WO2022153931A1

WO2022153931A1 - Method for producing liquid composition and composition

Info

Publication number: WO2022153931A1
Application number: PCT/JP2022/000323
Authority: WO
Inventors: 敦美光永; 剛長谷川; 満関; 創太結城
Original assignee: Ａｇｃ株式会社
Priority date: 2021-01-13
Filing date: 2022-01-07
Publication date: 2022-07-21
Also published as: KR20230132449A; TW202237710A; JPWO2022153931A1

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

Method for producing liquid composition and composition

The present invention relates to a method for producing a liquid composition and a liquid composition containing at least one of tetrafluoroethylene polymer particles and an aromatic resin or a predetermined inorganic particle.

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 physical properties to the surface of the base material, a liquid composition containing particles of a tetrafluoroethylene polymer and a liquid dispersion medium such as water is known.
Since a molded product having excellent electrical characteristics such as low dielectric constant and low dielectric loss tangent can be formed from such a liquid composition, the liquid composition is a material for forming a dielectric layer of a printed circuit board corresponding to a frequency in a high frequency band. It is attracting attention as.

In order to form a better dielectric layer, a mixture of a tetrafluoroethylene polymer and an aromatic resin has also been studied.
For example, Patent Document 1 discloses a polyimide-PTFE blend film prepared by mixing PTFE particles with a polyamic acid varnish and subjecting the PTFE particles to an imidization process. In Patent Document 2, a polyimide-PTFE produced by producing a polyamic acid varnish, taking out a part thereof, mixing it with PTFE particles, mixing the remaining varnish with the varnish, and subjecting it to a heat casting method. Blended films are disclosed.
Patent Document 3 proposes the use of a thickener for the purpose of improving the coatability of such a liquid composition. Patent Document 4 proposes the use of a polyamide-imide resin and a polyetherimide for the purpose of improving the adhesiveness of a molded product formed from such a liquid composition.
Further, since the tetrafluoroethylene polymer has extremely low dispersion stability, various proposals have been made from the viewpoint of obtaining a liquid composition having excellent dispersion stability.
For example, Patent Document 5 discloses a liquid composition containing PTFE particles, which is further mixed with inorganic particles of ceramics, from the viewpoint of improving dispersion stability.

Japanese Unexamined Patent Publication No. 2005-142572 International Publication No. 2016/159061 Japanese Unexamined Patent Publication No. 2018-408233 Japanese Unexamined Patent Publication No. 2019-218484 Japanese Unexamined Patent Publication No. 2016-194017

Tetrafluoroethylene-based polymer has low surface tension, does not easily interact with other components, and has extremely low dispersion stability. Therefore, in the aspect of the prior art document, the dispersion stability of the obtained mixture (composition) is low and it is easily altered, so that the uniformity and denseness of the component distribution of the molded product obtained from the mixture are lowered and the physical properties are exhibited. The present inventors are aware of the problem that it is difficult to do. Furthermore, the present inventors have also found that such a problem becomes remarkable when a molded product having a fine or complicated shape such as a base material having a convex portion is formed from such a mixture (composition).

Further, in the embodiment described in Patent Document 5, the dispersion stability and uniformity of the liquid composition were not sufficient due to the aggregation of the inorganic particles, and the liquid composition was easily denatured. Furthermore, the uniformity of the component distribution in the molded product obtained from such a liquid composition was still insufficient.

As a result of diligent studies, the present inventors have found that in the production of a liquid composition containing particles of a tetrafluoroethylene polymer and at least one of an aromatic resin or a specific inorganic particle, they are mixed under specific conditions. It was found that a liquid composition having excellent dispersion stability, uniformity and handleability can be obtained. Further, specifically, it was found that the content of the tetrafluoroethylene polymer particles and the aromatic resin in the composition can be increased.
In addition, the liquid composition is not only suitable for forming a dense molded product, but also has excellent low dielectric loss tangent and low linear expansion property, and is suitable for forming a molded product having a fine or complicated shape. They found out.

Specifically, the present inventors have also found that such a liquid composition is suitable for forming a dense molded product having excellent low dielectric loss tangent and low line expansion property.

Further, specifically, such a liquid composition is a dense molded product having a high degree of physical properties of a tetrafluoroethylene polymer and inorganic particles and having excellent low dielectric loss tangent, low linear expansion property, thermal conductivity and the like. The present inventors have also found that it is suitable for formation.

An object of the present invention is a method for producing a composition containing at least one of tetrafluoroethylene polymer particles and an aromatic resin or a predetermined inorganic particle, which is excellent in dispersion stability, uniformity and handleability, preferably a resist. It is the provision of such a composition, which is a composition.
Specifically, an object of the present invention is a method for producing a liquid composition containing tetrafluoroethylene polymer particles and an aromatic resin, which is excellent in dispersion stability and handleability, preferably a resist composition. Provided is a member with a convex portion having a convex portion having a predetermined pattern formed from the liquid composition and the resist composition.

Specifically, an object of the present invention is a liquid composition containing particles of a tetrafluoroethylene polymer, an aromatic polymer, a predetermined thickening polymer, and water, and having excellent dispersion stability, uniformity, and handleability. The present invention provides a method for producing the same, such a liquid composition, and a method for producing a laminate using the liquid composition.
Specifically, an object of the present invention is a composition capable of forming a liquid composition having excellent dispersion stability, uniformity and handleability, preferably a lumpy and clay-like solidified product (powder or wet powder). ) Is provided.

Specifically, an object of the present invention is a liquid composition containing particles of a tetrafluoroethylene-based polymer and predetermined inorganic particles, with little aggregation of the inorganic particles, and excellent dispersion stability, uniformity and handleability. The present invention provides a production method and a method for producing a laminate using the obtained liquid composition.

The present invention has the following aspects.
<1> A stirring mechanism by thin film swirling or a stirring mechanism by rotation and revolution of tetrafluoroethylene polymer particles, at least one of aromatic resin or new moth hardness of 12 or less inorganic particles, and a liquid compound. To obtain a liquid composition containing the particles of the tetrafluoroethylene-based polymer, at least one of the aromatic resin or the inorganic particles having a new Morse hardness of 12 or less, and the liquid compound, the mixture is mixed in a tank provided with the above. Method for producing the composition.
<2> A cylindrical portion having a plurality of holes formed by rotating tetrafluoroethylene polymer particles and an aromatic resin varnish inside a cylindrical stirring tank and the inner wall surface of the stirring tank. It is placed in the stirring tank of a stirrer having a rotating portion, and is stirred while spreading in a thin film cylindrical shape on the inner wall surface of the stirring tank by the centrifugal force due to the rotation of the rotating portion to obtain the tetrafluoroethylene polymer. The production method of <1>, which obtains a liquid composition containing the aromatic resin.
<3> The method for producing <2>, wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer having an oxygen-containing polar group containing a unit based on perfluoro (alkyl vinyl ether).
<4> The production method of <2> or <3>, wherein the ratio of the mass of the particles of the tetrafluoroethylene-based polymer to the mass of the aromatic resin is 0.5 to 10.
<5> The total content of the tetrafluoroethylene polymer particles and the aromatic resin is 50% by mass or more, and the tetrafluoroethylene polymer particles and the aromatic resin varnish are contained. A liquid composition used by mixing with an aromatic resin varnish having a mass ratio of particles of the tetrafluoroethylene polymer to the aromatic resin of 0.5 to 10.

<6> A stirring mechanism by swirling a thin film of tetrafluoroethylene polymer particles, an aromatic resin, at least one thickening polymer selected from the group consisting of polar vinyl polymers and polysaccharides, and water. Alternatively, a liquid composition containing the tetrafluoroethylene polymer particles, the aromatic resin, the thickening polymer, and water is obtained by mixing in a tank equipped with a stirring mechanism by rotation and revolution. 1> Manufacturing method.
<7> The particles of the tetrafluoroethylene polymer, the aromatic resin, the thickening polymer, and the water are mixed in a stirring mechanism by thin film swirling or in a tank equipped with a stirring mechanism by rotation and revolution. The production method of <6>, wherein water is further mixed to obtain the liquid composition.
<8> The method for producing <6> or <7>, wherein the tetrafluoroethylene-based polymer particles include heat-meltable tetrafluoroethylene-based polymer particles and non-heat-meltable tetrafluoroethylene-based polymer particles.
<9> The method for producing any of <6> to <8>, wherein the aromatic resin is an aromatic polyimide, an aromatic polyamideimide, an aromatic polyetherimide, or a precursor thereof.
<10> Further, any of <6> to <9>, wherein the inorganic particles are mixed in a stirring mechanism by thin film swirling or in a tank equipped with a stirring mechanism by rotation and revolution to obtain the liquid composition. Manufacturing method.
<11> The tetrafluoroethylene polymer contains particles of the tetrafluoroethylene polymer, an aromatic polymer, at least one thickening polymer selected from the group consisting of polar vinyl polymers and polysaccharides, and water. The composition in which the ratio of the content of the thickening polymer to the particles of the thickening polymer is 0.05 or less, the viscosity is 10000 Pa · s to 100,000 Pa · s by capillograph measurement at a temperature of 25 ° C. and a shear rate of 1 s ^-1 . thing.

<12> The particles of the tetrafluoroethylene-based polymer, the inorganic particles having a new moth hardness of 12 or less, and the liquid compound are mixed by swirling a thin film, and the particles of the tetrafluoroethylene-based polymer, the inorganic particles, and the liquid compound are mixed. The production method of <1>, which obtains a liquid composition containing a liquid compound.
<13> The production method of <12>, wherein the tetrafluoroethylene-based polymer particles include heat-meltable tetrafluoroethylene-based polymer particles and non-heat-meltable tetrafluoroethylene-based polymer particles.
<14> The method for producing <12> or <13>, wherein the inorganic particles are boron nitride particles or silica particles.
<15> The production method according to any one of <12> to <14>, wherein the viscosity of the liquid composition is 10,000 mPa · s or less.

According to the present invention, it is possible to produce a liquid composition containing tetrafluoroethylene polymer particles and an aromatic resin, which are excellent in dispersion stability and handleability. Such a composition is excellent in physical properties such as electrical characteristics, and is useful as, for example, a solder resist composition and a constituent material of a printed circuit board.

Further, according to the present invention, it is possible to produce a liquid composition containing particles of a tetrafluoroethylene-based polymer, an aromatic polymer, a predetermined thickening polymer, and water, which are excellent in dispersion stability, uniformity, and handleability. Such a liquid composition is excellent in physical properties such as electrical characteristics, and is useful as a constituent material of a printed circuit board, for example.
Further, according to the present invention, there is provided a composition capable of forming a liquid composition having excellent dispersion stability, uniformity and handleability.

Further, according to the present invention, it is possible to produce a liquid composition containing tetrafluoroethylene polymer particles and predetermined inorganic particles, which are excellent in dispersion stability and handleability. Such a liquid composition can form a molded product having excellent physical properties such as electrical characteristics, and is useful as a material for a printed circuit board, for example.

The "tetrafluoroethylene-based polymer" is a polymer containing a unit (hereinafter, also referred to as "TFE unit") based on tetrafluoroethylene (hereinafter, also referred to as "TFE"), and is also simply referred to as "F polymer". I will write it down.
The "average particle diameter (D50)" is a volume-based cumulative 50% diameter of an object (particle and filler) determined by a laser diffraction / scattering method. That is, the particle size distribution 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 diameter is the point at which the cumulative volume is 50% on the cumulative curve.
The D50 of the object is obtained by dispersing the object in water and analyzing it by a laser diffraction / scattering method using a laser diffraction / scattering type particle size distribution measuring device (LA-920 measuring device manufactured by HORIBA, Ltd.). ..
The "average particle size (D90)" is the cumulative volume particle size of the particles, and is the volume-based cumulative 90% diameter of the particles obtained in the same manner as in "D50".
The "heat-meltable resin" is a melt-fluid resin having a melt flow rate of 1 to 1000 g / 10 minutes at a temperature 20 ° C. or higher higher than the melt temperature of the resin under a load of 49 N. means.
The “non-thermally meltable resin” means a non-meltable fluid resin in which there is no temperature at which the melt flow rate is 1 to 1000 g / 10 minutes under the condition of a load of 49 N.
The "melting temperature" is the temperature corresponding to the maximum value of the melting peak of the polymer measured by the differential scanning calorimetry (DSC) method.
The "polymer melting temperature (melting point)" is the temperature corresponding to the maximum value of the polymer melting peak measured by the differential scanning calorimetry (DSC) method.
"Viscosity" is the viscosity of a liquid composition measured at 25 ° C. and a rotation speed of 30 rpm using a B-type viscometer. The measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
The "thixotropic ratio" is a value calculated by dividing the viscosity η ₁ of the liquid composition measured under the condition of a rotation speed of 30 rpm by the viscosity η ₂ measured under the condition of a rotation speed of 60 rpm. Each viscosity measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
The "new Mohs hardness" is a hardness obtained by measuring the hardness of 15 kinds of reference minerals. The reference minerals are talc, gypsum, talite, fluorite, phosphorous stone, regular length stone, molten quartz, crystal (quartz), and yellow jade (topaz) in the order of soft mineral (new Mohs hardness 1) to hard mineral (new Mohs hardness 15). , Quartz, molten zirconia, molten alumina, silicon carbide, boron carbide and diamond. In the present specification, the hardness is determined by the presence or absence of scratches when the target sample is rubbed with these reference minerals. For example, the new Mohs hardness of the target sample, which is not scratched by calcite and is scratched by fluorite, is 3.5.
The "unit" in a polymer means an atomic group based on the monomer formed by polymerization of the monomer. The unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of 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 production method of the present invention (hereinafter, also referred to as "the present method") includes F polymer particles (hereinafter, also referred to as "F particles") and aromatic resin or new moth hardness of 12 or less inorganic particles (hereinafter, also referred to as "F particles"). , "This inorganic particle") and the liquid compound are mixed in a tank equipped with a stirring mechanism by thin film swirling or a stirring mechanism by rotation and revolution, and F particles and aroma are mixed. This is a method for obtaining a liquid composition containing at least one of a group resin or the present inorganic particles and a liquid compound (hereinafter, also referred to as “the present liquid composition”).

