8 m2 / g, more preferably 1 to 3 m2 / g.

[0022] One type of F particles may be used, or two or more types may be used. In the case of using two types of F particles, it is preferable to include non-heat-fusible F polymer particles and heat-fusible F polymer particles, more preferably to include non-heat-fusible PTFE (preferably the above-mentioned number average molecular weight is 1 million to 100 million PTFE) particles, and F polymer (preferably a polymer with oxygen-containing polar groups including the above-mentioned TFE unit and PAVE unit) particles with a melting temperature of 200 to 320°C.

[0023] In this case, regarding the ratio of the contained mass of the two particles, the contained mass of the former particle may be greater than the contained mass of the latter particle, or the contained mass of the former particle may be less than the contained mass of the latter particle . Furthermore, it is more preferable that the contained mass of the former particle is larger than the contained mass of the latter particle. In this case, the ratio of the latter particles to the total of the former particles and the latter particles is preferably 25% by mass or less, more preferably 15% by mass or less. In addition, the ratio in this case is preferably at least 0.1% by mass, more preferably at least 1% by mass. This dispersion liquid not only tends to be excellent in dispersion stability, handleability, and long-term storage stability, but also easily forms a molded product based on PTFE with excellent physical properties and adhesive properties.

[0024] Also, when the content of the former particles is less than the content of the latter particles, it is preferable from the viewpoint of easily forming a molded product with excellent adhesiveness and surface smoothness. In this case, the ratio of the former particles to the total of the former particles and the latter particles is preferably less than 50% by mass, more preferably 25% by mass or less. Moreover, the said ratio is preferably 5 mass % or more, More preferably, it is 10 mass % or more.

[0025] When using non-thermally fusible F polymer particles and F polymer particles with a melting temperature of 200 to 320° C., it is preferred that the D50 of the non-thermally fusible PTFE particles be 0.1 to 1 μm and the melting temperature The D50 of F polymer particles at 200 to 320°C is 0.1 to 1 μm, and the D50 of F polymer particles with D50 of 0.1 to 1 μm and the melting temperature of non-heat-melting PTFE particles is 200 to 320°C It is the aspect of 1-4 μm.

[0026] The F particles may also contain resins or inorganic fillers other than the F polymer, preferably the F polymer as the main component. The content of the F polymer in the F particles is preferably at least 80% by mass, more preferably 100% by mass. Examples of the aforementioned resins include aromatic polyesters, polyamideimides, (thermoplastic) polyimides, polyphenyl ethers, polyphenylene oxides, and maleimides. Heat-resistant resins such as amines. Examples of inorganic fillers include silicon oxide (silica), metal oxides (beryllium oxide, cerium oxide, aluminum oxide, alkali aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate. (block talc). The inorganic filler may be surface-treated on at least a part of its surface. The F particles containing resins or inorganic fillers other than F polymers have a core-shell structure containing F polymers as cores and resins other than F polymers or inorganic fillers as shells, or may also have F particles containing F polymers as shells. Shell, core-shell structure containing resin other than F polymer or inorganic filler as core. The F particles can be obtained, for example, by coagulating (collision, aggregation, etc.) the F polymer particles with resins other than the F polymer or inorganic filler particles.

[0027] The imide-based resin P constituting the dispersion enhances the dispersion stability of the dispersion, and imparts flexibility such as flex resistance and UV absorption to the molded article obtained from the dispersion. In addition, when the dispersion liquid is applied to the surface of a resin film such as a polyimide film to form a polymer layer containing the F polymer, properties such as adhesiveness and adhesion to the resin film are imparted to the polymer layer.

[0028] As the imide resin P, for example: aromatic polyimide, aromatic polyimide precursor (polyamic acid or its salt), aromatic polyamide imide, aromatic polyimide Aromatic polyamide imide precursors, modified aromatic polyimides with polar functional groups such as carboxylic acid groups, modified aromatic polyimide precursors, modified aromatic polyamide imides , Modified aromatic polyamide imide precursor, aromatic polyetherimide or aromatic polyetherimide precursor. Among them, aromatic polyimides or their precursors (polyamic acid or its salts), aromatic polyamide imides or their precursors are preferred, and water-soluble aromatic polyimide precursors are more preferred. A substance, a water-soluble aromatic polyamide imide precursor, and more preferably a water-soluble aromatic polyamide imide precursor.

[0029] As the water-soluble aromatic polyimide precursor, it can be exemplified: the polyamic acid formed by polymerizing tetracarboxylic dianhydride and diamine in a solvent, or the polyamic acid and ammonia water or Polyamide salt formed by the reaction of organic amines. An aqueous solution of polyamic acid can be prepared by dissolving polyamic acid salt in water. As a tetracarboxylic dianhydride, a pyromellitic anhydride and a biphenyltetracarboxylic anhydride are mentioned, for example. As a diamine, N,N'- diamino diphenyl ether and p-diaminobenzene are mentioned, for example. As a solvent, N-methylpyrrolidone and N,N- dimethylformamide are mentioned, for example. Examples of organic amines include: primary amines such as methylamine, ethylamine, n-propylamine, 2-ethanolamine, 2-amino-2-methyl-1-propanol; dimethylamine, 2 - Secondary amines such as (methylamino)ethanol and 2-(ethylamino)ethanol; 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-dimethylamino-2-propanol and other tertiary amines; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

[0030] As the water-soluble aromatic polyamideimide resin or its precursor, there may be mentioned: obtained by reacting diisocyanate and / or diamine with tribasic acid anhydride (or tribasic acid chloride) as the acid component Polyamide imide resin or its precursor. Examples of diisocyanates include: 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 3,3 '-Diphenylmethane diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, toluene Diisocyanate, isophorone diisocyanate. These diisocyanates may be used alone or in combination of two or more. Furthermore, from the viewpoint of improving the stability of the aromatic polyamideimide resin, as the diisocyanate, a blocked isocyanate obtained by stabilizing isocyanate groups with a blocking agent can also be used. As a blocking agent, alcohol, phenol, an oxime, etc. are mentioned.

[0031] As diamines, for example, 3,3'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 4,4'-diamine Diphenyl ether, 4,4'-diaminodiphenylene, 3,3'-diaminodiphenylene, xylylenediamine, phenylenediamine, isophoronediamine. These diamines may be used individually by 1 type, and may use it in combination of 2 or more types.

[0032] As the tribasic acid anhydride, for example, trimellitic anhydride, and as the tribasic acid chloride, for example, trimellitic anhydride chloride. As the tribasic acid anhydride, trimellitic anhydride is preferred from the viewpoint of reducing the load on the environment.

[0033] When producing an aromatic polyamide imide resin, in addition to the above-mentioned tribasic acid anhydride (or tribasic acid chloride), as an acid component, it can also be within the range that does not damage the properties of the polyamide imide resin. Dicarboxylic acid, tetracarboxylic dianhydride, etc. are used. As the dicarboxylic acid, for example, terephthalic acid, isophthalic acid, adipic acid, and sebacic acid may be mentioned. As a tetracarboxylic dianhydride, a pyromellitic dianhydride, a benzophenone tetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride are mentioned, for example. These may be used alone or in combination of two or more. Regarding the total amount of carboxylic acids (dicarboxylic acids and tetracarboxylic acids) other than tribasic acids, it is preferably 0 to 30 moles of the total carboxylic acids from the viewpoint of maintaining the characteristics of the polyamide imide resin. ear % range.

[0034] Regarding the usage ratio of diisocyanate and / or diamine and acid component (the total amount of tribasic acid anhydride or tribasic anhydride acid chloride and dicarboxylic acid and tetracarboxylic dianhydride used as needed), the resulting From the viewpoint of the molecular weight and crosslinking degree of the polyamideimide resin, it is preferable to set the diisocyanate compound and / or diamine compound at 0.8 to 1.1 moles relative to the total amount of acid components of 1.0 moles, More preferably, it shall be 0.95-1.08 mol, More preferably, it shall be 1.0-1.08 mol.

[0035] The water-soluble aromatic polyamideimide resin or its precursor can be obtained by copolymerizing the above-mentioned diisocyanate and / or diamine and the above-mentioned acid component in a polar solvent. Examples of polar solvents include: N-methyl-2-pyrrolidone, N-formylmethanol, N-acetylylurea, N,N'-dimethylethyleneurea, N,N -Dimethylacetamide, N,N-dimethylformamide, γ-butyrolactone, etc. From the viewpoint of carrying out the imidization reaction at high temperature for a short time, a solvent with a high boiling point is preferable, and N-methyl-2-pyrrolidone is usually used from the viewpoint of solubility. From the viewpoint of work environment and easiness of safety management, N-formyl ?? The amount of polar solvent used is usually 50 to 500 parts by mass relative to 100 parts by mass of the total amount of diisocyanate or diamine and the acid component, depending on the solubility of the obtained aromatic polyamide imide resin or its precursor From a point of view it is better. The polymerization temperature is usually in the range of 80 to 180°C, and in order to reduce the influence of moisture in the air, it is preferably carried out under an atmosphere of nitrogen or the like.

