Method for producing liquid composition and composition

Abstract

[Problem] To provide a method for producing a liquid composition which contains particles of a tetrafluoroethylene-based polymer, exhibits excellent dispersion stability, homogeneity and handleability, yields a molded product that exhibits excellent physical properties such as electrical characteristics, and is useful as a constituent material of a solder resist composition or a printed substrate. [Solution] In this method for producing a liquid composition, particles of a tetrafluoroethylene-based polymer, at least one of an aromatic resin and inorganic particles having a new Mohs hardness of 12 or less, and a liquid compound are mixed in a tank having a stirring mechanism involving thin film rotation or a stirring mechanism involving rotation and revolution, thereby obtaining a liquid composition that contains the particles of a tetrafluoroethylene-based polymer, at least one of an aromatic resin and inorganic particles having a new Mohs hardness of 12 or less, and the liquid compound.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a liquid composition containing particles of a tetrafluoroethylene-based polymer and at least one of an aromatic resin and specified inorganic particles, and to the liquid composition. [Background 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 such as printed circuit boards. Liquid compositions containing tetrafluoroethylene-based polymer particles and a liquid dispersion medium such as water are known as coating agents used to impart these properties to the surface of a substrate. Such liquid compositions can be used to form molded articles with excellent electrical properties such as low dielectric constant and low dielectric loss tangent, and therefore such liquid compositions are attracting attention as materials for forming dielectric layers of printed circuit boards that are compatible with high-frequency band frequencies.

[0003] In order to form a better dielectric layer, a mixture of a tetrafluoroethylene-based polymer and an aromatic resin has also been investigated. For example, Patent Document 1 discloses a polyimide-PTFE blend film produced by mixing PTFE particles into a polyamic acid varnish and subjecting the mixture to an imidization process. Patent Document 2 discloses a polyimide-PTFE blend film produced by producing a polyamic acid varnish, extracting a portion of it and mixing it with PTFE particles, mixing this with the remaining varnish, and subjecting the mixture to a thermal casting method. Patent Document 3 proposes the use of a thickener to improve the coatability of such a liquid composition, and Patent Document 4 proposes the use of a polyamideimide resin and a polyetherimide to improve the adhesiveness of a molded article formed from such a liquid composition. Furthermore, tetrafluoroethylene polymers have extremely low dispersion stability, and therefore, various proposals have been made in the past with a view to obtaining liquid compositions with excellent dispersion stability. For example, Patent Document 5 discloses a liquid composition containing PTFE particles, which is further mixed with ceramic inorganic particles in order to improve dispersion stability. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-142572 [Patent Document 2] International Publication No. 2016 / 159061 [Patent Document 3] Japanese Patent Application Publication No. 2018-048233 [Patent Document 4] Japanese Patent Application Publication No. 2019-218484 [Patent Document 5] Japanese Patent Application Laid-Open No. 2016-194017 Summary of the Invention [Problem to be solved by the invention]

[0005] Tetrafluoroethylene-based polymers have low surface tension, are less likely to interact with other components, and have extremely low dispersion stability. Therefore, the present inventors have found that in the embodiments of the prior art documents, the resulting mixture (composition) has low dispersion stability and is easily altered, resulting in a problem that the uniformity and density of the component distribution of the molded article obtained therefrom are reduced, making it difficult for the molded article to exhibit its physical properties. Furthermore, the present inventors have found that this problem becomes more pronounced when such a mixture (composition) is used to form a molded article having a fine or complex shape, such as a substrate with protrusions.

[0006] In addition, in the embodiment described in Patent Document 5, the dispersion stability and uniformity of the liquid composition were insufficient due to aggregation of the inorganic particles, and the liquid composition was prone to deterioration. Furthermore, the uniformity of the component distribution in a molded product obtained from such a liquid composition was still insufficient.

[0007] As a result of intensive research, the present inventors have found that, in the production of a liquid composition containing tetrafluoroethylene-based polymer particles and at least one of an aromatic resin and specific inorganic particles, by mixing them under specific conditions, a liquid composition excellent in dispersion stability, uniformity, and handleability can be obtained. In addition, specifically, they have found that the contents of the tetrafluoroethylene-based polymer particles and the aromatic resin in the composition can be increased. In addition, the present inventors have discovered that such a liquid composition is not only suitable for forming dense molded articles, but also has excellent properties such as low dielectric tangent and low linear expansion, and is suitable for forming molded articles having fine or complex shapes.

[0008] Specifically, the present inventors have also found that such a liquid composition is suitable for forming a dense molded product having excellent properties such as a low dielectric loss tangent and a low linear expansion coefficient.

[0009] Furthermore, the present inventors have found that, specifically, such a liquid composition is suitable for forming a dense molded product that highly possesses the physical properties of a tetrafluoroethylene-based polymer and inorganic particles, and that has low dielectric tangent, low linear expansion, excellent thermal conductivity, etc.

[0010] An object of the present invention is to provide a method for producing a composition comprising tetrafluoroethylene-based polymer particles and at least one of an aromatic resin and specified inorganic particles, which has excellent dispersion stability, uniformity, and handleability, and which is preferably a resist composition. Specifically, an object of the present invention is to provide a method for producing a liquid composition containing tetrafluoroethylene-based polymer particles and an aromatic resin, which has excellent dispersion stability and handleability, preferably a resist composition, and a member with convex portions having a predetermined pattern formed from the resist composition.

[0011] More specifically, an object of the present invention is to provide a method for producing a liquid composition which contains particles of a tetrafluoroethylene-based polymer, an aromatic polymer, a specified thickening polymer, and water and which has excellent dispersion stability, uniformity, and handleability, as well as such a liquid composition and a method for producing a laminate using this liquid composition. More specifically, an object of the present invention is to provide a composition that can form a liquid composition having excellent dispersion stability, uniformity, and ease of handling, preferably a composition that is a lumpy, clay-like kneaded product (dough or wet powder).

[0012] More specifically, an object of the present invention is to provide a method for producing a liquid composition containing particles of a tetrafluoroethylene-based polymer and specified inorganic particles, which has little aggregation of the inorganic particles and is excellent in dispersion stability, uniformity, and handleability, and a method for producing a laminate using the obtained liquid composition. [Means for solving the problem]

[0013] The present invention has the following aspects. <1> A method for producing a liquid composition, comprising mixing particles of a tetrafluoroethylene-based polymer, at least one of an aromatic resin and inorganic particles having a new Mohs hardness of 12 or less, and a liquid compound in a tank equipped with a stirring mechanism using thin film rotation or a stirring mechanism using rotation and revolution, to obtain a liquid composition containing the particles of the tetrafluoroethylene-based polymer, at least one of an aromatic resin and inorganic particles having a new Mohs hardness of 12 or less, and the liquid compound. <2> The tetrafluoroethylene-based polymer particles and the aromatic resin varnish are placed in a cylindrical stirring tank of a stirrer equipped with a rotating part having a cylindrical part with a plurality of holes formed therein and rotating inside the inner wall surface of the stirring tank, and the mixture is stirred while being spread into a thin cylindrical film on the inner wall surface of the stirring tank by the centrifugal force caused by the rotation of the rotating part, thereby obtaining a liquid composition containing the tetrafluoroethylene-based polymer and the aromatic resin. <1> Manufacturing method. <3> The tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer having an oxygen-containing polar group containing a unit based on perfluoro(alkyl vinyl ether). <2> Manufacturing method. <4> the ratio of the mass of the tetrafluoroethylene polymer particles to the mass of the aromatic resin is 0.5 to 10; <2> or <3> Manufacturing method. <5> A liquid composition containing tetrafluoroethylene-based polymer particles and an aromatic resin varnish, wherein the total content of the tetrafluoroethylene-based polymer particles and the aromatic resin is 50 mass % or more, and the mass ratio of the content of the tetrafluoroethylene-based polymer particles to the aromatic resin is 0.5 to 10, and the liquid composition is used by mixing with the aromatic resin varnish.

[0014] <6> tetrafluoroethylene-based polymer particles, an aromatic resin, at least one thickening polymer selected from the group consisting of polar vinyl-based polymers and polysaccharides, and water are mixed in a tank equipped with a stirring mechanism based on thin film rotation or a stirring mechanism based on rotation and revolution, to obtain a liquid composition containing the tetrafluoroethylene-based polymer particles, the aromatic resin, the thickening polymer, and the water; <1> Manufacturing method. <7> The tetrafluoroethylene-based polymer particles, the aromatic resin, the thickening polymer, and the water are mixed in a tank equipped with a stirring mechanism based on thin film rotation or a stirring mechanism based on rotation and revolution, and water is further added thereto to obtain the liquid composition. <6> Manufacturing method. <8> the tetrafluoroethylene-based polymer particles include particles of a heat-fusible tetrafluoroethylene-based polymer and particles of a non-heat-fusible tetrafluoroethylene-based polymer; <6> or <7> Manufacturing method. <9> the aromatic resin is an aromatic polyimide, an aromatic polyamideimide, an aromatic polyetherimide, or a precursor thereof; <6> ~ <8> A manufacturing method of any of the above. <10> Furthermore, the inorganic particles are mixed in a tank equipped with a stirring mechanism based on thin film rotation or a stirring mechanism based on rotation and revolution to obtain the liquid composition. <6> ~ <9> A manufacturing method of any of the above. <11> The thickening polymer contains particles of a tetrafluoroethylene-based polymer, an aromatic polymer, at least one thickening polymer selected from the group consisting of polar vinyl-based polymers and polysaccharides, and water, and the ratio of the content of the thickening polymer to the particles of the tetrafluoroethylene-based polymer is 0.05 or less. The temperature is 25°C, the shear rate is 1 s -1 A composition having a viscosity measured by capillography of 10,000 Pa·s to 100,000 Pa·s.

[0015] <12> tetrafluoroethylene-based polymer particles, inorganic particles having a new Mohs hardness of 12 or less, and a liquid compound are mixed by thin film swirling to obtain a liquid composition containing the tetrafluoroethylene-based polymer particles, the inorganic particles, and the liquid compound; <1> Manufacturing method. <13> the tetrafluoroethylene-based polymer particles include particles of a heat-fusible tetrafluoroethylene-based polymer and particles of a non-heat-fusible tetrafluoroethylene-based polymer; <12> Manufacturing method. <14> The inorganic particles are boron nitride particles or silica particles. <12> or <13> Manufacturing method. <15> The viscosity of the liquid composition is 10,000 mPa·s or less. <12> ~ <14> A manufacturing method of any of the above. [Effects of the Invention]

[0016] According to the present invention, a liquid composition containing tetrafluoroethylene-based polymer particles and an aromatic resin can be produced, which has excellent dispersion stability and handleability. Such a composition has excellent physical properties such as electrical properties and is useful, for example, as a solder resist composition or a constituent material for printed circuit boards.

[0017] Furthermore, according to the present invention, a liquid composition containing tetrafluoroethylene-based polymer particles, an aromatic polymer, a predetermined thickening polymer, and water can be produced, which has excellent dispersion stability, uniformity, and handleability. Such a liquid composition has excellent physical properties such as electrical properties and is useful, for example, as a constituent material for printed circuit boards. Furthermore, the present invention provides a composition that can form a liquid composition that is excellent in dispersion stability, uniformity, and handleability.

[0018] Furthermore, according to the present invention, a liquid composition containing tetrafluoroethylene-based polymer particles and predetermined inorganic particles can be produced, which has excellent dispersion stability and handleability. Such a liquid composition can be used to form molded articles with excellent physical properties such as electrical properties, and is useful, for example, as a material for printed circuit boards. DETAILED DESCRIPTION OF THE INVENTION

[0019] A "tetrafluoroethylene-based polymer" is a polymer containing units (hereinafter also referred to as "TFE units") based on tetrafluoroethylene (hereinafter also referred to as "TFE"), and is also simply referred to as an "F polymer." "Average particle size (D50)" is the volume-based cumulative 50% diameter of a target object (particles and fillers) determined by laser diffraction / scattering. In other words, particle size distribution is measured by laser diffraction / scattering, and a cumulative curve is calculated with the total volume of the target object group as 100%. The average particle size (D50) is the particle size at the point on the cumulative curve where the cumulative volume is 50%. The D50 of a target object is determined by dispersing the target object in water and analyzing it by the laser diffraction / scattering method using a laser diffraction / scattering particle size distribution measuring device (LA-920 measuring device, manufactured by Horiba, Ltd.). "Average particle size (D90)" is the cumulative volume particle size of particles, and is the volume-based cumulative 90% diameter of particles determined in the same manner as "D50". "Hot-melt resin" means a resin with melt fluidity that has a melt flow rate of 1 to 1000 g / 10 min at a temperature 20°C or more higher than the melting temperature of the resin under a load of 49 N. The term "non-thermofusible resin" refers to a resin that is not melt-flowable and does not have a temperature at which the melt flow rate is 1 to 1000 g / 10 min under a load of 49 N. The "melting temperature" is the temperature corresponding to the maximum value of the melting peak of a polymer as measured by differential scanning calorimetry (DSC). The "melting temperature (melting point) of a polymer" is the temperature corresponding to the maximum value of the melting peak of the polymer as measured by differential scanning calorimetry (DSC). "Viscosity" refers to the viscosity of a liquid composition measured using a Brookfield viscometer at 25°C and a rotation speed of 30 rpm. The measurement is repeated three times, and the average value of the three measurements is used. The "thixotropy ratio" is a value calculated by dividing the viscosity η1 of a liquid composition measured at a rotation speed of 30 rpm by the viscosity η2 measured at a rotation speed of 60 rpm. Each viscosity measurement is repeated three times, and the average value of the three measurements is used. The "Mohs hardness scale" is a measure of hardness determined using the hardness of 15 reference minerals. The reference minerals, in order from soft (Mohs hardness 1) to hard (Mohs hardness 15), are talc, gypsum, calcite, fluorite, apatite, orthoclase, fused quartz, quartz, topaz, garnet, fused zirconia, fused alumina, silicon carbide, boron carbide, and diamond. In this specification, hardness is determined by the presence or absence of scratches when a target sample is rubbed with these reference minerals. For example, a target sample that is not scratched by calcite but is scratched by fluorite has a Mohs hardness of 3.5. The term "unit" in a polymer refers to an atomic group based on a monomer formed by polymerization of the monomer. The unit may be a unit formed directly by a polymerization reaction, or may be a unit in which a portion of the unit is converted into a different structure by processing the polymer. Hereinafter, a unit based on monomer a will also be referred to simply as a "monomer a unit."

[0020] The manufacturing method of the present invention (hereinafter also referred to as "this method") is a method in which particles of an F polymer (hereinafter also referred to as "F particles"), at least one of an aromatic resin or inorganic particles having a new Mohs hardness of 12 or less (hereinafter also referred to as "the present inorganic particles"), and a liquid compound are mixed in a tank equipped with a stirring mechanism that uses thin film rotation or a stirring mechanism that uses rotation and revolution, to obtain a liquid composition (hereinafter also referred to as "the present liquid composition") containing the F particles, at least one of the aromatic resin or the present inorganic particles, and the liquid compound.

[0021] The F polymer in the present invention may be either heat-fusible or non-heat-fusible. When the F polymer is heat-meltable, its melting temperature is preferably 200° C. or higher, more preferably 240° C. or higher, and even more preferably 260° C. or higher. The melting temperature of the F polymer is preferably 325° C. or lower, more preferably 320° C. or lower. The melting temperature of the F polymer is particularly preferably 200 to 320° C.

[0022] The glass transition point of the F polymer is preferably 50° C. or higher, more preferably 75° C. or higher. The glass transition point of the F polymer is preferably 150° C. or lower, more preferably 125° C. or lower. The surface tension of the F polymer is preferably 16 to 26 mN / m, more preferably 16 to 20 mN / m. The surface tension of the F polymer can be measured by placing a droplet of a wettability index reagent (manufactured by Wako Pure Chemical Industries, Ltd.) on a flat plate made of the F polymer. The fluorine content of the F polymer is preferably 70% by mass or more, more preferably 72 to 76% by mass. An F polymer with a high fluorine content has excellent physical properties such as electrical properties, but has low surface tension and is prone to poor dispersion stability in liquid compounds. However, in the present invention, the dispersion stability of such an F polymer is likely to be improved by the action mechanisms of the various aspects described below.

[0023] F polymer can be enumerated as polytetrafluoroethylene (PTFE), the polymer that comprises TFE unit and the unit based on ethylene, the polymer that comprises TFE unit and the unit based on propylene, the polymer that comprises TFE unit and the unit based on perfluoro(alkyl vinyl ether) (PAVE) (PAVE unit) (PFA), the polymer that comprises TFE unit and the unit based on hexafluoropropylene (FEP), the polymer that comprises TFE unit and the unit based on fluoroalkylethylene, the polymer that comprises TFE unit and the unit based on chlorotrifluoroethylene, preferably PFA or FEP, more preferably PFA.Above-mentioned polymer can further comprise the unit based on other comonomer. As PAVE, CF2=CFOCF3, CF2=CFOCF2CF3 or CF2=CFOCF2CF2CF3 (hereinafter also referred to as "PPVE") is preferred, and PPVE is more preferred.

