JP2022061412A - Production method of liquid composition and production method of laminate - Google Patents

Abstract

To provide a production method of a liquid composition which includes particles of a tetrafluoroethylene-based polymer and another resin or an inorganic filler and which has excellent liquid physical properties, and to provide a production method of a laminate which is highly provided with physical properties of the tetrafluoroethylene-based polymer and the other resin or the inorganic filler.SOLUTION: In a production method of a liquid composition, a dispersion including particles comprising a tetrafluoroethylene-based polymer, a silane coupling agent, and a liquid dispersion medium is subjected to a hydrolysis condition of the silane coupling agent and further is mixed with an additive comprising at least one other material selected from a group consisting of another resin and another inorganic filler. In a production method of a laminate, the laminate having a substrate layer and a polymer layer is obtained by applying the liquid composition to a surface of the substrate layer and heating.SELECTED DRAWING: None

Description

The present invention has a method for producing a liquid composition containing particles containing a tetrafluoroethylene polymer and another resin or an inorganic filler, and advanced physical properties of the tetrafluoroethylene polymer and another resin or an inorganic filler. The present invention relates to a method for producing a laminate provided in the above.

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. There is. As a coating agent used to impart the above physical properties to the surface of a base material, a dispersion liquid containing particles of a tetrafluoroethylene polymer is known.
On the other hand, since the surface tension of the tetrafluoroethylene polymer is low, the dispersion liquid containing the particles has low dispersion stability.
Patent Document 1 describes a dispersion liquid containing a predetermined dispersant in order to improve the dispersion stability of the particles of the tetrafluoroethylene polymer. Patent Document 2 describes composite particles having silica on the surface of the particles of polytetrafluoroethylene.

Japanese Unexamined Patent Publication No. 2011-225710 International Publication No. 2018/21279

However, the dispersion stability of the dispersion liquid containing the tetrafluoroethylene polymer is still insufficient. Further, when another functional material is blended with the dispersion liquid in order to obtain a more highly functional molded product from the dispersion liquid, not only the blendability itself is low, but also foaming and thickening due to aggregation and alteration of the components are performed. The present inventors have found that it is difficult to obtain a sufficient molded product due to such factors.
The present inventors have studied diligently, and after hydrolyzing the silane coupling agent in a dispersion liquid containing particles containing a tetrafluoroethylene polymer and a silane coupling agent, the liquid is mixed with other functional materials. It was found that a liquid composition having excellent physical properties can be directly obtained.

Further, from such a liquid composition, it is possible to form a dense molded product having highly possessed physical properties of the tetrafluoroethylene polymer and other functional materials, particularly low dielectric loss tangent property and low line expansion property. It was found that an excellent molded product can be obtained.
An object of the present invention is to provide a liquid composition having excellent liquid properties, and to provide a laminate having excellent physical properties obtained from such a liquid composition.

The present invention has the following aspects.
[1] A group consisting of particles containing a tetrafluoroethylene polymer, a dispersion liquid containing a silane coupling agent and a liquid dispersion medium, subject to conditions under which the silane coupling agent is hydrolyzed, and then another resin and an inorganic filler. A method for producing a liquid composition, which comprises mixing with an additive containing at least one other material selected from the above to obtain a liquid composition.
[2] The method for producing [1], wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer having a melting temperature of 200 to 325 ° C.
[3] The method for producing [1] or [2], wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer having an oxygen-containing polar group.
[4] The production method according to any one of [1] to [3], wherein the particles further contain an inorganic substance.
[5] The method for producing [4], wherein the particles are composite particles having the tetrafluoroethylene polymer as a core and the inorganic substance on the surface of the core.
[6] The production method according to [5], wherein the core of the tetrafluoroethylene polymer and the inorganic substance in the composite particles are each in the form of particles, and the average particle size of the core is larger than the average particle size of the inorganic substance.
[7] The silane coupling agent is a compound having a trialkoxysilyl group, a phenyl group, a vinyl group, an epoxy group, an acryloyloxy group, a methacryloyloxy group, an amino group, a ureido group, a mercapto group or an isocyanate group. , [1] to any one of [6].
[8] The production method according to any one of [1] to [7], wherein the liquid dispersion medium is at least one aprotic liquid dispersion medium selected from the group consisting of amides, ketones and esters.
[9] The production method according to any one of [1] to [8], wherein the content of the particles in the dispersion is 20 to 60% by mass.
[10] Any of [1] to [9], wherein the ratio of the content of the silane coupling agent to the content of the particles in the dispersion liquid by mass is 0.01 to 0.1. Production method.
[11] The production method according to any one of [1] to [10], wherein the other resin is an aromatic resin or a fluororesin, and the inorganic filler is an inorganic filler containing silica or boron nitride.
[12] The production method according to any one of [1] to [11], wherein the ratio of the content of the other material to the content of the tetrafluoroethylene polymer by mass is 0.01 or more.
[13] The production method according to any one of [1] to [12], wherein the additive is liquid.
[14] The production method according to any one of [1] to [13], wherein the liquid composition has a component dispersion layer ratio of 60% or more.
[15] The liquid composition obtained by any of the production methods of [1] to [14] is applied to the surface of the base material layer and heated to form a polymer layer, and the base material layer and the polymer layer are formed. A method for manufacturing a laminated body, which obtains a laminated body having the above in this order.

According to the present invention, a liquid composition containing particles containing a tetrafluoroethylene polymer and another resin or an inorganic filler and having excellent liquid physical characteristics can be easily produced. Further, from the liquid composition, a dense laminated body having highly possessed physical properties of the tetrafluoroethylene polymer and another resin or inorganic filler (particularly, excellent in low dielectric loss tangent property and low linear expansion coefficient property). It is possible to manufacture a molded product such as a laminated body.