[0036] The water-soluble aromatic polyamideimide resin or its precursor can be produced, for example, by the following method: (1) using an acid component, and a diisocyanate component and / or a diamine component at one time and reacting them (2) make the acid component react with excess diisocyanate component and / or diamine component, after synthesizing the amidoimide oligomer with isocyanate group or amine group at the end, add acid component, and The method of reacting the isocyanate group and / or amine group at the end; (3) making the excess acid component react with the diisocyanate component and / or diamine component to synthesize the amidoimide with acid or anhydride group at the end After the polymer is added, a diisocyanate component and / or a diamine component is added to react with the terminal acid or anhydride group.

[0037] The number average molecular weight (Mn) of the water-soluble aromatic polyimide resin or its precursor is preferably 5,000 or more, more preferably 10,000 or more, and more preferably 15,000 or more. On the other hand, Mn is preferably 50000 or less, more preferably 30000 or less, still more preferably 25000 or less. When Mn is within this range, mechanical properties such as the solubility of the aromatic polyamideimide resin or its precursor in water, and the flex resistance of the molded article obtained from the dispersion can be ensured. Furthermore, regarding the Mn of the aromatic polyamideimide resin or its precursor, the reaction solution is appropriately sampled during polymerization, and measured by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene, Polymerization is performed until it becomes the target Mn, and thereby it can be managed within the above-mentioned range.

[0038] As the aromatic polyetherimide, for example: an amorphous polymer having an imide bond and an ether bond in the main chain, preferably 2,2-bis[4-(3,4- A polycondensate of dicarboxyphenoxy)phenyl]propane and m-phenylenediamine. As a commercial item of aromatic polyether imide, "Ultem 1000F3SP" (made by SABIC company) is mentioned, for example.

[0039] The acid value of the imide resin P is 20-100 mg / KOH. In this dispersion liquid, the function is balanced by adjusting the acid value of the imide resin P within this range. That is, if the acid value of the imide resin P is less than 20 mg / KOH, when the molded product is formed from the dispersion, the reaction rate of the imide resin P is improved, and the physical properties of the molded product are improved. On the one hand, its dispersing effect is reduced, resulting in a reduction in the dispersion stability of the dispersion. Also, if the acid value of the imide resin P exceeds 100 mg / KOH, the dispersion of the imide resin P in the dispersion is improved. On the other hand, when forming a molded product from the dispersion, the imide The reaction rate of the amine resin P decreases, resulting in a decrease in the physical properties of the molded product. Furthermore, specifically, if the acid value is 20 mgKOH / g or more, since there are many acidic groups, the imide resin P tends to dissolve in water easily, and the imide resin P and F particles and water The tendency to interact easily means that the adhesiveness between the molded article formed from this dispersion and the base material tends to be excellent. Moreover, there exists a tendency for the storage stability of this dispersion liquid to improve that an acid value is 100 mgKOH / g or less. Also, from these viewpoints, the acid value of the imide resin P is preferably 35 to 70 mgKOH / g. In addition, when imide-type resin P has an acid anhydride group, the acid value at the time of ring-opening an acid anhydride group is made into the acid value of imide-type resin P.

[0040] Regarding the above-mentioned acid value, collect about 0.5 g of imide resin P, add about 0.15 g of 1,4-diazabicyclo [2.2.2] octane, and then add about 60 g of N -Methyl-2-pyrrolidone and about 1 ml of ion-exchanged water, stirred until the imide-based resin P is completely dissolved. The acid value can be determined by titrating with a potentiometric titration device using 0.05 mol / L ethanolic potassium hydroxide solution.

[0041] Preferred specific examples of the imide-based resin P include "HPC-1000" and "HPC-2100D" (both manufactured by Showa Denko Materials).

[0042] The content of the F particles in the dispersion is preferably at least 10% by mass, more preferably at least 25% by mass, relative to the overall mass of the dispersion. The content of the F particles is preferably at most 80% by mass, more preferably at most 70% by mass, based on the total mass of the dispersion. The content of the imide-based resin P in the dispersion is preferably at least 0.1% by mass, more preferably at least 0.3% by mass, based on the overall mass of the dispersion. The content of the imide resin P is preferably at most 30% by mass, more preferably at most 10% by mass.

[0043] The total content of F particles and imide-based resin P in the dispersion is preferably 20% by mass or more relative to the overall mass of the dispersion. The above-mentioned total content is more preferably at least 30% by mass, further preferably at least 40% by mass. The above-mentioned total content is preferably at most 80% by mass. As a specific example of the preferable range of the said total content, 30-80 mass % is mentioned. In this case, molded articles such as a coating film can be formed with high uniformity from this dispersion liquid, and the physical properties obtained from the F polymer and the physical properties obtained from the imide-based resin P can easily be highly expressed. That is, even if the content of the polymer component is within the relatively high range, the dispersion liquid can achieve excellent dispersion stability and improve the physical properties of its molded product through the above-mentioned action mechanism.

[0044] Also, the ratio of the mass of the above-mentioned imide-based resin P to the mass of the F particles in the dispersion is preferably 0.001 or more, more preferably 0.005 or more, and still more preferably 0.01 or more. The above-mentioned ratio is preferably at most 0.1, more preferably at most 0.09, still more preferably at most 0.05. As a specific example of the preferable range of the said ratio, 0.001-0.1 is mentioned. If the above-mentioned ratio is within the lower range, the dispersion stability of the F particles is improved, and the physical properties of the molded article obtained from this dispersion liquid are particularly likely to be improved. Although the reason is not necessarily clear, it is believed that the reason is that the acid value of the imide resin P and the pH value of the aqueous dispersion are in a specific range, and the imide resin P is a small amount of components relative to the F particles. In the solution, the imide resin P is easy to be used as a dispersant of low hydrophilic F particles and functions highly as a binder. In other words, when the imide resin P is attached to the surface of the F particles to form a molded product, Dense roasting of F particles.

[0045] The content of water in the dispersion is preferably at least 40% by mass, more preferably at least 50% by mass. The water content is preferably at most 90% by mass, more preferably at most 80% by mass. Within this range, the dispersion stability of the dispersion is more likely to be improved through the above-mentioned mechanism of action.

[0046] The dispersion liquid may further contain a water-soluble dispersion medium other than water as a dispersion medium. As the water-soluble dispersion medium, water-soluble compounds that are classified as polar under atmospheric pressure and are liquid at 25°C are preferred, for example, N,N-dimethylformamide, N,N-dimethylformamide, Methylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-methyl-2-pyrrolidone .

[0047] The dispersion may further include a surfactant. When the dispersion contains a surfactant, the surfactant is non-ionic, the hydrophobic part of the surfactant preferably has an ethynyl or polysiloxane group, and the hydrophilic part preferably has an oxyalkylene group Or alcoholic hydroxyl. That is, when the dispersion further contains a surfactant, it is preferably a nonionic surfactant having an alcoholic hydroxyl group, more preferably a polyoxyalkylene alkyl ether, an acetylene-based surfactant, or a silicone Department of surfactants. These surfactants may be used alone or in combination of two or more. From the perspective of stabilizing the long-term dispersibility of F particles, improving the liquid physical properties such as the viscosity of this dispersion, and improving the initial dispersibility of F particles, it is preferable to use polyoxyalkylene alkyl ether and silicone together. Department of surfactants. When this dispersion liquid further contains a surfactant, its amount is preferably 1 to 15% by mass relative to the mass of this dispersion liquid as a whole. In this case, the affinity between the components is enhanced, and the dispersion stability of the present dispersion is more likely to be improved.

[0048] From the point of view of suppressing the load on the environment, and from the point of view of the stability in this dispersion, it is preferable that the weight average molecular weight of the silicone-based surfactant is 3000 or less, and it is determined by the Griffin formula A polyoxyalkylene-modified polydimethylsiloxane with a calculated HLB value of 1-18.

[0049] The above-mentioned polyoxyalkylene-modified polydimethylsiloxane (hereinafter, also referred to as "modified polydimethylsiloxane") has a polyoxyalkylene structure as a hydrophilic group and has The polydimethylsiloxane structure is an organopolysiloxane with a hydrophobic group, preferably a linear polymer.