[0024] The PTFE may be a non-thermofusible PTFE or a thermofusible PTFE. The F polymer preferably has an oxygen-containing polar group, which facilitates the formation of microspherulites at the molecular aggregate level, improves the wettability of the F particles, and makes it easier to achieve the effects of the present invention. The oxygen-containing polar group may be contained in a unit in the F polymer or in a terminal group of the main chain of the F polymer. Examples of the latter include an F polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like, and an F polymer having an oxygen-containing polar group obtained by subjecting an F polymer to plasma treatment or ionizing radiation treatment. The oxygen-containing polar group is preferably a hydroxyl group-containing group, a carbonyl group-containing group, or a phosphono group-containing group. From the viewpoint of the dispersion stability of the liquid composition, a hydroxyl group-containing group or a carbonyl group-containing group is more preferred, and a carbonyl group-containing group is even more preferred.

[0025] The hydroxyl group-containing group is preferably a group containing an alcoholic hydroxyl group, more preferably -CF2CH2OH or -C(CF3)2OH. The carbonyl group-containing group is a group containing a carbonyl group (>C(O)), and is preferably a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH), an acid anhydride residue (-C(O)OC(O)-), an imide residue (-C(O)NHC(O)-, etc.), or a carbonate group (-OC(O)O-), with an acid anhydride residue being more preferred. In this case, the F particles are more likely to interact with the inorganic particles and the liquid compound, and the liquid composition is more likely to have excellent liquid physical properties, such as dispersion stability.

[0026] The F polymer is preferably a polymer having a carbonyl group-containing group containing TFE units and PAVE units, more preferably a polymer containing units based on a monomer having TFE units, PAVE units, and a carbonyl group-containing group, and even more preferably a polymer containing these units in the following amounts relative to the total units, in that order: 90 to 99 mol%, 0.5 to 9.97 mol%, and 0.01 to 3 mol%. The presence of a carbonyl group-containing group is preferred from the viewpoint of further improving the affinity and adhesion of the F polymer.

[0027] When the F polymer has a carbonyl group-containing group, the number of carbonyl group-containing groups in the F polymer is 1×10 6 The number per unit is preferably 10 to 5000, more preferably 100 to 3000, and further preferably 800 to 1500. The number of carbonyl group-containing groups in the F polymer can be quantified by the composition of the polymer or the method described in WO 2020 / 145133. The monomer having a carbonyl group-containing group is preferably itaconic anhydride, citraconic anhydride, or 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"). Specific examples of such polymers include the polymers described in WO 2018 / 16644.

[0028] The D50 of the F particles in the present invention is preferably 0.1 to 25 μm. The D50 of the F particles is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less. The D50 of the F particles is preferably 0.2 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more. With a D50 in this range, the flowability and dispersion stability of the F particles tend to be good. From the viewpoint of dispersion stability, the specific surface area of ​​F particles is 1 to 25 m 2 / g is preferred, and 1 to 8m 2 / g is more preferred.

[0029] One type of F particles may be used, or two or more types may be used. When two types of F particles are used, the F particles preferably contain particles of a heat-fusible F polymer and particles of a non-heat-fusible F polymer, and more preferably particles of an F polymer (preferably the above-mentioned polymer having an oxygen-containing polar group containing TFE units and PAVE units) with a melting temperature of 200 to 320°C and particles of non-heat-fusible PTFE. An even more preferred embodiment is one in which the content of the latter particles is greater than the content of the former particles. In this case, the F polymer is fibrillated to an appropriate degree while maintaining its physical properties, and the inorganic particles are easily supported in a molded article formed from the liquid composition, which tends to improve the strength of the molded article.

[0030] In this case, the proportion of the former particles in the total of the former and latter particles is preferably 50% by mass or less, more preferably 25% by mass or less, and in this case, the proportion is preferably 0.1% by mass or more, more preferably 1% by mass or more. The present liquid composition not only tends to be excellent in dispersion stability, uniformity and ease of handling, but also tends to form adhesive molded articles having excellent physical properties based on the non-thermofusible PTFE. In this case, preferred embodiments are those in which the D50 of the particles of the F polymer having a melting temperature of 200 to 320°C is 0.1 to 1 μm and the D50 of the particles of the non-thermofusible PTFE is 0.1 to 1 μm, and those in which the D50 of the particles of the F polymer having a melting temperature of 200 to 320°C is 1 to 4 μm and the D50 of the particles of the non-thermofusible PTFE is 0.1 to 1 μm.

[0031] The F particles may contain resins other than the F polymer, but preferably contain the F polymer as the main component. The content of the F polymer in the F particles is preferably 80% by mass or more, more preferably 100% by mass. Examples of the resin include heat-resistant resins such as aromatic polyester, polyamideimide, (thermoplastic) polyimide, polyphenylene ether, polyphenylene oxide, and maleimide. The content of F particles in the liquid composition is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the liquid composition, and is preferably 80% by mass or less, more preferably 70% by mass or less, based on the total mass of the liquid composition.

[0032] First, the first aspect of the present method (hereinafter also referred to as "the present method 1") will be described. Method 1 is a method in which particles (hereinafter also referred to as "F particles") of a tetrafluoroethylene-based polymer (hereinafter also referred to as "F polymer") and a varnish of an aromatic resin (hereinafter also referred to as "first aromatic resin") are mixed by a specific stirring means to obtain a composition containing the F particles and the first aromatic resin. Furthermore, the composition of the present invention (hereinafter also referred to as "the present composition 1") contains F particles and a first aromatic resin, the total content of the F particles and the first aromatic resin being 50 mass % or more, and the mass ratio of the content of the F particles to the first aromatic resin being 0.5 to 10. The present composition 1 is used by mixing with a varnish of an aromatic resin (hereinafter also referred to as "the second aromatic resin"), and is preferably a composition used in a negative resist composition.

[0033] The composition obtained by Method 1, for example, Composition 1, has excellent dispersion stability and ease of handling. The reason for this and its mechanism of action are not entirely clear, but it is presumed to be, for example, as follows. Because F polymers have low surface energy and poor dispersibility, F particles tend to form complex secondary particles and aggregate when mixed with an aromatic resin. Therefore, in Method 1, a specific stirring method is employed: a treatment liquid containing F particles and an aromatic resin is moved at high speed within a container, generating shear stress between the liquid film and the inner wall of the container, thereby preventing the F particles from deteriorating and loosening the secondary particles of the F particles while mixing the F particles and the aromatic resin. As a result, the present invention provides a composition with excellent dispersion stability. Furthermore, it is believed that a composition (e.g., Composition 1) with excellent handleability can be obtained even when the content of the F polymer and the first aromatic resin is increased. Composition 1 can be used to form a molded product that possesses the physical properties of the F polymer and the first aromatic resin to a high degree and has excellent electrical properties.

[0034] The aromatic resin in the first aromatic resin varnish used in the present invention is preferably an aromatic resin having an oxygen-containing polar group. Specific examples of the first aromatic resin include aromatic polyimide, aromatic polyimide precursor (polyamic acid), aromatic polyamideimide, aromatic polyamideimide precursor, epoxy resin, phenolic resin, aromatic polyester resin (such as liquid crystalline aromatic polyester), aromatic polyesteramide (such as liquid crystalline aromatic polyesteramide), polyphenylene ether, and aromatic maleimide resin. Among these, aromatic resins having epoxy groups or curable aromatic resins having carboxyl groups and an acid value of 150 mgKOH / g or less are more preferred.

[0035] Examples of aromatic resins having epoxy groups include phenol novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AF epoxy resins, naphthalene epoxy resins, trisphenol epoxy resins, tert-butylcatechol epoxy resins, aminophenol epoxy resins, biphenyl epoxy resins, and biphenylaralkyl epoxy resins. These epoxy resins may be solid (solid at 40°C), semi-solid (solid at 20°C and liquid at 40°C), or liquid (liquid at 20°C). These epoxy resins may be used alone or in combination of two or more. When the present composition 1 contains a semi-solid epoxy resin, the cured product obtained by curing the present composition 1 (preferably a negative resist composition) tends to have a high glass transition temperature (Tg), a low linear expansion coefficient, and excellent crack resistance. On the other hand, when the present composition 1 contains a solid epoxy resin, the cured product tends to have a high glass transition temperature and excellent heat resistance, and when the present composition 1 contains a liquid epoxy resin, the dry film tends to have excellent flexibility.

[0036] The curable aromatic resin having a carboxyl group and an acid value of 150 mgKOH / g or less is preferably a photosensitive resin having a carboxyl group and being an alkali-soluble resin. From the viewpoint of improving photocurability and developability, such a photosensitive resin preferably has an ethylenically unsaturated double bond in the molecule, and more preferably has a (meth)acryloyloxy group. In this specification, the term "(meth)acryloyloxy group" is a general term that refers to an acryloyloxy group, a methacryloyloxy group, and both. As such a resin, a carboxyl group-containing phenolic resin is preferred, and a carboxyl group-containing phenolic resin obtained by reacting a polyfunctional phenolic resin (e.g., a polyfunctional novolac epoxy resin) epoxidized by reacting epichlorohydrin with phenolic hydroxyl groups, reacting the polyfunctional phenolic resin with (meth)acrylic acid, and then adding a dibasic acid anhydride to the hydroxyl groups present in the side chain is more preferred. Such a carboxyl group-containing phenolic resin is preferred because it easily interacts with F polymers (especially F polymers having polar functional groups).

[0037] The acid value of the first aromatic resin is preferably 120 mgKOH / g or less, more preferably 90 mgKOH / g or less. The acid value is preferably 40 mgKOH / g or more, more preferably 45 mgKOH / g or more. A first aromatic resin having such an acid value interacts highly with the F polymer, thereby improving the dispersion stability of the F particles in the composition 1. Furthermore, such a first aromatic resin has good alkaline developability, and it is easy to obtain a molded product (protrusions) having the desired complex shape.

[0038] Examples of the solvent constituting the first aromatic resin varnish include N-methyl-2-pyrrolidone and cyclohexanone. The content of the first aromatic resin in the first aromatic resin varnish is preferably in the range of 20 to 90 mass %.

[0039] In this method, F particles and a varnish of a first aromatic resin are placed in a cylindrical stirring tank of a stirrer equipped with a rotating part having a cylindrical portion with multiple holes formed therein that rotates inside the inner wall surface of the stirring tank, and the mixture is stirred while being spread into a thin cylindrical film on the inner wall surface of the stirring tank by the centrifugal force caused by the rotation of the rotating part, thereby obtaining a composition containing F polymer and a first aromatic resin. Such stirring means is sometimes called a thin film swirling high-speed mixer, and by the above-mentioned mechanism of action, can mix the F particles and the first aromatic resin while breaking up the secondary particles without altering the F particles themselves. As a result, a composition with excellent dispersibility can be obtained with shorter stirring times. Furthermore, such a composition, particularly Composition 1, can form a composition with excellent dispersion stability even when further mixed with a second aromatic resin varnish and, if necessary, optional additives such as inorganic fillers.

[0040] The inner wall surface of the cylindrical stirring vessel may be provided with irregularities. The combination of the height and shape of such irregularities may be such that the depth (height) is about several μm to several hundred μm, and the irregularities have lattice-like grooves or dimples, and may be appropriately replaceable. Furthermore, the inner wall surface of the stirring vessel may be equally divided into, for example, upper, middle, and lower portions, and different irregularity patterns may be formed. The material of the stirring vessel can be processed to form irregularities and is resistant to wear, such as stainless steel or ceramic.

[0041] The stirring tank may have a plurality of inlets for the components to be stirred. That is, when producing the composition by Method 1, a premix of the F particles and the first aromatic resin varnish may be supplied to the stirring tank all at once, or the F particles and the first aromatic resin varnish may be supplied to the stirring tank separately. The stirring tank may be provided with an outlet for the mixture of the components to be stirred. Therefore, Method 1 can be carried out either batchwise or continuously.

[0042] The rotating part, which has a cylindrical part with multiple holes formed therein and rotates inside the inner wall surface of the stirring vessel, faces the inner wall surface of the stirring vessel via a small gap of about 1 to 10 mm. The peripheral speed of the rotating part and the stirring time can be set appropriately. The supplied varnish of F particles and first aromatic resin spreads throughout the gap between the inner wall surface of the mixing vessel and the outer circumferential surface of the cylindrical part of the rotating part, forming a film, which rotates at high speed within the mixing vessel as the rotating part rotates. At this time, the film is subjected to not only shear stress but also shear stress, achieving a high level of dispersion.

[0043] In Method 1, the amounts of F particles and the first aromatic resin varnish used are such that the ratio of the mass of F particles to the mass of the first aromatic resin in the varnish is preferably in the range of 0.5 to 10, more preferably in the range of 1 to 3.

[0044] Composition 1 contains F particles and a varnish of a first aromatic resin, the total content of the F particles and the first aromatic resin being 50 mass% or more, and the mass ratio of the content of the F particles to the first aromatic resin being 0.5 to 10, and is a composition that is used by mixing with a varnish of a second aromatic resin. Composition 1 is a composition with a high resin solid content, a high F polymer content in the resin solid content, and excellent dispersion stability and handleability. This tendency becomes more pronounced when the F particles and F polymer in the present composition 1 are each within the above-mentioned ranges, particularly when the F polymer is a polymer having an oxygen-containing polar group. Composition 1 is preferably prepared by stirring the F particles and the first aromatic resin varnish, preferably using the thin film rotary high-speed mixer described above. In this case, too, this tendency tends to become more pronounced.

[0045] The present composition 1 may further contain a surfactant as a dispersant, from the viewpoint of further improving dispersibility and ease of handling. The surfactant is preferably nonionic. The hydrophilic portion of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group, and the hydrophobic portion preferably has an acetylene group, a polysiloxane group, a perfluoroalkyl group, or a perfluoroalkenyl group. In other words, the surfactant is preferably an acetylene-based surfactant, a silicone-based surfactant, or a fluorine-based surfactant.

[0046] The composition 1 may further contain another resin. The other resin may be a thermosetting resin or a thermoplastic resin. Examples of the other resins include non-aromatic maleimide resins, urethane resins, polyimides, polyamic acids, polyamideimides, and polyvinyl acetal resins. Preferred examples of the other resins include maleimide resins, polyimides, and polyamic acids. In this case, molded articles formed from the present composition 1 tend to have excellent flexibility and adhesiveness.

[0047] In addition to these components, the present composition 1 may contain additives such as a silane coupling agent, a dehydrating agent, an antifoaming agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a release agent, a surface treatment agent, and a flame retardant.

[0048] The present composition 1 and the second aromatic resin varnish may be mixed together all at once, or the present composition 1 may be mixed with the second aromatic resin varnish sequentially, or the present composition 1 may be mixed with the second aromatic resin varnish sequentially. When any optional additive components such as inorganic fillers, photopolymerization initiators, curing agents or curing accelerators, dispersants, and other liquid dispersion media are further mixed, they can be mixed at any stage.

[0049] Methods for mixing the composition 1 and the second aromatic resin varnish include stirring with a stirring device equipped with uniaxial or multiaxial blades (stirring impellers) such as propeller blades, turbine blades, paddle blades, and shell-shaped blades, or with a Henschel mixer, pressure kneader, Banbury mixer, or planetary mixer; mixing with a disperser that uses media such as a ball mill, attritor, basket mill, sand mill, sand grinder, Dyno Mill (a bead mill using grinding media such as glass beads or zirconium oxide beads), Dispermat, SC mill, spike mill, or agitator mill; and mixing with a disperser that does not use media such as a high-pressure homogenizer such as a Microfluidizer, Nanomizer, or Ultimizer, an ultrasonic homogenizer, a Dissolver, a Disper, a high-speed impeller disperser, or a planetary mixer described below. Of these, a Henschel mixer, pressure kneader, Banbury mixer, planetary mixer, or planetary mixer is preferred, and a planetary mixer is more preferred. A planetary mixer has two agitating blades that rotate and revolve around each other, and is designed to agitate and knead the materials in the agitation vessel. This reduces the dead space in the agitation vessel where the agitating blades do not reach, reducing the load on the blades and allowing for thorough mixing of the contents. After mixing is complete, the resulting composition 1 can be directly added with a second aromatic resin varnish and, if necessary, optional additives such as inorganic fillers, to produce the composition 1 described below. The mixing may also be carried out using a twin-screw extrusion kneader or a millstone kneader. The twin-screw extrusion kneader is, for example, a twin-screw continuous kneading device that kneads the material to be kneaded by shear force between two screws arranged parallel to each other. The millstone kneader is, for example, a kneader having a cylindrical fixed part with an internal space through which the material to be kneaded can pass, and a rotating part that is arranged in the internal space of the fixed part and rotates to convey the material to be kneaded passing through the internal space in the direction of the rotation axis while continuously kneading it. Alternatively, the above-mentioned thin film swirl type high-speed mixer may be used.