The following terms have the following meanings.
The "glass transition point (Tg) of the polymer" is a value measured by analyzing the polymer by the dynamic viscoelasticity measurement (DMA) method.
The “polymer melting temperature (melting point)” is the temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
"D50" is an average particle diameter of particles, inorganic substances or fillers, and is a volume-based cumulative 50% diameter of an object determined by a laser diffraction / scattering method. That is, the particle size distribution of the object is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the group of objects as 100%, and the particle size at the point where the cumulative volume is 50% on the cumulative curve. be.
“D90” is the cumulative volume particle size of particles, inorganic substances or fillers, and is the volume-based cumulative 90% diameter of the object obtained in the same manner as in “D50”.
The "specific surface area" is a value calculated by measuring particles by a gas adsorption (constant volume method) BET multipoint method, and is obtained by using NOVA4200e (manufactured by Quantachrome Instruments).
The "viscosity" is a value measured for a dispersion liquid or a liquid composition using a B-type viscometer under the condition of a rotation speed of 30 rpm at room temperature (25 ° C.). The measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
The "monomer-based unit" means an atomic group based on the monomer formed by polymerization of the monomer. The unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by processing a polymer. Hereinafter, the unit based on the monomer a is also simply referred to as “monomer a unit”.
The "component dispersion layer ratio" is the height of the entire liquid composition in the screw tube before and after standing when 18 mL of the liquid composition is placed in a screw tube having an internal volume of 30 mL and allowed to stand at 25 ° C. for 14 days. It is a value calculated by the following formula from the height of the dispersion layer and the height of the dispersed layer. If the component dispersion layer is not confirmed after standing and the state does not change, it is assumed that the height of the entire liquid composition does not change, and the component dispersion layer ratio is 100%. The larger the component dispersion layer ratio, the better the dispersion stability.
Component dispersion layer ratio (%) = (height of dispersion layer) / (height of the entire liquid composition) × 100

The production method of the present invention (hereinafter, also referred to as "this method") includes particles containing a tetrafluoroethylene polymer (hereinafter, also referred to as "F polymer") (hereinafter, also referred to as "F particles"), and silane. Additives containing at least one other material selected from the group consisting of other resins and inorganic fillers after subjecting the dispersion containing the coupling agent and the liquid dispersion medium to conditions under which the silane coupling agent is hydrolyzed. This is a method for obtaining a liquid composition (hereinafter, also referred to as “the present composition”) by mixing with.
According to this method, the present composition having excellent liquid physical characteristics (dispersion stability, homogeneity, coatability, etc.) containing F particles and another resin or inorganic filler can be easily and directly produced. Further, from this composition, it is possible to produce a molded product such as a dense laminated body having highly possessed physical characteristics of each of the F polymer and other resin or inorganic filler. Such a molded product is particularly excellent in low dielectric loss tangent property and low linear expansion coefficient property. The reason is not always clear, but it can be considered as follows.

In this method, the silane coupling agent is hydrolyzed in the dispersion liquid containing F particles, and then the dispersion liquid and another material (other resin or inorganic filler) are mixed. The silane coupling agent, which can be regarded as amphipathic, is in a state of easily interacting with the surface of F particles in the dispersion liquid.
It is considered that when the silane coupling agent is hydrolyzed in such a state, the condensate is formed around the F particles, and the surface of the F particles is highly surface-treated with the condensate. The surface-treated F particles are further enhanced in dispersion stability, stress resistance (particularly, shear resistance) and affinity with other materials, and the powder dynamic friction angle of the F particles is increased. It is considered that these factors improve the liquid properties of the dispersion liquid.
As a result, it is considered that the present composition can be obtained even if the dispersion liquid and other materials are directly mixed, and then a molded product having the physical characteristics of the tetrafluoroethylene polymer and the physical characteristics of other materials can be formed. Be done.

The dispersion liquid in this method contains F particles containing an F polymer, a silane coupling agent, and a liquid dispersion medium.
The F polymer in this method is a polymer containing a unit (TFE unit) based on tetrafluoroethylene (TFE).
The fluorine content of the F polymer is preferably 70 to 76% by mass. Even in such an F polymer having a high fluorine content and a remarkably low surface tension, according to this method, a liquid composition having excellent liquid physical characteristics can be obtained by the above-mentioned action mechanism.

The F polymer may be heat-meltable or non-heat-meltable. The melting temperature of the heat-meltable F polymer is preferably 200 ° C. or higher, 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. In such a case, the present composition tends to have excellent liquid physical characteristics, and it is easy to form a dense molded product from the present composition.
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.

F-polymers are based on polytetrafluoroethylene (PTFE), polymers containing TFE units and ethylene-based units, polymers containing TFE units and propylene-based units, TFE units and perfluoro (alkyl vinyl ether) (PAVE). Polymers containing units (PAVE units) (PFA), polymers containing TFE units and units based on hexafluoropropylene (FEP), polymers containing TFE units and units based on fluoroalkylethylene, TFE units and chlorotrifluoro Examples thereof include polymers containing a unit based on ethylene, preferably PFA or FEP, and more preferably PFA. The polymer may further contain units based on other comonomeres.
As the PAVE, CF ₂ = CFOCF ₃ , CF ₂ = CFOCF ₂ CF ₃ or CF ₂ = CFOCF ₂ CF ₂ CF ₃ (hereinafter, also referred to as “PPVE”) is preferable, and PPVE is more preferable.

The PTFE may be a low molecular weight PTFE having a number average molecular weight of 10,000 to 200,000. The number average molecular weight of PTFE is a value calculated based on the following equation (1).
Mn = 2.1 × 10 ¹⁰ × ΔHc- ^5.16 ... (1)
In the formula (1), Mn indicates the number average molecular weight of PTFE, and ΔHc indicates the calorie of crystallization (cal / g) of PTFE measured by the differential scanning calorimetry method. The PTFE may contain a trace amount of units other than the TFE unit.

The F polymer preferably has an oxygen-containing polar group. Such an F polymer has excellent physical properties such as adhesiveness, and a liquid composition having excellent dispersion stability can be obtained.
The oxygen-containing polar group may be contained in the monomer unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer. Examples of the latter embodiment include an F polymer having the polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and a corona-treated, plasma-treated, ionizing-wire-treated, or radiation-treated F-polymer.
The oxygen-containing polar group is preferably a hydroxyl group-containing group or a carbonyl group-containing group, and a carbonyl group-containing group is particularly preferable.

The hydroxyl group-containing group is preferably a group containing an alcoholic hydroxyl group, more preferably -CF ₂ CH ₂ OH or -C (CF ₃ ) ₂ OH.
The carbonyl group-containing group is a group containing a carbonyl group (> C (O)), a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH ₂ ), and an acid anhydride residue. Group (-C (O) OC (O)-), imide residue (-C (O) NHC (O)-etc.) or carbonate group (-OC (O) O-) is preferred, and acid anhydride residue. Is more preferable.