[0050] The weight average molecular weight of the modified polydimethylsiloxane is less than 3000, preferably less than 2500, more preferably less than 2000. The weight average molecular weight is preferably at least 100, more preferably at least 500. The number average molecular weight of the modified polydimethylsiloxane is preferably 3000 or less, more preferably 1500 or less. The number average molecular weight is preferably at least 100, more preferably at least 500. The molecular weight dispersion of the modified polydimethylsiloxane is preferably not more than 2.0, more preferably not more than 1.8. The lower limit of the molecular weight dispersion is preferably more than 1.0.

[0051] The HLB value of the modified polydimethylsiloxane is 1 to 18, preferably 3 or more, more preferably 6 or more, further preferably 10 or more, and especially preferably 12 or more. The HLB value is preferably at most 16, more preferably at most 15.

[0052] The static surface tension of the modified polydimethylsiloxane is preferably below 28 mN / m, more preferably below 26 mN / m. The static surface tension is preferably at least 15 mN / m, more preferably at least 20 mN / m. The dynamic surface tension of the modified polydimethylsiloxane is preferably 40 mN / m or less, more preferably 35 mN / m or less, and the dynamic surface tension is preferably 20 mN / m or more.

[0053] Modified polydimethylsiloxane can also have a dimethylsiloxane unit (-(CH3) 2SiO2 / 2-) in the main chain, and can also have a dimethylsiloxane unit in the side chain, It is also possible to have a dimethylsiloxane unit in both the main chain and the side chain. The modified polydimethylsiloxane is preferably a modified polydimethylsiloxane containing dimethylsiloxane units in the main chain and having an oxyalkylene group in the side chain, or a modified polydimethylsiloxane containing dimethylsiloxane in the main chain. Modified polydimethylsiloxane with alkane unit and oxyalkylene group at the end of the main chain.

[0054] Specific examples of modified polydimethylsiloxane include: "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451" , "BYK-3455", "BYK-3456" (above, manufactured by BYK-Chemie Japan); "KF-6011", "KF-6043" (above, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0055] The weight average molecular weight of the modified polydimethylsiloxane is small, and the HLB value is in a specific range, so it can be said that its hydrophobicity and hydrophilicity are highly balanced. It is considered that the interaction between the modified polydimethylsiloxane and the F particles tends to be enhanced, and as a result, it is considered that the dispersion stability of the present dispersion is improved. Also, since the modified dimethylsiloxane has excellent thermal decomposability, it is easily decomposed when the dispersion is heated to form a baked product. As a result, the calcined product tends to have high physical properties based on the F polymer.

[0056] polyoxyethylene alkyl ether is preferably polyoxyethylene decyl ether, polyoxyethylene undecyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene Myristyl ether, triethylene glycol monomethyl ether, polyethylene glycol trimethyl nonyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, more preferably polyoxygen Ethylene decyl ether, polyoxyethylene undecyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, or polyoxyethylene myristyl ether.

[0057] Polyoxyalkylene alkyl ethers can be obtained as commercial products, specifically, "Tergitol TMN-100X" (manufactured by Dow Chemical Company); "Lutensol TO8", "Lutensol XL70" , "Lutensol XL80", "Lutensol XL90", "Lutensol XP80", "Lutensol M5" (the above, manufactured by BASF); "Newcol 1305", "Newcol 1308FA", "Newcol 1310" (the above, manufactured by Nippon Emulsifier ); "LEOCOL TDN-90-80", "LEOCOL SC-90" (above, manufactured by Lion Specialty Chemicals).

[0058] When the dispersion liquid includes a surfactant, the polyoxyalkylene alkyl ether can be obtained as a commercial product, specifically, for example: "Tergitol TMN-100X" (Dow Chemical Company Manufacturing); "Lutensol TO8". Also, when the present dispersion further contains a surfactant, the amount thereof is preferably at least 0.1% by mass, more preferably at least 0.1% by mass, based on the mass of the entire dispersion. Moreover, the above-mentioned amount is preferably 15% by mass or less.

[0059] The dispersion may further contain at least one nonionic polymer selected from the group consisting of polyvinyl alcohol-based polymers, polyvinylpyrrolidone-based polymers, and polysaccharides. The nonionic polymer is most preferably a water-soluble polymer. In this case, through the interaction between the water-soluble polymer and the imide resin P, not only the dispersion stability of the dispersion is improved, but also the rheological properties are improved, and the film-forming properties of the dispersion are improved. Etc. operability can be improved easily. As a result, it becomes easier to form a thick molded product or a molded product of any shape obtained from the dispersion. In particular, when the above-mentioned water-soluble polymer has a nonionic hydroxyl group, this tendency tends to become prominent. Polyvinyl alcohol-based polymers can be polyvinyl alcohol obtained by partial acetylation or partial acetalization. Examples of polysaccharides include glycogen, pullulan, dextrin, dextran, fructan, chitin, amylose, agarose, pullulan, Cellulose. The celluloses may, for example, be methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose or hydroxypropylcellulose.

[0060] The water-soluble nonionic macromolecule is preferably nonionic polysaccharides, more preferably nonionic celluloses, and further preferably hydroxymethylcellulose, hydroxyethylcellulose or hydroxypropyl cellulose prime. Specific examples of the nonionic polysaccharides include: "Sunrose (registered trademark)" series (manufactured by Nippon Paper Co., Ltd.), "Metolose (registered trademark)" series (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), "HEC CF grade" (manufactured by Sumitomo Seika Chemical Co., Ltd.).

[0061] Also, when the dispersion further contains a water-soluble nonionic polymer, the amount thereof is preferably at least 0.01% by mass, more preferably at least 0.1% by mass, relative to the mass of the entire dispersion. Moreover, it is preferable that the said amount is less than 1 mass %. The ratio of the mass of the water-soluble nonionic polymer in the present dispersion to the mass of the F particles is preferably at least 0.001, more preferably at least 0.01. Moreover, the above-mentioned ratio is preferably less than 0.1. As mentioned above, through the interaction between the water-soluble polymer and the imide resin P, the effect of improving the liquid physical properties and film-forming properties of the present dispersion obtained by containing the water-soluble polymer in a small amount is easily obtained. As a result, the residual amount of the above-mentioned water-soluble polymer in the molded article obtained from the present dispersion is reduced, and a molded article having more excellent physical properties such as electrical characteristics can be easily obtained from the present dispersion. This tendency is remarkable especially when the said water-soluble polymer has a nonionic hydroxyl group.

[0062] The present dispersion may further contain amines or ammonia. It is considered that amine or ammonia also functions as a pH adjuster and contributes to improving the dispersion stability or storage stability of the dispersion. When the present dispersion liquid further contains amine or ammonia, the amount thereof may be such that the pH value of the present dispersion liquid is 5-10.

[0063] The amine may, for example, be dimethylamine, diethylamine, diisopropylamine, diethanolamine, triethanolamine, tripranolamine, triethylamine, tripentylamine, pyridine, or N-methylmethanolamine. In this case, a pH buffering agent may be further added to stabilize the pH of the liquid composition. Examples of the pH buffering agent include tris(hydroxymethyl)aminomethane, ethylenediaminetetraacetic acid, ammonium bicarbonate, ammonium carbonate, and ammonium acetate.

[0064] From the viewpoint of improving the adhesiveness and low linear expansion of the molded article formed by the dispersion, the dispersion may further include resin materials other than the F polymer and the imide resin P. The resin material can be thermosetting, or thermoplastic, or modified, and can be dissolved in the dispersion, or dispersed without being dissolved. Examples of such resin materials include acrylic resins, phenolic resins, liquid crystalline polyesters, liquid crystalline polyesteramides, polyolefin resins, modified polyphenylene ethers, polyfunctional cyanate resins, and polyfunctional maleic acid resins. Diimide-cyanate resin, polyfunctional maleimide, aromatic elastomer such as styrene elastomer, vinyl ester resin, urea resin, diallyl phthalate resin, Melamine resin, guanamine resin, melamine-urea co-condensation resin, polycarbonate, polyarylate, polyarylene, polyarylene, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyarylether Ketones, polyphenylene ethers, epoxy resins, etc. When this dispersion liquid further contains a resin material, its content is preferably 40% by mass or less with respect to the mass of this dispersion liquid as a whole.