The F polymer in the present invention may be heat-meltable or non-heat-meltable.
When the F polymer is thermally meltable, its melting temperature is preferably 200 ° C. or higher, more preferably 240 ° C. or higher, still 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.

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 wetting 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. The F polymer having a high fluorine content is excellent in physical properties such as electrical properties, but has a low surface tension, and the dispersion stability in a liquid compound tends to be lowered. , The dispersion stability of the F polymer is likely to be improved.

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 Polymers containing units based on ethylene can be mentioned, with PFA or FEP being preferred, and PFA being more preferred. 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 non-heat-meltable PTFE or a heat-meltable PTFE.
The F polymer preferably has an oxygen-containing polar group. In this case, it becomes easy to form microspherulites at the molecular assembly level, the wettability of F particles is improved, and the effect of the present invention is highly likely to be exhibited.
The oxygen-containing polar group may be contained in a unit in the F polymer, or may be contained in the terminal group of the main chain of the F polymer. In the latter aspect, an F polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and an F having an oxygen-containing polar group obtained by plasma-treating or ionizing the F polymer. Polymers can be mentioned. The oxygen-containing polar group is preferably a hydroxyl group-containing group, a carbonyl group-containing group and a phosphono group-containing group, and from the viewpoint of dispersion stability of the present liquid composition, a hydroxyl group-containing group and a carbonyl group-containing group are more preferable, and a carbonyl group-containing group is preferable. Is even more preferable.

The hydroxyl group-containing group is preferably an alcoholic hydroxyl group-containing 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. A group (-C (O) OC (O)-), an imide residue (-C (O) NHC (O)-etc.) or a carbonate group (-OC (O) O-) is preferred, and an acid anhydride residue. Is more preferable. In this case, the F particles are likely to interact with the inorganic particles and the liquid compound, and the liquid composition is likely to have excellent liquid physical characteristics such as dispersion stability.

The F polymer is preferably a polymer having a carbonyl group-containing group containing TFE units and PAVE units, and more preferably a polymer containing units based on TFE units, PAVE units and a monomer having a carbonyl group-containing group. It is more preferable that the polymer contains 90 to 99 mol%, 0.5 to 9.97 mol%, 0.01 to 3 mol% of these units in this order with respect to all the units. The presence of a carbonyl group-containing group is preferable from the viewpoint of further improving the affinity and adhesion of the F polymer.

When the F polymer has a carbonyl group-containing group, the number of carbonyl group-containing groups in the F polymer is preferably 10 to 5000, more preferably 100 to 3000, and more preferably 800, per 1 × 10 ⁶ carbon atoms in the main chain. ~ 1500 pieces are more preferable. 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 International Publication No. 2020/145133.
The monomer having a carbonyl group-containing group is preferably itaconic anhydride, citraconic anhydride or 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter, also referred to as “NAH”). Specific examples of such polymers include the polymers described in WO 2018/16644.

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. In D50 in this range, the fluidity and dispersion stability of F particles tend to be good.
From the viewpoint of dispersion stability, the specific surface area of the F particles is preferably 1 to 25 m ² / g, more preferably 1 to 8 m ² / g.

One type of F particle 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-meltable F polymer and particles of a non-heat-meltable F polymer, and the F polymer having a melting temperature of 200 to 320 ° C. (preferably). More preferably contains particles of (a polymer having an oxygen-containing polar group) containing the above-mentioned TFE units and PAVE units) and particles of non-heat-meltable PTFE. Further, it is more preferable that the content of the latter particles is larger than the content of the former particles.
In this case, the F polymer is appropriately fibrillated while maintaining its physical properties, and the inorganic particles are likely to be supported in the molded product formed from the liquid composition, and the strength of the molded product is likely to be improved.

In this case, the ratio of the former particles to the total of the former particles and the latter particles is preferably 50% by mass or less, more preferably 25% by mass or less. Further, the ratio in this case is preferably 0.1% by mass or more, and more preferably 1% by mass or more.
Such a liquid composition is not only easy to be excellent in dispersion stability, uniformity and handleability, but is also easy to form an adhesive molded product having excellent physical properties based on non-thermally meltable PTFE.
Further, in this case, the D50 of the F polymer particles having a melting temperature of 200 to 320 ° C. is 0.1 to 1 μm, and the D50 of the non-thermally meltable PTFE particles is 0.1 to 1 μm, that is, the melting temperature. It is preferable that the D50 of the F polymer particles having a temperature of 200 to 320 ° C. is 1 to 4 μm and the D50 of the non-thermally meltable PTFE particles is 0.1 to 1 μm.

The F particles may contain a resin other than the F polymer, but it is preferable that the F polymer is 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, polyamide-imide, (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. The content of F particles is preferably 80% by mass or less, more preferably 70% by mass or less, based on the total mass of the liquid composition.

First, the first aspect of this method (hereinafter, also referred to as "this method 1") will be described.
In this method 1, particles of a tetrafluoroethylene polymer (hereinafter, also referred to as “F polymer”) (hereinafter, also referred to as “F particles”) and an aromatic resin (hereinafter, “first aromatic resin”) The varnish is mixed by a specific stirring means to obtain a composition containing the F particles and the first aromatic resin.
Further, the composition of the present invention (hereinafter, also referred to as "the present composition 1") contains F particles and a first aromatic resin, and the total content of the F particles and the first aromatic resin. Is 50% by mass or more, and the mass ratio of the content of F particles to the first aromatic resin is 0.5 to 10. The present composition 1 is used by mixing with a varnish of an aromatic resin (hereinafter, also referred to as "second aromatic resin"), and is preferably a composition used for a negative type resist composition. be.

The composition obtained by the present method 1, for example, the present composition 1, is excellent in dispersion stability and handleability. The reason and its mechanism of action are not always clear, but it is estimated as follows, for example.
Since the F polymer has low surface energy and low dispersibility, the F particles tend to form complex secondary particles and aggregate when mixed with the aromatic resin. Therefore, in the present method 1, a specific stirring means, that is, a treatment liquid containing F particles and an aromatic resin is moved at high speed in the container, and a slip stress is generated between the liquid film and the inner wall of the container. As a result, the F particles and the aromatic resin are mixed while suppressing the alteration of the F particles and loosening the secondary particles of the F particles. As a result, according to the present invention, a composition having excellent dispersion stability can be obtained, and further, a composition having excellent handleability even if the contents of the F polymer and the first aromatic resin are increased (for example, It is considered that the present composition 1.) was obtained. By using this composition 1, it is possible to form a molded product having a high degree of physical properties of the F polymer and the first aromatic resin and having excellent electrical characteristics and the like.

The aromatic resin in the varnish of the first aromatic resin 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, phenol resin, and aromatic polyester resin. Examples thereof include (liquid crystal aromatic polyester and the like), aromatic polyester amide (liquid liquid and aromatic polyester amide and the like), polyphenylene ether, and aromatic maleimide resin.
Of these, an aromatic resin having an epoxy group or a curable aromatic resin having a carboxyl group and an acid value of 150 mgKOH / g or less is more preferable.

Examples of aromatic resins having an epoxy group include phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, trisphenol type epoxy resin, and tert-butyl catechol. Examples thereof include epoxy resins such as type epoxy resins, aminophenol type epoxy resins, biphenyl type epoxy resins, and biphenyl aralkyl type 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 glass transition temperature (Tg) of the cured product obtained by curing the present composition 1 (preferably a negative resist composition) is high, and the coefficient of linear expansion is low. Therefore, it tends to have excellent crack resistance. On the other hand, when the solid epoxy resin is contained, the glass transition temperature of the cured product tends to be high and the heat resistance tends to be excellent, and when the liquid epoxy resin is contained, the flexibility of the dry film tends to be excellent.

The curable aromatic resin having a carboxyl group and having an acid value of 150 mgKOH / g or less is preferably a photosensitive resin having a carboxyl group and 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 addition, in this specification, a (meth) acryloyloxy group is a term which collectively refers to an acryloyloxy group, a methacryloyloxy group, and both of them.
As such a resin, a carboxyl group-containing phenol resin is preferable, and a polyfunctional phenol resin (for example, a polyfunctional novolac type epoxy resin) which is epoxidized by reacting a phenolic hydroxyl group with epichlorohydrin is mixed with (meth) acrylic. A carboxyl group-containing phenol resin in which a dibasic acid anhydride is added to a hydroxyl group existing in the side chain after the acid is reacted is more preferable. Such a carboxyl group-containing phenol resin is preferable because it easily interacts with an F polymer (particularly, an F polymer having a polar functional group).

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, and more preferably 45 mgKOH / g or more. The first aromatic resin having such an acid value highly interacts with the F polymer to enhance the dispersion stability of the F particles in the composition 1.
In addition, the first aromatic resin has good alkali developability, and it is easy to obtain a molded product (convex portion) having a desired complicated shape.

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

In this method, the F particles and the varnish of the first aromatic resin are rotated by a cylindrical stirring tank and a cylindrical portion having a plurality of holes formed inside the inner wall surface of the stirring tank. It is placed in the stirring tank of a stirrer provided with a portion, and is stirred while spreading in a thin cylindrical shape on the inner wall surface of the stirring tank by the centrifugal force due to the rotation of the rotating portion, and the F polymer and the first aromatic property. A composition containing a resin is obtained.
Such a stirring means may also be referred to as a thin film swirling high-speed mixer, and the F particles and the first aromatic resin are loosened by the above-mentioned action mechanism without deteriorating the F particles themselves. Can be mixed.
As a result, a composition having excellent dispersibility can be obtained by stirring for a shorter time. Further, such a composition, particularly the present composition 1, is a composition having excellent dispersion stability even when further mixed with a second aromatic resin varnish and, if necessary, an optional additive component such as an inorganic filler. Can be formed.

The inner wall surface of the cylindrical stirring tank may be provided with irregularities. The combination of the height and shape of the unevenness is provided with a depth (height) of about several μm to several hundred μm, a grid-like groove, or dimples, and may be appropriately replaceable. Further, the inner wall surface of the stirring tank may be divided into equal parts, for example, upper, middle and lower parts, and different uneven patterns may be formed.
As the material of the stirring tank, for example, stainless steel or ceramic, which can be processed to form unevenness and is not easily worn, can be used.

The stirring tank may be provided with a plurality of inlets for components constituting the stirring target. That is, when producing the composition by the present method 1, a mixture in which F particles and the varnish of the first aromatic resin are premixed may be collectively supplied into the stirring tank, and the F particles and the first aromatic resin may be supplied together. The aromatic resin varnish of the above may be separately supplied into the stirring tank.
Further, the stirring tank may be provided with a discharge port of a mixture in which the components constituting the stirring target are mixed. Therefore, this method 1 can be carried out by either a batch method or a continuous method.

The rotating portion having a cylindrical portion having a plurality of holes formed inside the inner wall surface of the stirring tank faces the inner wall surface of the stirring tank with a slight gap of about 1 to 10 mm. The peripheral speed and stirring time of the rotating part can be set as appropriate.
The supplied F particles and the varnish of the first aromatic resin spread over the gap between the inner wall surface of the stirring tank and the outer peripheral surface of the cylindrical portion of the rotating portion to form a film, which accompanies the rotation of the rotating portion. And swirl at high speed in the stirring tank. At this time, high-level dispersion is achieved by receiving not only shear stress but also shear stress.

In the present method 1, the amount of the F particles and the varnish of the first aromatic resin used is such that the ratio of the mass of the F particles to the mass of the first aromatic resin in the varnish is 0.5 to 10. The range is preferable, and the range of 1 to 3 is more preferable.

The present composition 1 contains F particles and a varnish of a first aromatic resin, and the total content of the F particles and the first aromatic resin is 50% by mass or more, and the first The composition has a mass ratio of the content of F particles to the aromatic resin of No. 1 of 0.5 to 10, and is used by being mixed with the varnish of the second aromatic resin.
The present composition 1 is a composition having a high content of resin solid content and a high content of F polymer in the resin solid content, and is excellent in dispersion stability and handleability.
This tendency becomes remarkable when the F particles and the F polymer in the present composition 1 are in the above-mentioned ranges, particularly when the F polymer is a polymer having an oxygen-containing polar group.
The present composition 1 is preferably prepared by stirring the F particles and the varnish of the first aromatic resin by stirring using the above-mentioned thin film swirling high-speed mixer. In this case as well, this tendency tends to be remarkable.

The present composition 1 may further contain a surfactant as a dispersant from the viewpoint of further improving dispersibility and handleability.
The surfactant is preferably nonionic.
The hydrophilic moiety of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group, and the hydrophobic moiety 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.

The present composition 1 may further contain other resins. The other resin may be a thermosetting resin or a thermoplastic resin.
Examples of other resins include maleimide resins, urethane resins, polyimides, polyamic acids, polyamideimides, and polyvinyl acetal resins, which do not have aromaticity. As other resins, maleimide resin, polyimide and polyamic acid are preferable. In this case, the molded product formed from the present composition 1 tends to be excellent in flexibility and adhesiveness.

In addition to these components, the present composition 1 contains a silane coupling agent, a dehydrating agent, a defoaming agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, and a coloring agent. It may contain additives such as agents, conductive agents, mold release agents, surface treatment agents, and flame retardants.