[0050] The aromatic resin constituting the second aromatic resin varnish is preferably an aromatic resin having an oxygen-containing polar group, more preferably an aromatic resin having an epoxy group or an aromatic resin having a carboxyl group. Details and preferred examples of the second aromatic resin are the same as those of the first aromatic resin described above. Furthermore, in the mixing, the first aromatic resin and the second aromatic resin constituting the present composition 1 may be different, but it is preferable to use the same type of resin.

[0051] When mixing the present composition 1 with the second aromatic resin varnish, an inorganic filler may be further mixed in. The inorganic filler is not particularly limited as long as it is a component containing inorganic particles. Examples of inorganic fillers include fillers composed of oxides, nitrides, elemental metals, alloys, and carbon. Preferred are fillers of silicates (silicon oxide (silica), wollastonite, talc, mica), metal oxides (beryllium oxide, cerium oxide, aluminum oxide, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite). Fillers of inorganic oxides containing at least one element selected from aluminum, magnesium, silicon, titanium, and zinc are more preferred. Fillers of silica, titanium oxide, zinc oxide, steatite, and boron nitride are even more preferred, and silica fillers are particularly preferred. The inorganic filler may also be ceramic. One type of inorganic filler may be used, or two or more types may be mixed and used. When two or more types of inorganic fillers are used in combination, two types of silica fillers may be mixed and used, or a silica filler and a metal oxide filler may be mixed and used. The use of a silica filler can sufficiently reduce the linear expansion coefficient of the resulting molded product. When the inorganic filler is a silica filler, the silica content in the inorganic filler is preferably 50% by mass or more, more preferably 75% by mass, and is preferably 100% by mass or less.

[0052] At least a portion of the surface of the inorganic filler is preferably surface-treated. The surface treatment agent used for such surface treatment is preferably a silane coupling agent, and more preferably 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, or 3-isocyanatopropyltriethoxysilane.

[0053] The inorganic filler preferably has a D50 of 25 μm or less, more preferably 15 μm or less, and more preferably 0.1 μm or more. The shape of the inorganic filler may be any of granular, needle-like (fibrous), and plate-like. Specific shapes of the inorganic filler include spherical, scale-like, layer-like, leaf-like, apricot-like, columnar, cockscomb-like, equiaxed, leaf-like, mica-like, block-like, flat, wedge-like, rosette-like, net-like, and prismatic. The inorganic filler may be hollow, or may contain hollow fillers and non-hollow fillers.

[0054] Specific examples of suitable inorganic fillers include silica fillers (such as the "Admafine (registered trademark)" series manufactured by Admatechs Co., Ltd.), zinc oxide surface-treated with an ester such as propylene glycol dicaprate (such as the "FINEX (registered trademark)" series manufactured by Sakai Chemical Industry Co., Ltd.), spherical fused silica (such as the "SFP (registered trademark)" series manufactured by Denka Co., Ltd.), titanium oxide coated with a polyhydric alcohol and an inorganic substance (such as the "Tipaque (registered trademark)" series manufactured by Ishihara Sangyo Kaisha, Ltd.), and rutile-type titanium oxide surface-treated with alkylsilane (such as the "Tipaque (registered trademark)" series manufactured by Teika Co., Ltd.). JMT (registered trademark) series, etc.), hollow silica fillers (the E-SPHERES series manufactured by Taiheiyo Cement Corporation, the Silinax series manufactured by Nittetsu Mining Co., Ltd., the Ecocosfire series manufactured by Emerson & Cumming Co., Ltd., etc.), talc fillers (the SG series manufactured by Nippon Talc Co., Ltd., etc.), steatite fillers (the BST series manufactured by Nippon Talc Co., Ltd., etc.), boron nitride fillers (the UHP series manufactured by Showa Denko KK, the Denka Boron Nitride series (GP, HGP grades), etc.) manufactured by Denka Co., Ltd.

[0055] When an inorganic filler is mixed, the content of the inorganic filler is preferably 0.1 to 75 mass %, more preferably 1 to 60 mass %. By mixing the inorganic filler in this range, the linear expansion coefficient of the resulting molded product (cured product) can be reduced. Therefore, even if the molded product is subjected to a heat treatment, its deformation can be prevented.

[0056] When mixing the composition 1 with the second aromatic resin varnish, a photopolymerization initiator (sensitizer) may be further mixed in. Examples of the photopolymerization initiator include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, 2,2'-azobisisobutyronitrile, and benzoyl peroxide.

[0057] When mixing the composition 1 with the second aromatic resin varnish, it is preferable to further mix a curing agent or curing accelerator, and more preferably a curing agent or curing accelerator capable of undergoing a thermosetting reaction with the aromatic resin. When the F polymer has a carbonyl group-containing group (such as a carboxyl group or an acid anhydride residue), the curing agent or curing accelerator may undergo a thermosetting reaction with the F polymer. Adding a curing agent or curing accelerator can further increase the hardness of a molded article formed from the resulting composition. Such a curing agent or curing accelerator is preferably at least one selected from the group consisting of amines, imidazoles, phenols, acid anhydrides, compounds having a phenolic hydroxyl group, compounds having a cyanate ester group, and compounds having a maleimide group, and is more preferably an amine or imidazole from the viewpoint of improving the stability of the composition 1 and the adhesiveness and electrical properties of the molded product formed. One curing agent or curing accelerator may be used alone, or two or more may be used in combination. It is preferable to select a curing agent or curing accelerator so that the curing initiation temperature of the resulting composition is 120 to 200° C. The "curing initiation temperature" is the temperature that indicates the first change point when the resulting composition is heated, as confirmed by differential scanning calorimetry (DSC).

[0058] As the amine, aliphatic polyamines (such as alkylenediamines, polyalkylenepolyamines, and aliphatic polyamines having an aromatic ring), adduct compounds thereof (such as reaction products with phenyl glycidyl ether, tolyl glycidyl ether, or alkyl glycidyl ether), alicyclic polyamines (such as isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, and laromine), or adduct compounds thereof (such as reaction products with n-butyl glycidyl ether or bisphenol A diglycidyl ether).

[0059] Preferable imidazoles include 2-methylimidazole, 4-methyl-2-ethylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, azine compounds of imidazole, isocyanurates of imidazole, hydroxymethyl imidazole, and adducts thereof (such as a reaction product of an epoxy resin and imidazole).

[0060] The phenol is preferably hydroquinone, resorcinol, or bisphenol A. The acid anhydride is preferably phthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, or benzophenonetetracarboxylic acid.

[0061] Examples of the compound having a phenolic hydroxyl group include phenol novolac resin, alkylphenol novolac resin, bisphenol A novolac resin, dicyclopentadiene-type phenol resin, Xylok-type phenol resin, terpene-modified phenol resin, cresol / naphthol resin, polyvinylphenols, phenol / naphthol resin, α-naphthol skeleton-containing phenol resin, triazine skeleton-containing cresol novolac resin, biphenylaralkyl-type phenol resin, and Xylok-type phenol novolac resin.

[0062] Examples of compounds having a cyanate ester group include phenol novolac cyanate ester resins, alkylphenol novolac cyanate ester resins, dicyclopentadiene cyanate ester resins, bisphenol A cyanate ester resins, bisphenol F cyanate ester resins, and bisphenol S cyanate ester resins. Also, a partially triazine-modified prepolymer may be used.

[0063] Examples of compounds having a maleimide group include 4,4'-diphenylmethane bismaleimide, phenylmethane bismaleimide, m-phenylene bismaleimide, 3,3'-dimethyl-5,5'-dimethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, (1,6-bismaleimide-2,2,4-trimethyl)hexane, and oligomers thereof, as well as diamine condensates having a maleimide skeleton.

[0064] When mixing the present composition 1 with the second aromatic resin varnish, a dispersant may be further mixed in. Examples of the dispersant include the same surfactants as those that may be contained in the present composition 1 as dispersants.

[0065] When mixing the present composition 1 with the second aromatic resin varnish, a liquid dispersion medium (another liquid dispersion medium) other than the liquid dispersion medium (e.g., the solvent constituting the first aromatic resin varnish) that may be contained in the present composition 1 and the solvent contained in the second aromatic resin varnish may be further mixed. The proportion of the other liquid dispersion medium during mixing is preferably 25% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on the total amount of the second aromatic resin varnish. The lower limit of the proportion (content) of the liquid dispersion medium in the present composition 1 is 0%. Specific examples of other liquid dispersion media include cellosolve-based solvents, ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, and aromatic hydrocarbon-based solvents.

[0066] When mixing the present composition 1 with the second aromatic resin varnish, the content (ratio) of the aromatic resin, as the total amount of the first aromatic resin and the second aromatic resin, is preferably greater than the content (ratio) of the F polymer. In this case, the physical properties of the resulting composition, such as handleability, curability, and developability, are further improved. Specifically, the mass ratio of the aromatic resin content to the F polymer content is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1.5 to 3. The content of the F polymer in the resulting composition is preferably from 1 to 30% by mass, more preferably from 10 to 25% by mass. The content of the aromatic resin in the resulting composition is preferably 20 to 90 mass %, more preferably 30 to 80 mass %, as the total amount of the first aromatic resin and the second aromatic resin. Furthermore, when the resulting composition contains a curing agent or a curing accelerator, the content thereof is preferably from 0.01 to 15% by mass, more preferably from 0.5 to 10% by mass.

[0067] The present composition 1 can be suitably used as a negative resist composition. The resist composition can be applied to the surface of the substrate by a coating method such as screen printing, bar coating, or blade coating. After application, the coating is preferably dried to obtain a dry to the touch condition, preferably at 75 to 95°C for 40 to 70 minutes. For drying, a hot air circulation drying oven or a far-infrared drying oven can be used. The thickness of the coating film after drying (dried film) is preferably from 10 to 150 μm, more preferably from 20 to 60 μm, from the viewpoint of improving the developability of the dried film.

[0068] Next, the dried film is irradiated with exposure light using an exposure mask having a predetermined exposure pattern (openings). Examples of exposure light sources that can be used include halogen lamps, high-pressure mercury lamps, laser beams, metal halide lamps, black lamps, and electrodeless lamps. A pattern can also be formed in the dried film using a laser direct imaging device without using an exposure mask.

[0069] Next, the exposed dry film is developed with a developer, whereby unnecessary portions of the dry film are removed, and a dry film having a predetermined pattern is obtained. The developer can be applied to the dried film after exposure by spraying, immersion, or the like. The developer is preferably an aqueous alkaline solution containing an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or sodium silicate, and more preferably a dilute aqueous alkaline solution containing an alkali at a concentration of 1.5% by mass or less. Composition 1 allows the use of a dilute alkaline aqueous solution as a developer, resulting in a dried film with minimal damage and excellent resolution. After development, the dried film is preferably washed with water or neutralized with an acid to remove any excess developer.

[0070] Next, the resulting dry coating after development is cured (post-cured) by irradiation with ultraviolet light (active energy rays). If the present composition 1 contains the above-mentioned curing agent, the dry coating after development can also be cured by heating. This results in a cured coating (molded object such as a convex portion) with excellent adhesion and crack resistance.

[0071] The composition 1 can also be suitably used as a filling material for filling through-holes or recesses in multilayer printed wiring boards. Multilayer printed wiring boards have multiple circuit patterns laminated with insulating layers interposed between them. The insulating layers are made of polyphenylene ether, polyphenylene oxide, cyanate ester, polyimide, fluoropolymer, etc. The circuit patterns are made of metal films formed by plating or other methods. This multilayer printed wiring board has through holes or recesses that penetrate through the board in its thickness direction. The through holes or recesses are formed by drilling or laser processing. A conductive film is formed on the inner surface of the through holes or recesses, electrically connecting predetermined circuit patterns to each other. When the present composition 1 is filled into such through-holes or recesses and cured, the through-holes or recesses can be filled.

[0072] The through-holes or recesses can be filled with the composition 1 by screen printing, roll coating, die coating, or vacuum printing. In this case, the composition 1 is preferably filled to the extent that it overflows from the through-holes or recesses. When the present composition 1 contains a curing agent or a curing accelerator, the present composition 1 filled in the through-holes or recesses is preferably cured by heating. The heating conditions for composition 1 are preferably 80 to 160°C for 30 to 180 minutes. From the viewpoint of suppressing outgassing during curing of composition 1, composition 1 is preferably cured in two stages: a preliminary curing stage and a main curing stage. The preliminary curing conditions are preferably 80 to 110°C for 30 to 90 minutes. The main curing conditions are preferably 130 to 160°C for 30 to 180 minutes. Since composition 1 has a small volume change rate during curing, it can prevent a decrease in the shape stability of multilayer printed wiring boards. In addition, during the pre-curing or curing stage of the present composition 1, unnecessary portions that protrude from the through-holes or recesses of the molded product may be removed to achieve flattening. Thereafter, a metal film may be formed on the surface of the multilayer printed wiring board by plating or the like, and then patterned into a predetermined pattern to form a circuit pattern. Here, prior to forming the metal film, the surface of the multilayer printed wiring board may be subjected to a roughening treatment using a potassium permanganate aqueous solution or the like, as necessary.

[0073] Composition 1 can also be suitably used to prepare a dry film. Such a dry film can be produced by applying the present composition 1 onto a carrier film and drying it to form a resin film as a dry coating. If necessary, a protective film may be laminated on the dry film. The carrier film is a film that functions to support the dry film. Examples of such carrier films include polyolefin films, polyester films, polyimide films, polyamideimide films, polytetrafluoroethylene films, polystyrene films, and surface-treated paper substrates. Among these, polyester films are preferred from the viewpoints of heat resistance, mechanical strength, handleability, etc. The surface of the carrier film may be subjected to a release treatment.

[0074] The protective film is a film that is attached to the surface of the dry film opposite the carrier film for the purposes of preventing dust and the like from adhering to the surface of the dry film and improving its handling properties. The protective film may be, for example, the same film or paper substrate as those mentioned above for the carrier film, and is preferably a polyolefin film or polyester film. The thickness of the protective film is preferably 10 to 150 μm. The surface of the protective film may be subjected to a release treatment.

[0075] The following method can be used to manufacture a printed wiring board from a laminate film having a dry film, a carrier film, and a protective film. First, either the carrier film or the protective film is peeled off from the dry film. If the composition 1 contains a curing agent or a curing accelerator, it is then pressed onto a circuit board on which a circuit pattern has been formed, and then thermally cured. An oven, a heat press, or the like can be used for thermal curing. After that, through-holes (via holes) are formed by laser processing or drilling at predetermined locations on the circuit board, exposing the circuit pattern. This results in a printed wiring board. Note that if unnecessary components (smears) remain on the circuit pattern due to incomplete removal, it is preferable to perform a desmearing process. The other of the carrier film and the protective film is peeled off from the dry film at a predetermined stage. Note that, for electrical connection between circuit patterns, a conductive film formed on the inner surface of the through hole, or a pillar or post housed in the through hole can be used.

[0076] The substrate with convex portions of the present invention (hereinafter also referred to as "substrate with convex portions") has a substrate and convex portions provided on the surface of the substrate and having a predetermined pattern formed from composition 1. The convex portions can be produced by the above-mentioned method using composition 1 as a negative resist composition. The substrate may be, for example, Substrate I: an active matrix substrate on which pixel electrodes, switching elements and wiring are formed, or Substrate II: a laminated plate in which a polymer film and a metal layer are laminated. In the case of the substrate I, the convex portions are provided as a frame on the surface of the active matrix substrate so as to expose the pixel electrodes, for example. In this case, an organic EL layer (electron transport layer, light-emitting layer, hole transport layer, etc.) and an electrophoretic dispersion liquid containing electrophoretic particles are disposed in the space defined by the convex portions, and a counter substrate equipped with a common electrode, etc. is disposed opposite the active matrix substrate, whereby a display device (electronic device) can be produced.

[0077] In such a configuration, the convex portions can function as spacers that define the distance between the two substrates and as black matrices that prevent crosstalk between unit pixels. Furthermore, since the convex portions of the substrate with convex portions have excellent water and oil repellency and few defects, the ink and electrophoretic dispersion liquid that form the organic EL layer are less likely to adhere to the convex portions, resulting in a display device with excellent display performance. Furthermore, since the convex portions also have excellent electrical properties (low dielectric constant), parasitic capacitance is less likely to occur in the display device, and deterioration of switching characteristics can be prevented.