[0065] As a preferable aspect of the resin material, an aromatic polymer may be mentioned. The aromatic polymer is preferably polyphenylene ether or an aromatic elastomer (styrene elastomer, etc.). In this case, not only the adhesiveness and low linear expansion of the molded article formed by this dispersion are further improved, but also the liquid physical properties (viscosity, thixotropic ratio, etc.) of this dispersion are also balanced, so its handling is easy get improved. Here, examples of the styrene elastomer include copolymers of styrene and conjugated diene or (meth)acrylate (styrene-butadiene rubber, styrene-based core-shell copolymer, styrene It is a block copolymer, etc.), preferably a styrene elastomer that has properties of both rubber and plastic, and is plasticized by heating to exhibit flexibility.

[0066] The present dispersion may further contain an inorganic filler. In this case, the electrical characteristics and low linear expansion of the molded article produced from this dispersion liquid tend to become excellent. In addition, this dispersion liquid may also contain inorganic fillers. Due to the above-mentioned mechanism of action, the dispersion stability is excellent, and it is easy to obtain a dense molded product. Therefore, it is easy to manufacture a molded article highly possessing the physical properties of each of the F polymer, the imide-based resin P, and the inorganic filler from the present dispersion containing the inorganic filler. Inorganic fillers are preferably nitride fillers or inorganic oxide fillers, more preferably boron nitride fillers, aluminum nitride fillers, beryllium oxide fillers (fillers of beryllium oxides), silicate fillers (silicon dioxide fillers, silicon dioxide fillers) Limestone filler, talc filler), or metal oxide (cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.) filler, and more preferably silica filler. The inorganic filler is preferably at least a part of its surface by a silane coupling agent (3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxy propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.) for surface treatment.

[0067] The D50 of the inorganic filler is preferably less than 20 μm, more preferably less than 10 μm. D50 is preferably at least 0.01 μm, more preferably at least 0.1 μm. The shape of the inorganic filler can be any of granular, needle-like (fibrous) and plate-like. Specific shapes of inorganic fillers include: spherical, scaly, layered, leaf-shaped, almond-shaped, columnar, cockscomb, equiaxed, leaf-shaped, mica-shaped, massive, flat-shaped, wedge-shaped, rose Flower-like, net-like, keratinous. An inorganic filler may be used individually by 1 type, and may use 2 or more types together. When this dispersion liquid further contains an inorganic filler, its amount is preferably 1 to 50 mass %, more preferably 5 to 40 mass %, based on the mass of this dispersion liquid as a whole.

[0068] As preferred specific examples of inorganic fillers, for example: silica fillers ("Admafine (registered trademark)" series manufactured by Admatechs Co., Ltd., etc.), oxidation of surface treatment by esters such as propylene glycol dicaprate Zinc ("FINEX (registered trademark)" series manufactured by Sakai Chemical Industry Co., Ltd., etc.), spherical fused silica ("SFP (registered trademark)" series manufactured by DENKA Corporation, etc.), polyalcohol and inorganic substances Coated titanium oxide ("Tipaque (registered trademark)" series manufactured by Ishihara Sangyo Co., Ltd., etc.), rutile-type titanium oxide surface-treated with alkylsilane ("JMT (registered trademark)" series manufactured by Imperial Chemical Co., Ltd., etc.) ), hollow silica fillers ("E-SPHERES" series manufactured by Taiheiyo Cement, "SiliNax" series manufactured by Nippon Steel Mining Corporation, "Ecco sphere" series manufactured by Emerson & Cuming, etc.), talc fillers ( "SG" series manufactured by NIPPON TALC, etc.), steatite fillers ("BST" series manufactured by NIPPON TALC, etc.), boron nitride fillers ("UHP" series manufactured by Showa Denko, "Denka Boron" manufactured by DENKA) Nitride" series ("GP", "HGP" grades), etc.).

[0069] In addition to the above-mentioned components, the dispersion can further include thixotropy-imparting agents, viscosity regulators, defoamers, silane coupling agents, dehydrating agents, plasticizers, and weathering agents within the scope of not impairing the effects of the present invention. , Antioxidant, heat stabilizer, lubricant, antistatic agent, brightener, colorant, conductive agent, release agent, surface treatment agent, flame retardant, various fillers and other ingredients.

[0070] The viscosity of the dispersion is preferably above 10 mPa·s, more preferably above 30 mPa·s, further preferably above 50 mPa·s. The viscosity of the dispersion is preferably not more than 3000 mPa·s, more preferably not more than 1000 mPa·s, still more preferably not more than 800 mPa·s. The viscosity of the dispersion is preferably 50-3000 mPa·s, more preferably 50-1000 mPa·s.

[0071] The thixotropic ratio of the dispersion is preferably above 1.0. The thixotropic ratio of this dispersion is preferably at most 3.0, more preferably at most 2.0. In this case, the dispersion liquid is excellent in applicability and homogeneity, and it is easy to form a denser molded product (polymer layer, etc.). The pH of the dispersion is 5-10. In this dispersion, by adjusting the pH to this range, the functions of the imide-based resin P can be balanced. That is, if the pH of the dispersion is less than 5, the reactivity of the imide-based resin P becomes high, and on the other hand, its dispersing action decreases, resulting in a decrease in the dispersion stability of the dispersion. Also, if the pH of the dispersion exceeds 10, the dispersing effect of the imide resin P increases, and on the other hand, its reactivity decreases, resulting in a decrease in the physical properties of the molded product obtained from the dispersion. The pH value of the dispersion is preferably 7-9. In this case, the color phase and long-term storage stability of this dispersion liquid tend to become excellent.

[0072] In this dispersion liquid, the dispersion layer ratio is preferably more than 60%, more preferably more than 70%, and more preferably more than 80%. Here, the ratio of the dispersion layer refers to putting the dispersion liquid (18 mL) into a spiral tube (inner volume: 30 mL), and standing at 25°C for 14 days, according to the total dispersion liquid in the spiral tube after standing The height and the height of the sedimentation layer (dispersion layer) are calculated by the following formula. In addition, when no precipitate layer was confirmed after standing still and the state did not change, it was assumed that the overall height of the dispersion liquid did not change, and the dispersion layer ratio was made 100%. Dispersion layer rate (%) = (height of precipitation layer) / (height of overall dispersion liquid) × 100

[0073] The present dispersion is excellent in dispersion stability, especially long-term storage stability, due to the above-mentioned mechanism of action. When the dispersion is left to stand at 25° C. for 30 days, the variation range (absolute value) of the thixotropic ratio of the dispersion before and after standing is preferably 3 or less, more preferably less than 1.

[0074] This dispersion liquid can be prepared by mixing F particles, imide resin P, and water as a dispersion medium. As a mixing method, for example: the method of adding F particles and imide resin P to water at one time or sequentially adding and mixing; F particles and water, imide resin P and water are mixed in advance, and then mixed The method of mixing the two mixtures obtained; etc. With regard to this dispersion liquid, it is advantageous and preferable to disperse the F particles more uniformly in the following way: after the F particles are pre-dispersed in water, the imide resin P is mixed as it is (directly) or mixed with Prepare this dispersion liquid in the order of adding and mixing in the state of water; or add and mix the F particles as they are (directly) or in the state of mixing in water after pre-mixing the imide resin P in water This dispersion was prepared sequentially. Furthermore, when the dispersion liquid further contains a surfactant, other resin materials, or inorganic fillers, it is preferable to add them at the same time when the F particles are previously dispersed in water, or to add them to water before dispersing the F particles.

[0075] As the mixing method for preparing the dispersion, for example, it can be exemplified: a stirring device that utilizes single-shaft or multi-shaft blades (stirring blades) such as propeller blades, turbine blades, paddle blades, shell blades, etc. Agitation by a Scheer mixer, pressure kneader, Bambry mixer or planetary mixer; using a ball mill, attritor, basket mill, sand mill, sand mill Grinder), DYNO-MILL (bead mill using glass beads or zirconia beads and other grinding media), Dispermat, SC grinder, nail crusher or stirring mill and other medium-based dispersing machines; using micro-spray Homogenizer, Nanomizer, Ultimaizer and other high-pressure homogenizers, ultrasonic homogenizers, dissolvers (dissolvers), dispersers, high-speed rotor dispersers, self-rotating and revolving mixers, film rotary high-speed mixers and other dispersing machines that do not use media the mixing performed.