The varnish of the present composition 1 and the second aromatic resin may be mixed with the varnish of the present composition 1 and the second aromatic resin in a batch, and the composition 1 may be mixed with the second aromatic resin. The composition 1 may be sequentially mixed with the varnish of the sex resin, or may be sequentially mixed with the varnish of the second aromatic resin.
When any additional components such as an inorganic filler, a photopolymerization initiator, a curing agent or a curing accelerator, a dispersant, and another liquid dispersion medium, which will be described later, are further mixed, they can be mixed at any stage.

As a method of mixing the varnish of the present composition 1 and the second aromatic resin, a stirring device provided with blades (stirring blades) such as propeller blades, turbine blades, paddle blades, shell-shaped blades, etc. Stirring with Henschel mixer, pressurized kneader, Banbury mixer or planetary mixer; ball mill, attritor, basket mill, sand mill, sand grinder, dyno mill (bead mill using crushing medium such as glass beads or zirconium oxide beads), dispermat, Mixing with a disperser using media such as SC mill, spike mill or agitator mill; high-pressure homogenizer such as microfluidizer, nanomizer, ultimateizer, ultrasonic homogenizer, resolver, dispenser, high-speed impeller disperser, rotation / revolution stirring described later. Mixing using a disperser that does not use media such as a machine can be mentioned, and a Henschel mixer, a pressurized kneader, a Banbury mixer, a planetary mixer, or a rotation / revolution stirrer is preferable, and a planetary mixer is more preferable. The planetary mixer has a biaxial stirring blade that rotates and revolves with each other, and has a structure for stirring and kneading the kneaded material in the stirring tank. Therefore, there is little dead space in the stirring tank that the stirring blades do not reach, the load on the blades can be reduced, and the contents can be highly mixed. After the mixing is completed, the obtained composition 1 is subsequently added with a second aromatic resin varnish and, if necessary, an optional additive component such as an inorganic filler, and the composition described later is used as it is. 1 can be manufactured.
Further, the mixing may be carried out using a twin-screw extrusion kneader or a millstone kneader. The twin-screw extrusion kneader is, for example, a twin-screw type continuous kneading device that kneads an object to be kneaded by a shearing force between two screws arranged in parallel in close proximity to each other. The stone mill type kneader is, for example, a cylindrical fixed portion having an internal space through which the kneaded material can pass, and a kneaded material which is arranged in the internal space of the fixed portion and passes through the internal space by rotating. It is a kneading machine having a rotating portion that conveys in the direction of the rotation axis while kneading.
Further, the above-mentioned thin film swirl type high-speed mixer may be used.

The aromatic resin constituting the varnish of the second aromatic resin is preferably an aromatic resin having an oxygen-containing polar group, and is an aromatic resin having an epoxy group or an aromatic resin having a carboxyl group. More preferably, it is a group resin. The details and suitable specific examples of the second aromatic resin are the same as those of the first aromatic resin described above.
Further, in the mixing, the first aromatic resin and the second aromatic resin constituting the present composition 1 may be different, and it is preferable to use the same kind.

When mixing the varnish of the present composition 1 and the second aromatic resin, an inorganic filler may be further mixed. The inorganic filler is not particularly limited as long as it is a component containing inorganic particles.
Examples of the inorganic filler include fillers composed of oxides, nitrides, simple metals, alloys and carbon, and silicates (silicon oxide (silica), wollastonite, talc, mica) and metal oxides (oxidation). Fillers of beryllium, cerium oxide, aluminum oxide, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride and magnesium metasilicate (steatite) are preferable, and are selected from aluminum, magnesium, silicon, titanium and zinc. Inorganic oxide fillers containing at least one of the elements are more preferred, silica, titanium oxide, zinc oxide, steatite and boron nitride fillers are even more preferred, and silica fillers are particularly preferred. Moreover, the inorganic filler may be ceramics. As the inorganic filler, 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 and used, two kinds of silica fillers may be mixed and used, or a silica filler and a metal oxide filler may be mixed and used.
If a silica filler is used, the coefficient of linear expansion of the obtained molded product can be sufficiently reduced.
When the inorganic filler is a silica filler, the content of silica in the inorganic filler is preferably 50% by mass or more, more preferably 75% by mass. The silica content is preferably 100% by mass or less.

It is preferable that at least a part of the surface of the inorganic filler is surface-treated. As the surface treatment agent used for such surface treatment, a silane coupling agent is preferable, and 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. , 3-Methyloxypropyltriethoxysilane, 3-Isocyanoxidetriethoxysilane is more preferred.

The D50 of the inorganic filler is preferably 25 μm or less, more preferably 15 μm or less. The D50 of the inorganic filler is preferably 0.1 μm or more.
The shape of the inorganic filler may be granular, needle-like (fibrous), or plate-like. Specific shapes of the inorganic filler include spherical, scaly, layered, leafy, apricot kernel, columnar, chicken crown, equiaxed, leafy, mica, block, flat, wedge, rosette, and mesh. Shape and prismatic shape. The inorganic filler may be hollow or may contain a hollow filler and a non-hollow filler.

Suitable specific examples of the inorganic filler include 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.), Tarku Filler (Nippon Tarku Co., Ltd." SG "series, etc.), Steatite Filler (Steatite Filler) Nippon Tarku's "BST" series, etc.), boron nitride filler (Showa Denko's "UHP" series, Denka's "Denka Boron Nitride" series ("GP", "HGP" grade), etc.) Can be mentioned.

When the inorganic filler is mixed, the content of the inorganic filler is preferably 0.1 to 75% by mass, more preferably 1 to 60% by mass. By mixing the inorganic filler in such a range, the coefficient of linear expansion of the obtained molded product (cured product) can be reduced. Therefore, even if the molded product is heat-treated, its deformation can be prevented.

When mixing the varnish of the present composition 1 and the second aromatic resin, a photopolymerization initiator (sensitizer) may be further mixed. Examples of the photopolymerization initiator include an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a benzoin-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, and 2,2'-azobisisobutyronitrile. Benzoyl peroxide can be mentioned.

When mixing the varnish of the present composition 1 and the second aromatic resin, it is preferable to further mix a curing agent or a curing accelerator, and a curing agent or a curing accelerator capable of thermosetting with the aromatic resin. Is more preferable to mix. When the F polymer has a carbonyl group-containing group (carboxyl group, acid anhydride residue, etc.), the curing agent or curing accelerator may undergo a thermal curing reaction with the F polymer. By mixing a curing agent or a curing accelerator, the hardness of the molded product formed from the obtained composition can be further increased.
The curing agent or curing accelerator is 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. Is preferable, and amine or imidazole is more preferable from the viewpoint of enhancing the stability of the present composition 1 and the adhesiveness and electrical properties of the formed molded product. As the curing agent or curing accelerator, one type may be used alone, or two or more types may be used in combination.
It is preferable to select a curing agent or a curing accelerator so that the curing start temperature of the obtained composition is 120 to 200 ° C. The "curing start temperature" is a temperature indicating the first change point when the obtained composition is heated, which is confirmed by differential scanning calorimetry (DSC).

Examples of the amine include an aliphatic polyamine (alkylenediamine, polyalkylene polyamine, an aliphatic polyamine having an aromatic ring, etc.), an adduct compound thereof (a reaction product with phenylglycidyl ether, trillglycidyl ether, alkyl glycidyl ether, etc.), and an alicyclic type. Polyamines (isophoronediamine, 1,3-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, laromine, etc.) or adduct compounds thereof (n-butylglycidyl ether or (Reactant with bisphenol A diglycidyl ether, etc.) is preferable.

Examples of the imidazole include 2-methylimidazole, 4-methyl-2-ethylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole, and 2-isopropylimidazole. , 1-Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, imidazole azine compound, imidazole isocyanurate, imidazole hydroxymethyl form, or , These adduct compounds (reactants of epoxy resin and imidazole, etc.) are preferable.

As the phenol, hydroquinone, resorcinol, or bisphenol A is preferable. As the acid anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, or benzophenone tetracarboxylic acid are preferable.

Examples of the compound having a phenolic hydroxyl group include phenol novolac resin, alkylphenol volac resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, cresol / naphthol resin, polyvinylphenols, and phenol. / Naftor resin, α-naphthol skeleton-containing phenol resin, triazine skeleton-containing cresol novolac resin, biphenyl aralkyl type phenol resin, Zyroc type phenol novolac resin and the like can be mentioned.

Examples of the compound having a cyanate ester group include phenol novolac type cyanate ester resin, alkylphenol novolac type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, and bisphenol S type. Cyanate ester resin can be mentioned. Further, it may be a prepolymer in which a part is triazine-ized.

Examples of the compound having a maleimide group include 4,4'-diphenylmethanebismaleimide, phenylmethanebismaleimide, m-phenylenebismaleimide, and 3,3'-dimethyl-5,5'-dimethyl-4,4'-diphenylmethanebis. Maleimide, 4-methyl-1,3,-phenylene bismaleimide, (1,6-bismaleimide-2,2,4-trimethyl) hexane, and oligomers thereof, and diamine condensates having a maleimide skeleton can be mentioned.

When mixing the varnish of the present composition 1 and the second aromatic resin, a dispersant may be further mixed. Examples of the dispersant include the same as the surfactant as the dispersant that may be contained in the present composition 1.

When mixing the varnish of the composition 1 and the second aromatic resin, the liquid dispersion medium (for example, the solvent constituting the varnish of the first aromatic resin) and the second can be contained in the composition 1. A liquid dispersion medium (another liquid dispersion medium) other than the solvent contained in the varnish of the aromatic resin may be further mixed. The ratio of the other liquid dispersion medium at the time of mixing is preferably 25% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, based on the total amount of the second aromatic resin varnish. Further, the lower limit of the ratio (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.

When the composition 1 and the varnish of the second aromatic resin are mixed, the content (ratio) of the aromatic resin is set as the total amount of the first aromatic resin and the second aromatic resin. It is preferably higher than the content (ratio) of the F polymer. In this case, the physical properties such as handleability, curability, and developability of the obtained composition are further improved. Specifically, the ratio of the content of the aromatic resin to the content of the F polymer by mass 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 obtained composition is preferably 1 to 30% by mass, more preferably 10 to 25% by mass.
The content of the aromatic resin in the obtained composition is preferably 20 to 90% by mass, preferably 30 to 80% by mass, as the total amount of the first aromatic resin and the second aromatic resin. More preferred.
When the obtained composition contains a curing agent or a curing accelerator, the content thereof is preferably 0.01 to 15% by mass, more preferably 0.5 to 10% by mass.

The present composition 1 can be suitably used as a negative type resist composition.
The resist composition can be applied to the surface of the base material by a coating method such as a screen printing method, a bar coating method, or a blade coating method.
After coating, it is preferable to dry the coating film in order to obtain dryness to the touch. The drying conditions are preferably 75 to 95 ° C. for 40 to 70 minutes.
A hot air circulation type drying oven or a far infrared drying oven can be used for drying.
The thickness of the coating film (dry film) after drying is preferably 10 to 150 μm, more preferably 20 to 60 μm from the viewpoint of improving the developability of the dry film.

Next, an exposure mask having a predetermined exposure pattern (aperture) is used to irradiate the dry film with exposure light.
As the exposure light source, a halogen lamp, a high-pressure mercury lamp, a laser beam, a metal halide lamp, a black lamp, an electrodeless lamp, or the like can be used. A pattern may be formed on the dry film by a laser direct imaging device without using an exposure mask.

Next, the dry film after exposure is developed with a developing solution. As a result, 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 dry film after exposure by a spray method, a dipping method or the like.
As the developing solution, it is preferable to use an alkaline aqueous solution containing an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, etc., and a dilute alkaline aqueous solution containing an alkali at a concentration of 1.5% by mass or less is used. It is more preferable to use.
According to the present composition 1, since a dilute alkaline aqueous solution can be used as the developing solution, a dry film having less damage and excellent resolution can be obtained. The dried film after development is preferably washed with water or acid-neutralized in order to remove unnecessary developing solution.

Next, the obtained dried film after development is cured (post-cured) by irradiation with ultraviolet rays (active energy rays). When the present composition 1 contains the above-mentioned curing agent, the dried film after development can be cured by heating. As a result, a cured film (molded product such as a convex portion) having excellent adhesion and crack resistance can be obtained.

The present composition 1 can also be suitably used as a filling material used for filling through holes or recesses in a multilayer printed wiring board.
The multilayer printed wiring board has a plurality of circuit patterns laminated via an insulating layer. The insulating layer is composed of polyphenylene ether, polyphenylene oxide, cyanate ester, polyimide, fluoropolymer and the like. Further, the circuit pattern is composed of a metal film formed by plating or the like.
This multilayer printed wiring board has a through hole or a recessed recess that penetrates in the thickness direction thereof. The through hole or recess is formed by drilling or laser machining. A conductive film is formed on the inner surface of the through hole or the recess, and predetermined circuit patterns are electrically connected to each other.
When the composition 1 is filled in the through hole or the recess and cured, the through hole or the recess can be filled.

The through holes or recesses of the composition 1 can be filled by a screen printing method, a roll coating method, a die coating method, or a vacuum printing method. At this time, it is preferable to fill the composition 1 to such an extent that it protrudes from the through hole or the recess.
When the present composition 1 contains a curing agent or a curing accelerator, it is preferable to cure the present composition 1 filled in the through holes or recesses by heating.
The heating conditions for the composition 1 are preferably 80 to 160 ° C. for 30 to 180 minutes. From the viewpoint of suppressing outgassing in the curing of the composition 1, it is preferable to cure the composition 1 in two stages, a temporary curing step and a main curing step. The conditions for temporary curing are preferably 80 to 110 ° C. for 30 to 90 minutes. The conditions for the main curing are preferably 130 to 160 ° C. for 30 to 180 minutes. Since the volume change rate of the present composition 1 at the time of curing is small, it is possible to prevent a decrease in the shape stability of the multilayer printed wiring board.
In the temporary curing step or the curing step of the present composition 1, unnecessary portions protruding from the through holes or recesses of the molded product may be removed and flattened. After that, a metal film may be formed on the surface of the multilayer printed wiring board by plating or the like, and a predetermined pattern may be patterned to form a circuit pattern. Here, the surface of the multilayer printed wiring board may be roughened with an aqueous solution of potassium permanganate or the like, if necessary, prior to the formation of the metal film.