The F polymer preferably contains PAVE units and 1.5 to 5 mol% of PAVE units with respect to all units and has a melting temperature of 280 to 320 ° C., preferably contains PAVE units and has an oxygen-containing polar group. A polymer (1) or a polymer (2) having no oxygen-containing polar group, which contains PAVE units and contains 2 to 5 mol% of PAVE units with respect to all monomer units, is more preferable. Since these polymers form microspherulites in the molded product, the characteristics of the molded product are likely to be improved.

The polymer (1) is preferably a polymer containing a TFE unit, a PAVE unit, and a monomer having a hydroxyl group-containing group or a carbonyl group-containing group. The polymer (1) has 90 to 98 mol% of TFE units, 1.5 to 9.97 mol% of PAVE units, and 0.01 to 3 mol% of units based on the above-mentioned monomers with respect to all the units. It is preferable to include it. The monomer is preferably itaconic anhydride, citraconic anhydride or 5-norbornen-2,3-dicarboxylic acid anhydride (also known as hymic anhydride; hereinafter also referred to as "NAH").
Specific examples of the polymer (1) include the polymers described in International Publication No. 2018/16644.

The polymer (2) is composed of only TFE units and PAVE units, and preferably contains 95 to 98 mol% of TFE units and 2 to 5 mol% of PAVE units with respect to all the monomer units.
The content of PAVE units in the polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, based on all the monomer units.

The polymer (2) does not have oxygen-containing polar groups when the number of oxygen-containing polar groups contained in the polymer is less than 500 per 1 × 10 ⁶ carbon atoms constituting the polymer main chain. It means that there is. The number of oxygen-containing polar groups is preferably 100 or less, more preferably less than 50. The lower limit of the number of oxygen-containing polar groups is usually 0.
The polymer (2) may be produced by using a polymerization initiator, a chain transfer agent, or the like that does not generate an atomic group containing an oxygen atom as a terminal group of the polymer chain, and may be an F polymer having an atomic group containing an oxygen atom. It may be manufactured by fluorination treatment. Examples of the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314).

The F particles in this method are particles containing an F polymer, may be particles consisting only of the F polymer, or may be particles containing the F polymer and another resin or inorganic filler different from the F polymer. good. The F particles (particularly, the former F particles) may contain components used in the production of the F polymer (residues of the surfactant, polymerization initiator, etc. used in the polymerization).
The content of the F polymer in the F particles is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more. The upper limit of the content of the F polymer is 100% by mass.

The D50 of the F particles is preferably 100 μm or less, more preferably 10 μm or less, further preferably 6 μm or less, and particularly preferably 3 μm or less. The D50 of the F particles is preferably 0.1 μm or more, more preferably 0.5 μm or more. The D90 of the F particles is preferably 100 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less. In this case, the present composition tends to be more excellent in liquid properties.
The specific surface area of the F particles is preferably 1 to 8 m ² / g, more preferably 1 to 3 m ² / g.

Examples of the resin different from the F polymer include aromatic polyimides, aromatic maleimides, aromatic elastomers such as styrene elastomers, and aromatic polyamic acids.
The inorganic substances are preferably oxides, nitrides, simple metals, alloys and carbons, and silicon oxide (silica) and metal oxides (berylium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.). , Boron nitride, and magnesium metasilicate (steatite) are more preferred, inorganic oxides containing at least one element selected from aluminum, magnesium, silicon, titanium, and zinc are even more preferred, and silica and boron nitride are particularly preferred. Preferably, silica is most preferred. Further, the inorganic substance may be ceramics. As the inorganic substance, one kind may be used, or two or more kinds may be mixed and used. When two or more kinds of inorganic substances are mixed, two kinds of silica may be used, or silica and a metal oxide may be used.

The inorganic substance is preferably in the form of particles, and the shape of the inorganic substance may be granular, needle-like (fibrous), or plate-like. Specific shapes of inorganic substances include spherical, scale-like, layered, flat plate-like, leaf-like, apricot kernel-like, columnar, chicken crown-like, equiaxed, leaf-like, mica-like, block-like, flat plate-like, wedge-like, and rosette-like. , Mesh, and prismatic. The inorganic substance may be hollow, or may contain a hollow inorganic substance and a non-hollow inorganic substance. The shape of the inorganic substance is preferably spherical or scaly.
The surface of the inorganic substance may be surface-treated with a silane coupling agent, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, It is more preferable that the surface is treated with 3-methacryloxypropyltriethoxysilane or 3-isocyanuppropyltriethoxysilane.

The F particles preferably contain an inorganic substance, and more preferably silica. In such a case, the above-mentioned mechanism of action is enhanced, and the physical characteristics of the obtained liquid composition are likely to be further improved.
The F particles containing an inorganic substance (hereinafter, also referred to as “composite particles”) have a particulate F polymer as a core, and the particulate inorganic substance is attached to the surface of the core of the F polymer (hereinafter, “Aspect I”). It is also preferable that the particle-like inorganic substance is used as the core and the particulate or non-particle-like F polymer is attached to the surface of the inorganic substance, and the embodiment I is more preferable. In the case of the aspect I, it can be said that the surface of the F polymer is covered with an inorganic substance, the F particles are not easily deteriorated, and the dispersion stability is easily excellent. Here, the "core" means a core (central part) necessary for forming the particle shape of the composite particle, and does not mean the main component in the composition of the composite particle.

The inorganic substance adhering to the surface of the core may be adhering only to a part of the surface of the core, or may be adhering to most or the entire surface thereof. In the former case, it can be said that the inorganic substance clings to the surface of the core like dust, in other words, a large part of the surface of the core is exposed. In the latter case, it can be said that the inorganic substance is evenly sprinkled on the surface of the core or is in a state of covering the surface of the core, and such composite particles consist of a core and a shell covering the core. It can be said that it has a core-shell structure.