[0076] As a preferable aspect of the method for producing the dispersion liquid, an aspect in which a composition containing F particles and water is kneaded to obtain a kneaded product, and then the kneaded product is mixed with water can be exemplified. At this time, the imide-based resin P may be added to the composition, or may be added when the kneaded product is further mixed with water, but the former is preferable. That is, it is preferable to knead a composition containing F particles, imide-based resin P, and water to obtain a kneaded product, and further mix the kneaded product with water. The kneading can be carried out by the above-mentioned mixing method, preferably using a Henschel mixer, a pressure kneader, a Banbury mixer, a self-rotating mixer or a planetary mixer, and more preferably using a planetary mixer. The planetary mixer has a structure that has two shaft stirring blades that rotate and revolve mutually, and stirs and kneads the kneaded material in the stirring tank. Therefore, there is less dead space in the stirring tank that cannot be reached by the stirring blades, which can reduce the load on the blades and thus highly knead the composition. That is, the aggregation of F particles can be suppressed, and the F particles can be wetted by water, and the F particles can be highly interacted with the imide resin P, and can be kneaded. Therefore, if the kneaded product is further mixed with water , it is easy to obtain the dispersion liquid excellent in dispersion stability. In addition, it is easy to adjust the component concentration of the present dispersion, and it is easy to obtain the present dispersion capable of forming a thick molded article (polymer layer, etc.) with excellent surface smoothness and uniformity.

[0077] The content of F particles in the composition is preferably at least 20% by mass, more preferably at least 40% by mass, relative to the total mass of the composition. The content of F particles is preferably at most 90% by mass. Also, the content of the imide-based resin P in the composition is preferably at least 0.1% by mass, more preferably at least 0.3% by mass, based on the overall mass of the composition. The content of the imide-based resin P is preferably at most 10% by mass. The total content of F particles and imide resin P in the composition is preferably at least 40% by mass, more preferably at least 60% by mass, based on the total mass of the composition. The above-mentioned total content is preferably at most 90% by mass.

[0078] Also, the ratio of the mass of the imide-based resin P in the composition to the mass of the F particles is preferably 0.001 or more, more preferably 0.005 or more, and still more preferably 0.01 or more. The above-mentioned ratio is preferably at most 0.1, more preferably at most 0.09, still more preferably at most 0.05. If the content of the F particles, the content of the imide resin P, or the above-mentioned ratio is in the lower range, then during the kneading of the composition, the F particles and the imide resin P can be highly interacted with each other. Mixing on one side. Therefore, when this kneaded product is further mixed with water, the present dispersion liquid having excellent dispersion stability in which the ratio of the mass of the imide resin P to the mass of the F particles is in the range of 0.001 to 0.1 can be easily obtained.

[0079] The kneaded product is a semi-solid or solid sticky substance, preferably a kneaded slurry or kneaded powder. Furthermore, the kneaded slurry is a hard sticky substance in a fluid and viscous state, and the kneaded powder means a hard sticky substance in a lumpy and clay-like state. The viscosity of the kneaded slurry is preferably 800-100000 mPa·s, more preferably 1000-10000 mPa·s or more. The moisture content of the kneaded powder is preferably at most 50% by mass, more preferably at most 40% by mass. The moisture content of the kneaded powder is preferably at least 20% by mass, more preferably at least 25% by mass.

[0080] Also, in this aspect, when the dispersion liquid further contains surfactants, other resin materials or inorganic fillers, these can be added to the composition, or the kneaded product can be mixed with water when added. The present dispersion containing other resin materials or inorganic fillers can also be obtained by kneading a composition containing F particles, other resin materials or inorganic fillers, and water to obtain a kneaded product, and mixing the mixed The product and the mixture containing imide resin P and water are mixed. In this case, the dispersion stability and long-term storage stability of the present dispersion liquid are likely to be improved.

[0081] The dispersion liquid is also excellent in dispersion stability and long-term storage stability, and can be formed into a molded product that exhibits firm adhesion to the base material and is excellent in flexibility such as flex resistance, that is, in crack resistance. If this dispersion is given to at least one surface of the substrate to form a liquid film, the liquid film is heated, the dispersion medium is removed to form a dry film, and the film is dried by heating, and the F polymer is fired, then the surface of the substrate can be obtained. A laminate (hereinafter also referred to as "this laminate") of a polymer layer (hereinafter also referred to as "F layer") of a polymer and an imide-based resin P. In addition, if this dispersion is applied to both surfaces of the base material, heated, and the F polymer is fired, a laminate having F layers on both sides of the base material layer including the above base material can be obtained.

[0082] As the base material, for example: metal substrates (metal foils such as copper, nickel, aluminum, titanium, alloys thereof, etc.), resin films (including tetrafluoroethylene polymers, polyimides, polyarylenes, etc.) Heat resistance such as ester, polyamide, polyarylene, polyamide, polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystalline polyester, liquid crystalline polyester amide, etc. More than one kind of resin heat-resistant resin film, which can be a single-layer film or a multi-layer film), prepreg (precursor of fiber-reinforced resin substrate), ceramic substrate (silicon carbide, aluminum nitride, nitrogen Silicon and other ceramic substrates), glass substrates. Among them, a resin film is preferable, and the resin constituting the resin film is more preferably a polyimide-based resin. This dispersion can be preferably used to form an F layer by applying to at least one surface of a resin film and drying. As a shape of a base material, a flat shape, a curved shape, and a concave-convex shape are mentioned, for example. In addition, the shape of the substrate may be any of foil shape, plate shape, film shape, and fiber shape.

[0083] As the method of imparting the dispersion to the surface of the substrate, as long as it is a method of forming a stable liquid film (wet film) containing the dispersion on the surface of the resin film (substrate), it can be exemplified : Coating method, droplet discharge method, dipping method, preferably coating method. If the coating method is used, a liquid film can be efficiently formed on the surface of the resin film with simple equipment. As the coating method, spray method, roll coating method, spin coating method, gravure coating method, micro gravure coating method, gravure offset method, knife coating method, contact coating method, bar coating method, etc. Cloth method, die coating method, spray Meile rod method, slot coating method, slot die coating method, dip coating method.

[0084] When drying the liquid coating, heat the liquid coating at a temperature at which the dispersion medium (water) volatilizes to form a dry coating on the surface of the resin film. The heating temperature in this drying is preferably from 100 to 200°C. In addition, air may be blown in the step of removing the dispersion medium. During drying, the dispersion medium does not necessarily have to be completely volatilized, but only needs to be volatilized to such an extent that the shape of the layer is kept stable and a self-supporting film can be maintained.

[0085] When the F polymer is fired, it is preferable to heat and dry the film at a temperature above the melting temperature of the F polymer. The heating temperature is preferably below 380°C. As each heating method, a method using an oven, a method using a ventilated drying oven, and a method of irradiating hot rays such as infrared rays may, for example, be mentioned. Heating can be performed under either normal pressure or reduced pressure. Also, the heating atmosphere may be any of oxidizing gas atmosphere (oxygen, etc.), reducing gas atmosphere (hydrogen, etc.), inert gas atmosphere (helium, neon, argon, nitrogen, etc.). The heating time is preferably from 0.1 to 30 minutes, more preferably from 0.5 to 20 minutes. If heating is performed under the above-mentioned conditions, high productivity can be maintained and the F layer can be preferably formed.

[0086] The thickness of the F layer is preferably 0.1-150 μm, more preferably 10 μm or more. When the substrate layer is a metal foil, the thickness of the F layer is preferably 10-30 μm. When the substrate layer is a resin film, the thickness of the F layer is preferably from 10 to 150 μm, more preferably from 15 to 50 μm. The peel strength between the F layer and the substrate layer is preferably at least 10 N / cm, more preferably at least 15 N / cm. The aforementioned peel strength is preferably 100 N / cm or less. This laminate can be easily formed without impairing the physical properties of the F polymer in the F layer by using the present dispersion.

[0087] The porosity of the F layer is preferably 30% or less, more preferably 20% or less. The porosity is preferably at least 0.1%, more preferably at least 1%. The F layer with a relatively low porosity can be easily formed from this dispersion. In particular, even when the porosity of the dry film is 1% or more, it is easy to form the F layer with a low porosity. Furthermore, the porosity is based on the SEM photograph of the cross-section of the molded product observed with a scanning electron microscope (SEM), and the void portion of the F layer is determined by image processing, and the area occupied by the void portion is divided by the F layer The ratio (%) obtained from the area. The area occupied by the void portion can be obtained by approximating the void portion to a circle.

[0088] The dispersion liquid may be applied to only one surface of the substrate, or may be applied to both sides of the substrate. If it is the former, a base material layer including the above base material and a present laminate having an F layer on one surface of the base material layer can be obtained, and if it is the latter, a base material layer including the above base material, And the present laminate having F layers on both surfaces of the substrate layer. Since the latter laminate is less likely to warp, it has excellent workability during processing. Specific examples of this laminate include: a metal foil, and a metal foil laminate having an F layer on at least one surface of the metal foil; a polyimide film, and two of the polyimide film. A multilayer film with an F layer on the surface. Since these laminates have excellent electrical properties and many other physical properties, they are preferably used as printed substrate materials, etc., and can be used to manufacture flexible printed substrates or rigid printed substrates.