The composition 1 can also be suitably used for producing a dry film.
Such a dry film can be produced by applying the present composition 1 on a carrier film and drying it to form a resin film as a dry film. A protective film may be laminated on the dry film, if necessary.
The carrier film is a film having a function of supporting a dry film. Examples of such a carrier film include a polyolefin film, a polyester film, a polyimide film, a polyamide-imide film, a polytetrafluoroethylene film, a polystyrene film, and a surface-treated paper substrate. Among them, a polyester film is preferable from the viewpoint of heat resistance, mechanical strength, handleability and the like.
The surface of the carrier film may be subjected to a mold release treatment.

The protective film is a film that is attached to the surface of the dry film opposite to the carrier film for the purpose of preventing dust and the like from adhering to the surface of the dry film and improving its handleability.
As the protective film, for example, the same film or paper base material as mentioned in the above carrier film is used, and a polyolefin film or a polyester film is preferable.
The thickness of the protective film is preferably 10 to 150 μm. The surface of the protective film may be subjected to a mold release treatment.

Examples of a method for producing a printed wiring board from a laminated film having a dry film, a carrier film, and a protective film include the following methods.
First, either the carrier film or the protective film is peeled off from the dry film. When the present composition 1 contains a curing agent or a curing accelerator, it is then pressure-bonded to a circuit board on which a circuit pattern is formed and then thermosetting. An oven, a heat press, or the like can be used for thermosetting. After that, a through hole (via hole) is formed at a predetermined position on the circuit board by laser processing or drilling to expose the circuit pattern. As a result, a printed wiring board can be obtained. If unnecessary components (smear) remain on the circuit pattern because they cannot be completely removed, it is preferable to perform desmear treatment.
The other of the carrier film and the protective film is peeled from the dry film at a predetermined stage. For the electrical connection between the circuit patterns, a conductive film formed on the inner surface of the through hole, a pillar or a post housed in the through hole can be used.

The base material with a convex portion of the present invention (hereinafter, also referred to as “base material with a convex portion”) is provided on the base material and the surface of the base material, and has a predetermined pattern formed from the present composition 1. It has a convex portion. The convex portion can be produced by the above-mentioned method using the present composition 1 as a negative type resist composition.
As the base material, a base material I: an active matrix substrate in which a pixel electrode, a switching element and wiring are formed on the substrate, and a base material II: a laminated plate in which a polymer film and a metal layer are laminated can be used.
In the case of the base material I, the convex portion is 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 electrophoretic dispersion containing an organic EL layer (electron transport layer, light emitting layer, hole transport layer, etc.) and electrophoretic particles is arranged in the space partitioned by the convex portion, and a common electrode or the like is provided. A display device (electronic device) can be manufactured by arranging the facing substrate facing the active matrix substrate.

In such a configuration, the convex portion can be provided with a function as a spacer that defines the separation distance between the two substrates and a black matrix that prevents crosstalk between unit pixels.
Further, since the convex portion of the base material with the convex portion has excellent water and oil repellency and few defects, the ink forming the organic EL layer and the electrophoresis dispersion liquid do not easily adhere to the convex portion, and the display performance is excellent. A display device is obtained. Further, since the convex portion is also excellent in electrical characteristics (low dielectric constant), parasitic capacitance is unlikely to occur in the display device, and deterioration of switching characteristics can be prevented.

In the case of the base material II, the polymer film may be a single-layer film composed of only a polymer layer, and is a laminated film having a polymer layer as a surface layer and a support layer supporting the surface layer (polymer layer). May be good.
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, and a film having a prepreg layer.
The prepreg is a sheet-like substrate in which a fiber base material (tow, woven fabric, etc.) of reinforcing fibers (glass fiber, carbon fiber, etc.) is impregnated with a thermosetting resin or a thermoplastic resin.

The heat-resistant resin film is a film containing one or more heat-resistant resins. Examples of the heat-resistant resin include polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, liquid crystal polyester, and liquid crystal polyester amide. Fluororesin other than polyimide (particularly aromatic polyimide), F polymer, and F polymer is preferable.
The polymer layer preferably contains the above-mentioned heat-resistant resin, and more preferably contains an F polymer. In such a case, the base material tends to have excellent low dielectric loss tangent properties, and the convex portion and the base material tend to adhere firmly.

The polymer layer containing the F polymer may be obtained by melt-kneading the F polymer and extrusion molding. In this case, the laminated film is obtained by thermocompression bonding a film containing an F polymer and a support layer.
The polymer layer containing the F polymer may be obtained by applying a dispersion liquid containing F particles and a liquid dispersion medium to a base material and heating the substrate. In this case, if the base material is peeled off, a single-layer film containing the F polymer is obtained, and if the film constituting the support layer is used as the base material and the base material is not peeled off, a laminated film is obtained.
The laminated board as the base material II can be produced by thermocompression bonding a polymer film and a metal foil.
Examples of the material of the metal foil include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, titanium alloy and the like.
The metal foil is preferably a copper foil, more preferably a rolled copper foil or an electrolytic copper foil.

A preferred embodiment of the laminated board as the base material II is a polymer layer / metal layer containing a prepreg layer / F polymer. The metal layer may have a predetermined pattern. Further, a printed wiring board may be obtained by forming a main convex portion on a metal layer having no pattern and using this convex portion as a mask to etch the metal layer and process it into a circuit.

Although the present method 1, the present composition 1, and the base material with a convex portion have been described above, the present invention is not limited to the configuration of the above-described embodiment.
For example, the present method 1 may additionally have any other step in the configuration of the above embodiment, or may be replaced with any step that produces the same action. Further, in the configuration of the above-described embodiment, the present composition 1 may be added with any other configuration, or may be replaced with an arbitrary configuration exhibiting the same function.

Subsequently, the second aspect of this method (hereinafter, also referred to as “this method 2”) will be described.
In this method 2, F particles, an aromatic resin, at least one thickening polymer selected from the group consisting of polar vinyl polymers and polysaccharides, and water are stirred by a thin film swirl or a rotation. A method of obtaining a liquid composition containing F particles, an aromatic resin, a thickening polymer, and water (hereinafter, also referred to as "this composition 2") by mixing in a tank equipped with a stirring mechanism by revolution. Is.
The present composition 2 is excellent in dispersion stability, uniformity and handleability. Further, from the present composition 2, it is possible to form a molded product having excellent electrical characteristics and low linear expansion property, which has a high degree of physical characteristics of the F polymer and the physical characteristics of the aromatic resin. The reason and its mechanism of action are not always clear, but are estimated as follows, for example.

F polymer has low dispersibility due to its low surface energy. When the F particles and the aromatic resin are mixed in water by applying a strong shearing force to improve the dispersibility of the liquid composition, the F polymer is modified by fibrillation and the like to form complex secondary particles. It becomes easy to aggregate. Even when a thickening polymer is used, the interaction within a single component is conversely enhanced rather than the interaction between the components, and for example, the thickening polymer itself tends to aggregate. As described above, it has been difficult to obtain a liquid composition having excellent dispersion stability, uniformity and handleability by mixing the F particles and the aromatic resin while suppressing component aggregation.

In this method 2, F particles, an aromatic resin, a thickening polymer, and water are mixed by a stirring mechanism by thin film swirling or in a tank equipped with a stirring mechanism by rotation and revolution. Each of the aromatic resins is mixed with the thickening polymer highly impregnated. In other words, it can be considered that the thickening polymer alleviates the impact of collision generated when the two are mixed, and suppresses the denaturation of F particles and the aggregation of components. Further, it can be considered that the collision between the F particles and the aromatic resin promotes the formation of the coalesced particles of both (composite particles in which the aromatic resin is bonded to the surface of the F particles, etc.).

Due to these factors, the F particles are highly mixed with the aromatic resin at the individual particle level, so that a liquid composition having excellent dispersion stability, uniformity and handleability and suppressed foaming can be obtained by this method 2. It is believed that it was obtained.
Further, since uniform particles typified by the coalesced particles are contained, when a liquid component such as water is removed from the composition 2, it becomes easy to form a uniform and dense packing structure of particles. .. As a result, it is considered that from the present composition 2, the aromatic resin was densely arranged in the F polymer, and a molded product having excellent electrical characteristics and low linear expansion property was obtained.

The aromatic resin (also referred to as “aromatic polymer”) in the present invention improves the liquid physical characteristics such as the dispersion stability of the present composition 2 by the above-mentioned action mechanism, and is a molded product obtained from the present composition 2. In addition, flexibility such as bending resistance and UV absorption can be imparted. Further, when the composition 2 is applied to the surface of a base material such as a polyimide film or a metal foil to form a polymer layer containing an F polymer, the aromatic polymer has adhesiveness to the resin film of the polymer layer. It is possible to impart characteristics such as adhesion.
The aromatic polymer may be thermosetting, thermoplastic or modified. The aromatic polymer may be contained 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 composition 2.

The acid value of the aromatic polymer is preferably 20 to 100 mg / KOH, more preferably 35 to 70 mgKOH / 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 opened is defined as the acid value of the aromatic polymer.
As for the acid value, about 0.5 g of aromatic polymer was collected, about 0.15 g of 1,4-diazabicyclo [2.2.2] octane was added thereto, and about 60 g of N-methyl-2-pyrrolidone and ions were added. Add about 1 mL of replacement water and stir until the aromatic polymer is completely dissolved. This can be measured by titrating with a potentiometric titrator using a 0.05 mol / L ethanolic potassium hydroxide solution.

The average molecular weight of the aromatic polymer is preferably 5000 or more, more preferably 10000 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 dissolved in water. Further, the molded product obtained from the present composition 2 tends to have excellent mechanical properties such as bending resistance.
Examples of the aromatic polymer include an aromatic imide resin, an aromatic sulfide resin, an aromatic sulfone resin, and a phenol resin, and an aromatic imide resin is preferable.

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

Examples of the water-soluble aromatic polyimide precursor include a polyamic acid obtained by polymerizing a tetracarboxylic acid dianhydride and a diamine in a solvent, and a polyamic acid salt obtained by reacting the polyamic acid with aqueous ammonia or an organic amine. Can be mentioned. An aqueous solution of a polyamic acid can be prepared by dissolving the polyamic acid salt in water.
Examples of the tetracarboxylic acid dianhydride include pyromellitic acid anhydride and biphenyltetracarboxylic acid anhydride. Examples of the diamine include N, N'-diaminodiphenyl ether and p-diaminobenzene. Examples of the solvent include N-methylpyrrolidone and N, N-dimethylformamide.

Examples of the organic amine include primary amines such as methylamine, ethylamine, n-propylamine, 2-ethanolamine and 2-amino-2-methyl-1-propanol; dimethylamine, 2- (methylamino) ethanol, and the like. Secondary amines such as 2- (ethylamino) ethanol; Tertiary amines such as 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-dimethylamino-2-propanol; A quaternary ammonium salt can be mentioned.

As the water-soluble aromatic polyamide-imide or its precursor, the aromatic polyamide-imide obtained by reacting diisocyanate and / or diamine with tribasic acid anhydride (or tribasic acid chloride) as an acid component or its precursor. Examples include precursors.
Examples of the diisocyanate include 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'-diphenylmethane diisocyanate, and 3,3'-dimethoxybiphenyl-4. , 4'-diisocyanate, paraphenylenediocyanate, hexamethylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, tolylene diisocyanate, isophorone diisocyanate. These diisocyanates may be used alone or in combination of two or more.

From the viewpoint of improving the stability of the aromatic polyamide-imide, a blocked isocyanate having an isocyanate group stabilized by a blocking agent may be used as the diisocyanate. Examples of the blocking agent include alcohol, phenol, oxime and the like.
Examples of the diamine include 3,3'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'. -Diaminodiphenyl sulfone, xylylene diamine, phenylenediamine, isophoronediamine can be mentioned. These diamines may be used alone or in combination of two or more.

Examples of the tribasic acid anhydride include trimellitic acid anhydride, and examples of the tribasic acid chloride include trimellitic acid anhydride chloride. As the tribasic acid anhydride, trimellitic acid anhydride is preferable from the viewpoint of reducing the burden on the environment.
When producing an aromatic polyamideimide, in addition to the above tribasic acid anhydride (or tribasic acid chloride), dicarboxylic acid, tetracarboxylic acid dianhydride, etc. are used as acid components, and the characteristics of the aromatic polyamideimide. May be used as long as the above is not impaired.

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

The proportion of diisocyanate and / or diamine and acid component (total amount of tribasic acid anhydride or tribasic acid chloride and dicarboxylic acid and tetracarboxylic acid dianhydride used as needed) is the aromatic polyamideimide produced. From the viewpoint of the molecular weight and the degree of cross-linking of the acid component, the amount of the diisocyanate compound and / or the diamine compound is preferably 0.8 to 1.1 mol with respect to the total amount of the acid component of 1.0 mol.
Specific examples of the water-soluble aromatic polyamide-imide or its precursor include "HPC-1000" and "HPC-2100D" (both manufactured by Showa Denko Materials Co., Ltd.).