In the case of Aspect I, the core of the F polymer is preferably composed of a single particle of the F polymer or an aggregate of particles of the F polymer. For the composite particles of the aspect I, it is preferable to set the D50 of the core of the F polymer to be larger than the D50 of the inorganic substance, and to set the amount of the F polymer to be larger than that of the inorganic substance.
In the case of the aspect I, the D50 of the core of the F polymer is preferably 0.1 μm or more, more preferably 1 μm or more. The D50 of the core of the F polymer is preferably 50 μm or less, more preferably 10 μm or less.
In the case of the aspect I, the D50 of the inorganic substance is preferably 0.01 μm or more, more preferably 0.02 μm or more. The inorganic D50 is preferably 20 μm or less, more preferably 10 μm or less, further preferably 1 μm or less, and particularly preferably 0.1 μm or less.

In the composite particles of aspect I, the D50 of the core of the F polymer is preferably larger than the inorganic D50. The D50 of the core of the F polymer is preferably 2 to 1000, more preferably 5 to 100, based on the inorganic D50.
The D50 of the composite particle of the aspect I is preferably 50 μm or less, more preferably 10 μm or less. The D50 of the composite particle of the aspect I is preferably 0.1 μm or more, and more preferably 1 μm or more.
The amount of the inorganic substance in the composite particle of the aspect I is preferably 1 part by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the F polymer. The amount of the inorganic substance is preferably 60 parts by mass or less, more preferably 40 parts by mass or less.
Further, the inorganic substance may be embedded in the core of the F polymer.

The composite particles are a method of colliding F polymer particles and an inorganic substance at a temperature equal to or higher than the melting temperature of the F polymer and in a suspended state, a method of colliding the F polymer particles and an inorganic substance in a pressed or sheared state, and F. It is preferable to produce a liquid composition containing polymer particles and an inorganic substance by a method of shearing the F polymer particles to coagulate them.

The silane coupling agent in this method is a compound having a hydrolyzable silyl group and an organic group, and is a trialkoxysilyl group, a phenyl group, a vinyl group, an epoxy group, an acryloyloxy group, a methacryloyloxy group, an amino group, and the like. A compound having a ureido group, a mercapto group or an isocyanate group is preferable, and a compound having a trialkoxysilyl group and an amino group is more preferable.
The thermal decomposition temperature of the silane coupling agent is preferably 200 ° C. or higher, more preferably 300 ° C. or higher. The upper limit of the thermal decomposition temperature is preferably 400 ° C. In this case, the molded product formed from the present composition tends to have excellent heat resistance. The thermal decomposition temperature of the silane coupling agent is a temperature at which the mass of the silane coupling agent becomes 50% at the start of temperature increase when the temperature of the silane coupling agent is raised from 50 ° C. to 400 ° C. at 5 ° C./min. Is.

Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, and vinyl. Trimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane , 3-Methoxyloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acrylicoxyoxypropyltrimethoxysilane, n-phenyl-3-aminopropyltrimethoxysilane.

The liquid dispersion medium in this method is a liquid compound that does not react with the F polymer. The boiling point of the liquid dispersion medium is preferably 75 ° C. or higher, more preferably 100 ° C. or higher. The boiling point of the liquid dispersion medium is preferably 300 ° C. or lower, more preferably 250 ° C. or lower.
The liquid dispersion medium is preferably an aprotic liquid dispersion medium, more preferably at least one aprotic liquid dispersion medium selected from the group consisting of amides, ketones and esters, and N-methyl-2-pyrrolidone and γ-butyrolactone. , Cyclohexanone or cyclopentanone is more preferred.
The liquid dispersion medium may be one kind or a mixture of two or more kinds. The liquid dispersion medium is preferably degassed from the viewpoint of reducing the uniformity of the component distribution of the molded product obtained from the present composition and suppressing voids.

The dispersion further preferably contains organosilazane. In this case, the liquid physical characteristics of the present composition are likely to be improved. As the organosilazane, tetramethyldisilazane, hexamethyldisilazane, and pentamethyldisilazane are preferable.
The organosilazane may be mixed with the dispersion liquid after subjecting the dispersion liquid to conditions under which the silane coupling agent hydrolyzes.
From the viewpoint of controlling the reaction of the silane coupling agent, the dispersion liquid may further contain stabilizers such as 3,5-dibutyl-4-hydroxytoluene and p-methoxyphenol.

The content of F particles in the dispersion is preferably 20% by mass or more, more preferably 30% by mass or more. The content is preferably 60% by mass or less, more preferably 50% by mass or less.
Due to the above-mentioned mechanism of action, according to this method, it is easy to directly obtain the present composition having excellent liquid characteristics even from a dispersion liquid having a high content of F particles.
The content of the silane coupling agent in the dispersion is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more. The content is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less.

The ratio of the content of the silane coupling agent to the content of the F particles in the dispersion liquid is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.05 or more. The above ratio is preferably 0.3 or less, more preferably 0.1 or less.
When the content of the silane coupling agent or the above ratio (mass ratio) is in such a range, the above-mentioned mechanism of action is further enhanced, and the present composition having excellent liquid characteristics can be easily obtained directly.
The content of the liquid dispersion medium in the dispersion is preferably 30 to 80% by mass, more preferably 40 to 70% by mass.

The viscosity of the dispersion at 25 ° C. is preferably 10 to 10000 mPa · s, more preferably 50 to 5000 mPa · s. The thixotropy of the dispersion is preferably 1 to 2.5, more preferably 1.2 to 2. In this case, the physical characteristics of the obtained composition are likely to be further improved.
The dispersion is obtained by mixing F particles, a silane coupling agent, and a liquid dispersion medium. The dispersion is preferably obtained by mixing a mixture of F particles and a liquid dispersion medium with a silane coupling agent.

Additives in this method include at least one other material selected from the group consisting of other resins and inorganic fillers. The other material contained in the additive may be only another resin, only an inorganic filler, or both other resin and an inorganic filler.
The additive may be liquid or powdery, and is preferably liquid.
When the additive is liquid, the other resin or inorganic filler may be dissolved in the additive or dispersed in the form of particles. When dispersed in the form of particles, the D50 is preferably smaller than the D50 of the F particles. In this case, the above-mentioned mechanism of action is enhanced, and the physical characteristics of the obtained composition are likely to be further improved.
When the additive is liquid, the additive preferably contains a liquid dispersion medium. Examples of the liquid dispersion medium include the same liquid dispersion medium as the liquid dispersion medium in the above-mentioned dispersion liquid.
When the additive is in the form of powder, its D50 is preferably smaller than the D50 of the F particles. In this case, the above-mentioned mechanism of action is enhanced, and the physical characteristics of the obtained composition are likely to be further improved.