[0078] In the case of substrate II, the polymer film may be a single-layer film consisting of only a polymer layer, or may be a laminated film having a polymer layer as a surface layer and a support layer that supports the surface layer (polymer layer). The support layer can be composed of a heat-resistant resin film, a prepreg which is a precursor of a fiber-reinforced resin plate, a film having a heat-resistant resin layer, or a film having a prepreg layer. The prepreg is a sheet-like substrate in which a fiber base material (tow, woven fabric, etc.) made of reinforcing fibers (glass fiber, carbon fiber, etc.) is impregnated with a thermosetting resin or a thermoplastic resin.

[0079] The heat-resistant resin film is a film containing one or more heat-resistant resins, such as polyimide, polyarylate, polysulfone, polyarylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystalline polyester, and liquid crystalline polyesteramide, and polyimide (particularly, aromatic polyimide), F polymer, and fluororesin other than F polymer are preferred. The polymer layer preferably contains the above heat-resistant resin, more preferably polymer F. In this case, the substrate tends to have a low dielectric loss tangent, and the convex portions and the substrate tend to adhere firmly to each other.

[0080] The polymer layer containing the F polymer may be obtained by melt-kneading the F polymer and extruding it. In this case, the laminated film is obtained by thermocompression bonding the film containing the F polymer and the support layer. The polymer layer containing the F polymer may be obtained by applying a dispersion containing F particles and a liquid dispersion medium to a substrate and heating the applied dispersion. In this case, a single-layer film containing the F polymer can be obtained by peeling off the substrate, and a laminated film can be obtained by using the film constituting the support layer as the substrate and not peeling off the substrate. The laminate as the substrate II can be produced by thermocompression bonding a polymer film and a metal foil. Examples of materials for the metal foil include copper, copper alloys, stainless steel, nickel, nickel alloys (including 42 alloy), aluminum, aluminum alloys, titanium, and titanium alloys. The metal foil is preferably a copper foil, more preferably a rolled copper foil or an electrolytic copper foil.

[0081] A preferred embodiment of the laminate as the substrate II is a prepreg layer / polymer layer containing an F polymer / metal layer. The metal layer may have a predetermined pattern. Alternatively, the convex portions may be formed on a metal layer without a pattern, and the metal layer may be etched using the convex portions as a mask to form a circuit, thereby obtaining a printed wiring board.

[0082] Although the present method 1, the present composition 1, and the substrate with protrusions have been described above, the present invention is not limited to the configurations of the above-described embodiments. For example, Method 1 may have any other step added to the configuration of the above embodiment, or may be replaced with any step that produces a similar effect. Furthermore, Composition 1 may have any other step added to the configuration of the above embodiment, or may be replaced with any step that produces a similar function.

[0083] Next, a second aspect of the present method (hereinafter also referred to as "the present method 2") will be described. Method 2 is a method in which F particles, an aromatic resin, at least one thickening polymer selected from the group consisting of polar vinyl polymers and polysaccharides, and water are mixed in a tank equipped with a stirring mechanism that uses thin film swirling or a stirring mechanism that uses rotation and revolution, to obtain a liquid composition containing F particles, an aromatic resin, a thickening polymer, and water (hereinafter also referred to as "Composition 2"). Composition 2 has excellent dispersion stability, uniformity, and ease of handling. Furthermore, from Composition 2, molded articles can be formed that combine the physical properties of the F polymer and the aromatic resin to a high degree, and that have excellent electrical properties and low linear expansion. The reasons for this and the mechanism of action are not entirely clear, but are presumed to be as follows.

[0084] F polymers have low dispersibility due to their low surface energy. When F particles and an aromatic resin are mixed in water with strong shearing force to improve the dispersibility of the liquid composition, the F polymer undergoes denaturation, such as fibrillation, forming complex secondary particles that are prone to aggregation. Even when a thickening polymer is used, interactions within a single component are enhanced rather than interactions between the components, resulting in, for example, the thickening polymer itself becoming more prone to aggregation. Thus, it has been difficult to obtain a liquid composition with excellent dispersion stability, uniformity, and ease of handling by mixing F particles and an aromatic resin while suppressing component aggregation.

[0085] In Method 2, F particles, aromatic resin, thickening polymer, and water are mixed in a tank equipped with a thin film swirling stirring mechanism or a rotational and revolution stirring mechanism, and the F particles and aromatic resin are mixed in a state where the thickening polymer is deeply penetrated into each of them. In other words, the thickening polymer can be considered to mitigate the impact of collisions that occur when the two are mixed, thereby suppressing the denaturation of the F particles and the aggregation of the components. Furthermore, collisions between the F particles and aromatic resin can be considered to promote the formation of coalescence particles (e.g., composite particles in which the aromatic resin is coalesced onto the surface of the F particles).

[0086] These factors are thought to be responsible for the high degree of mixing of the F particles with the aromatic resin at the individual particle level, resulting in the production of a liquid composition by Method 2 that is excellent in dispersion stability, uniformity, and ease of handling, and in which foaming is suppressed. Furthermore, the inclusion of uniform particles such as the coalesced particles facilitates the formation of a uniform and dense particle packing structure when liquid components such as water are removed from Composition 2. As a result, it is believed that Composition 2 allows the aromatic resin to be densely arranged in the F polymer, resulting in a molded product with excellent electrical properties and low linear expansion.

[0087] The aromatic resin (also referred to as "aromatic polymer") of the present invention, by the above-mentioned mechanism of action, improves the liquid physical properties such as dispersion stability of composition 2, and can impart flexibility such as flex resistance and UV absorption properties to a molded product obtained from composition 2. Furthermore, when composition 2 is applied to the surface of a substrate such as a polyimide film or metal foil to form a polymer layer containing an F polymer, the aromatic polymer can impart properties such as adhesiveness and adhesion to the resin film to the polymer layer. The aromatic polymer may be a thermosetting or thermoplastic polymer, or may be modified. The aromatic polymer may be included in the present composition 2 as a precursor thereof. The aromatic polymer is preferably water-soluble, in other words, the aromatic polymer is preferably dissolved in the present composition 2.

[0088] The acid value of the aromatic polymer is preferably 20 to 100 mg KOH / g, more preferably 35 to 70 mg KOH / g, from the viewpoint of dispersion stability of the present composition 2. When the aromatic polymer has an acid anhydride group, the acid value when the acid anhydride group is ring-opened is defined as the acid value of the aromatic polymer. The acid value can be measured by titrating approximately 0.5 g of aromatic polymer with approximately 0.15 g of 1,4-diazabicyclo[2.2.2]octane, approximately 60 g of N-methyl-2-pyrrolidone, and approximately 1 mL of ion-exchanged water until the aromatic polymer is completely dissolved using a 0.05 mol / L ethanolic potassium hydroxide solution in a potentiometric titrator.

[0089] The average molecular weight of the aromatic polymer is preferably 5,000 or more, more preferably 10,000 or more. The average molecular weight of the aromatic polymer is preferably 50,000 or less, more preferably 30,000 or less. In this case, the aromatic polymer is easily soluble in water. Furthermore, molded articles obtained from this composition 2 tend to have excellent mechanical properties such as flex resistance. Examples of aromatic polymers include aromatic imide resins, aromatic sulfide resins, aromatic sulfone resins, and phenol resins, with aromatic imide resins being preferred.

[0090] Examples of aromatic imide resins include aromatic polyimides, aromatic polyamideimides, aromatic polyetherimides, and precursors thereof, which may be modified and may have polar functional groups such as carboxylic acid groups. As the aromatic imide-based resin, an aromatic polyimide or a precursor thereof (a polyamic acid or a salt thereof), or an aromatic polyamideimide or a precursor thereof is preferred, a water-soluble aromatic polyimide precursor or a water-soluble aromatic polyamideimide precursor is more preferred, and a water-soluble aromatic polyamideimide precursor is even more preferred.

[0091] Examples of water-soluble aromatic polyimide precursors include polyamic acids obtained by polymerizing tetracarboxylic dianhydrides and diamines in a solvent, and polyamic acid salts obtained by reacting such polyamic acids with aqueous ammonia or organic amines. An aqueous solution of polyamic acid can be prepared by dissolving the polyamic acid salt in water. Examples of tetracarboxylic dianhydrides include pyromellitic anhydride and biphenyltetracarboxylic anhydride. Examples of diamines include N,N'-diaminodiphenyl ether and p-diaminobenzene. Examples of solvents include N-methylpyrrolidone and N,N-dimethylformamide.

[0092] Examples of organic amines include primary amines such as methylamine, ethylamine, n-propylamine, 2-ethanolamine, and 2-amino-2-methyl-1-propanol; secondary amines such as dimethylamine, 2-(methylamino)ethanol, and 2-(ethylamino)ethanol; tertiary amines such as 2-dimethylaminoethanol, 2-diethylaminoethanol, and 1-dimethylamino-2-propanol; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

[0093] Examples of water-soluble aromatic polyamideimides or precursors thereof include aromatic polyamideimides or precursors thereof obtained by reacting diisocyanate and / or diamine with a tribasic acid anhydride (or tribasic acid chloride) as an acid component. 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, paraphenylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, tolylene diisocyanate, and isophorone diisocyanate. These diisocyanates may be used alone or in combination of two or more.

[0094] In order to improve the stability of the aromatic polyamideimide, a blocked isocyanate in which the isocyanate group is stabilized with a blocking agent may be used as the diisocyanate. Examples of the blocking agent include alcohol, phenol, and oxime. Examples of diamines include 3,3'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, xylylenediamine, phenylenediamine, and isophoronediamine. These diamines may be used alone or in combination of two or more.

[0095] Examples of tribasic acid anhydrides include trimellitic anhydride, and examples of tribasic acid chlorides include trimellitic anhydride chloride. As the tribasic acid anhydride, trimellitic anhydride is preferred from the viewpoint of reducing the burden on the environment. When producing an aromatic polyamideimide, in addition to the above-mentioned tribasic acid anhydride (or tribasic acid chloride), a dicarboxylic acid, a tetracarboxylic acid dianhydride, or the like may be used as an acid component within a range that does not impair the properties of the aromatic polyamideimide.

[0096] Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, adipic acid, and sebacic acid. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more. The total amount of carboxylic acids other than tribasic acids (dicarboxylic acids and tetracarboxylic acids) is preferably in the range of 0 to 30 mol % of the total carboxylic acids, from the viewpoint of maintaining the properties of the aromatic polyamideimide.

[0097] The ratio of diisocyanate and / or diamine to acid component (total amount of tribasic acid anhydride or tribasic acid chloride and dicarboxylic acid and tetracarboxylic acid dianhydride used as needed) used is preferably 0.8 to 1.1 moles of diisocyanate compound and / or diamine compound per 1.0 mole of total amount of acid component, from the viewpoint of molecular weight and degree of crosslinking of the aromatic polyamideimide to be produced. Specific examples of the water-soluble aromatic polyamideimide or its precursor include "HPC-1000" and "HPC-2100D" (both manufactured by Showa Denko Materials Co., Ltd.).

[0098] Examples of aromatic polyetherimides include amorphous polymers having imide bonds and ether bonds in the main chain, and a polycondensate of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane and m-phenylenediamine is preferred. A specific example of aromatic polyetherimides is "Ultem 1000F3SP" (manufactured by SABIC). An example of the aromatic sulfide resin is polyphenylene sulfide. An example of the aromatic sulfone resin is polyphenylsulfone.

[0099] The content of the aromatic polymer in the present composition 2 is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more, relative to the total mass of the present composition 2. The content of the aromatic polymer is preferably 30% by mass or less, and more preferably 10% by mass or less, relative to the total mass of the present composition 2. The ratio of the aromatic polymer content to the F particle content in the composition 2 is preferably 0.001 or more, more preferably 0.005 or more, and is preferably 0.1 or less, more preferably 0.05 or less.

[0100] The thickening polymer in the present invention is at least one polymer selected from the group consisting of polar vinyl polymers and polysaccharides. The polar vinyl polymer is a vinyl polymer having a polar functional group in the main chain or side chain of the polymer. Examples of the polar functional group include an ether bond, an ester bond, an amide bond, an imide bond, a thioether bond, a sulfide bond, a disulfide bond, a carbonyl group-containing group, a hydroxyl group-containing group, a thiol group, a sulfide group, a sulfonyl group, a sulfoxyl group, an amino group, and an amide group.

[0101] The thickening polymer may be a thermosetting or thermoplastic polymer, or may be modified. The thickening polymer may be included in Composition 2 as a precursor thereof. The thickening polymer is preferably water-soluble, in other words, the thickening polymer is preferably dissolved in the present composition 2.

[0102] The thickening polymer preferably has a carbonyl group-containing group or a hydroxyl group-containing group, which improves the affinity of the thickening polymer with the F particles and the aromatic polymer, making the composition 2 more likely to have excellent physical properties such as dispersion stability, and also making the thickening polymer more likely to function as a binder. The average molecular weight of the thickening polymer is preferably 3,000 or more, more preferably 10,000 or more, even more preferably 100,000 or more, and particularly preferably 300,000 or more. The average molecular weight of the thickening polymer is preferably 1,000,000 or less, more preferably 500,000 or less. In this case, the present composition 2 is likely to have excellent physical properties such as dispersion stability.

[0103] The thermal decomposition temperature of the thickening polymer is preferably 150°C or higher, more preferably 200°C or higher. The thermal decomposition temperature of the thickening polymer is preferably 320°C or lower, more preferably 300°C or lower. The thermal decomposition temperature is preferably lower than the melting temperature of the F polymer. In this case, the thickening polymer is likely to have excellent function as a binder. Furthermore, the thickening polymer is unlikely to remain in a molded product formed from this composition 2, and the molded product is likely to have excellent physical properties such as electrical properties.

[0104] Examples of polar vinyl polymers include vinyl alcohol polymers such as polyvinyl alcohol, vinylpyrrolidone polymers such as polyvinylpyrrolidone, acrylic acid polymers such as polyacrylic acid, and carboxyvinyl polymers such as carboxyvinyl polymers, with vinyl alcohol polymers being preferred.

[0105] Preferred vinyl alcohol polymers are polyvinyl alcohol, polyvinyl acetate, partially acetylated polyvinyl alcohol, partially acetalized polyvinyl alcohol, and copolymers of vinyl alcohol, vinyl butyral, and vinyl acetate. Specific examples of vinyl alcohol-based polymers include the "S-LEC (registered trademark) B" series, the "S-LEC (registered trademark) K (KS)" series, and the "S-LEC (registered trademark) SV" series (all manufactured by Sekisui Chemical Co., Ltd.), and the "Mobital (registered trademark)" series (manufactured by Kuraray Co., Ltd.).

[0106] Examples of acrylic acid polymers include polyacrylic acid, polyacrylates such as polymethyl acrylate and polyethyl acrylate, poly-α-haloacrylate, poly-α-cyanoacrylate, polyacrylamide, and sodium polyacrylate.

[0107] Examples of polysaccharides include glycogen, amylose, agarose, amylopectin, cellulose, dextrin, glucan, fructan, chitin, xanthan gum, guar gum, casein, gum arabic, gelatin, agaropectin, arabinan, curdlan, callose, carboxymethyl starch, chitin, chitosan, quince seed, glucomannan, gellan gum, tamarin seed gum, dextran, nigeran, hyaluronic acid, pustulan, funoran, pectin, porphyran, laminaran, lichenan, carrageenan, alginic acid, tragacanth gum, alkaloid gum, and locust bean gum. Among the above, nonionic polysaccharides are preferred as thickening polymers, with glycogen, amylose, agarose, amylopectin, cellulose, dextrin, glucan, fructan, and chitin being preferred, and carboxymethylcellulose and hydroxyethylcellulose being preferred as cellulose. Carboxymethylcellulose may be a carboxymethylcellulose salt such as sodium carboxymethylcellulose or ammonium carboxymethylcellulose. Hydroxyethylcellulose is preferred when the average number of moles added, which is an index indicating the degree of ethylene oxide addition, is 1.5 or more and 2.5 or less, from the viewpoint of suppressing foaming and aggregation due to air entrapment during mixing. Specific examples of polysaccharides include the "Sunrose (registered trademark)" series (manufactured by Nippon Paper Industries Co., Ltd.), the "Metolose (registered trademark)" series (manufactured by Shin-Etsu Chemical Co., Ltd.), and "HEC CF Grade" (manufactured by Sumitomo Seika Chemicals Co., Ltd.).

[0108] The content of the thickening polymer in Composition 2 is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more, relative to the total mass of Composition 2. The content of the thickening polymer is preferably 30% by mass or less, and more preferably 10% by mass or less, relative to the total mass of Composition 2. The ratio of the thickening polymer content to the F particle content in the present composition 2 is preferably 0.001 or more, more preferably 0.003 or more, and is preferably 0.05 or less, more preferably 0.03 or less, and even more preferably 0.01 or less.