Examples of the aromatic polyetherimide include an amorphous polymer having an imide bond and an ether bond in the main chain, and 2,2-bis [4- (3,4-dicarboxyphenyloxy) phenyl] propane and m. -A polycondensate with phenylenediamine is preferable. Specific examples of the aromatic polyetherimide include "Ultem 1000F3SP" (manufactured by SABIC).
Examples of the aromatic sulfide resin include polyphenylene sulfide.
Examples of the aromatic sulfone resin include polyphenylsulfone.

The content of the aromatic polymer in the composition 2 is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, based on the total mass of the present composition 2. The content of the aromatic polymer is preferably 30% by mass or less, more preferably 10% by mass or less, based on the total mass of the composition 2.
The ratio of the content of the aromatic polymer to the content of the F particles in the composition 2 is preferably 0.001 or more, more preferably 0.005 or more. The ratio of such contents is preferably 0.1 or less, more preferably 0.05 or less.

The thickening polymer in the present invention is at least one polymer selected from the group consisting of polar vinyl-based 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.
Polar functional groups include ether bond, ester bond, amide bond, imide bond, thioether bond, sulfide bond, disulfide bond, carbonyl group-containing group, hydroxyl group-containing group, thiol group, sulfide group, sulfonyl group, sulfoxyl group and amino group. , Amid group.

The thickening polymer may be thermosetting, thermoplastic or modified. The thickening polymer may be contained in the present composition 2 as a precursor thereof.
The thickening polymer is preferably water soluble. In other words, the thickening polymer is preferably dissolved in the composition 2.

The thickening polymer preferably has a carbonyl group-containing group or a hydroxyl group-containing group. In this case, the affinity of the thickening polymer with the F particles and the aromatic polymer is improved, the composition 2 tends to have excellent physical properties such as dispersion stability, and the thickening polymer has an excellent action as a binder. Cheap.
The average molecular weight of the thickening polymer is preferably 3000 or more, more preferably 10000 or more, further 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 tends to be excellent in physical properties such as dispersion stability.

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 equal to or lower than the melting temperature of the F polymer. In this case, the thickening polymer tends to have an excellent action as a binder. Further, the thickening polymer is unlikely to remain in the molded product formed from the present composition 2, and the molded product tends to have excellent physical properties such as electrical characteristics.

Examples of the polar vinyl polymer include vinyl alcohol-based polymers such as polyvinyl alcohol, vinylpyrrolidone-based polymers such as polyvinylpyrrolidone, acrylic acid-based polymers such as polyacrylic acid, and carboxyvinyl-based polymers such as carboxyvinyl polymer. Based polymers are preferred.

As the vinyl alcohol-based polymer, polyvinyl alcohol, polyvinyl acetate, a partially acetylated product of polyvinyl alcohol, a partially acetal product of polyvinyl alcohol, and a copolymer of vinyl alcohol, vinyl butyral, and vinyl acetate are preferable.
Specific examples of vinyl alcohol-based polymers include "Eslek (registered trademark) B" series, "Eslek (registered trademark) K (KS)" series, and "Eslek (registered trademark) SV" series (all manufactured by Sekisui Chemical Co., Ltd.). ) ”,“ Mobital (registered trademark) ”series (manufactured by Kuraray).

Examples of acrylic acid-based polymers include polyacrylates such as polyacrylic acid, methyl polyacrylate, and ethyl polyacrylate, poly-α-haloacrylate, poly-α-cyanoacrylate, polyacrylamide, and sodium polyacrylate.

Polysaccharides include glycogen, amylose, agarose, amyropectin, cellulose, dextrin, glucan, fructan, chitin, xanthan gum, guar gum, casein, arabic gum, gelatin, agaropectin, arabinan, curdran, carose, carboxymethyl starch, chitin, chitosan. , Quince seed, glucomannan, gellan gum, tamarin seed gum, dextran, nigeran, hyaluronic acid, cellulose, funoran, pectin, porphyran, laminaran, likenan, carrageenan, alginic acid, tragacanto gum, alkathy gum, locust bean gum and the like.
Among the above, the thickening polymer is preferably a nonionic polysaccharide, preferably glycogen, amylose, agarose, amylopectin, cellulose, dextrin, glucan, fructan, or chitin, and preferably carboxymethyl cellulose or hydroxyethyl cellulose as the cellulose. The carboxymethyl cellulose may be a carboxymethyl cellulose salt such as sodium carboxymethyl cellulose or ammonium carboxymethyl cellulose. Hydroxyethyl cellulose has an average number of moles of 1.5 or more and 2.5 or less, which is an index indicating the degree of ethylene oxide addition, from the viewpoint that foaming and aggregation due to air entrainment can be suppressed during mixing. preferable.
Specific examples of polysaccharides include "Sunrose (registered trademark)" series (manufactured by Nippon Paper Industries), "Metros (registered trademark)" series (manufactured by Shin-Etsu Chemical Co., Ltd.), and "HEC CF grade" (Sumitomo Seika Chemical Co., Ltd.). Made by).

The content of the thickening polymer in the present composition 2 is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the total mass of the present composition 2. The content of the thickening polymer is preferably 30% by mass or less, more preferably 10% by mass or less, based on the total mass of the composition 2.
The ratio of the content of the thickening polymer to the content of F particles in the present composition 2 is preferably 0.001 or more, more preferably 0.003 or more. The ratio of such contents is preferably 0.05 or less, more preferably 0.03 or less, still more preferably 0.01 or less.

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

In the first aspect of the second method (hereinafter, also referred to as "aspect 2-1"), F particles, an aromatic resin, a thickening polymer, and water are mixed in a tank equipped with a stirring mechanism by thin film swirling. That is, these components are swirled and mixed while spreading in a thin film to obtain the present composition 2.
In the second aspect, the mixing is preferably carried out by applying a centrifugal force associated with swirling to each component developed in a thin film. In this case, the thickening polymer is highly permeated into each of the F particles and the aromatic polymer, and the mixing proceeds. Specifically, the mixing is preferably performed by the thin film swirl type high-speed mixer described in the present method 1.

The details of the stirring tank in the thin film swirling high-speed mixer and the rotating portion having the cylindrical portion in which a plurality of holes are formed are as described above.
In mixing, F particles, an aromatic resin, a thickening polymer, and water may be collectively supplied into the stirring tank, or may be separately supplied into the stirring tank using a plurality of inlets. May be good.
Mixing can be carried out in batch or continuous manner. In the case of the continuous type, one stirring tank may be used to supply the mixture taken out from the discharge port again from the input port and mixed, or a plurality of stirring tanks may be used to prepare the stirring tank in the previous stage. The mixture taken out from the discharge port may be supplied from the input port of the stirring tank in the subsequent stage and mixed. The supplied F particles, aromatic resin, thickening polymer, and water spread over the gap between the inner wall surface of the stirring tank and the outer peripheral surface of the cylindrical portion of the rotating portion to form a film, which accompanies the rotation of the rotating portion. And swirl at high speed in the stirring tank. At this time, by receiving not only shear stress but also shear stress, dispersion mixing at a high level is achieved.

In aspect 2-1 the mixing is a stirrer comprising a truncated cone-shaped and cylindrical stator and a disk rotating inside the inner wall surface of the stator, in which F particles, an aromatic polymer, a thickening polymer, and water are mixed. , The cylinder may be passed through a cylindrical gap between the stator and the disc while being swiveled by the rotation of the disc. In this case, it is preferable that the inner wall surface of the stator and the disk are provided with an uneven structure. Examples of such a concavo-convex structure include a structure having grid-like grooves or dimples having a height (depth) of about several μm to several hundred μm. Such agitating means is sometimes referred to as a colloid mill.

The outer peripheral surface of the disc faces the inner wall surface of the stator with a slight gap of about 1 to 10 mm. The peripheral speed and stirring time of the disc can be set as appropriate.
In this case, the supplied F particles, aromatic resin, thickening polymer, and water form a film when passing through the gap between the inner wall surface of the stator and the outer peripheral surface of the disk, and become a film as the disk rotates. It turns at high speed in the stator. At this time, by receiving not only shear stress but also shear stress, dispersion mixing at a high level is achieved.

In aspect 2-1 it is preferable to mix the composition containing F particles, an aromatic resin, a thickening polymer, and water by swirling a thin film. That is, it is preferable that the F particles, the aromatic resin, the thickening polymer, and water are premixed before being swirled in a thin film and mixed. In this case, the mechanism of action of the method 2 described above is enhanced, foaming of the composition 2 is suppressed, and physical properties such as dispersion stability are likely to be further improved.

Examples of the premixing method include the same method as the above-mentioned mixing method for mixing the varnish of the present composition 1 and the second aromatic resin.
The composition containing the F particles, the aromatic resin, the thickening polymer, and water is preferably a kneaded product obtained by premixing the F particles, the aromatic resin, the 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 the above-mentioned method 2 is likely to be enhanced. The kneaded product is preferably a solidified product (paste) having fluidity and viscosity, or a lumpy and clay-like solidified product (powder).

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

In the second aspect of this method 2 (hereinafter, also referred to as "aspect 2-2"), F particles, an aromatic resin, a thickening polymer, and water are mixed in a tank equipped with a stirring mechanism by rotation and revolution. Then, the present composition 2 is obtained. Here, the stirring mechanism by rotation is a mechanism that stirs the object by rotating the tank containing the stirring object around the rotation axis. The direction of the rotation axis may be any direction with respect to the tank. On the other hand, the stirring mechanism by revolution is a mechanism in which the tank orbits around a fixed point outside the tank containing the stirring object to stir the object. The layer may be vertical, horizontal or inclined with respect to the revolution surface. Such agitating means may be referred to as a rotation / revolution agitator.
In the second aspect, it is preferable that the mixing is performed under the condition that the rotation speed is twice or more the revolution speed or the revolution speed is twice or more the rotation speed. In this case, foaming and aggregation due to air entrainment are suppressed, and the present composition 2 having excellent dispersibility and dispersion stability can be easily obtained.
Also in the second aspect, the composition containing the F particles, the aromatic polymer, the thickening polymer, and water may be mixed in a tank equipped with a stirring mechanism by rotation and revolution. That is, the F particles, the aromatic polymer, the thickening polymer, and water may be premixed before being mixed in a tank provided with a stirring mechanism by rotation and revolution.

Further, F particles, an aromatic resin, a thickening polymer and water may be mixed in any of aspects 2-1 and 2-2, and water may be further mixed to obtain the present composition 2.
Further, as a method for mixing water, a method that may be used for the above-mentioned premixing of Aspects 2-1 and 2-2 and the above-mentioned premixing can be adopted, and Aspects 2-1 and 2-2 are preferable. In particular, it is preferable to mix the F particles, the aromatic resin, the thickening polymer, and water with water in the same manner, and it is preferable to mix the two in the second mode. .. In this case, the mechanism of action of the present method 2 described above is enhanced, and the physical properties such as the dispersion stability of the present composition 2 are likely to be further improved.

In the mixing, inorganic particles may be further added. The step of adding the inorganic particles may be before or during mixing. For example, a composition containing F particles, an aromatic resin, a thickening polymer, water and inorganic particles may be prepared and used for mixing.
As the inorganic particles, nitride particles or inorganic oxide particles are preferable, and boron nitride particles, beryllia particles (particles of berylium oxide), silicate particles (silica particles, wollastonite particles, talc particles), or metals. Oxide (cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.) particles are more preferable, boron nitride particles and silica particles are more preferable, and silica particles are particularly preferable.

At least a part of the surface of the inorganic particles is a silane coupling agent (3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3). -It is preferable that the surface is treated with (methacryloxypropyltriethoxysilane, 3-isocyanuppropyltriethoxysilane, etc.).
The D50 of the inorganic particles is preferably 20 μm or less, more preferably 10 μm or less. D50 is preferably 0.01 μm or more, more preferably 0.1 μm or more.

The shape of the inorganic particles may be spherical, needle-shaped (fibrous), or plate-shaped, and is preferably spherical or plate-shaped.
Specific shapes of the inorganic particles include spherical, scaly, layered, leafy, apricot kernel, columnar, chicken crown, equiaxed, leafy, mica, block, flat, wedge, rosette, and mesh. Shape and prismatic shape.
As the inorganic particles, one type may be used alone, or two or more types may be used in combination. When the composition 2 further contains inorganic particles, the amount thereof is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, based on the total mass of the composition 2.
Preferable specific examples of the inorganic particles include the same specific examples of the inorganic filler that may be further mixed when the composition 1 and the varnish of the second aromatic resin are mixed.

In both aspects 2-1 and 2-2, it is preferable that the F particles are mixed in a powder state in advance and crushed prior to mixing. That is, it is preferable to perform a treatment in which the agglomerated state of the F particles is eliminated in advance so that the F particles are in a dispersed state.
The crushing of the F particles can be carried out by a method that may be used for the premixing of Aspect 2-2 and the above-mentioned premixing, and is preferably carried out by the method of Aspect 2-2.
When the above-mentioned inorganic particles are further added, it is preferable that the F particles and the inorganic particles are mixed in advance in the state of a powder mixture as described above, crushed, and subjected to the present method 2.
Further, when the F particles, the aromatic resin, the thickening polymer, and the water are premixed before being mixed by swirling the thin film or before being mixed in a tank equipped with a stirring mechanism by rotation and revolution, the F particles are mixed. Crushing is preferably performed prior to premixing.

In mixing, a surfactant may be further added. The step of adding the surfactant may be before or during mixing. For example, a composition containing F particles, an aromatic resin, a thickening polymer and water, and a surfactant may be prepared and used for mixing.
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. The present composition 2 may contain a silicone-based surfactant and a glycol monoalkyl ether.