The other resin in this method may be a thermosetting resin or a thermoplastic resin. Other resins are preferably aromatic resins and fluororesins.
Other resins include aromatic polyimide, aromatic polyamic acid, aromatic maleimide, acrylic resin, phenol resin, liquid crystal polyester, liquid crystal polyesteramide, polyolefin resin, modified polyphenylene ether, polyfunctional cyanate ester resin, and polyfunctional. Maleimide-Cyanic acid ester resin, polyfunctional maleimide, aromatic elastomer such as styrene elastomer, vinyl ester resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine-urea cocondensation resin, polycarbonate, polyallylate, Examples thereof include polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, polyphenylene ether, epoxy resin, and fluororesin. Since the dispersion has excellent blending properties, the present composition tends to have excellent liquid properties even when it contains such other resins.

The other resin is preferably an aromatic resin or a fluororesin.
The aromatic resin is preferably aromatic polyimide, aromatic maleimide, polyphenylene ether, aromatic polyamic acid, liquid crystal aromatic polyester or aromatic elastomer (styrene elastomer or the like).
The fluororesin may be an F polymer or a fluororesin other than the F polymer. As the fluororesin, F polymer is preferable. In such a case, it is easy to form a molded product having excellent electrical characteristics from the present composition.

The inorganic filler is preferably an inorganic filler containing an oxide, a nitride, a simple substance of a metal, an alloy and carbon, and is preferably silicon oxide (silica), a metal oxide (berylium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, etc. Inorganic fillers containing (titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite) are more preferred, and include inorganic oxides containing at least one element selected from aluminum, magnesium, silicon, titanium, and zinc. Inorganic fillers are more preferred, inorganic fillers containing silica and boron nitride are particularly preferred, and inorganic fillers containing silica are most preferred. Further, the inorganic filler may be ceramics. As the inorganic substance, one kind may be used, or two or more kinds may be mixed and used. When two or more kinds of inorganic fillers are mixed, an inorganic filler containing two kinds of silica may be used, or an inorganic filler containing silica and a metal oxide may be used.

The inorganic filler is preferably in the form of particles, and the shape of the inorganic filler may be granular, needle-like (fibrous), or plate-like. Specific shapes of the inorganic filler include spherical, scale-like, layered, flat plate-like, leaf-like, apricot kernel-like, columnar, chicken crown-like, equiaxed, leaf-like, mica-like, block-like, flat plate-like, wedge-like, and rosette. Examples include shape, mesh, and prismatic shape. The inorganic filler may be hollow, or may contain a hollow inorganic filler and a non-hollow inorganic filler. The shape of the inorganic filler is preferably spherical or scaly.
The D50 of the inorganic filler is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 1 μm or less. The D50 of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more.

Suitable specific examples of the inorganic filler are silica filler (“Admafine (registered trademark)” series manufactured by Admatex Co., Ltd.), zinc oxide surface-treated with an ester such as propylene glycol dicaprate (Sakai Chemical Industry Co., Ltd.). "FINEX (registered trademark)" series, etc.), spherical fused silica ("SFP (registered trademark)" series, etc. manufactured by Denka Co., Ltd.), titanium oxide coated with polyhydric alcohol and inorganic substances (manufactured by Ishihara Sangyo Co., Ltd.) "Typake (registered trademark)" series, etc.), rutile-type titanium oxide surface-treated with alkylsilane ("JMT (registered trademark)" series manufactured by Teika, etc.), hollow silica filler ("E" manufactured by Pacific Cement Co., Ltd.) -SPHERES "series, Nittetsu Mining Co., Ltd." Sirinax "series, Emerson & Cumming Co., Ltd." Ecocos Fire "series, etc.), Tarkufiller (Nippon Tarku Co., Ltd." SG "series, etc.), Steatite Filler (Steatite Filler) "BST" series manufactured by Nippon Tark Co., Ltd.), boron nitride filler ("UHP" series manufactured by Showa Denko Co., Ltd., "Denca Boron Night Ride" series manufactured by Denka Co., Ltd. ("GP", "HGP" grade), etc.) Can be mentioned.

The surface of the inorganic filler may be surface-treated with a silane coupling agent. Examples of the silane coupling agent include the above-mentioned silane coupling agent.
The content of the other material in the additive is preferably 10% by mass or more, more preferably 20% by mass or more. The content is preferably 100% by mass or less.

In this method, the dispersion is subjected to conditions under which the silane coupling agent is hydrolyzed (hereinafter, also referred to as “hydrolyzed conditions”), and then mixed with an additive containing other materials to form the present composition. To get.
The mixing in this method may be carried out at the stage where the silane coupling agent is partially hydrolyzed, or may be carried out at the stage where the silane coupling agent is completely hydrolyzed. That is, the mixing may be performed at the stage where the hydrolysis of the silane coupling agent is in progress.

The hydrolysis conditions are not particularly limited as long as they allow an effective amount of proton source to exist in the dispersion liquid, and are preferably conditions in which an effective amount of water or protonic acid is present in the dispersion liquid.
The water content of the dispersion is preferably 20 ppm or more, more preferably 100 ppm or more. The water content is preferably 200,000 ppm or less, more preferably 20,000 ppm or less. The water content of the dispersion may be adjusted by using water as the liquid dispersion medium, or may be adjusted by the amount of water contained in the liquid dispersion medium other than water or the F particles, and is used when preparing the dispersion. It may be adjusted from the water content (humidity) of the atmosphere, or may be adjusted from the water content (humidity) of the atmosphere under the hydrolysis conditions.

The pH of the dispersion under the hydrolysis conditions is preferably 1 to 7, more preferably 1 to 5. The pH may be adjusted with a protonic acid (organic acid such as carboxylic acid, inorganic acid such as hydrochloric acid and sulfuric acid).
Further, the hydrolysis conditions and the reaction rate of hydrolysis of the silane coupling agent may be adjusted by adjusting the temperature or using a catalyst. Further, when a commercially available silane coupling agent is used, the stabilizer contained therein may be removed or deactivated to adjust the reaction rate of hydrolysis of the silane coupling agent.