[0109] The water content in Composition 2 is preferably 30% by mass or more, more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 60% by mass or less. Within this range, the liquid physical properties of the present composition 2, such as dispersion stability, are more likely to be improved. Composition 2 may further contain a water-soluble dispersion medium other than water as the dispersion medium. Such a water-soluble dispersion medium is preferably a water-soluble compound that is classified as polar and is liquid at 25°C under atmospheric pressure, such as N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and N-methyl-2-pyrrolidone.

[0110] In the first embodiment of Method 2 (hereinafter also referred to as "Embodiment 2-1"), F particles, aromatic resin, thickening polymer, and water are mixed in a tank equipped with a stirring mechanism using thin film swirling, i.e., these components are mixed by swirling while spreading them in a thin film, to obtain Composition 2. In the embodiment 2-1, the mixing is preferably carried out by applying centrifugal force due to swirling to each component spread in a thin film. In this case, the thickening polymer penetrates deeply into each of the F particles and the aromatic polymer, and mixing proceeds. Specifically, the mixing is preferably carried out using the thin film swirling high-speed mixer described above in the present method 1.

[0111] The details of the stirring vessel and the rotating part having a cylindrical part with a plurality of holes formed therein in the thin film rotation type high-speed mixer are as described above. In mixing, the F particles, aromatic resin, thickening polymer, and water may be supplied into the stirring tank all at once, or may be supplied into the stirring tank separately using multiple inlets. Mixing can be carried out either batchwise or continuously. In the case of a continuous system, a single mixing vessel may be used, with the mixture removed from the outlet and then fed back through the inlet for mixing. Alternatively, multiple mixing vessels may be used, with the mixture removed from the outlet of a previous mixing vessel being fed through the inlet of a subsequent mixing vessel for mixing. The F particles, aromatic resin, thickening polymer, and water supplied fill the gap between the inner wall surface of the mixing vessel and the outer circumferential surface of the cylindrical part of the rotating part, forming a film that rotates at high speed within the mixing vessel as the rotating part rotates. At this time, the mixture is subjected to not only shear stress but also shear stress, achieving a high level of dispersion and mixing.

[0112] In embodiment 2-1, mixing may be performed using a mixer equipped with a cylindrical, truncated cone-shaped stator and a disk rotating inside the inner wall of the stator, by passing the F particles, aromatic polymer, thickening polymer, and water through a cylindrical gap between the stator and the disk while rotating the disk. In this case, the inner wall of the stator and the disk preferably have an uneven structure. Examples of such an uneven structure include a structure having lattice-like grooves or dimples with a height (depth) of several μm to several hundred μm. Such a mixing means is sometimes called a colloid mill.

[0113] The outer circumferential surface of the disc faces the inner wall surface of the stator with a small gap of about 1 to 10 mm between them. The peripheral speed of the disc and the stirring time can be set appropriately. In this case, the supplied F particles, aromatic resin, thickening polymer, and water form a film as they pass through the gap between the inner wall of the stator and the outer surface of the disc, and as the disc rotates, they swirl at high speed inside the stator. At this time, they are subjected to not only shear stress but also shear stress, achieving a high level of dispersion and mixing.

[0114] In the embodiment 2-1, a composition containing F particles, an aromatic resin, a thickening polymer, and water is preferably mixed by thin film swirling. That is, the F particles, the aromatic resin, the thickening polymer, and the water are preferably premixed before being mixed by thin film swirling. In this case, the mechanism of action of the above-mentioned method 2 is enhanced, foaming of the composition 2 is suppressed, and physical properties such as dispersion stability are likely to be further improved.

[0115] The pre-mixing method may be the same as the mixing method used when mixing the present composition 1 and the second aromatic resin varnish, as described above. The composition containing F particles, aromatic resin, thickening polymer, and water is preferably a kneaded product obtained by premixing F particles, aromatic resin, thickening polymer, and water. Water may be further added to the kneaded product to adjust the viscosity. In this case, the mechanism of action of Method 2 described above is likely to be enhanced. Such a kneaded product is preferably a solidified product (paste) having fluidity and viscosity, or a clumpy, clay-like solidified product (dough).

[0116] The solid content of the paste is preferably 40 to 90% by mass, more preferably 60 to 80% by mass, and the solid content of the dough is preferably 50 to 99% by mass, more preferably 60 to 95% by mass. The solid content of the paste and the batter means the total amount of substances that form the solid content in the molded product formed from the present composition 2. For example, when the paste contains the F polymer, the aromatic resin, and the inorganic particles described below, the total content of these components is the solid content of the paste and the batter.

[0117] In a second embodiment of Method 2 (hereinafter also referred to as "Embodiment 2-2"), F particles, aromatic resin, thickening polymer, and water are mixed in a tank equipped with a rotational and revolutional stirring mechanism to obtain Composition 2. Here, the rotational stirring mechanism is a mechanism in which a tank containing an object to be stirred is rotated around a rotation axis to stir the object. The direction of the rotation axis may be in either direction relative to the tank. On the other hand, the revolutional stirring mechanism is a mechanism in which a tank containing an object to be stirred is rotated around a fixed point outside the tank to stir the object. The layer may be vertical, horizontal, or inclined relative to the revolution plane. Such stirring means is sometimes called a rotational and revolutional mixer. In Aspect 2-2, the mixing is preferably carried out under conditions in which the rotation speed is at least twice the revolution speed, or the revolution speed is at least twice the rotation speed, which suppresses foaming and aggregation due to entrainment of air, and makes it easier to obtain Composition 2 having excellent dispersibility and dispersion stability. In embodiment 2-2, the composition containing the F particles, aromatic polymer, thickening polymer, and water may be mixed in a tank equipped with a rotational and revolutional stirring mechanism. That is, the F particles, aromatic polymer, thickening polymer, and water may be premixed before being mixed in the tank equipped with a rotational and revolutional stirring mechanism.

[0118] Alternatively, the present composition 2 may be obtained by mixing the F particles, aromatic resin, thickening polymer, and water in either embodiment 2-1 or embodiment 2-2, and then further adding water. The method for further mixing water can be the same as that used in Mode 2-1, Mode 2-2, or the premixing described above, with Modes 2-1 and 2-2 being preferred. It is particularly preferred that the mixing of the F particles, aromatic resin, thickening polymer, and water, and the mixing with the addition of water, be carried out in the same mode, and it is preferred that the mixing of both be carried out in Mode 2-2. In this case, the mechanism of action of Method 2 described above is enhanced, and the physical properties of Composition 2, such as the dispersion stability, are likely to be further improved.

[0119] In the mixing, inorganic particles may be further added. The inorganic particles may be added before or during the mixing. For example, a composition containing F particles, an aromatic resin, a thickening polymer, water, and inorganic particles may be prepared and then mixed. As the inorganic particles, nitride particles or inorganic oxide particles are preferred, boron nitride particles, beryllia particles (beryllium oxide particles), silicate particles (silica particles, wollastonite particles, talc particles), or metal oxide particles (cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.) are more preferred, boron nitride particles and silica particles are even more preferred, and silica particles are particularly preferred.

[0120] It is preferable that at least a portion of the surface of the inorganic particles is surface-treated with a silane coupling agent (3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.). The inorganic particles preferably have a D50 of 20 μm or less, more preferably 10 μm or less, and preferably have a D50 of 0.01 μm or more, more preferably 0.1 μm or more.

[0121] The shape of the inorganic particles may be any of spherical, needle-like (fibrous) and plate-like, and is preferably spherical or plate-like. Specific shapes of the inorganic particles include spherical, scale-like, layer-like, leaf-like, apricot-like, columnar, cockscomb-like, equiaxial, leaf-like, micaceous, block-like, tabular, wedge-like, rosette-like, net-like, and prismatic shapes. The inorganic particles may be used alone or in combination of two or more types. When the present composition 2 further contains inorganic particles, the amount thereof is preferably 1 to 50 mass %, more preferably 5 to 40 mass %, based on the total mass of the present composition 2. Suitable specific examples of inorganic particles include the same as the specific examples of inorganic fillers that may be further mixed when the present composition 1 and the second aromatic resin varnish are mixed.

[0122] In both of the embodiments 2-1 and 2-2, it is preferable to pre-mix and disintegrate the F particles in a powder state prior to mixing, i.e., to pre-treat the F particles to dissolve their agglomerated state and make them dispersed. The crushing of the F particles can be carried out by the method that may be used in embodiment 2-2 and the above-mentioned premixing, and is preferably carried out by the method in embodiment 2-2. When the above-mentioned inorganic particles are further added, it is preferable to previously mix the F particles and the inorganic particles in the form of a powder mixture, crush the mixture as described above, and then subject the mixture to Method 2. Furthermore, when F particles, aromatic resin, thickening polymer, and water are premixed before being mixed by thin film swirling or before being mixed in a tank equipped with a stirring mechanism that rotates and revolves, it is preferable to disintegrate the F particles prior to premixing.

[0123] A surfactant may be further added during mixing. The surfactant may be added before or during mixing. For example, a composition containing F particles, an aromatic resin, a thickening polymer, water, and a surfactant may be prepared and then mixed. The surfactant is preferably a nonionic surfactant. The nonionic surfactant is preferably a glycol monoalkyl ether, an acetylene-based surfactant, a silicone-based surfactant, or a fluorine-based surfactant, and more preferably a glycol monoalkyl ether or a silicone-based surfactant. Composition 2 may contain a silicone-based surfactant and a glycol monoalkyl ether.

[0124] Specific examples of nonionic surfactants include the "Ftergent" series (manufactured by Neos Corporation, Ftergent is a registered trademark), the "Surflon" series (manufactured by AGC Seimi Chemical Co., Ltd., Surflon is a registered trademark), the "Megafac" series (manufactured by DIC Corporation, Megafac is a registered trademark), the "Unidyne" series (manufactured by Daikin Industries, Ltd., Unidyne is a registered trademark), "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451", "BYK-3455", "BYK-3456" (manufactured by BYK Japan Co., Ltd.), "KF-6011", "KF-6043" (manufactured by Shin-Etsu Chemical Co., Ltd.), the "Tergitol" series (manufactured by The Dow Chemical Company, "Tergitol TMN-100X", etc.), "Lutensol T08", "Lutensol XL70", "Lutensol XL80", "Lutensol XL90", "Lutensol Examples of such surfactants include "XP80" and "Lutensol M5" (both manufactured by BASF), "Newcol 1308FA" and "Newcol 1310" (both manufactured by Nippon Nyukazai Co., Ltd.), "Leocol TDN-90-80" and "Leocol SC-90" (both manufactured by Lion Specialty Chemicals). When the present composition 2 contains a surfactant, the content of the surfactant in the present composition 2 is preferably 0.1 to 15 mass %, more preferably 1 to 10 mass %.

[0125] From the viewpoint of pH adjustment, the present composition 2 may further contain a pH adjuster or a pH buffer. In this case, the pH of the present composition 2 is preferably adjusted to 5 to 10, more preferably 7 to 9, by the pH adjuster or pH buffer. Examples of pH adjusters include amines, ammonia, and citric acid. Examples of pH buffers include tris(hydroxymethyl)aminomethane, ethylenediaminetetraacetic acid, ammonium hydrogen carbonate, ammonium carbonate, and ammonium acetate. The pH adjuster or pH buffer may be added either before or during mixing. Composition 2 may further be subjected to a defoaming treatment, which is preferably carried out using a planetary centrifugal mixer.

[0126] A water-soluble solvent may be further added to the present composition 2. Due to the above-mentioned mechanism of action, the present composition 2 has excellent dispersion stability and can be easily mixed with a water-soluble solvent. Examples of the water-soluble solvent include the same compounds as the water-soluble solvents that can be used in the present composition 2. In addition to the above-mentioned components, composition 2 may further contain a thixotropic agent, a viscosity modifier, an antifoaming agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a release agent, a surface treatment agent, a flame retardant, an antiseptic, an antifungal agent, an organic filler, and the like. Due to the above-mentioned mechanism of action, the present composition 2 has excellent dispersion stability, and the liquid properties can be easily adjusted by adding these.

[0127] The viscosity of composition 2 is preferably 10 mPa·s or more, more preferably 50 mPa·s or more, and even more preferably 100 mPa·s or more. The viscosity of composition 2 is preferably 10,000 mPa·s or less, more preferably 3,000 mPa·s or less, and even more preferably 1,000 mPa·s or less. In this case, composition 2 is likely to have excellent liquid physical properties such as dispersion stability. The thixotropy ratio of the present composition 2 is preferably 1.0 or more. The thixotropy ratio of the present composition 2 is preferably 3.0 or less, and more preferably 2.0 or less. In this case, the present composition 2 has excellent liquid physical properties such as dispersion stability, and is likely to form a denser molded product.

[0128] The dispersion layer ratio of the present composition 2 is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. The present composition 2 has excellent dispersion stability, so the dispersion layer ratio is likely to fall within this range. Here, the dispersion layer ratio is a value calculated by the following formula from the height of the entire liquid composition and the height of the sedimentation layer (dispersion layer) in the screw tube after the liquid composition (18 mL) is placed in a screw tube (internal volume: 30 mL) and left to stand at 25° C. for 14 days. If no sedimentation layer is observed after standing and there is no change in the state, the dispersion layer ratio is considered to be 100%, assuming that there is no change in the height of the entire liquid composition. Dispersion layer rate (%) = (height of settled layer) / (height of entire liquid composition) × 100

[0129] The dispersity of Composition 2 is preferably 100 μm or less, more preferably 70 μm or less, and even more preferably 50 μm or less. The dispersity of Composition 2 is preferably 10 μm or more. Because the aggregation of F particles is suppressed in Composition 2 by the above-mentioned mechanism of action, the dispersity is likely to fall within the above range. The degree of dispersion means the size of coarse particles present in the liquid composition, as measured using a grindometer in accordance with JIS K5600-2-5.

[0130] Composition 2 has excellent liquid physical properties such as dispersion stability, and due to the above-mentioned mechanism of action, it can form molded articles based on F polymer and aromatic resin, which have excellent physical properties, and can also form molded articles that exhibit strong adhesion to substrates. The method for producing a laminate of the present invention is a method for producing a laminate in which the present composition 2 is applied to the surface of a substrate, and heated to form a polymer layer containing an F polymer and an aromatic resin (hereinafter also referred to as "F layer 1"), thereby obtaining a laminate having a substrate layer composed of the substrate and the F layer 1. More specifically, the composition is applied to the surface of a substrate to form a liquid coating, which is then heated to remove the dispersant to form a dry coating, and the dry coating is further heated to bake the F polymer, thereby obtaining a laminate having an F layer 1 on the surface of the substrate layer.

[0131] Examples of the substrate include metal substrates (metal foils of copper, nickel, aluminum, titanium, alloys thereof, etc.), heat-resistant resin films (films containing one or more heat-resistant resins such as polyimide, polyarylate, polysulfone, polyarylsulfone, polyamide, polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystalline polyester, liquid crystalline polyesteramide, and tetrafluoroethylene-based polymer, and may be single-layer or multi-layer films), prepregs (precursors of fiber-reinforced resin substrates), and glass. The metal substrate may be a low-roughening copper foil or a non-roughening copper foil. When the metal substrate is a low-roughening copper foil or a non-roughening copper foil, the laminate tends to have excellent transmission characteristics. The ten-point average roughness of the surface of the substrate is preferably 0.01 to 0.05 μm. The shape of the substrate may be flat, curved or irregular, and may further be any of foil, plate, film or fiber.

[0132] The method for applying the present composition 2 to the surface of the substrate may be any method that forms a stable liquid coating (wet film) of the present composition 2 on the surface of the substrate, and examples thereof include a coating method, a droplet discharging method, and a dipping method, with the coating method being preferred. The coating method allows for efficient formation of a liquid coating on the surface of the substrate using simple equipment. Examples of the coating method include spraying, roll coating, spin coating, gravure coating, microgravure coating, gravure offset, knife coating, kiss coating, bar coating, die coating, fountain-meyer bar coating, slot die coating, and dip coating.

[0133] When drying the liquid coating, the liquid coating is heated to a temperature at which the liquid components (including water) volatilize, and a dry coating is formed on the surface of the substrate. The heating temperature for such drying is preferably 100 to 200° C. Air may be blown in the step of removing the liquid components. During drying, the liquid component does not necessarily have to be completely evaporated, but it is sufficient to evaporate it to an extent that the layer shape after holding is stable and a free-standing film can be maintained. When baking the F polymer, it is preferable to heat the dried coating to a temperature equal to or higher than the melting point of the F polymer, preferably 380°C or lower, more preferably 350°C or lower.

[0134] Examples of heating methods include a method using an oven, a method using a ventilation drying furnace, and a method using heat rays such as infrared rays. Heating may be performed under either normal pressure or reduced pressure. The heating atmosphere may be any of an oxidizing gas atmosphere (oxygen gas, etc.), a reducing gas atmosphere (hydrogen gas, etc.), or an inert gas atmosphere (helium gas, neon gas, argon gas, nitrogen gas, etc.). The heating time is preferably 0.1 to 30 minutes, more preferably 0.5 to 20 minutes. By heating under the above conditions, the F layer 1 can be suitably formed while maintaining high productivity.