[0089] The present laminate having the F layer on both sides of the substrate layer is preferably obtained by applying the dispersion to one surface of the substrate, heating to remove the liquid dispersion medium, and The dispersion liquid is applied to the other surface of the substrate, and the liquid dispersion medium is removed by heating, and the F polymer is further fired by heating to form each F layer.

[0090] Also, the present laminate having the F layer on both sides of the substrate layer can also be obtained by applying the dispersion to both surfaces of the substrate and heating to remove the liquid dispersion medium. , and then heated to bake the F polymer, and at the same time form the F layer on both surfaces. In this case, it is preferable to obtain the present laminate having the F layer on both sides of the substrate layer by immersing the substrate in the present dispersion and applying the present dispersion to the substrate. After both surfaces, the substrate is heated by passing it through a firing furnace. Specifically, it is more preferably obtained by passing the substrate through a calcination furnace while pulling the substrate from the dispersion after immersing the substrate in the dispersion. The direction in which the substrate is pulled up and passed through the furnace is preferably vertically upward. In this case, it is easy to form a smooth F layer. After the substrate is pulled up vertically, the substrate can be further heated while being pulled vertically downward, or the substrate can be pulled vertically without heating. Moreover, the amount of this dispersion liquid to apply to a base material can be adjusted by passing the base material to which this dispersion liquid adhered between a pair of rolls. The present laminate can be preferably produced by using an apparatus having a dip coater and a firing furnace for the present laminate. As a baking furnace, a vertical baking furnace is mentioned, for example. Moreover, as this apparatus, the glass-cloth coating apparatus by Tabata Machine Industry Co., Ltd. is mentioned, for example.

[0091] Here, regarding the outermost surface of the substrate, in order to further improve its low linear expansion or adhesiveness, the outermost surface of the substrate can also be further surface treated. The surface treatment method may, for example, be annealing treatment, corona treatment, plasma treatment, ozone treatment, excimer treatment, or silane coupling treatment. Regarding the conditions in the annealing treatment, it is preferable to set the temperature at 120 to 180° C., the pressure at 0.005 to 0.015 MPa, and the time at 30 to 120 minutes. Examples of the gas used in the plasma treatment include oxygen, nitrogen, rare gases (such as argon), hydrogen, ammonia, and vinyl acetate. These gases may be used alone or in combination of two or more. The ten-point average roughness of the surface of the substrate is preferably 0.01-0.05 μm.

[0092] The laminate in which the substrate layer is a resin film (preferably a polyimide film) can be used as a release film or a carrier film. Since the layer F of this laminate has excellent adhesion to the substrate layer, interlayer delamination is not easy to occur, so it can be used repeatedly as a carrier film. Also, since the F layer is excellent in heat resistance, even if it is used repeatedly, the release property is not likely to deteriorate.

[0093] Specifically, if the dispersion liquid or varnish containing resin or inorganic filler is coated on the surface of the F layer of the laminated body, dried to form a coating film, and then the laminated body is peeled off from the coating film , an independent coating film can be obtained. For example, if the above-mentioned coating film is formed on the surface of the F layer of the laminate, the coating film side of the laminate having the coating film is bonded to other substrates, and the laminate is peeled off, then other products can be obtained. Laminated body of base material and coating film. When forming a coating film on the surface of the layer F of this laminate, for example, heating may be performed at a temperature below the melting point of the F polymer during drying. Since this laminate has excellent heat resistance, it is not easily deformed even if heat treatment is repeated.

[0094] Specifically, this laminate can be used as a carrier film for ceramic green sheet formation, a carrier film for secondary battery formation, a carrier film for solid polymer electrolyte membrane formation, and a catalyst for solid polymer electrolyte membranes. Form the carrier film. In the case of using this laminate as a carrier film, from the viewpoint of obtaining the above-mentioned coating film with a uniform thickness, the ratio of the thickness of the end portion of this laminate to the thickness of the central portion is preferably 1.1 or less, more preferably It is 1.07 or less, more preferably 1.04 or less. The thickness ratio is 1 or more.

[0095] It is also possible to laminate other substrates on the outermost surface of the laminate. Examples of other substrates include metal substrates, heat-resistant resin films, prepregs of precursors for fiber-reinforced resin sheets, laminates with heat-resistant resin film layers, and laminates with prepreg layers. . Furthermore, the prepreg system is a sheet-like substrate obtained by impregnating a thermosetting resin or a thermoplastic resin in a base material (tow, woven fabric, etc.) of reinforcing fibers (glass fiber, carbon fiber, etc.). As a metal substrate, the said metal substrate is mentioned. The heat-resistant resin film is a film containing one or more heat-resistant resins, and the heat-resistant resin may, for example, be the above-mentioned resins.

[0096] The lamination method may, for example, be a method of hot-pressing this laminate with other substrates. As for the hot pressing conditions when the other substrate is a prepreg, it is preferable to set the temperature at 120 to 400°C, set the atmospheric pressure to a vacuum of 20 kPa or less, and set the pressing pressure to 0.2 to 10 MPa. Since this laminate has an F layer with excellent electrical properties, it is preferably used as a printed substrate material. Specifically, it can be used to manufacture printed substrates in the form of flexible metal foil laminates or rigid metal foil laminates. In particular, it is preferable to manufacture a flexible printed substrate in the form of a flexible metal foil laminate.

[0097] If the metal foil of the base laminate (metal foil with F layer) is a metal foil, and the base laminate is a resin film with an F layer, the metal foil is further laminated. Metal foil laminate (metal foil with resin film and F layer) is etched to form a transmission circuit, and a printed circuit board can be obtained. Specifically, the printed substrate can be manufactured by the following method, that is, the method of etching the metal foil to process it into a specific transmission circuit, or by the electroplating method (semi-additive method (SAP method), MSAP (Modified Semi -Additive, modified semi-additive method, etc.) and the method of processing metal foil into a specific transmission circuit. A printed circuit board manufactured from metal foil with F layer and metal foil with resin film and F layer has a transmission circuit and F layer formed of metal foil in this order. Specific examples of the composition of the printed circuit board include: transmission circuit / F layer / prepreg layer, transmission circuit / F layer / prepreg layer / F layer / transmission circuit, transmission circuit / F layer / polyamide Amine film layer, transmission circuit / F layer / polyimide film layer / F layer / transmission circuit. In the manufacture of the printed circuit board, an interlayer insulating film may be formed on the transmission circuit, a solder resist may be laminated on the transmission circuit, and a coverlay film may be laminated on the transmission circuit. These interlayer insulating films, solder resists, and coverlay films can also be formed from this dispersion.

[0098] Since the base layer is a metal substrate, the laminate has excellent insulation and heat dissipation properties, so it can also be used as a heat dissipation substrate, especially a substrate for mounting power semiconductors. In this case, the shape of the base material is preferably a plate shape, and the base material is preferably a copper plate or an aluminum plate. The thickness of the substrate is preferably 0.1-3 mm. In the production of this laminate in this case, a slit coating method is preferable as a method of coating this dispersion liquid on a base material. The F polymer in this case is preferably an F polymer having a melting temperature of 200° C. to 320° C., more preferably a polymer having an oxygen-containing polar group including the above-mentioned TFE unit and PAVE unit.

[0099] As the imide resin P in this case, it is preferably an aromatic polyimide, an aromatic polyimide precursor, an aromatic polyimide or an aromatic polyimide Amine precursors. In this case, it is preferable that the F layer further contains an inorganic filler. As the inorganic filler, boron nitride filler, aluminum nitride filler or alumina filler is preferred. That is, in the present laminate used as a heat dissipation substrate, the F polymer is a polymer having an oxygen-containing polar group including the above-mentioned TFE unit and a PAVE unit, preferably the imide resin P is an aromatic polymer. Amide, aromatic polyamide imide precursor, aromatic polyamide imide or aromatic polyamide imide precursor, and preferably in the F layer contains boron nitride filler, nitride Aluminum filler or alumina filler. In this case, it is particularly easy to improve the insulation and heat dissipation properties of the heat dissipation substrate as the laminate.