The temperature of the dispersion under the hydrolysis conditions is preferably 30 ° C. or higher, more preferably 40 ° C. or higher. The temperature is preferably lower than the decomposition temperature of the silane coupling agent and lower than the boiling point of the liquid dispersion medium, and more preferably 200 ° C. or lower.
It is also considered that the F particles contained in the dispersion liquid after being subjected to the hydrolysis conditions are in a state of being surface-treated with a silane coupling agent by the above-mentioned mechanism of action. Therefore, if the liquid dispersion medium is removed from the dispersion liquid, F particles surface-treated with a silane coupling agent can be obtained.

The mixing in this method may be carried out by adding an additive containing other materials to the dispersion liquid subjected to the hydrolysis conditions, or by adding the dispersion liquid subjected to hydrolysis to the additive containing other materials. May be good. According to this method, the present composition having excellent liquid characteristics can be easily obtained by the above-mentioned mechanism of action regardless of the mixing mode.
Further, in the mixing, the dispersion liquid subjected to the hydrolysis conditions may be mixed with the additive containing other materials as it is, and a part of the above dispersion liquid (liquid dispersion medium, silane cup such as alcohol accompanying hydrolysis) may be mixed. After removing the residue of the ring agent, etc.), it may be mixed with an additive containing other materials.

In the mixing, the ratio (mass ratio) of the mass of the additive containing other materials to the mass of the dispersion liquid is preferably 0.01 or more, more preferably 0.01 or more. The above ratio is preferably 3 or less, more preferably 1 or less.
Further, in the mixing, the ratio of the content of F particles in the dispersion to the content of other materials in the composition by mass is preferably 0.01 or more, more preferably 0.1 or more. The above ratio is preferably 3 or less, more preferably 1 or less.
When any of these ratios (mass ratio) is within such a range, the above-mentioned mechanism of action is enhanced, and the present composition having excellent liquid physical characteristics can be easily obtained directly.

The hydrolysis conditions and mixing in this method are preferably carried out under stirring.
For stirring, a mixer with a stirring blade, a Henschel mixer, a ribbon blender, a swing type mixer, a vibration type mixer, a rotary type mixer and the like can be used, and specifically, a homodisper, a homogenizer, a ball mill and the like can be used.
The hydrolysis conditions and mixing may be either batch type or continuous type. For the batch type, it is preferable to use a Henschel mixer, a pressurized kneader, a Banbury mixer or a planetary mixer.

This composition is a liquid composition containing F particles, other materials, and a liquid dispersion medium, which is obtained by subjecting the dispersion liquid to hydrolysis conditions and then mixing it as an additive containing other materials. It is also considered that the F particles in the present composition are in a state of being surface-treated with a silane coupling agent. Therefore, by removing the liquid dispersion medium from the present composition, it is possible to obtain a composite powder in which F particles and other materials are highly composited and integrated.

The content of the F polymer in the present composition is preferably 10% by mass or more, more preferably 20% by mass or more. The content of the F polymer is preferably 70% by mass or less, more preferably 50% by mass or less.
The content of the other material in the present composition is preferably 0.1% by mass or more, more preferably 1% by mass or more. The content of the other material is preferably 50% by mass or less, more preferably 40% by mass or less.
The ratio of the content of the F polymer to the content of the other material in the present composition by mass is preferably 0.01 or more, more preferably 0.1 or more. The ratio of the contents of other materials by mass is preferably 3 or less, and more preferably 1 or less. In this case, the liquid physical characteristics of the obtained composition are likely to be improved.
The content of the liquid dispersion medium in the present composition is preferably 30 to 80% by mass, more preferably 40 to 70% by mass.

The viscosity of the present composition at 25 ° C. is preferably 10 to 10000 mPa · s, more preferably 50 to 5000 mPa · s. The thixotropy of the present composition is preferably 1 to 2.5, more preferably 1.2 to 2. In this case, the physical characteristics of the obtained composition are likely to be improved.
The component dispersion layer ratio of the present composition is preferably 60% or more, more preferably 70% or more. The upper limit of the component dispersion layer ratio is 100%. Since the present composition is excellent in dispersion stability, it is easy to adjust the component dispersion layer ratio.

The dispersion liquid, the additive or the present composition in this method may further contain a surfactant from the viewpoint of improving dispersibility. The surfactant is preferably nonionic. Examples of the surfactant include an acetylene-based surfactant, a silicone-based surfactant, and a fluorine-based surfactant. When a surfactant is contained, the content of the surfactant in the dispersion liquid, the additive or the present composition is preferably 1 to 15% by mass.
Further, the dispersion liquid, the additive and the present composition in this method further use a thioxogenic agent, a viscosity modifier, a defoaming agent, a dehydrating agent, a plasticizer, a weather resistant agent, an antioxidant, a heat stabilizer, and a lubricant. , Antistatic agent, whitening agent, colorant, conductive agent, mold release agent, surface treatment agent, flame retardant.

When the present composition is applied to the surface of the base material and heated to form a polymer layer, the laminate having the base material layer and the polymer layer (hereinafter, also referred to as “F layer”) in this order can get.
As the base material layer, a metal substrate (copper, nickel, aluminum, titanium, metal foil such as an alloy thereof, etc.), a heat-resistant resin film (polyimide, polyarylate, polysulfone, polyallylsulfone, polyamide, polyetheramide, polyphenylene, etc.) A film containing one or more of heat-resistant resins such as sulfide, polyallyl ether ketone, polyamideimide, liquid crystal polyester, and liquid crystal polyester amide, which may be a single-layer film or a multilayer film), prepreg (fiber). A precursor of a reinforced resin substrate).

As a method of applying the present composition to the surface of the base material layer, any method may be used as long as a stable liquid film (wet film) composed of the present composition is formed on the surface of the base material layer, and a coating method or a droplet is used. Examples thereof include a discharge method and a dipping method, and a coating method is preferable.
When the liquid film is dried, the liquid film is heated at a temperature at which the liquid dispersion medium volatilizes to form a dry film on the surface of the substrate. The heating temperature is preferably not more than the boiling point of the liquid dispersion medium, and more preferably not more than the boiling point of −20 ° C. The specific temperature during drying is preferably 80 ° C to 200 ° C. Air may be blown in the step of removing the liquid dispersion medium.
At the time of drying, the liquid dispersion medium does not necessarily have to be completely volatilized, and may be volatilized to the extent that the layer shape after holding is stable and the self-supporting film can be maintained.