[0135] The thickness of the F layer 1 is preferably 0.1 μm or more, more preferably 10 μm or more, and even more preferably 50 μm or more. The thickness of the F layer 1 is preferably 500 μm or less, more preferably 250 μm or less. Since the present composition 2 has excellent physical properties such as dispersion stability, a thick F layer 1 can be easily formed from the present composition 2. The peel strength between the F layer 1 and the substrate layer is preferably 10 N / cm or more, more preferably 15 N / cm or more. The peel strength is preferably 100 N / cm or less. By using the present composition 2, the present laminate can be easily formed without impairing the physical properties of the F polymer in the F layer 1.

[0136] The composition 2 may be applied to only one surface of the substrate, or to both surfaces of the substrate. In the former case, a laminate having a substrate layer made of the substrate and an F layer 1 on one surface of the substrate layer is obtained, while in the latter case, a laminate having a substrate layer made of the substrate and an F layer 1 on both surfaces of the substrate layer is obtained. The latter laminate is less likely to warp, and therefore has excellent handling properties during processing. Specific examples of such laminates include a metal-clad laminate having a metal foil and an F layer 1 on at least one surface of the metal foil, and a multilayer film having a polyimide film and an F layer 1 on both surfaces of the polyimide film. These laminates are suitable as printed circuit board materials and the like because they have excellent physical properties such as electrical properties, and can be used to produce flexible printed circuit boards and rigid printed circuit boards.

[0137] The present laminate having F layers 1 on both surfaces of the substrate layer may be obtained by applying the present composition 2 to both surfaces of the substrate, heating to remove the liquid components, and further heating to bake the F polymer, thereby simultaneously forming F layers 1 on both surfaces.

[0138] The present laminate having the F layer 1 on both surfaces of the substrate layer may be obtained by immersing the substrate in the present composition 2, applying the present composition 2 to both surfaces of the substrate, and then passing through a firing furnace and heating. Specifically, the laminate may be obtained by immersing the substrate in the present composition 2, and then passing through a firing furnace and heating the substrate while removing it from the present composition 2. The laminate can be suitably produced using an apparatus having a dip coater and a firing furnace, such as a vertical firing furnace or a glass cloth coating machine manufactured by Tabata Kikai Kogyo Co., Ltd.

[0139] As described above, use of composition 2 allows for the production of laminates with excellent component uniformity and electrical properties. Composition 2 is particularly suitable for producing multilayer films containing F layer 1 on both surfaces of a polyimide film by a roll-to-roll process. Such multilayer films can be effectively used as materials for printed wiring boards, particularly flexible printed wiring boards, and exhibit the physical properties of the F polymer well.

[0140] Furthermore, by removing the substrate from the present laminate, it is possible to produce a sheet comprising the F layer 1. Methods for removal include peeling and etching. Laminates of the F layer 1 and the base layer and sheets comprising the F layer 1 are useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry products, heat dissipation parts, paints, cosmetics, etc.

[0141] Specifically, these include electrical wire coating materials (aircraft electrical wires, etc.), enameled wire coating materials used in motors for electric vehicles, etc., electrical insulating tape, insulating tape for oil drilling, 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.), copy rolls, covers for furniture, automobile dashboards, and home appliances, sliding parts (load bearings, sliding shafts, valves, bearings, bushings, seals, thrust washers, wear rings, pistons, slide switches, gears, cams, belt conveyors, food transport belts, etc.), wear pads, wear strips, tube lamps, test sockets, wafer guides, wear parts for centrifugal pumps, hydrocarbon, chemical and water supply pumps, tools (shovels, files, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, dies, toilets, container coating materials, power devices, transistors, thyristors, rectifiers, transformers, power MOS It can also be suitably used as a heat dissipation component for FETs, CPUs, heat dissipation fins, metal heat sinks, blades for wind turbines, wind power generation equipment, aircraft, etc., heat dissipation substrates for automobiles, and wireless communication devices (for example, the wireless communication devices described in WO2020 / 008691 and WO2020 / 031419).

[0142] The laminate, whose base layer is a resin film (preferably a polyimide resin film), is useful as a release film or carrier film. The laminate has excellent adhesion between the F layer 1 and the base layer, making it difficult for delamination to occur, and can be used repeatedly as a carrier film. Furthermore, the F layer 1 has excellent heat resistance, so its release properties are unlikely to deteriorate even after repeated use. Specifically, the present laminate is useful as a carrier film for forming ceramic green sheets, a carrier film for forming secondary batteries, a carrier film for forming solid polymer electrolyte membranes, and a carrier film for forming catalysts for solid polymer electrolyte membranes.

[0143] The liquid composition of the present invention is a liquid composition comprising F particles, an aromatic resin, at least one thickening polymer selected from the group consisting of polar vinyl polymers and polysaccharides, and water, wherein the ratio of the content of the thickening polymer to the F particles is 0.05 or less. The definitions and ranges of the F particles, aromatic resin, thickening polymer, and water in the liquid composition of the present invention, including preferred ranges, are the same as those in Composition 2 of Method 2. The physical properties of the liquid composition of the present invention are also the same as those in Composition 2 of Method 2. The liquid composition of the present invention can be suitably produced by Method 2.

[0144] The composition of the present invention comprises F particles, an aromatic resin, at least one thickening polymer selected from the group consisting of polar vinyl polymers and polysaccharides, and water, and the ratio of the content of the thickening polymer to the F particles is 0.05 or less, and the temperature is 25°C, the shear rate is 1 s -1 The composition of the present invention has a viscosity of 10,000 Pa·s to 100,000 Pa·s as measured by capillography. Because the composition of the present invention has excellent uniformity, when the composition of the present invention is mixed with water, a liquid composition having excellent dispersion stability, uniformity, and handleability is obtained.

[0145] The definitions and ranges of the F particles, aromatic resin, thickening polymer, and water in the composition of the present invention, including preferred ranges, are the same as those in Composition 2 of Method 2. The temperature of the composition of the present invention is 25°C, the shear rate is 1 s -1 The viscosity measured by capillography is preferably 15,000 Pa·s or more, more preferably 50,000 Pa·s or less, and more preferably 30,000 Pa·s or less. The composition of the present invention preferably contains sufficient water and is a powder containing highly wet F particles, that is, a clumpy, clay-like paste (dough or wet powder).

[0146] The content of F particles in the composition of the present invention is preferably 40% by mass or more, more preferably 50% by mass or more, based on the total mass of the composition of the present invention. The content of F particles is preferably 90% by mass or less, more preferably 80% by mass or less. The content of the aromatic resin in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, based on the total mass of the composition of the present invention, and is preferably 30% by mass or less, more preferably 10% by mass or less. The content of the thickening polymer in the composition of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total mass of the composition of the present invention, and is preferably 30% by mass or less, more preferably 10% by mass or less. The water content in the composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total mass of the composition of the present invention, and is preferably 50% by mass or less, more preferably 40% by mass or less. In the composition of the present invention, the ratio of the content of the thickening polymer to the F particles is 0.05 or less, preferably 0.03 or less, more preferably 0.01 or less, and preferably 0.001 or more, more preferably 0.03 or more. The solid content of the composition of the present invention is preferably from 40 to 99% by mass, more preferably from 50 to 80% by mass.

[0147] The composition of the present invention is preferably obtained by mixing F particles, an aromatic resin, a thickening polymer, and water in a tank equipped with a thin film swirling stirring mechanism or a rotation and revolution stirring mechanism. The mixing method, including the preferred ranges, is the same as that in Method 2. The liquid composition obtained by mixing the composition of the present invention with water has the same configuration as that of Composition 2 of Method 2, including the preferred ranges.

[0148] The method for producing composition 2, the method for producing a laminate using composition 2, the liquid composition of the present invention, and the composition of the present invention have been described above, but the present invention is not limited to the configurations of the above-mentioned embodiments. For example, the method for producing composition 2 and the method for producing a laminate using composition 2 may have any other step added to the configuration of the above embodiment, or may be replaced with any step that produces a similar effect. Furthermore, composition 2, the liquid composition of the present invention, and the composition of the present invention may have any other step added to the configuration of the above embodiment, or may be replaced with any step that exhibits a similar function.

[0149] Next, a third aspect of the present method (hereinafter also referred to as "the present method 3") will be described. Method 3 is a method in which F particles, inorganic particles having a new Mohs hardness of 12 or less (the present inorganic particles), and a liquid compound are mixed by swirling in a thin film to obtain a liquid composition containing F particles, the present inorganic particles, and the liquid compound (hereinafter also referred to as "the present composition 3"). Composition 3 exhibits minimal aggregation of the inorganic particles and is excellent in dispersion stability, uniformity, and ease of handling. Furthermore, from Composition 3, molded articles can be formed that combine the physical properties of the F polymer and the inorganic particles to a high degree, and that have excellent electrical properties, low linear expansion coefficient, and thermal conductivity. The reasons for this are not entirely clear, but are presumed to be as follows.

[0150] When F polymers with low surface energy are mixed with inorganic particles, the interactions between the inorganic particles themselves are stronger than the interactions between the inorganic particles and the F particles, making the inorganic particles more likely to aggregate. This tendency is particularly pronounced when inorganic particles that have formed secondary particles are mixed. When a strong shear force is applied to a liquid composition to eliminate the aggregation of inorganic particles, the F polymer is fibrillated or otherwise modified, which tends to impair the physical properties of the F polymer. Furthermore, in the case of inorganic particles with low hardness, the particles themselves are easily crushed into fine powder, which further tends to aggregate. Thus, it has been difficult to obtain a liquid composition with excellent dispersion stability, uniformity, and ease of handling by mixing F particles and inorganic particles while suppressing the aggregation of the inorganic particles.

[0151] This method involves mixing F particles, the inorganic particles, and a liquid compound by swirling them in a thin film, allowing the liquid compound to penetrate deeply into both the F particles and the inorganic particles, resulting in the mixture being wet. In other words, the liquid compound can be considered to mitigate the impact that occurs when the two particles collide, thereby preventing the denaturation of the F particles and the excessive crushing of the inorganic particles. The collision between the F particles and the inorganic particles can also be considered to promote the formation of coalescent particles of the inorganic particles and the F particles (e.g., composite particles in which inorganic particles are coalesced onto the surface of F particles). Furthermore, when inorganic particles that have formed secondary particles are mixed, the penetration of the liquid compound can also be considered to promote the dissolution of the secondary particles.

[0152] These factors are believed to result in a high degree of mixing of the F particles and the present inorganic particles at the individual particle level, which is why this method has yielded a liquid composition with excellent dispersion stability, uniformity, and ease of handling. Furthermore, the inclusion of uniform particles, such as the coalesced particles, facilitates the formation of a uniform and dense particle packing structure when the liquid compound is removed from Composition 3. As a result, it is believed that Composition 3 has inorganic particles densely arranged in the F polymer, resulting in a molded product with excellent electrical properties, low linear expansion, and thermal conductivity.

[0153] The inorganic particles in Method 3 are particles of an inorganic compound having a new Mohs hardness of not more than 12. One type of inorganic particle may be used alone, or two or more types may be used in combination. The new Mohs hardness of the inorganic particles is preferably 10 or less, more preferably 8 or less, even more preferably 5 or less, and particularly preferably 3 or less. The new Mohs hardness of the inorganic particles is preferably 1 or more, more preferably 2 or more.

[0154] The inorganic particles may be spherical, acicular (fibrous), or plate-like, with plate-like being preferred. In this case, it is believed that coalescence particles of the inorganic particles and F particles are likely to be formed, and the composition 3 is likely to have excellent physical properties such as dispersion stability. As a result, a molded product formed from the composition 3 is likely to have excellent electrical properties and low linear expansion. In addition, the inorganic particles are likely to form paths in the molded product, and the molded product is likely to have excellent thermal conductivity. Specific shapes of the inorganic particles include spherical, scale-like, layer-like, leaf-like, apricot-like, columnar, cockscomb-like, equiaxial, leaf-like, micaceous, block-like, tabular, wedge-like, rosette-like, net-like, and prismatic shapes.

[0155] The inorganic particles are preferably carbon particles, nitride particles, and inorganic oxide particles, and more preferably carbon fiber particles, boron nitride particles (modified Mohs hardness: 2), aluminum nitride particles, beryllia particles (beryllium oxide particles), silicate particles (silica particles (modified Mohs hardness: 8), wollastonite particles, talc particles (modified Mohs hardness: 1)), and metal oxide particles (cerium oxide, aluminum oxide (modified Mohs hardness: 12), magnesium oxide, zinc oxide, titanium oxide, etc.). From the viewpoints of the dispersion stability of Composition 3 and the electrical properties and low linear expansion of molded articles formed from Composition 3, boron nitride particles and silica particles are even more preferred, and boron nitride particles are particularly preferred. Furthermore, from the viewpoint of the thermal conductivity of molded articles formed from Composition 3, boron nitride particles and aluminum oxide particles are preferred.

[0156] The D50 of the inorganic particles is preferably 20 μm or less, more preferably 10 μm or less. The D50 is preferably 0.01 μm or more, more preferably 0.1 μm or more. The ratio of the D50 of the inorganic particles to the D50 of the F particles is preferably 1 or more, more preferably 2 or more. This ratio is preferably 20 or less, more preferably 10 or less. The specific surface area of ​​this inorganic particle is 1 to 20 m 2 / g is preferred. The aspect ratio of the inorganic particles is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. The aspect ratio of the inorganic particles is preferably 10,000 or less. Inorganic particles with such an aspect ratio and a small new Mohs hardness tend to aggregate or break during mixing due to their shape anisotropy, but the present method allows for high-level mixing with F particles due to the above-mentioned mechanism of action.

[0157] From the viewpoint of wettability, at least a portion of the surface of the inorganic particles may be surface-treated with a silane coupling agent (3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.). Suitable specific examples of the present inorganic particles include the same as the specific examples of the inorganic filler in the present method 1 and the inorganic particles in the present method 2 described above.

[0158] The content of the inorganic particles in the present composition 3 is preferably 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the present composition 3. The content of the inorganic particles is preferably 60% by mass or less, and more preferably 50% by mass or less, relative to the total mass of the present composition 3. The ratio of the content of the present inorganic particles to the content of the F particles in the present composition 3 is preferably 0.1 to 3, more preferably 0.2 to 1. In this case, secondary particles of the present inorganic particles are easily eliminated, and the present composition 3 tends to have excellent physical properties such as dispersion stability.

[0159] In Method 3, the liquid compound means a compound that is liquid at atmospheric pressure and 25°C. The liquid compounds include hydrocarbons, water, alcohols, amides, ketones and esters, with water, amides, ketones and esters being preferred. The boiling point of the liquid compound is preferably in the range of 50 to 240° C. One type of liquid dispersion medium may be used alone, or two or more types may be used in combination.

[0160] Alcohols include methanol, ethanol, isopropanol, and glycol. Examples of the amide include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-diethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone.

[0161] Examples of ketones include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, and cycloheptanone. Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl 3-ethoxypropionate, γ-butyrolactone, and γ-valerolactone.

[0162] Specific examples of suitable liquid compounds include water, N-methyl-2-pyrrolidone, γ-butyrolactone, cyclohexanone, and cyclopentanone. The content of the liquid compound in the present composition 3 is preferably 30 to 90 mass %, more preferably 50 to 80 mass %. Within this range, the liquid physical properties of the present composition 3, such as dispersion stability, are more likely to be improved.

[0163] In this method, the F particles, the present inorganic particles, and the liquid compound are mixed by swirling in a thin film, i.e., these components are mixed by swirling while being spread in a thin film, to obtain the present composition 3. The centrifugal force caused by the swirling acts effectively on each component spread in a thin film, and the liquid compound penetrates deeply into both the F particles and the present inorganic particles, thereby progressing the mixing. The mixing is preferably carried out using the thin film swirling type high speed mixer described above in Methods 1 and 2. The details of the stirring vessel and the rotating part having a cylindrical part with a plurality of holes formed therein in the thin film rotation type high-speed mixer are as described above. In mixing, the F particles, the present inorganic particles, and the liquid compound may be supplied into the stirring tank all at once, or may be supplied into the stirring tank separately using multiple inlets. The mixing can be carried out either batchwise or continuously. In the case of a continuous system, one stirring tank may be used, and the mixture removed from the discharge port may be fed again through the inlet and mixed, or multiple stirring tanks may be used, and the mixture removed from the discharge port of a previous stirring tank may be fed again through the inlet of a subsequent stirring tank and mixed.