Specific examples of nonionic surfactants include the "Futergent" series (Futergent manufactured by Neos Co., Ltd. is a registered trademark), the "Surflon" series (Surflon manufactured by AGC Seimi Chemical Co., Ltd. is a registered trademark), and the "Megafuck" series. (Megafuck manufactured by DIC Co., Ltd. is a registered trademark), "Unidyne" series (Unidyne manufactured by Daikin Kogyo Co., Ltd. is a registered trademark), "BYK-347", "BYK-349", "BYK-378", "BYK-3450" , "BYK-3451", "BYK-3455", "BYK-3456" (manufactured by Big Chemie Japan Co., Ltd.), "KF-6011", "KF-6043" (manufactured by Shinetsu Chemical Industry Co., Ltd.), " Tergitol "series (manufactured by Dow Chemical Co., Ltd." Tergitol TMN-100X "etc.)," Lutensol T08 "," Lutensol XL70 "," Lutensol XL80 "," Lutensol XL90 "," Lutensol XP80 "," Lutensol XP80 "," Lutensol , BASF), "New Call 1308FA", "New Call 1310" (above, manufactured by Nippon Embroidery Co., Ltd.), "Leocol TDN-90-80", "Leocol SC-90" (above, Lion Specialty Chemicals) Made by).
When the present composition 2 contains a surfactant, the content of the surfactant in the present composition 2 is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass.

The present composition 2 may further contain a pH adjuster or a pH buffer from the viewpoint of pH adjustment. In this case, the pH of the present composition 2 is preferably adjusted to 5 to 10 and more preferably 7 to 9 with a pH adjuster or a pH buffer.
Examples of the pH adjuster include amines, ammonia and citric acid.
Examples of the pH buffer include tris (hydroxymethyl) aminomethane, ethylenediaminetetraacetic acid, ammonium hydrogencarbonate, ammonium carbonate, and ammonium acetate.
The step of adding the pH adjuster or pH buffer may be before or during mixing.
The present composition 2 may be further subjected to a defoaming treatment. Defoaming is preferably performed using a rotation / revolution stirrer.

A water-soluble solvent may be further added to the composition 2. Due to the mechanism of action described above, the composition 2 has excellent dispersion stability and can be easily mixed with a water-soluble solvent. Examples of the water-soluble solvent include compounds similar to the water-soluble solvent that can be used in the above-mentioned composition 2.
In addition to the above-mentioned components, the present composition 2 contains a thixo-imparting agent, a viscosity modifier, an antifoaming agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antioxidant, a whitening agent, and the like. Coloring agents, conductive agents, mold release agents, surface treatment agents, flame retardants, preservatives, fungicides, organic fillers and the like may be further added.
Since the composition 2 is excellent in dispersion stability due to the above-mentioned mechanism of action, the liquid physical characteristics can be easily adjusted by adding these.

The viscosity of the 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 the composition 2 is preferably 10,000 mPa · s or less, more preferably 3000 mPa · s or less, and even more preferably 1000 mPa · s or less. In this case, the present composition 2 tends to be excellent in liquid physical properties such as dispersion stability.
The thixotropy of the composition 2 is preferably 1.0 or more. The thixotropy of the composition 2 is preferably 3.0 or less, more preferably 2.0 or less. In this case, the present composition 2 is excellent in liquid physical characteristics such as dispersion stability, and it is easy to form a more dense molded product.

The dispersed layer ratio of the present composition 2 is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more. Since the present composition 2 is excellent in dispersion stability, it is easy to take a value in the range where the dispersion layer ratio is applied.
Here, the dispersed layer ratio is the liquid composition in the screw tube after the liquid composition (18 mL) is placed in a screw tube (internal volume: 30 mL) and allowed to stand at 25 ° C. for 14 days. It is a value calculated by the following formula from the total height and the height of the sedimentation layer (dispersion layer). If the sedimented layer is not confirmed after standing and the state does not change, the height of the entire liquid composition does not change, and the dispersed layer ratio is set to 100%.
Dispersed layer ratio (%) = (height of sedimented layer) / (height of the entire liquid composition) × 100

The dispersity of the 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 the composition 2 is preferably 10 μm or more. In the present composition 2, since the aggregation of F particles is suppressed by the above-mentioned mechanism of action, the degree of dispersion tends to be in the above range.
The degree of dispersion means the size of coarse particles existing in the liquid composition, which is measured according to JIS K5600-2-5 using a grind meter.

The present composition 2 is excellent in liquid physical properties such as dispersion stability, and can form a molded product having excellent physical properties based on an F polymer and an aromatic resin by the above-mentioned mechanism of action. In addition, it is possible to form a molded product that exhibits strong adhesiveness to the base material.
In the method for producing a laminate of the present invention, the composition 2 is applied to the surface of a base material and heated to form a polymer layer containing an F polymer and an aromatic resin (hereinafter, also referred to as “F layer 1”). Is a method for producing a laminate, which comprises forming a laminate having a substrate layer composed of a substrate and an F layer 1.
More specifically, the present composition is applied to the surface of the base material to form a liquid film, the liquid film is heated to remove the dispersion medium to form a dry film, and the dry film is further heated. By firing the F polymer, a laminate having the F layer 1 on the surface of the base material layer can be obtained.

As the base material, a metal substrate (copper, nickel, aluminum, titanium, metal foil such as an alloy thereof, etc.), a heat-resistant resin film (polyethylene, polyarylate, polysulfone, polyallylsulfone, polyamide, polyetheramide, polyphenylene sulfide, etc.) , Polyallyl ether ketone, polyamideimide, liquid crystal polyester, liquid crystal polyester amide, tetrafluoroethylene polymer, and other heat-resistant resins. (May be good), prepreg (precursor of fiber-reinforced resin substrate), glass.
The metal substrate may be a low-roughened copper foil or a non-roughened copper foil. When the metal substrate is a low-roughened copper foil or a non-roughened copper foil, the laminate tends to have excellent transmission characteristics.
The ten-point average roughness of the surface of the base material is preferably 0.01 to 0.05 μm.
Examples of the shape of the base material include a flat shape, a curved surface shape, and an uneven shape, and further, any of a foil shape, a plate shape, a film shape, and a fibrous shape may be used.

The method of applying the composition 2 to the surface of the base material may be any method as long as a stable liquid film (wet film) composed of the present composition 2 is formed on the surface of the base material, and is a coating method or droplets. Examples thereof include a discharge method and a dipping method, and a coating method is preferable. If the coating method is used, a liquid film can be efficiently formed on the surface of the base material with simple equipment.
The coating methods include spray method, roll coating method, spin coating method, gravure coating method, micro gravure coating method, gravure offset method, knife coating method, kiss coating method, bar coating method, die coating method, fountain Mayer bar method, and slot die coating. The method and the dip coat method can be mentioned.

When the liquid film is dried, the liquid film is heated at a temperature at which liquid components (including water) volatilize to form a dry film on the surface of the base material. The heating temperature in such drying is preferably 100 to 200 ° C. Air may be blown in the step of removing the liquid component.
At the time of drying, the liquid component 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.
When firing the F polymer, it is preferable to heat the dry film at a temperature equal to or higher than the melting temperature of the F polymer. The heating temperature is preferably 380 ° C. or lower, more preferably 350 ° C. or lower.

Examples of each heating method include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating 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.), 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.
By heating under the above conditions, the F layer 1 can be suitably formed while maintaining high productivity.

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 is excellent in 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 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 the present composition 2, such a laminated body can be easily formed without impairing the physical characteristics of the F polymer in the F layer 1.

The present composition 2 may be applied only to one surface of the base material, or may be applied to both sides of the base material. In the former, a base material layer composed of a base material and a laminate having an F layer 1 on one surface of the base material layer are obtained, and in the latter, a base material layer composed of a base material and such a base material are obtained. A laminate having the F layer 1 on both surfaces of the material layer is obtained. Since the latter laminate 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 1 on at least one surface of the metal foil, a polyimide film, and a multilayer having an F layer 1 on both surfaces of the polyimide film. Film is mentioned. Since these laminates are excellent in various physical properties such as electrical characteristics, they are suitable as printed circuit board materials and the like, and can be used for manufacturing flexible printed circuit boards and rigid printed circuit boards.

In this laminate having the F layer 1 on both surfaces of the base material layer, the composition 2 is applied to both surfaces of the base material, heated to remove liquid components, and further heated to obtain an F polymer. It may be obtained by firing to form the F layer 1 on both surfaces at the same time.

This laminate having the F layer 1 on both surfaces of the base material layer is heated by immersing the base material in the present composition 2 to apply the present composition 2 to both surfaces of the base material, and then passing the base material through a firing furnace. You may get it. Specifically, after immersing the base material in the present composition 2, the base material may be obtained by passing it through a firing furnace while pulling it up from the present composition 2 and heating it.
Such a laminate can be suitably produced by using an apparatus having a dip coater and a firing furnace. Examples of the firing furnace include a vertical firing furnace. Further, as such a device, a glass cloth coating device manufactured by Tabata Machinery Co., Ltd. can be mentioned.

As described above, when the present composition 2 is used, a laminate having excellent uniform distribution of components and excellent electrical characteristics can be obtained. The present composition 2 is particularly suitable when a multilayer film containing the F layer 1 on both surfaces of the polyimide film is produced by a roll-to-roll process. Such a multilayer film can be effectively used as a material for a printed wiring board, particularly a flexible printed wiring board, and can satisfactorily exhibit the physical characteristics of the F polymer.

Further, by removing the base material from the present laminate, a sheet made of F layer 1 can be manufactured. The method of removal includes peeling or etching.
The laminate of the F layer 1 and the base material layer and the sheet composed of the F layer 1 are useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry supplies, heat dissipation parts, paints, cosmetics, etc. Is.

Specifically, wire coating materials (aircraft wires, etc.), enamel wire coating materials used for motors of electric vehicles, etc., electrically insulating tapes, insulating tapes for oil drilling, materials for printed substrates, separation films (precision). Filtration membrane, ultrafiltration membrane, back-penetration membrane, ion exchange membrane, dialysis membrane, gas separation membrane, etc.), electrode binder (for lithium secondary battery, fuel cell, etc.), copy roll, furniture, automobile dashboard, home appliances Product covers, sliding members (load bearings, sliding shafts, valves, bearings, bushes, 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, worn parts of centrifugal pumps, hydrocarbon / chemical and water supply pumps, tools (shovels, shavings, cuttings, saws, etc.), boilers, hoppers, pipes, ovens, baking molds. , Chute, die, toilet bowl, container coating material, power device, transistor, thyristor, rectifier, transformer, power MOS FET, CPU, heat dissipation fin, metal heat dissipation plate, blade of windmill, wind power generation equipment, aircraft, etc., heat dissipation for automobiles It can also be suitably used as a heat radiating member for a substrate and a wireless communication device (for example, the wireless communication device described in International Publication No. 2020/008691 and International Publication No. 2020/031419).

This laminate in which the base material layer is a resin film (preferably a polyimide-based resin film) is useful as a release film or a carrier film. Since this laminate has excellent adhesiveness between the F layer 1 and the base material layer and is difficult to delaminate, it can be used repeatedly as a carrier film. Further, since the F layer 1 has excellent heat resistance, the releasability is unlikely to deteriorate even after repeated use.
Specifically, the laminate is a carrier film for forming a ceramic green sheet, a carrier film for forming a secondary battery, a carrier film for forming a solid polymer electrolyte membrane, and a carrier film for forming a catalyst for a solid polymer electrolyte membrane. It is useful as.

The liquid composition of the present invention contains F particles, an aromatic resin, at least one thickening polymer selected from the group consisting of polar vinyl polymers and polysaccharides, and water, and is a thickening polymer for F particles. It is a liquid composition having a content ratio of 0.05 or less.
The definitions and ranges of F particles, aromatic resin, thickening polymer, and water in the liquid composition of the present invention are the same as those in the present composition 2 of the present method 2 including suitable ranges. Further, the physical characteristics of the liquid composition of the present invention are the same as those in the present composition 2 of the present method 2.
The liquid composition of the present invention can be suitably produced by the present method 2.

The composition of the present invention contains F particles, an aromatic resin, at least one thickening polymer selected from the group consisting of polar vinyl polymers and polysaccharides, and water, and is a thickening polymer for F particles. A composition having a content ratio of 0.05 or less, a temperature of 25 ° C., a shear rate of 1s ^-1 , and a viscosity measured by a capillograph of 10000 Pa · s to 100,000 Pa · s. Since the composition of the present invention is excellent in uniformity, a liquid composition excellent in dispersion stability, uniformity and handleability can be obtained by mixing the composition of the present invention with water.

The definitions and ranges of F particles, aromatic resins, thickening polymers, and water in the composition of the present invention are the same as those in the present composition 2 of the present method 2 including suitable ranges.
The viscosity of the composition of the present invention as measured by capillograph, where the temperature is 25 ° C. and the shear rate is 1s ^-1 , is preferably 15,000 Pa · s or more. The viscosity is preferably 50,000 Pa · s or less, and more preferably 30,000 Pa · s or less.
The composition of the present invention is preferably a powder containing sufficiently water and highly wet F particles, that is, a lumpy and clay-like solidified product (powder or wet powder).

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. The content of the aromatic resin 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. The content of the thickening polymer is preferably 30% by mass or less, more preferably 10% by mass or less.
The content of water in the composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the composition of the present invention. The water content is preferably 50% by mass or less, more preferably 40% by mass or less.
The ratio of the content of the thickening polymer to the F particles in the composition of the present invention is 0.05 or less, preferably 0.03 or less, and more preferably 0.01 or less. Such a ratio is preferably 0.001 or more, and more preferably 0.03 or more.
The solid content in the composition of the present invention is preferably 40 to 99% by mass, more preferably 50 to 80% by mass.