[0100] When using this laminate as a heat dissipation substrate, this laminate is preferably processed into a laminate having a metal layer, an F layer, and a metal layer in this order. This laminate can be obtained by thermocompression bonding the metal substrate on the surface of the F layer of this laminate, or by laminating two of this laminate so that the F layer faces each other and thermocompression bonding the F layer. and obtained, preferably the latter. As a method of thermocompression bonding, thermocompression is preferable. The thicknesses of the two metal layers in the laminate may be the same or different. In addition, the metals in the two metal layers may be the same or different. For example, if the F layer of the laminate having an F layer on the surface of an aluminum plate with a thickness of 1 mm and the F layer of the laminate having an F layer on the surface of a copper plate with a thickness of 0.5 mm are thermocompressed and bonded by thermocompression, Then, a laminate having an aluminum plate, an F layer, and a copper plate in this order and having two metal layers with different thicknesses can be obtained.

[0101] This laminate, or the laminate of this laminate and other substrates, can be used as antenna parts, printed substrates, aircraft parts, automotive parts, sports equipment, food industry supplies, coatings, heat dissipation parts, cosmetics etc. Specifically, it can be used as wire covering materials (aircraft wires, etc.), electrical insulating tapes, insulating tapes for petroleum exploration, materials for printed circuit boards, separation membranes (microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, Ion exchange membranes, dialysis membranes, gas separation membranes, etc.), electrode binders (for lithium secondary batteries, fuel cells, etc.), replica rolls, furniture, automobile dashboards, home appliances, etc., outer covers, sliding members (load bearings, Sliding shafts, valves, bearings, gears, cams, belt conveyors, conveyor belts for food transfer, etc.), tools (shovels, files, awls, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, Molds, toilets, container covering materials, heat dissipation substrates for power devices, transistors, thyristors, rectifiers, transformers, power MOS FETs (Metal-Oxide-Semiconductor Field, metal oxide semiconductor field-effect transistors), CPU (Central Processing Unit, central processing unit), heat sinks, metal heat sinks, blades of windmills or wind power generation equipment or aircraft, housings of computers or monitors, electronic device components, interior and exterior components of automobiles, heat treatment under low oxygen Sealing components of processing machines or vacuum ovens, plasma processing devices, etc., heat dissipation parts in processing units such as sputtering or various dry etching devices, and electromagnetic wave shielding components.

[0102] The dispersion, the method for producing the dispersion, and the laminate have been described above, but the present invention is not limited to the configuration of the above-mentioned embodiment. For example, this dispersion liquid and this laminated body may add another arbitrary structure to the structure of the said embodiment, and may replace it with the arbitrary structure which performs the same function. Moreover, the manufacturing method of this dispersion liquid may also have other arbitrary steps by adding to the structure of the said embodiment, and may replace with the arbitrary steps which produce the same effect. [Example]

[0103] Hereinafter, the present invention will be described in detail by examples, but the present invention is not limited thereto. 1. Details of each component [F particle] F particle 1: Contains 97.9 mol% of TFE unit, 0.1 mol% of NAH unit, and 2.0 mol% of PPVE unit, and the carbon number per 1×106 main chain Particles (D50: 2.1 μm) formed of a polymer (melting temperature: 300° C.) with 1000 carbonyl-containing groups in F particle 2: TFE units containing 97.5 mol%, and 2.5 mol% PPVE units and Particles (D50: 1.8 μm) formed by polymers (melting temperature 305°C) with 25 carbonyl groups per 1×106 main chain carbons (D50: 1.8 μm) F Particles 3: Particles containing non-heat-melting PTFE (D50: 0.2 μm) [F dispersion liquid] F dispersion liquid 1: Aqueous dispersion liquid containing 60% by mass of F particles 3 ("AD-911E" manufactured by AGC Corporation) [Varnish of imide resin] Varnish 1: Contains fragrance Water-based varnish [Surfactant] Surfactant 1: The main chain has a dimethylsiloxane unit and the main chain end or Polyoxyalkylene modified polydimethylsiloxane with oxyethylene groups in the side chain (weight average molecular weight: 1600, degree of dispersion: 1.5, HLB value: 13, static surface tension: 25 mN / m, 0.1 mass Dynamic surface tension of % aqueous solution: 30 mN / m) [pH adjuster] Amine 1: Triethanolamine acid 1: Formic acid [Non-ionic polymer] Polysaccharide 1: Hydroxyethyl cellulose (manufactured by Sumitomo Seika Co., Ltd. "HEC CF-Y") [Water-soluble polymer with non-ionic hydroxyl group] [Resin film (substrate)] Polyimide film 1: Aromatic polyimide film with a thickness of 25 μm (PI Advanced "FG-100" manufactured by Materials Corporation)

[0104] 2. Manufacture and evaluation of dispersion liquid [Example 1-1] F particle 1, varnish 1, surfactant 1 and water were put into a crucible, and zirconia balls were put into it. Thereafter, the crucible was rotated at 150 rpm for 1 hour, and amine 1 was added to obtain a mixture containing F particle 1 (60 parts by mass), PAI1 (0.6 parts by mass), surfactant 1 (3 parts by mass) and water (46.4 parts by mass). The dispersion liquid 1. The obtained dispersion 1 had a viscosity of 1000 mPa·s and a pH of 8.0. Even when the dispersion liquid 1 was stored at 25° C. for a long period of time, no aggregates were observed, and the dispersibility was excellent.

[0105] [Example 1-2] F particle 1, varnish 1, surfactant 1 and water were put into a crucible and mixed to prepare a composition. The composition was taken out after kneading in a planetary mixer to obtain a compound containing F particle 1 (60 parts by mass), PAI1 (0.6 parts by mass), surfactant 1 (3 parts by mass) and water (20 parts by mass). The mixing powder 1. Water was added to the kneaded powder 1 several times, and stirred while defoaming at 2000 rpm by a self-rotating mixer. Furthermore, water was added several times while stirring, and amine 1 was added to obtain a mixture containing F particle 1 (60 parts by mass), PAI1 (0.6 parts by mass), surfactant 1 (3 parts by mass) and water (46.4 parts by mass). ) of the dispersion 2. The obtained dispersion 2 had a viscosity of 800 mPa·s and a pH of 8.0. [Example 1-3]~[Example 1-6] As shown in Table 1, change the type or amount of F particles, varnish, pH value regulator and water, except that, the same as Example 1-2 Dispersions 3-6 were obtained in this way.

[0107] [Example 1-7] F particles 1, varnish 1, surfactant 1 and water were put into a crucible and mixed to prepare a composition. The composition was taken out after kneading in a planetary mixer to obtain a compound containing F particle 1 (50 parts by mass), PAI (0.6 parts by mass), surfactant 1 (3 parts by mass) and water (20 parts by mass). The mixing powder7. Add F dispersion liquid 1 to the kneading powder 7, and then add water several times, and stir while defoaming at 2000 rpm with a self-rotating mixer. Furthermore, water was added several times while stirring, and amine 1 was added to obtain a mixture containing F particle 1 (50 parts by mass), F particle 3 (10 parts by mass), PAI1 (0.6 parts by mass), surfactant 1 (3 parts by mass). parts by mass) and water (46.4 parts by mass) of the dispersion 7. The obtained dispersion 7 had a viscosity of 700 mPa·s and a pH of 8.0.

[0108] [Example 1-8] F particle 1, varnish 1, surfactant 1, polysaccharide 1 and water were put into a crucible and mixed to prepare a composition. The composition was taken out after kneading in a planetary mixer to obtain F particles 1 (50 parts by mass), PAI (0.6 parts by mass), surfactant 1 (3 parts by mass), polysaccharides 1 (0.3 parts by mass). parts by mass) and water (20 parts by mass) of kneading powder 8. Add F dispersion 1 to the kneaded powder 8, and then add water several times, and stir while defoaming at 2000 rpm with a self-rotating and revolving mixer. Furthermore, water was added several times while stirring, and amine 1 was added to obtain a mixture containing F particle 1 (50 parts by mass), F particle 3 (10 parts by mass), PAI1 (0.6 parts by mass), surfactant 1 (3 parts by mass). parts by mass), polysaccharide 1 (0.3 parts by mass) and water (46.1 parts by mass) dispersion 8. The obtained dispersion 8 had a viscosity of 3000 mPa·s and a pH of 8.0.