The temperature at the time of heating is preferably a temperature at which the firing of the F polymer proceeds, and more preferably 380 ° C. or lower.
The 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.), and 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.

The thickness of the F layer is preferably 0.1 to 150 μm. Specifically, when the base material layer is a metal foil, the thickness of the F layer is preferably 1 to 30 μm. When the base material layer is a heat-resistant resin film, the thickness of the F layer is preferably 1 to 150 μm.
The peel strength between the F layer and the base material 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 this composition, a laminate can be easily formed without impairing the physical characteristics of the F polymer in the F layer.

The present composition may be applied to only one surface of the base material layer, or may be applied to both sides of the base material layer. In the former, a base material layer and a laminate having an F layer on one surface of the base material layer are obtained, and in the latter, a laminate having an F layer on both the surfaces of the base material layer and the base material layer is obtained. Be done. Since the latter laminated body is less likely to warp, it is excellent in handleability during its processing.
Specific examples of such a laminate include a metal foil, a metal-clad laminate having an F layer on at least one surface of the metal foil, a polyimide film, and a multilayer film having an F layer on both surfaces of the polyimide film. Can be mentioned.

Since such a laminate has an F layer having excellent electrical characteristics, it is suitable as a printed circuit board material, and specifically, it can be used as a flexible metal-clad laminate or a rigid metal-clad laminate for manufacturing a printed circuit board, and is particularly flexible. It can be suitably used for manufacturing a flexible printed circuit board as a metal-clad laminate.
In the manufacture of such a printed circuit board, an interlayer insulating film may be formed on the transmission circuit, a solder resist may be laminated on the transmission circuit, or a coverlay film may be laminated on the transmission circuit. These interlayer insulating films, solder resists and coverlay films may be formed of the present composition.

Such laminates are useful as antenna parts, printed substrates, aircraft parts, automobile parts, sports equipment, food industry supplies, paints, cosmetics, etc., and specifically, wire coating materials (aircraft wires, etc.), Electrical insulating tape, insulating tape for oil drilling, material for printed substrate, separation membrane (precision filtration membrane, ultrafiltration membrane, reverse osmosis membrane, ion exchange membrane, dialysis membrane, gas separation membrane, etc.), electrode binder (lithium II) Covers for next batteries, fuel cells, etc.), copy rolls, furniture, automobile dashboards, home appliances, etc., sliding members (load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, food transport belts, etc.) Etc.), tools (shovels, shavings, cuttings, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, dies, toilet bowls, container covering materials.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
1. 1. Preparation of each component [Particles]
Particle 1: From polymer 1 (melting temperature: 300 ° C.) containing 97.9 mol%, 0.1 mol%, 2.0 mol% of TFE unit, NAH unit and PPVE unit in this order and having an oxygen-containing polar group. Particles (D50: 2.1 μm)
Particle 2: A polymer 1 obtained by treating particles obtained by mixing 70 parts by mass of particles 1 and 30 parts by mass of spherical silica filler (D50: 250 nm) by a hybridization method is used as a core, and the surface of the core is covered with the above. Spherical composite particles (D50: 3 μm) with a core-shell structure in which a shell is formed by adhering silica filler.
Particle 3: Particles (D50: 1.8 μm) made of a polymer having no oxygen-containing polar group (melting temperature 305 ° C.) consisting of TFE units and PPVE units.
The hybridization method is a powder treatment method in which particles are agitated by a stirring blade that rotates at high speed in a cylindrical container, and the particles are sandwiched between the inner wall of the container and the stirring body to apply stress. It is a method of applying stress between them to composite different kinds of particles.

[Silane coupling agent]
Agent 1: Vinyltrimethoxysilane Agent 2: n-Phenyl-3-aminopropyltrimethoxysilane [Liquid dispersion medium]
NMP: N-methyl-2-pyrrolidone [inorganic filler]
Filler 1: Spherical silica filler (D50: 3 μm)
[Other resins]
Varnish 1: Varnish in which thermoplastic aromatic polyimide (PI1) is dissolved in NMP (PI1 content: 20% by mass)

2. 2. Preparation of liquid composition (Example 1)
50 parts by mass of particles 1, 5 parts by mass of agent 1 and 45 parts by mass of NMP were put into the tank, and the inside of the tank was stirred to prepare a dispersion liquid 1.
10 parts by mass of filler 1 and 90 parts by mass of varnish 1 were put into another tank, and the inside of the tank was stirred to prepare additive 1.
After confirming that the water content of the dispersion liquid 1 was adjusted to 8000 ppm, the temperature inside the tank was maintained at 60 ° C. while stirring the inside of the tank, and the agent 1 was hydrolyzed by a catalyst under acidic conditions.
Next, the composition 1 having the same mass as the dispersion liquid 1 in the tank was added to the tank and stirred to obtain a liquid composition 1.

(Example 2)
The liquid composition 2 was obtained in the same manner as in Example 1 except that the agent 2 was used instead of the agent 1.
(Example 3)
The liquid composition 3 was obtained in the same manner as in Example 1 except that the particles 2 were used instead of the particles 1.
(Example 4)
The liquid composition 4 was obtained in the same manner as in Example 1 except that the particles 3 were used instead of the particles 1 and the agent 2 was used instead of the agent 1.
(Example 5)
50 parts by mass of particles 3, 5 parts by mass of agent 2, 45 parts by mass of NMP, 10 parts by mass of filler 1 and 90 parts by mass of varnish 1 are put into a tank, and the mixture is stirred as it is to prepare the liquid composition 5. Obtained.

3. 3. Production of Laminate A liquid composition 1 was applied to the surface of a long copper foil (thickness 18 μm) using a bar coater to form a liquid film. Next, the copper foil on which the liquid film was formed was passed through a drying oven at 120 ° C. for 5 minutes and dried by heating to obtain a dry film. Then, the dry film was heated at 380 ° C. for 3 minutes in a nitrogen oven. As a result, a laminated body 1 having a copper foil and a polymer layer (thickness 10 μm) containing a melt-fired product of the polymer 1 on the surface thereof was manufactured.
Laminates 2 to 5 were produced in the same manner as the laminate 1 except that the liquid composition 1 was changed to each of the liquid compositions 2 to 5.