[0164] The supplied F particles, inorganic particles, and liquid compound fill the gap between the inner wall of the mixing vessel and the outer periphery of the rotating cylindrical part, forming a film, which then swirls at high speed within the mixing vessel as the rotating part rotates. At this time, they are subjected to not only shear stress but also shear stress, achieving a high level of dispersion and mixing. In this method, it is preferable to mix a composition containing F particles, the present inorganic particles, and a liquid compound by thin film swirling. That is, in this method, it is preferable to premix the F particles, the present inorganic particles, and the liquid compound before mixing by thin film swirling. In this case, the above-mentioned mechanism of action of this method is enhanced, and the physical properties of the present composition 3, such as dispersion stability, are likely to be further improved. The pre-mixing method may be the same as the mixing method described above in Method 1 and Method 2.

[0165] The composition containing the F particles, the present inorganic particles, and a liquid compound is preferably a kneaded product obtained by premixing the F particles, the present inorganic particles, and the liquid compound. A liquid compound may be further added to the kneaded product to adjust the viscosity. In this case, the above-described mechanism of action of the present method is likely to be enhanced. Such a kneaded product is preferably a solidified product (paste) having fluidity and viscosity, or a clumpy, clay-like solidified product (dough).

[0166] The solid content of the paste is preferably 40 to 90% by mass, more preferably 60 to 80% by mass, and the solid content of the dough is preferably 50 to 99% by mass, more preferably 60 to 95% by mass. The solid content of the paste and the dough has the same meaning as that described above in Method 2.

[0167] In the mixing, a polymer different from the F polymer may be further added. The different polymer may be added before or during the mixing. For example, a composition containing the F particles, the inorganic particles, the liquid compound, and the different polymer may be prepared and then mixed. The different polymers may be thermosetting or thermoplastic, or may be modified. The different polymers may be dissolved or dispersed in the composition 3. The different polymers may be present in the composition 3 as precursors thereof.

[0168] Examples of different polymers include acrylic resins, phenolic resins, liquid crystalline polyesters, liquid crystalline polyesteramides, polyolefin resins, modified polyphenylene ethers, polyfunctional cyanate ester resins, polyfunctional maleimide-cyanate ester resins, polyfunctional maleimides, aromatic elastomers such as styrene elastomers, vinyl ester resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea co-condensation resins, polycarbonates, polyarylates, polysulfones, polyarylsulfones, aromatic polyamides, aromatic polyamideimides, aromatic polyetheramides, polyphenylene sulfides, polyaryl ether ketones, polyphenylene ethers, and epoxy resins.

[0169] A preferred embodiment of the different polymer is an aromatic polymer. The aromatic polymer is preferably polyphenylene ether or an aromatic elastomer (such as a styrene elastomer). In this case, not only is the adhesiveness and low linear expansion of the molded article formed from the composition 3 further improved, but the liquid properties (viscosity, thixotropy ratio, etc.) of the composition 3 are well balanced, which tends to improve the handleability of the article. When the present composition 3 contains the different polymer, the content thereof is preferably 40% by mass or less relative to the total mass of the present composition 3.

[0170] A surfactant may be further added during mixing. The surfactant may be added before or during mixing. For example, a composition containing the F particles, the inorganic particles, a liquid compound, and a surfactant may be prepared and then mixed. The surfactant is preferably a nonionic surfactant. Specific examples of the nonionic surfactant include the same surfactants as those that may be added to the present composition 2, as described above. When the present composition 3 contains a nonionic surfactant, the content of the nonionic surfactant in the present composition 3 is preferably 0.1 to 15 mass %, more preferably 1 to 10 mass %.

[0171] A silane coupling agent may be further added during mixing. In this case, the binding strength between the F particles and the present inorganic particles is likely to be improved, and peeling of the present inorganic particles is likely to be suppressed in a molded product formed from the present composition 3. Examples of the silane coupling agent include compounds similar to the silane coupling agents that can be used for surface treatment of the present inorganic particles. The silane coupling agent may be added before or during mixing. For example, a composition containing the F particles, the present inorganic particles, the liquid compound, and the silane coupling agent may be prepared and then mixed. When the present composition 3 contains a silane coupling agent, the content of the silane coupling agent in the present composition 3 is preferably 1 to 10 mass % relative to the content of the F particles.

[0172] When the liquid compound in this method is water, a pH adjuster or a pH buffer may be further used to adjust the pH of the composition 3. In this case, the pH of the composition 3 is preferably adjusted to 5 to 10, more preferably 7 to 9, using the pH adjuster or pH buffer. Examples of the pH adjuster or pH buffer include the same compounds as those described above in the present composition 2. The pH adjuster or pH buffer may be added either before or during mixing. The composition 3 may be further subjected to a defoaming treatment, which is preferably carried out using a planetary centrifugal mixer.

[0173] A liquid compound may be further added to the present composition 3. Due to the above-described mechanism of action, the present composition 3 has excellent dispersion stability and can be easily mixed with the liquid compound. The liquid compound further added may be the same as or different from the liquid compound in the present method. In addition to the liquid compound, composition 3 may further contain the above-mentioned components (a polymer different from the F polymer, a surfactant, a silane coupling agent, a pH adjuster, a pH buffer), a thixotropic agent, a viscosity modifier, an antifoaming agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a release agent, a surface treatment agent, a flame retardant, an antiseptic, an antifungal agent, etc. Due to the above-mentioned mechanism of action, the present composition 3 has excellent dispersion stability, and the liquid properties can be easily adjusted by adding these.

[0174] The viscosity of composition 3 is preferably 10 mPa·s or more, more preferably 50 mPa·s or more, and even more preferably 100 mPa·s or more. The viscosity of composition 3 is preferably 10,000 mPa·s or less, more preferably 3,000 mPa·s or less, and even more preferably 1,000 mPa·s or less. In this case, composition 3 is likely to have excellent liquid physical properties such as dispersion stability. The thixotropy ratio of the present composition 3 is preferably 1.0 or more. The thixotropy ratio of the present composition 3 is preferably 3.0 or less, and more preferably 2.0 or less. In this case, the present composition 3 has excellent liquid physical properties such as dispersion stability, and is likely to form a denser molded product.

[0175] The dispersion layer ratio of the present composition 3 is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. The present composition 3 has excellent dispersion stability, so the dispersion layer ratio is likely to be within this range. The dispersion layer ratio is as described above for the present composition 2.

[0176] The dispersity of Composition 3 is preferably 100 μm or less, more preferably 70 μm or less, and even more preferably 50 μm or less. The dispersity of Composition 3 is preferably 10 μm or more. Composition 3 has the above-mentioned mechanism of action to suppress aggregation of the inorganic particles, so the dispersity is likely to fall within the above range. The dispersity is as described above for Composition 2.

[0177] Composition 3 has excellent liquid physical properties such as dispersion stability, and due to the above-mentioned mechanism of action, it can form molded articles based on the F polymer and the inorganic particles, which have excellent physical properties.In addition, it can form molded articles that exhibit strong adhesion to substrates. The method for producing a laminate of the present invention is a method for producing a laminate in which the present composition 3 is applied to the surface of a substrate, and heated to form a polymer layer (hereinafter also referred to as "F layer 2") containing the F polymer and the present inorganic particles, thereby obtaining a laminate having a substrate layer composed of the substrate and the F layer 2. More specifically, the composition 3 is applied to the surface of a substrate to form a liquid coating, which is then heated to remove the dispersant to form a dry coating, and the dry coating is further heated to bake the F polymer, thereby obtaining a laminate having an F layer 2 on the surface of the substrate layer.

[0178] Examples of the substrate include those similar to those described above in Method 2. The metal substrate may be a low-roughening copper foil or a non-roughening copper foil. When the metal substrate is a low-roughening copper foil or a non-roughening copper foil, the laminate tends to have excellent transmission characteristics. The shape of the substrate may be flat, curved or irregular, and may further be any of foil, plate, film or fiber.

[0179] The method for applying the present composition 3 to the surface of the substrate, the method for drying the formed liquid coating, and the method for heating are the same as those for producing a laminate in the present method 2 described above.

[0180] The thickness of the F layer 2 is preferably 0.1 μm or more, more preferably 10 μm or more, and even more preferably 50 μm or more. The thickness of the F layer 2 is preferably 500 μm or less, more preferably 250 μm or less. Since the present composition 3 has excellent physical properties such as dispersion stability, a thick F layer 2 can be easily formed from the present composition 3. The peel strength between the F layer 2 and the substrate layer is preferably 10 N / cm or more, more preferably 15 N / cm or more. The peel strength is preferably 100 N / cm or less. By using the present composition 3, the present laminate can be easily formed without impairing the physical properties of the F polymer in the F layer 2.

[0181] The composition 3 may be applied to only one surface of the substrate, or to both surfaces of the substrate. In the former case, a laminate having a substrate layer made of the substrate and an F layer 2 on one surface of the substrate layer is obtained, while in the latter case, a laminate having a substrate layer made of the substrate and an F layer 2 on both surfaces of the substrate layer is obtained. The latter laminate is less likely to warp, and therefore has excellent handleability during processing. Specific examples of such laminates include a metal-clad laminate having a metal foil and an F layer 2 on at least one surface of the metal foil, and a multilayer film having a polyimide film and an F layer 2 on both surfaces of the polyimide film. These laminates are suitable as printed circuit board materials and the like because they have excellent physical properties such as electrical properties, and can be used to produce flexible printed circuit boards and rigid printed circuit boards.

[0182] Furthermore, by removing the substrate from the present laminate, it is possible to produce a sheet comprising the F layer 2. Methods for removal include peeling and etching. The laminate of the F layer 2 and the substrate layer and the sheet comprising the F layer 2 are useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry products, heat dissipation parts, paints, cosmetics, etc. Specific examples are as described above in Method 2.

[0183] The above describes the method for producing the present composition 3 and the method for producing a laminate using the present composition 3, but the present invention is not limited to the configurations of the above-mentioned embodiments. For example, the method for producing the present composition 3 and the method for producing a laminate using the present composition 3 may have any other steps added to the configurations of the above-mentioned embodiments, or may be replaced with any other steps that produce the same effect. [Example]

[0184] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Details of each component used are shown below. [F particle] F particle 1: Contains 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE units, NAH units, and PPVE units, in that order, and has a carbonyl group-containing group with a main chain carbon number of 1×10 6 Particles (D50: 2.1 μm) made of F polymer 1 (melting temperature: 300 °C) with 1000 particles per particle F Particle 2: Particles (D50: 1.8 μm) made of a polymer (melting temperature 305° C.) containing 97.5 mol% TFE units and 2.5 mol% PPVE units, in that order, and having no oxygen-containing polar groups. F Particle 3: Non-melting particles made of non-thermofusible polytetrafluoroethylene (D50: 0.3 μm) [Liquid dispersion medium (liquid compound)] NMP: N-methyl-2-pyrrolidone Tol: Toluene [Aromatic resin (aromatic polymer) varnish] Varnish 1: A varnish (solvent: Tol, solid content: 65% by mass) of a carboxyl group-containing phenolic resin (aromatic resin 1, acid value: 80 mg KOH / g) obtained by reacting acrylic acid with an epoxidized multifunctional phenolic resin and then adding phthalic anhydride to the hydroxyl groups present in the side chains. Varnish 2: Water varnish containing a precursor of aromatic polyamide-imide (PAI1) (acid value: 50 mg KOH / g) [Inorganic particles] Particle 1: Plate-shaped and scaly boron nitride particles (D50: 14.6 μm, new Mohs hardness: 2) Particle 2: Spherical boron carbide particles (D50: 12.2 μm, new Mohs hardness: 14) [Thickening polymer] Thickening polymer 1: Carboxymethyl cellulose (molecular weight: 350,000, thermal decomposition temperature: 300°C) Thickening polymer 2: Hydroxyethyl cellulose (Sumitomo Seika Chemicals "HEC CF-Y") [Resin film] Polyimide film 1: Aromatic polyimide film (PI Advanced Materials "FG-100") with a thickness of 25 μm

[0185] Example and Evaluation of Aspect 1 1-1. Example of composition production [Example 1-1] (1) F particles 1, varnish 1, and NMP were placed in the stirring vessel of a stirrer equipped with a cylindrical stirring vessel and a rotating part having a cylindrical part with multiple holes formed therein that rotates inside the inner wall surface of the stirring vessel, and the rotating part was rotated at high speed to mix the ingredients, thereby obtaining composition 1-1 (viscosity: 10,000 mPa·s) containing F particles 1 (30 parts by mass), aromatic resin 1 (20 parts by mass), Tol (10 parts by mass), and NMP (30 parts by mass). (2) Composition 1 and varnish 1 were placed in a pot and shaken to obtain a liquid composition 1-1 (viscosity: 400 mPa·s) containing F particles 1 (30 parts by mass), aromatic resin 1 (80 parts by mass), Tol (40 parts by mass), and NMP (60 parts by mass). Composition 1-1 and Liquid Composition 1-1 were excellent in dispersibility, with no visible aggregates even after storage at 25°C for 30 days.

[0186] [Example 1-2] (1) Composition 1-2 was obtained in the same manner as in Example 1-1(1), except that F particles 1 were changed to F particles 2. (2) Liquid composition 1-2 was obtained in the same manner as in (2) of Example 1-1, except that composition 1 was changed to composition 2. In Composition 1-2 and Liquid Composition 1-2, aggregates were visible even after storage at 25°C for 30 days, and re-dispersion was required. [Example 1-3] F particles 2 (30 parts by mass), aromatic resin 1 (80 parts by mass), Tol (40 parts by mass), and NMP (60 parts by mass) were placed in a pot, and zirconia balls were then placed in. The pot was then rolled at 150 rpm for 1 hour in an attempt to prepare a liquid composition, but the composition became viscous, and a uniform dispersion could not be directly obtained.

[0187] 1-2. Example of manufacturing a substrate with convex portions In a laminate of a film of F Polymer 1 and an electrolytic copper foil ("CF-T49A-DS-HD2" manufactured by Fukuda Metal Foil & Powder Co., Ltd.), Liquid Composition 1-1 was applied to the surface of the electrolytic copper foil opposite to the film to form a coating on the laminate. This coating was dried at 80°C for 10 minutes to obtain a dry coating (thickness: 50 μm). Next, an exposure mask having openings of a predetermined pattern is used to irradiate the film with ultraviolet light (integrated light amount: 150 mJ / cm 2 ) was irradiated onto the dried film. Next, the dried film after ultraviolet irradiation was developed with a 1.0 mass % aqueous solution of sodium carbonate to form convex portions. When the protrusions were examined under an optical microscope, no particles were found to have fallen off from the protrusions. The pencil hardness of the protrusions was 4H, which was equivalent to the pencil hardness of the protrusions formed from Varnish 1 alone.

[0188] 1-3. Film manufacturing example Liquid composition 1-1 was applied to an electrolytic copper foil (manufactured by Fukuda Metal Foil and Powder Co., Ltd., "CF-T49A-DS-HD2") to form a coating film, and this coating film was dried at 80°C for 10 minutes to obtain a dry film (thickness: 50 μm). Next, the entire dried film was irradiated with ultraviolet light without using an exposure mask. The integrated dose of ultraviolet light was 150 mJ / cm 2 2 The electrolytic copper foil was then etched with an aqueous solution of ferric chloride to obtain a film. The electrical properties of this film were measured at 10 MHz using a split post dielectric resonator (SPDR) and a network analyzer, and the dielectric constant was found to be 3 or less and the dielectric dissipation factor was 0.05 or less, indicating excellent electrical properties.

[0189] Example and Evaluation of Aspect 2 2-1. Example of production of liquid composition [Example 2-1] First, varnish 2, thickening polymer 1, and water were added to a pot and mixed. Furthermore, F particles 1 were added to the pot and mixed to prepare a composition. Next, the prepared composition was added to a planetary mixer and kneaded to obtain dough 2-1 containing F particles 1 (40 parts by mass), PAI 1 (0.4 parts by mass), thickening polymer 1 (0.6 parts by mass), and water (29 parts by mass). Dough 2-1 was lumpy and clay-like. Water was added to the dough 2-1 in several batches and stirred, and the mixture was placed in a mixing vessel of a mixer equipped with a cylindrical mixing vessel and a rotating part with a cylindrical part formed with multiple holes that rotates inside the inner wall of the mixing vessel, and the rotating part was rotated at high speed of 7500 rpm for 30 seconds to mix. This produced a liquid composition 2-1 (viscosity: 300 mPa s) containing F particles 1 (40 parts by mass), PAI 1 (0.4 parts by mass), thickening polymer 1 (0.6 parts by mass), and water (59 parts by mass). The ratio of the content of the thickening polymer to the content of the F particles in Liquid Composition 2-1 was 0.015.