In the composition of the present invention, F particles, an aromatic resin, a thickening polymer, and water are mixed in a tank equipped with a stirring mechanism by thin film swirling or a stirring mechanism by rotation and revolution. It is preferable to obtain it. The mixing method is the same as that in the present method 2 including a suitable range.
Moreover, the aspect of the liquid composition obtained by mixing the composition of the present invention with water is the same as that of the present composition 2 of the present method 2 including a suitable range.

The method for producing the present composition 2, the method for producing a laminate using the present composition 2, the liquid composition of the present invention and the composition of the present invention have been described above. Not limited.
For example, the method for producing the present composition 2 and the method for producing a laminate using the present composition 2 may additionally have any other step in the configuration of the above embodiment, and the same action is produced. It may be replaced with any step. In addition, the composition 2, the liquid composition of the present invention, and the composition of the present invention may be added with any other composition in the configuration of the above embodiment, or any configuration exhibiting the same function. May be replaced with.

Subsequently, a third aspect of this method (hereinafter, also referred to as “this method 3”) will be described.
In this method 3, F particles, inorganic particles having a new moth hardness of 12 or less (this inorganic particles), and a liquid compound are mixed by swirling a thin film to include F particles, the present inorganic particles, and a liquid compound. This is a method for obtaining a liquid composition (hereinafter, also referred to as “this composition 3”).
The composition 3 has less aggregation of the inorganic particles and is excellent in dispersion stability, uniformity and handleability. Further, from the present composition 3, it is possible to form a molded product having excellent electrical characteristics, low linear expansion property and thermal conductivity, which has the physical characteristics of the F polymer and the physical characteristics of the inorganic particles to a high degree. The reason is not always clear, but it is estimated as follows, for example.

When the F polymer having a low surface energy and the inorganic particles are mixed, the interaction between the inorganic particles is higher than the interaction between the inorganic particles and the F particles, and the aggregation of the inorganic particles is likely to occur. In particular, when the inorganic particles forming the secondary particles are subjected to mixing, this tendency tends to be remarkable.
When a strong shearing force is applied to the liquid composition in order to eliminate the aggregation of the inorganic particles, the F polymer is easily denatured by fibrillation or the like, and the physical properties of the F polymer are easily impaired. Not only that, in the case of low-hardness inorganic particles, the particles themselves are crushed into fine particles and are more likely to aggregate. As described above, it has been difficult to obtain a liquid composition having excellent dispersion stability, uniformity and handleability by mixing the F particles and the inorganic particles while suppressing the aggregation of the inorganic particles.

In this method, a means is adopted in which the F particles, the present inorganic particles, and the liquid compound are swirled in a thin film and mixed, the liquid compound is highly permeated into each of the F particles and the present inorganic particles, and both are mixed in a wet state. .. In other words, it can be considered that the liquid compound alleviates the impact generated when the two collide with each other, and suppresses the denaturation of the F particles and the excessive crushing of the present inorganic particles. Further, it can be considered that the collision between the F particles and the inorganic particles promotes the formation of the coalesced particles of the inorganic particles and the F particles (composite particles in which the inorganic particles are fused on the surface of the F particles, etc.). Further, when the inorganic particles forming the secondary particles are subjected to mixing, it can be considered that the permeation of the liquid compound promotes the elimination of the secondary particles.

Due to these factors, the F particles and the present inorganic particles are highly mixed at the individual particle level, and it is considered that a liquid composition having excellent dispersion stability, uniformity and handleability was obtained by this method. .. Further, since the uniform particles typified by the coalesced particles are contained, when the liquid compound is removed from the composition 3, it becomes easy to form a uniform and dense particle packing structure. As a result, it is considered that from the present composition 3, inorganic particles are densely arranged in the F polymer, and a molded product having excellent electrical characteristics, low linear expansion and thermal conductivity is obtained.

The present inorganic particles in the present method 3 are particles of an inorganic compound having a new Mohs hardness of 12 or less. One type of the inorganic particles 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, further preferably 5 or less, and particularly preferably 3 or less. The new Mohs hardness of the inorganic particles is preferably 1 or more, and more preferably 2 or more.

The shape of the inorganic particles may be spherical, needle-shaped (fibrous), or plate-shaped, and is preferably plate-shaped. In this case, it is considered that coalesced particles of the inorganic particles and the F particles are likely to be formed, and the composition 3 is likely to be excellent in physical properties such as dispersion stability. As a result, the molded product formed from the present composition 3 tends to be excellent in electrical characteristics and low line expandability. In addition, the inorganic particles tend to form paths in the molded product, and the molded product tends to have excellent thermal conductivity.
Specific shapes of the inorganic particles include spherical, scaly, layered, leafy, apricot kernel, columnar, chicken crown, equiaxed, leafy, mica, block, flat, wedge, rosette, etc. Examples include mesh-like and prismatic.

The inorganic particles are preferably carbon particles, nitride particles and inorganic oxide particles, and are carbon fiber particles, boron nitride particles (new Morse hardness: 2), aluminum nitride particles, beryllia particles (particles of berylium oxide), and Kay. Acidic acid particles (silica particles (new moth hardness: 8), wollastonite particles, talc particles (new moth hardness: 1)), and metal oxide particles (cerium oxide, aluminum oxide (new moth hardness: 12), oxidation (Magnet, zinc oxide, titanium oxide, etc.) are more preferable, and boron nitride particles and silica are preferable from the viewpoint of the dispersion stability of the composition 3 and the electrical characteristics and low linear expansion of the molded product formed from the composition 3. Particles are more preferred, and boron nitride particles are particularly preferred. Further, from the viewpoint of thermal conductivity of the molded product formed from the present composition 3, boron nitride particles and aluminum oxide particles are preferable.

The D50 of the inorganic particles is preferably 20 μm or less, more preferably 10 μm or less. D50 is preferably 0.01 μm or more, more preferably 0.1 μm or more. The ratio of D50 of the present inorganic particles to D50 of the F particles is preferably 1 or more, and more preferably 2 or more. The ratio is preferably 20 or less, more preferably 10 or less.
The specific surface area of the inorganic particles is preferably 1 to 20 m ² / g.
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 having such an aspect ratio and a small Mohs hardness are likely to be aggregated or crushed in mixing due to their shape anisotropy. A high degree of mixing is possible.

From the viewpoint of wettability, at least a part of the surface of the inorganic particles is a silane coupling agent (3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxy). It may be surface-treated with propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isopropylpropyltriethoxysilane, etc.).
Preferable specific examples of the inorganic particles include the specific examples of the inorganic filler in the above-mentioned method 1 and the same as the inorganic particles in the present method 2.

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

The liquid compound in this method 3 means a compound that is liquid at 25 ° C. under atmospheric pressure.
Examples of the liquid compound 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.

Examples of the alcohol include methanol, ethanol, isopropanol and glycol.
As amides, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy- Examples thereof include N, N-dimethylpropanamide, N, N-diethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like.

Examples of the ketone include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, and cycloheptanone.
Esters include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl 3-ethoxypropionate, γ-butyrolactone, γ- Valerolactone can be mentioned.

Suitable specific examples of the liquid compound include water, N-methyl-2-pyrrolidone, γ-butyrolactone, cyclohexanone and cyclopentanone.
The content of the liquid compound in the composition 3 is preferably 30 to 90% by mass, more preferably 50 to 80% by mass. In such a range, the liquid physical characteristics such as the dispersion stability of the present composition 3 are more likely to be improved.

In this method, the F particles, the inorganic particles, and the liquid compound are swirled and mixed in a thin film, that is, these components are swirled and mixed while spreading in a thin film shape to obtain the composition 3. Centrifugal force associated with swirling effectively acts on each of the components developed in the form of a thin film, and the liquid compound is highly permeated into each of the F particles and the present inorganic particles, and the mixing proceeds.
The mixing is preferably performed by the thin film swirl type high-speed mixer described in the present method 1 and the present method 2.
The details of the stirring tank in the thin film swirling high-speed mixer and the rotating portion having the cylindrical portion in which a plurality of holes are formed are as described above.
In mixing, the F particles, the present inorganic particles, and the liquid compound may be collectively supplied into the stirring tank, or may be separately supplied into the stirring tank using a plurality of inlets.
Mixing can be carried out in batch or continuous manner. In the case of the continuous type, one stirring tank may be used to supply the mixture taken out from the discharge port again from the input port and mixed, or a plurality of stirring tanks may be used to prepare the stirring tank in the previous stage. The mixture taken out from the discharge port may be supplied from the input port of the stirring tank in the subsequent stage and mixed.

The supplied F particles, the present inorganic particles, and the liquid compound spread over the gap between the inner wall surface of the stirring tank and the outer peripheral surface of the cylindrical portion of the rotating portion to form a film, and as the rotating portion rotates, the stirring tank becomes a film. Turn at high speed inside. At this time, by receiving not only shear stress but also shear stress, dispersion mixing at a high level is achieved.
In this method, it is preferable that the composition containing the F particles, the present inorganic particles and the liquid compound is swirled in a thin film and mixed. That is, in this method, it is preferable that the F particles, the inorganic particles, and the liquid compound are premixed before being swirled in a thin film and mixed. In this case, the mechanism of action of the present method described above is enhanced, and the physical properties such as the dispersion stability of the present composition 3 are likely to be further improved.
Examples of the premixing method include the same methods as those described above in the present method 1 and the present method 2.

The composition containing the F particles, the present inorganic particles and the 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 mechanism of action of this method described above is likely to be enhanced. The kneaded product is preferably a solidified product (paste) having fluidity and viscosity, or a lumpy and clay-like solidified product (powder).

The solid content in the paste is preferably 40 to 90% by mass, more preferably 60 to 80% by mass. The solid content in the dough is preferably 50 to 99% by mass, more preferably 60 to 95% by mass.
The solid content in the paste and the kneaded powder has the same meaning as described above in the present method 2.

In the mixing, a polymer different from the F polymer may be further added. The step of adding the different polymer may be before or during mixing. For example, a composition containing F particles, the present inorganic particles and a liquid compound, and a different polymer may be prepared and used for mixing.
The different polymers may be thermosetting, thermoplastic or modified. Further, different polymers may be dissolved in the present composition 3 or may be dispersed without being dissolved. Different polymers may be included in the composition 3 as precursors thereof.

Different polymers include acrylic resin, phenolic resin, liquid crystal polyester, liquid crystal polyesteramide, polyolefin resin, modified polyphenylene ether, polyfunctional cyanate ester resin, polyfunctional maleimide-cyanic acid ester resin, polyfunctional maleimide, styrene elastomer. Aromatic elastomers such as vinyl ester resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine-urea cocondensate resin, polycarbonate, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyamideimide , Aromatic polyether amide, polyphenylensulfide, polyallyl ether ketone, polyphenylene ether, epoxy resin and the like.

Preferred embodiments of different polymers include aromatic polymers. The aromatic polymer is preferably a polyphenylene ether or an aromatic elastomer (styrene elastomer or the like). In this case, not only the adhesiveness and low linear expansion property of the molded product formed from the present composition 3 are further improved, but also the liquid physical characteristics (viscosity, thixotropy, etc.) of the present composition 3 are balanced. Its handleability is likely to improve.
When the composition 3 contains the above-mentioned different polymers, the content thereof is preferably 40% by mass or less with respect to the total mass of the composition 3.

In mixing, a surfactant may be further added. The step of adding the surfactant may be before or during mixing. For example, a composition containing F particles, the present inorganic particles, a liquid compound, and a surfactant may be prepared and used for mixing.
The surfactant is preferably a nonionic surfactant.
Specific examples of the nonionic surfactant include the same surfactants that may be added to the composition 2 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% by mass, more preferably 1 to 10% by mass.

In mixing, a silane coupling agent may be further added. In this case, the binding force between the F particles and the present inorganic particles is likely to be improved, and the exfoliation of the present inorganic particles is likely to be suppressed in the molded product formed from the present composition 3. Examples of the silane coupling agent include compounds similar to the silane coupling agent that can be used for the surface treatment of the present inorganic particles.
The step of adding the silane coupling agent may be before or during mixing. For example, a composition containing F particles, the present inorganic particles and a liquid compound, and a silane coupling agent may be prepared and used for mixing.
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% by mass with respect to the content of the F particles.

When the liquid compound in this method is water, a pH adjuster or a pH buffer may be further used from the viewpoint of pH adjustment. In this case, it is preferable to adjust the pH of the present composition 3 to 5 to 10 with a pH adjuster or a pH buffer, and it is more preferable to adjust the pH to 7 to 9.
Examples of the pH adjuster or pH buffer include compounds similar to those described above in the present composition 2.
The step of adding the pH adjuster or pH buffer may be before or during mixing.
The present composition 3 may be further subjected to a defoaming treatment. Defoaming is preferably performed using a rotation / revolution stirrer.

A liquid compound may be further added to the composition 3. Due to the mechanism of action described above, the composition 3 has excellent dispersion stability and can be easily mixed with the liquid compound. The liquid compound to be further added may be the same as or different from the liquid compound in this method.
In addition to the liquid compound, the present composition 3 contains the above-mentioned components (polymer different from F polymer, surfactant, silane coupling agent, pH adjuster, pH buffer), tyxo property imparting agent, and viscosity adjusting agent. Agents, defoamers, plasticizers, weather resistant agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, flame retardants, preservatives, An antifungal agent or the like may be further added.
Since the composition 3 is excellent in dispersion stability due to the above-mentioned mechanism of action, the liquid physical characteristics can be easily adjusted by adding these.

The viscosity of the 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 the composition 3 is preferably 10,000 mPa · s or less, more preferably 3000 mPa · s or less, and even more preferably 1000 mPa · s or less. In this case, the present composition 3 tends to be excellent in liquid physical properties such as dispersion stability.
The thixotropy ratio of the present composition 3 is preferably 1.0 or more. The thixotropy of the composition 3 is preferably 3.0 or less, more preferably 2.0 or less. In this case, the present composition 3 is excellent in liquid physical characteristics such as dispersion stability, and it is easy to form a more dense molded product.