[0109] [Table 1] Dispersion No. 1 2 3 4 5 6 7 8 F particle F particle 1 (60) F particle 1 (60) F particle 1 (50) F particle 2 (60) F particle 2 (60) F particle 2 (60) F particle 1 (50) F particle 3 (10) F particle 1 (50) F particle 3 (10) imide resin PAI1(0.6) PAI1(0.6) PAI1(15) PAI1(0.6) PAI1(0.6) PAI1(0.6) PAI1(0.6) PAI1(0.6) Surfactant Surfactant 1 (3) Surfactant 1 (3) Surfactant 1 (3) Surfactant 1 (3) Surfactant 1 (3) Surfactant 1 (3) Surfactant 1 (3) Surfactant 1 (3) dispersion medium water (46.4) water (46.4) water (46.4) water (46.4) water (46.4) water (46.4) water (46.4) water (46.1) pH adjuster Amine 1 Amine 1 Amine 1 Amine 1 acid 1 Amine 1 Amine 1 Amine 1 nonionic polymer - - - - - - - Polysaccharides 1 (0.3) Viscosity [mPa・s] 1000 800 1100 1300 1300 1400 700 3000 pH value 8.0 8.0 8.0 8.0 4.8 13.0 8.0 8.0 ※The numbers in parentheses in each ingredient column indicate the content (parts by mass).

[0110] 3. Manufacture and evaluation of laminate [Example 2-1] The dispersion liquid 1 obtained in Example 1-1 was coated on polyamide by the small-diameter reverse gravure method by the roll-to-roll process One side of the amine film 1 was passed through a ventilated drying oven (oven temperature: 150° C.) for 3 minutes to remove water and form a dry film. Also, in the same manner, the dispersion liquid 1 was applied to the other surface of the polyimide film 1 and dried to form a dry film. Next, it takes 5 minutes to make the polyimide film 1 with a dry film formed on both sides pass through a far-infrared ray furnace (the temperature of the furnace near the entrance and exit of the furnace is 300°C, and the temperature of the furnace near the center is 360°C), so that the F particles 1 Melt roasting. In this way, a polymer layer comprising the melt-fired product of F particles 1 and PAI1 is formed on both sides of the polyimide film 1, and the polymer layer and the polyimide film layer are directly formed in sequence by a roll-to-roll process. and a laminate of polymer layers (multilayer film 1). The thickness of the polymer layer in the multilayer film 1 is 25 μm. [Example 2-2] to [Example 2-8] Multilayer films 2 to 7 were obtained in the same manner as in Example 2-1, except that dispersion liquid 2 to 8 was used instead of dispersion liquid 1. The porosity of the polymer layer of each multilayer film gradually decreases in the order of multilayer film 2, multilayer film 1, multilayer film 3 and 4, multilayer film 5 and 6, and the polymer layer of multilayer film 2 is the lowest. Dense.

[0112] 4. Evaluation 4-1. Evaluation of the dispersion layer rate of the dispersion liquid Each dispersion liquid (18 mL) was put into a spiral tube (inner volume: 30 mL), and allowed to stand at 25°C for 14 days. Based on the overall height of the dispersion liquid in the spiral tube after standing still and the height of the sedimentation layer (dispersion layer), the dispersion layer rate was calculated by the following formula, and the dispersion stability was evaluated according to the following criteria. [Evaluation criteria] 〇: The dispersion layer ratio is 80% or more. Δ: The dispersed layer ratio is 60% or more and less than 80%. ×: The dispersion layer ratio is less than 60%.

[0113] 4-2. Variation range of the thixotropic ratio of the dispersion. Store each dispersion in a container at 25°C for 30 days, measure the variation range of the thixotropic ratio before and after storage, and evaluate the thixotropic stability according to the following criteria sex. [Evaluation criteria] 〇: The variation range (absolute value) of the thixotropic ratio is less than 1. △: The variation range (absolute value) of the thixotropic ratio is 1 to 3. ×: The variation range (absolute value) of the thixotropic ratio exceeds 3.

[0114] 4-3. Evaluation of surface smoothness of multilayer film The surface of the polymer layer of each multilayer film was visually confirmed, and the surface smoothness was evaluated according to the following criteria. [Evaluation criteria] ○: There are no pinholes on the surface of the polymer layer. X: There are pinholes on the surface of the polymer layer.

[0115] 4-4. Evaluation of interlayer adhesion of multilayer films Cut out rectangular (length 100 mm, width 10 mm) test pieces from each multilayer film, and place them at a position 50 mm away from one end of the test piece in the longitudinal direction Fixed, at a tensile speed of 50 mm / min, peel off the polymer layer and the polyimide film layer from one end in the length direction to the test piece at 90°. The maximum load applied at this time was defined as the peel strength, and the interlayer adhesiveness was evaluated according to the following criteria. [Evaluation criteria] ◯: The peel strength is 15 N / cm or more. Δ: The peel strength is 10 N / cm or more and less than 15 N / cm. ×: Peel strength is less than 10 N / cm. The respective evaluation results are collectively shown in Table 2 below.

[0116] [Table 2] Dispersion or Multilayer Film No. 1 2 3 4 5 6 7 8 dispersion stability 〇 〇 △ △ x x 〇 〇 Variation range of thixotropic ratio △ 〇 △ x x x 〇 〇 Surface smoothness 〇 〇 〇 △ x x 〇 〇 Adhesiveness between layers △ 〇 △ △ x △ 〇 〇

[0117] Furthermore, the dielectric loss factor of each multilayer film was measured by the SPDR (separated column dielectric resonance) method (measurement frequency: 10 GHz). As a result, the dielectric loss factor of multilayer films 7 and 8 was the lowest, and the two The electrical characteristics of the multilayer film are more excellent. In addition, the thickness of the polymer layer having surface smoothness and interlayer adhesion that can be formed by a single manufacturing process of the laminate is the largest when the dispersion liquid 8 is used. [Industrial availability]

[0118] The aqueous dispersion of the present invention has excellent dispersion stability and can be easily processed into films, fiber-reinforced films, prepregs, and metal laminates (metal foil with resin). The obtained processed articles can be used as materials for antenna parts, printed substrates, aircraft parts, automobile parts, sports equipment, food industry supplies, sliding bearings, etc. In addition, since the laminate of the present invention has excellent heat resistance and release properties, it can also be used as a carrier film for forming ceramic green sheets, a carrier film for secondary battery electrode film formation, and a solid polymer electrolyte membrane. The supporting film used for the formation of the catalyst of the solid polymer electrolyte membrane.

Claims

1. An aqueous dispersion comprising tetrafluoroethylene polymer particles, an aromatic acetamiprid resin with an acid value of 20-100 mg / KOH, and water, wherein the mass ratio of the aromatic acetamiprid resin to the mass of the tetrafluoroethylene polymer particles is in the range of 0.001-0.1, the total content of the particles and the aromatic acetamiprid resin in the aqueous dispersion is 30-80% by mass relative to the total mass of the aqueous dispersion, the content of the particles is 25-90% by mass, the content of the aromatic acetamiprid resin is 0.1% by mass or more, and the pH value of the aqueous dispersion is 5-10.

2. The aqueous dispersion of claim 1, wherein the aforementioned tetrafluoroethylene polymer is a tetrafluoroethylene polymer having an oxygen-containing polar group comprising a perfluorinated (alkyl vinyl ether) unit.

3. The aqueous dispersion of claim 1 or 2, wherein the aforementioned tetrafluoroethylene polymer particles comprise non-thermally molten tetrafluoroethylene polymer particles and thermally molten tetrafluoroethylene polymer particles.

4. The aqueous dispersion of claim 1 or 2, wherein the aromatic polyamide resin is a water-soluble aromatic polyamide precursor or a water-soluble aromatic polyamide precursor.

5. The aqueous dispersion of claim 1 or 2 further comprises inorganic filler.

6. The aqueous dispersion of claim 1 or 2 further comprises a nonionic surfactant.

7. The aqueous dispersion of claim 1 or 2 further comprises at least one nonionic polymer selected from the group consisting of polyvinyl alcohol polymers, polyvinylpyrrolidone polymers and polysaccharides.

8. The aqueous dispersion of claim 1 or 2 contains amine or ammonia.

9. The aqueous dispersion of the requested item 1 or 2 has a viscosity of 50 to 3000 mPa·s.

10. The aqueous dispersion of claim 1 or 2, used to form a polymer layer comprising a tetrafluoroethylene polymer by applying it to at least one surface of a resin film and heating it.

11. The aqueous dispersion of claim 10, wherein the resin constituting the resin film is a polyimide resin.

12. A method for manufacturing an aqueous dispersion, comprising the method for manufacturing an aqueous dispersion according to any one of claims 1 to 11, wherein a composition containing the above-mentioned tetrafluoroethylene polymer particles, the above-mentioned aromatic amide resin and water is kneaded to obtain a mixture, and the above-mentioned mixture is mixed with water to obtain the above-mentioned aqueous dispersion.

13. A laminate comprising applying an aqueous dispersion of any one of claims 1 to 11 to both surfaces of a resin film, heating the film to form a polymer layer comprising a tetrafluoroethylene-based polymer, wherein the polymer layer is present on both sides of a substrate layer comprising the resin film.