4. Evaluation 4-1. Dispersion stability of the liquid composition 18 mL each of the liquid compositions 1 to 5 was placed in a screw tube having an internal volume of 30 mL and allowed to stand at 25 ° C. for 14 days. From the total height of the liquid composition in the screw tube and the height of the component dispersion layer before and after standing, the component dispersion layer ratio was calculated by the following formula.
Component dispersion layer ratio (%) = (height of component dispersion layer) / (total height of liquid composition) × 100
When no sedimentation was confirmed after standing and there was no change in the state, it was assumed that there was no change in the overall height of the liquid composition, and the component dispersion layer ratio was set to 100%.
Then, the dispersion stability of the liquid composition was evaluated according to the following criteria.
[Evaluation criteria]
〇: The component dispersion layer ratio is 80% or more.
Δ: The component dispersion layer ratio is 60% or more and less than 80%.
X: The component dispersion layer ratio is less than 60%.

4-2. Linear expansion coefficient of polymer layer For each of the laminated bodies 1 to 5, the copper foil of the laminated body was removed by etching with an aqueous ferric chloride solution to prepare a single polymer layer.
A 180 mm square test piece was cut out from a single polymer layer, and the coefficient of linear expansion of the polymer layer was measured in the range of 25 ° C. or higher and 260 ° C. or lower by the measuring method specified in JIS C 6471: 1995.
Then, the coefficient of linear expansion of the polymer layer was evaluated according to the following criteria.
[Evaluation criteria]
◯: The coefficient of linear expansion of the polymer layer is 30 ppm / ° C. or less.
X: The coefficient of linear expansion of the polymer layer is more than 30 ppm / ° C.

4-3. Electrical Characteristics of Polymer Layer For each of the laminated bodies 1 to 5, the copper foil of the laminated body was removed by etching with an aqueous ferric chloride solution to prepare a single polymer layer.
The dielectric loss tangent (measurement frequency: 10 GHz) of the polymer layer was measured by the SPDR (split post dielectric resonance) method.
Then, the electrical properties of the polymer layer were evaluated according to the following criteria.
[Evaluation criteria]
◯: The dielectric loss tangent of the polymer layer is less than 0.0010.
Δ: The dielectric loss tangent of the polymer layer is 0.0010 or more and 0.0025 or less.
X: The dielectric loss tangent of the polymer layer is more than 0.0025.

The results of each evaluation are summarized in Table 1 below.

The liquid composition of the present invention has excellent liquid physical properties, and has physical properties based on a tetrafluoroethylene polymer and properties based on an inorganic filler or other resin (film, impregnated material such as prepreg, laminated board, etc.). ) Can be used for manufacturing. The laminate produced by the present invention is useful as antenna parts, printed boards, aircraft parts, automobile parts, sports equipment, food industry supplies, heat dissipation parts paints, cosmetics, etc., and specifically, wire covering materials. (Air wires, etc.), enamel wire coating materials used for motors of electric vehicles, etc., electrical insulating tapes, insulating tapes for oil drilling, materials for printed boards, separation membranes (precision filtration membranes, ultrafiltration membranes, etc.) Reverse permeation membrane, ion exchange membrane, dialysis membrane, gas separation membrane, etc.), electrode binder (for lithium secondary batteries, fuel cells, etc.), copy rolls, furniture, automobile dashboards, covers for home appliances, sliding members, etc. (Load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, food transport belts, etc.), tools (shovels, shavings, cuttings, saws, etc.), tension ropes, structural members, oil drilling equipment, oil transportation hoses , Sporting goods, boilers, hoppers, pipes, ovens, baking molds, chutes, dies, toilets, container coverings, power devices, transistors, psyllistas, rectifiers, transformers, power MOS FETs, CPUs, heat dissipation fins and metal heat dissipation plates. Is.

Claims (15)

A dispersion containing particles containing a tetrafluoroethylene polymer, a silane coupling agent and a liquid dispersion medium is subjected to conditions under which the silane coupling agent is hydrolyzed, and then selected from the group consisting of other resins and inorganic fillers. A method for producing a liquid composition, which comprises mixing with an additive containing at least one other material to obtain a liquid composition. The production method according to claim 1, wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer having a melting temperature of 200 to 325 ° C. The production method according to claim 1 or 2, wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer having an oxygen-containing polar group. The production method according to any one of claims 1 to 3, wherein the particles further contain an inorganic substance. The production method according to claim 4, wherein the particles are composite particles having the tetrafluoroethylene polymer as a core and the inorganic substance on the surface of the core. The production method according to claim 5, wherein the core of the tetrafluoroethylene polymer and the inorganic substance in the composite particles are each in the form of particles, and the average particle size of the core is larger than the average particle size of the inorganic substance. The silane coupling agent is a compound having a trialkoxysilyl group and a phenyl group, a vinyl group, an epoxy group, an acryloyloxy group, a methacryloyloxy group, an amino group, a ureido group, a mercapto group or an isocyanate group. The production method according to any one of 1 to 6. The production method according to any one of claims 1 to 7, wherein the liquid dispersion medium is at least one aprotic liquid dispersion medium selected from the group consisting of amides, ketones and esters. The production method according to any one of claims 1 to 8, wherein the content of the particles in the dispersion is 20 to 60% by mass. The production according to any one of claims 1 to 9, wherein the ratio of the content of the silane coupling agent to the content of the particles in the dispersion liquid by mass is 0.01 to 0.1. Method. The production method according to any one of claims 1 to 10, wherein the other resin is an aromatic resin or a fluororesin, and the inorganic filler is an inorganic filler containing silica or boron nitride. The production method according to any one of claims 1 to 11, wherein the ratio of the content of the other material to the content of the tetrafluoroethylene polymer by mass is 0.01 or more. The production method according to any one of claims 1 to 12, wherein the additive is in a liquid state. The production method according to any one of claims 1 to 13, wherein the component dispersion layer ratio of the liquid composition is 60% or more. The liquid composition obtained by the production method according to any one of claims 1 to 14 is applied to the surface of a base material layer and heated to form a polymer layer, and the base material layer and the polymer layer are formed. A method for manufacturing a laminated body, which obtains a laminated body having the above in this order.