[0190] [Example 2-2] Liquid composition 2-2 (viscosity: 600 mPa s) containing F particles 2 (40 parts by mass), PAI 1 (0.4 parts by mass), thickening polymer 1 (0.6 parts by mass), and water (59 parts by mass) was obtained in the same manner as in Example 2-1, except that F particles 1 were changed to F particles 2. [Example 2-3] Liquid composition 2-3 (viscosity: 500 mPa s) containing F particles 1 (20 parts by mass), F particles 3 (20 parts by mass), PAI 1 (0.4 parts by mass), thickening polymer 1 (0.6 parts by mass), and water (59 parts by mass) was obtained in the same manner as in Example 2-1, except that F particles 1 (40 parts by mass) was changed to F particles 1 (20 parts by mass) and F particles 3 (20 parts by mass).

[0191] [Example 2-4] F particles 1, varnish 2, thickening polymer 1, and water were placed in a pot, followed by the addition of zirconia balls. The pot was then rolled at 150 rpm for 1 hour to obtain Liquid Composition 2-4 (viscosity: 900 mPa s) containing F particles 1 (40 parts by mass), PAI 1 (0.4 parts by mass), thickening polymer 1 (0.6 parts by mass), and water (59 parts by mass). [Example 2-5] Liquid composition 2-5 (viscosity: 1000 mPa·s) containing F particles 1 (40 parts by mass), PAI 1 (0.4 parts by mass), thickening polymer 1 (2.6 parts by mass), and water (57 parts by mass) was obtained in the same manner as in Example 2-1, except that the amounts of thickening polymer 1 and water were changed to 2.6 parts by mass and 27 parts by mass, respectively, when varnish 2, thickening polymer 1, and water were added to the pot and mixed. The ratio of the content of the thickening polymer to the content of the F particles in Liquid Composition 2-5 was 0.065.

[0192] [Example 2-6] F Particles 2, Varnish 2, Thickening Polymer 1, and water were placed in a pot, followed by the addition of zirconia balls. The pot was then rolled at 150 rpm for 1 hour to obtain Liquid Composition 2-6 (viscosity: 3000 mPa s) containing F Particles 2 (40 parts by mass), PAI 1 (0.4 parts by mass), Thickening Polymer 1 (2.6 parts by mass), and water (57 parts by mass). The ratio of the content of the thickening polymer to the content of the F particles in Liquid Composition 2-6 was 0.065.

[0193] [Example 2-7] First, F particles 1 were placed in a planetary centrifugal mixer and pre-dispersed by stirring. The pre-dispersed F particles 1, varnish 2, thickening polymer 2, and water were then placed in the planetary centrifugal mixer and stirred at a ratio of the rotation speed to the revolution speed of 2 to produce a dough 2-7 (temperature: 25°C, shear rate: 1 s) containing F particles 1 (40 parts by mass), PAI 1 (0.4 parts by mass), thickening polymer 2 (0.6 parts by mass), and water (19 parts by mass). -1 The viscosity measured by capillography was 20,000 Pa·s. Water was added to the dough 2-7 in several batches while mixing with a centrifugal mixer with a ratio of rotation speed to revolution speed of 2 to obtain a liquid composition 2-7 (viscosity: 400 mPa·s) containing F particles 1 (40 parts by mass), PAI 1 (0.4 parts by mass), thickening polymer 2 (0.6 parts by mass), and water (59 parts by mass). The ratio of the content of the thickening polymer to the content of the F particles in Liquid Composition 2-7 was 0.015. The time from production of Liquid Composition 2-7 until foaming disappeared was shorter than the time from production of Liquid Composition 2-1 until foaming disappeared, and Liquid Composition 7 was excellent in handleability.

[0194] 2-2. Example of laminate manufacturing Liquid composition 2-1 was applied to the surface of a long copper foil with a thickness of 18 μm using a bar coater to form a wet film. The copper foil with this wet film formed thereon was then passed through a drying oven at 110°C for 5 minutes to dry it, forming a dry film. The substrate with the dry film formed thereon was heated in a nitrogen oven at 380°C for 3 minutes. This produced a laminate 2-1 having copper foil and a 200 μm thick polymer layer as a molded product on its surface, which contained a melt-sintered product of F particles 1 and PAI1. Laminates 2-2 to 2-7 were obtained in the same manner as for laminate 2-1, except that liquid composition 2-1 was changed to liquid compositions 2-2 to 2-7.

[0195] 2-3. Evaluation of liquid compositions <Dispersion stability of liquid composition> Each liquid composition (18 mL) was placed in a screw tube (internal volume: 30 mL) and allowed to stand for 14 days at 25° C. The dispersion layer ratio was calculated using the following formula from the height of the entire liquid composition in the screw tube and the height of the sedimentation layer (dispersion layer) before and after standing, and the dispersion stability was evaluated according to the following criteria. [Evaluation criteria] ◎: The dispersion layer rate is 80% or more. ◯: The dispersion layer rate is 70% or more and less than 80%. △: The dispersion layer rate is 60% or more and less than 70%. ×: The dispersion layer rate is less than 60%.

[0196] 2-4. Evaluation of laminates <Electrical properties of laminate> The copper foil of each laminate was removed by etching with an aqueous solution of ferric chloride to produce a sheet of a single polymer layer. The dielectric loss tangent (measurement frequency: 10 GHz) of the produced sheet was measured using the SPDR (split post dielectric resonance) method and evaluated according to the following criteria. [Evaluation criteria] Good: The dielectric loss tangent is less than 0.0010. △: The dielectric loss tangent is 0.0010 or more and 0.0025 or less. ×: The dielectric loss tangent is more than 0.0025. The evaluation results are summarized in Table 1.

[0197] [Table 1]

[0198] Furthermore, the sheet obtained from the laminate 2-3 was superior in bendability and sheet strength compared to the sheet obtained from the laminate 2-1.

[0199] 2-5. Example of laminated film manufacturing Liquid composition 2-7 was applied to one side of polyimide film 1 by a roll-to-roll process using a small-diameter gravure reverse method, and the film was passed through a forced-air drying oven (oven temperature 150°C) for 3 minutes to remove water and form a dry film. Liquid composition 2-7 was also applied to the other side of polyimide film 1 in the same way, and the film was dried to form a dry film. Next, the polyimide film 1 with the dry film formed on both sides was passed through a far-infrared furnace (furnace temperature near the entrance and exit of the furnace: 300°C, furnace temperature near the center: 360°C) for 5 minutes to melt and bake the F particles 1. As a result, polymer layers (thickness: 25 μm) containing the molten and baked F particles 1 and PAI 1 were formed on both sides of the polyimide film 1, and a laminate (laminated film 2-1) in which a polymer layer, a polyimide film layer, and a polymer layer were directly formed in this order was obtained by a roll-to-roll process. A rectangular test piece (100 mm long, 10 mm wide) was cut out from the laminated film 2-1, and the test piece was fixed at a position 50 mm from one end in the longitudinal direction. The polymer layer and the polyimide film layer were peeled off from one end in the longitudinal direction at a 90° angle to the test piece at a pulling rate of 50 mm / min. The maximum load applied during this process was 15 N / cm or more, and the laminated film 2-1 had excellent interlayer adhesion. A square test piece measuring 180 mm square was cut out from the laminated film 2-1, and the linear expansion coefficient of the test piece was measured using the measurement method specified in JIS C 6471:1995. The result was less than 20 ppm / °C, demonstrating that the laminated film 2-1 had excellent low linear expansion properties.

[0200] Example and Evaluation of Aspect 3 3-1. Example of production of liquid composition [Example 3-1] First, a powder mixture of F particles 1 and particles 1 and NMP were added to a pot and mixed to prepare a composition. Next, the prepared composition was added to a planetary mixer and kneaded to obtain a dough 3-1 containing F particles 1 (20 parts by mass), particles 1 (20 parts by mass), and NMP (30 parts by mass). The dough 3-1 was lumpy and clay-like. NMP was added to the dough 3-1 in several batches and stirred, and the mixture was placed in a mixing vessel of a mixer equipped with a cylindrical mixing vessel and a rotating part with a cylindrical part formed with multiple holes that rotates inside the inner wall of the mixing vessel, and the rotating part was rotated at high speed of 7500 rpm for 30 seconds to mix. This produced a liquid composition 3-1 (viscosity: 500 mPa s) containing F particles 1 (20 parts by mass), particles 1 (20 parts by mass), and NMP (60 parts by mass).

[0201] [Example 3-2] A liquid composition 3-2 (viscosity: 800 mPa·s) containing F particles 2 (20 parts by mass), particles 1 (20 parts by mass), and NMP (60 parts by mass) was obtained in the same manner as in Example 3-1, except that F particles 1 were changed to F particles 2. [Example 3-3] Liquid composition 3-3 (viscosity: 700 mPa s) containing F particles 1 (10 parts by mass), F particles 2 (10 parts by mass), particles 2 (20 parts by mass), and NMP (60 parts by mass) was obtained in the same manner as in Example 3-1, except that F particles 1 (20 parts by mass) was changed to F particles 1 (10 parts by mass) and F particles 3 (10 parts by mass).

[0202] [Example 3-4] A liquid composition 3-4 (viscosity: 2000 mPa·s) containing F particles 2 (20 parts by mass), particles 2 (20 parts by mass), and NMP (60 parts by mass) was obtained in the same manner as in Example 3-1, except that F particles 1 were changed to F particles 2 and particles 1 were changed to particles 2. [Example 3-5] F Particles 2, Particles 1, and NMP were placed in a pot, followed by the addition of zirconia balls. The pot was then rolled at 150 rpm for 1 hour to obtain Liquid Composition 3-5 (viscosity: 3000 mPa s) containing F Particles 2 (20 parts by mass), Particles 1 (20 parts by mass), and NMP (60 parts by mass).

[0203] 3-2. Example of laminate manufacturing Liquid Composition 3-1 was applied to the surface of a long copper foil with a thickness of 18 μm using a bar coater to form a wet film, and then the copper foil with the wet film formed thereon was passed through a drying oven at 110° C. for 5 minutes to dry it, thereby forming a dry film. The substrate on which the dry film was formed was passed between two pairs of rolls heated to 120° C., which were adjusted to press the dry film at 0.5 MPa, to press the dry film. The substrate was then further heated in a nitrogen oven at 380°C for 3 minutes, thereby producing a laminate 3-1 having a copper foil and, on its surface, a polymer layer having a thickness of 200 µm as a molded product containing the molten and fired product of F particles 1 and particles 1. Laminates 3-2 to 3-5 were obtained in the same manner as for laminate 3-1, except that liquid composition 3-1 was changed to liquid compositions 3-2 to 3-5.

[0204] 3-3. Evaluation of liquid composition <Dispersion stability of liquid composition> Each liquid composition (18 mL) was placed in a screw tube (internal volume: 30 mL) and allowed to stand for 14 days at 25° C. The dispersion layer ratio was calculated using the following formula from the height of the entire liquid composition in the screw tube and the height of the sedimentation layer (dispersion layer) before and after standing, and the dispersion stability was evaluated according to the following criteria. [Evaluation criteria] ○: The dispersion layer rate is 80% or more. △: The dispersion layer rate is 60% or more and less than 80%. ×: The dispersion layer rate is less than 60%.

[0205] 3-4. Evaluation of laminate 3-4-1. Linear expansion of laminated body For each laminate, the copper foil of the laminate was removed by etching with an aqueous ferric chloride solution to produce a sheet of a single polymer layer. Square test pieces measuring 180 mm square were cut from the produced sheet, and the linear expansion coefficient of the test pieces was measured in the range of 25°C to 260°C in accordance with the measurement method specified in JIS C 6471:1995, and evaluated according to the following criteria. [Evaluation criteria] ◯: The linear expansion coefficient is 50 ppm / °C or less. △: The linear expansion coefficient is more than 50 ppm / °C and 75 ppm / °C or less. ×: The linear expansion coefficient exceeds 75 ppm / °C.

[0206] 3-4-2. Thermal conductivity of laminates For each laminate, the copper foil was removed by etching with an aqueous solution of ferric chloride to produce a sheet of a single polymer layer. A 10mm x 10mm test piece was cut from the center of the sheet, and the thermal conductivity (W / m K) in the in-plane direction was measured and evaluated according to the following criteria. [Evaluation criteria] 〇: Thermal conductivity is 5 W / m·K or higher. ×: Thermal conductivity is less than 5 W / m·K. The evaluation results are summarized in Table 2.

[0207] [Table 2]

[0208] Furthermore, the sheet obtained from the laminate 3-3 was superior in bendability and sheet strength compared to the sheet obtained from the laminate 3-1. [Industrial Applicability]

[0209] The liquid composition produced by the method of the present invention is excellent in dispersion stability, uniformity and ease of handling. The liquid composition obtained by the production method of embodiment 1 is also useful as, for example, a solder resist composition or a filling material used to fill through-holes or recesses in multilayer printed wiring boards. Molded articles having excellent physical properties such as low linear expansion, thermal conductivity, and electrical properties can be formed from the liquid composition obtained by the method of embodiment 2 or embodiment 3. Therefore, such liquid compositions can be easily processed into films, fiber-reinforced films, prepregs, metal laminates (resin-coated metal foils), etc. The processed articles obtained can be used as materials for antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry products, sliding bearings, etc.

Claims

1. A method for producing a liquid composition, comprising mixing particles of a tetrafluoroethylene-based polymer, the particles having an average particle size (D50) of 0.1 to 25 μm and being a polymer containing tetrafluoroethylene units and units based on perfluoro(alkyl vinyl ether) or a polymer containing tetrafluoroethylene units and units based on hexafluoropropylene, with an aromatic resin and a liquid compound in a tank equipped with a stirring mechanism using thin film swirling or a stirring mechanism using rotation and revolution, to obtain a liquid composition containing the particles of the tetrafluoroethylene-based polymer, the aromatic resin and the liquid compound and having a viscosity of 10,000 mPa·s or less.

2. 2. The method according to claim 1, wherein tetrafluoroethylene-based polymer particles and aromatic resin varnish are placed in a cylindrical stirring tank of a stirrer equipped with a rotating part having a cylindrical part with a plurality of holes formed therein and rotating inside the inner wall surface of the stirring tank, and the mixture is stirred while being spread into a thin cylindrical film on the inner wall surface of the stirring tank by centrifugal force caused by the rotation of the rotating part, thereby obtaining a liquid composition containing the tetrafluoroethylene-based polymer and the aromatic resin.

3. The method according to claim 2, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer having an oxygen-containing polar group containing a unit based on perfluoro(alkyl vinyl ether).

4. 4. The method according to claim 2, wherein the ratio of the mass of the tetrafluoroethylene-based polymer particles to the mass of the aromatic resin is 0.5 to 10.

5. 2. The manufacturing method according to claim 1, wherein tetrafluoroethylene-based polymer particles, an aromatic resin, at least one thickening polymer selected from the group consisting of polar vinyl-based polymers and polysaccharides, and water are mixed in a tank equipped with a stirring mechanism based on thin film rotation or a stirring mechanism based on rotation and revolution to obtain a liquid composition containing the tetrafluoroethylene-based polymer particles, the aromatic resin, the thickening polymer, and the water.

6. The manufacturing method according to claim 5, wherein the tetrafluoroethylene-based polymer particles, the aromatic resin, the thickening polymer, and the water are mixed in a tank equipped with a stirring mechanism based on thin film rotation or a stirring mechanism based on rotation and revolution, and further mixed with water to obtain the liquid composition.

7. The method according to claim 5 or 6, wherein the particles of the tetrafluoroethylene-based polymer include particles of a heat-fusible tetrafluoroethylene-based polymer and particles of a non-heat-fusible tetrafluoroethylene-based polymer.

8. The method according to any one of claims 5 to 7, wherein the aromatic resin is an aromatic polyimide, an aromatic polyamideimide, an aromatic polyetherimide, or a precursor thereof.

9. The method according to any one of claims 5 to 8, further comprising mixing the inorganic particles in a tank equipped with a stirring mechanism based on thin film rotation or a stirring mechanism based on rotation and revolution to obtain the liquid composition.

10. A method for producing a liquid composition, comprising: mixing, by thin film swirling, particles of a tetrafluoroethylene-based polymer, the particles having an average particle size (D50) of 0.1 to 25 μm and being a polymer containing tetrafluoroethylene units and units based on perfluoro(alkyl vinyl ether) or a polymer containing tetrafluoroethylene units and units based on hexafluoropropylene; inorganic particles having a new Mohs hardness of 12 or less, the particles being boron nitride particles or silica particles; and a liquid compound, to obtain a liquid composition having a viscosity of 10,000 mPa·s or less, the liquid composition containing the particles of the tetrafluoroethylene-based polymer, the inorganic particles, and the liquid compound.

11. The production method according to claim 10, wherein the particles of the tetrafluoroethylene-based polymer include particles of a heat-fusible tetrafluoroethylene-based polymer and particles of a non-heat-fusible tetrafluoroethylene-based polymer.

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