The dispersed layer ratio of the present composition 3 is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more. Since the present composition 3 is excellent in dispersion stability, it is easy to take a value in the range where the dispersion layer ratio is applied. The dispersed layer ratio is as described above in the present composition 2.

The dispersity of the 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 the composition 3 is preferably 10 μm or more. In the present composition 3, since the aggregation of the present inorganic particles is suppressed by the above-mentioned mechanism of action, the degree of dispersion tends to be in the above range. The dispersity is as described above in the present composition 2.

The present composition 3 is excellent in liquid physical properties such as dispersion stability, and a molded product having excellent physical properties based on the F polymer and the present inorganic particles can be formed by the above-mentioned action mechanism. In addition, it is possible to form a molded product that exhibits strong adhesiveness to the base material.
In the method for producing a laminate of the present invention, the composition 3 is applied to the surface of a base material and heated to form a polymer layer containing the F polymer and the inorganic particles (hereinafter, also referred to as “F layer 2”). Is a method for producing a laminate, which comprises forming a laminate having a substrate layer composed of a substrate and an F layer 2.
More specifically, the present composition 3 is applied to the surface of the base material to form a liquid film, the liquid film is heated to remove the dispersion medium to form a dry film, and the dry film is further heated. By firing the F polymer, a laminate having the F layer 2 on the surface of the base material layer can be obtained.

Examples of the base material include those similar to those described above in the present method 2.
The metal substrate may be a low-roughened copper foil or a non-roughened copper foil. When the metal substrate is a low-roughened copper foil or a non-roughened copper foil, the laminate tends to have excellent transmission characteristics.
Examples of the shape of the base material include a flat shape, a curved surface shape, and an uneven shape, and further, any of a foil shape, a plate shape, a film shape, and a fibrous shape may be used.

The method of applying the composition 3 to the surface of the base material, the method of drying the formed liquid film, and the method of heating are the same as the method for producing the laminate in the above-mentioned method 2.

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 is excellent in 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 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 the present composition 3, such a laminated body can be easily formed without impairing the physical characteristics of the F polymer in the F layer 2.

The present composition 3 may be applied only to one surface of the base material, or may be applied to both sides of the base material. In the former, a base material layer composed of a base material and a laminate having an F layer 2 on one surface of the base material layer are obtained, and in the latter, a base material layer composed of a base material and such a base material are obtained. A laminate having the F layer 2 on both surfaces of the material layer is obtained. Since the latter laminate 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 2 on at least one surface of the metal foil, a polyimide film, and a multilayer having an F layer 2 on both surfaces of the polyimide film. Film is mentioned. Since these laminates are excellent in various physical properties such as electrical characteristics, they are suitable as printed circuit board materials and the like, and can be used for manufacturing flexible printed circuit boards and rigid printed circuit boards.

Further, by removing the base material from the present laminate, a sheet made of the F layer 2 can be manufactured. The method of removal includes peeling or etching.
The laminate of the F layer 2 and the base material layer and the sheet composed of the F layer 2 are useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry supplies, heat dissipation parts, paints, cosmetics, etc. Is. Specific examples are as described above in this method 2.

Although the method for producing the present composition 3 and the method for producing a laminate using the present composition 3 have been described above, the present invention is not limited to the configuration of the above-described embodiment. For example, the method for producing the present composition 3 and the method for producing a laminate using the present composition 3 may additionally have any other step in the configuration of the above embodiment, and have the same action. It may be replaced with any step that occurs.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
Details of each component used are shown.
[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 this order, and contains carbonyl group-containing groups per 1 × 10 ⁶ main chain carbon atoms. Particles (D50: 2.1 μm) composed of 1000 F-polymer 1 (melting temperature: 300 ° C.)
F particle 2: Particles (D50: 1.8 μm) composed of a polymer (melting temperature 305 ° C.) containing 97.5 mol% and 2.5 mol% of TFE units and PPVE units in this order and having no oxygen-containing polar group. )
F particle 3: Non-meltable particle (D50: 0.3 μm) made of non-heat-meltable polytetrafluoroethylene
[Liquid dispersion medium (liquid compound)]
NMP: N-methyl-2-pyrrolidone Tol: Toluene [Aromatic resin (aromatic polymer) varnish]
Alligator 1: A carboxyl group-containing phenol resin (aromatic resin 1, acid value: 1, which is obtained by reacting an epoxidized polyfunctional phenol resin with an acrylic acid and then adding a phthalic acid anhydride to a hydroxyl group existing in a side chain. 80 mgKOH / g) varnish (solvent: Tol, solid content: 65% by mass)
Varnish 2: Water varnish containing a precursor (acid value: 50 mgKOH / g) of aromatic polyamide-imide (PAI1) [inorganic particles]
Particle 1: Plate-like 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, pyrolysis temperature: 300 ° C)
Thickening polymer 2: Hydroxyethyl cellulose ("HEC CF-Y" manufactured by Sumitomo Seika Chemical Co., Ltd.) [Resin film]
Polyimide film 1: Aromatic polyimide film with a thickness of 25 μm (“FG-100” manufactured by PI Advanced Materials)

<< Examples and Evaluations of Aspect 1 >>
1-1. Production Example of Composition [Example 1-1]
(1) Stirring of F particles 1, varnish 1, and NMP with a cylindrical stirring tank and a rotating portion having a cylindrical portion having a plurality of holes formed inside the inner wall surface of the stirring tank. Put it in the stirring tank of the machine, rotate the rotating part at high speed and mix it, F particle 1 (30 parts by mass), aromatic resin 1 (20 parts by mass), Tol (10 parts by mass), NMP (30 parts by mass) Part) was obtained as a composition 1-1 (viscosity: 10000 mPa · s).
(2) The composition 1 and the varnish 1 are put into a pot and shaken to shake F particles 1 (30 parts by mass), aromatic resin 1 (80 parts by mass), Tol (40 parts by mass) and NMP (20 parts by mass). A liquid composition 1-1 (viscosity: 400 mPa · s) containing 60 parts by mass) was obtained.
The composition 1-1 and the liquid composition 1-1 were excellent in dispersibility, with no visible agglomerates even after storage at 25 ° C. for 30 days.

[Example 1-2]
(1) Composition 1-2 was obtained in the same manner as in (1) of Example 1-1 except that F particle 1 was changed to F particle 2.
(2) A liquid composition 1-2 was obtained in the same manner as in (2) of Example 1-1 except that the composition 1 was changed to the composition 2.
In the composition 1-2 and the liquid composition 1-2, aggregates were visually recognized even after storage at 25 ° C. for 30 days, and a redispersion operation 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 put into the pot, and zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to try to prepare a liquid composition, but the liquid composition became viscous, and a uniform dispersion could not be directly obtained.

1-2. Example of manufacturing a base material with a convex portion In a laminate of an F polymer 1 film and an electrolytic copper foil (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., "CF-T49A-DS-HD2"), the opposite side of the electrolytic copper foil film. The liquid composition 1-1 was applied to the surface of the laminate to form a coating film on the laminate. This coating film was dried at 80 ° C. for 10 minutes to obtain a dry film (thickness: 50 μm).
Next, the dry film was irradiated with ultraviolet rays (integrated light intensity: 150 mJ / cm ² ) using an exposure mask having a predetermined pattern of openings. Next, the dry film after irradiation with ultraviolet rays was developed with a 1.0% by mass aqueous sodium carbonate solution to form convex portions.
As a result of confirming this convex portion with an optical microscope, no dropout of particles from the convex portion was confirmed. The pencil hardness of the convex portion was 4H, which was equivalent to the pencil hardness of the convex portion formed only from the varnish 1.

1-3. Example of Film Production A liquid composition 1-1 is applied to an electrolytic copper foil (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., "CF-T49A-DS-HD2") to form a coating film, and this coating film is applied at 80 ° C. It was dried for 10 minutes to obtain a dry film (thickness: 50 μm).
Next, ultraviolet rays were applied to the entire dry film without using an exposure mask. The integrated amount of ultraviolet rays was set to 150 mJ / cm ² . Next, the electrolytic copper foil was etched with an aqueous ferric chloride solution to obtain a film. As a result of measuring the electrical characteristics of this film at 10 MHz using an SPDR (split post dielectric resonator) and a network analyzer, the dielectric constant is 3 or less and the dielectric loss tangent is 0.05 or less, which are excellent in electrical characteristics. rice field.

<< Examples and Evaluations of Aspect 2 >>
2-1. Production Example of Liquid Composition [Example 2-1]
First, varnish 2, thickening polymer 1 and water were put into a pot and mixed. Further, F particle 1 was put into a pot and mixed to prepare a composition. Subsequently, the prepared composition was put into a planetary mixer, kneaded, and F particles 1 (40 parts by mass), PAI 1 (0.4 parts by mass), thickening polymer 1 (0.6 parts by mass) and water. A kneaded powder 2-1 containing (29 parts by mass) was obtained. The kneaded powder 2-1 was lumpy and clay-like.
Water is added to the kneaded powder 2-1 in a plurality of times and stirred, and has a cylindrical stirring tank and a cylindrical portion having a plurality of holes formed which rotates inside the inner wall surface of the stirring tank. It was placed in a stirring tank of a stirrer equipped with a rotating portion, and the rotating portion was rotated at a high speed of 7500 rpm for 30 seconds to mix. As a result, the liquid composition 2-1 (viscosity:) 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). 300 mPa · s) was obtained.
The ratio of the content of the thickening polymer to the F particles in the liquid composition 2-1 is 0.015.

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

[Example 2-4]
F particles 1, varnish 2, thickening polymer 1 and water were put into the pot, and zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to add F particle 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). A liquid composition containing 2-4 (viscosity: 900 mPa · s) was obtained.
[Example 2-5]
Example 2-1 except that the amounts of the thickening polymer 1 and water when the varnish 2 and the thickening polymer 1 and water were put into the pot and mixed were changed to 2.6 parts by mass and 27 parts by mass, respectively. Liquid composition 2-5 (similar to) 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). Viscosity: 1000 mPa · s) was obtained.
The ratio of the content of the thickening polymer to the F particles in the liquid composition 2-5 is 0.065.

[Example 2-6]
F particles 2, varnish 2, thickening polymer 1 and water were put into the pot, and zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to add 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). A liquid composition containing 2-6 (viscosity: 3000 mPa · s) was obtained.
The ratio of the content of the thickening polymer to the F particles in the liquid composition 2-6 is 0.065.

[Example 2-7]
First, F particles 1 were put into a rotation / revolution stirrer, stirred, and pre-dispersed. Further, the pre-dispersed F particles 1, the varnish 2, the thickening polymer 2, and water are put into the rotation / revolution stirrer, and the mixture is stirred with the ratio of the rotation speed to the revolution speed being 2, and the F particles 1 (40 parts by mass). ), ^PAI1 (0.4 parts by mass), thickening polymer 2 (0.6 parts by mass) and water (19 parts by mass). Viscosity measured by capillograph: 20000 Pa · s) was obtained.
While adding water to the kneaded powder 2-7 in several portions, the ratio of the rotation speed to the revolution speed was set to 2 and mixed with a rotation revolution stirrer, and F particles 1 (40 parts by mass) and PAI1 (0.4 by mass) were mixed. A liquid composition 2-7 (viscosity: 400 mPa · s) containing (by mass), thickening polymer 2 (0.6 parts by mass) and water (59 parts by mass) was obtained.
The ratio of the content of the thickening polymer to the F particles in the liquid composition 2-7 is 0.015.
The time from the production of the liquid composition 2-7 to the disappearance of foaming is shorter than the time from the production of the liquid composition 2-1 to the disappearance of foaming, and the liquid composition 7 is easy to handle. It was excellent.

2-2. Production Example of Laminated Liquid Composition 2-1 was applied to the surface of a long copper foil having a thickness of 18 μm using a bar coater to form a wet film. Next, the copper foil on which the wet film was formed was dried by passing it through a drying oven at 110 ° C. for 5 minutes to form a dry film. The substrate on which the dry film was formed was heated in a nitrogen oven at 380 ° C. for 3 minutes. As a result, a laminate 2-1 having a copper foil and a polymer layer having a thickness of 200 μm as a molded product containing a melt-fired product of F particles 1 and PAI1 on the surface thereof was produced.
Laminated bodies 2-2 to 2-7 were obtained in the same manner as in laminated body 2-1 except that the liquid composition 2-1 was changed to liquid compositions 2-2 to 2-7.

2-3. 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 at 25 ° C. for 14 days. 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, the dispersion layer ratio was calculated by the following formula, and the dispersion stability was evaluated according to the following criteria.
[Evaluation criteria]
⊚: The dispersed layer ratio is 80% or more.
〇: The dispersed layer ratio is 70% or more and less than 80%.
Δ: The dispersed layer ratio is 60% or more and less than 70%.
X: The dispersed layer ratio is less than 60%.

2-4. Evaluation of laminated body <Electrical characteristics of laminated body>
For each laminate, the copper foil of the laminate was removed by etching with an aqueous ferric chloride solution to prepare a sheet as a single polymer layer. The dielectric loss tangent (measurement frequency: 10 GHz) of the prepared sheet was measured by the SPDR (split post dielectric resonance) method and evaluated according to the following criteria.
[Evaluation criteria]
〇: The dielectric loss tangent is less than 0.0010.
Δ: The dielectric loss tangent is 0.0010 or more and 0.0025 or less.
X: The dielectric loss tangent is more than 0.0025.
The results of each evaluation are summarized in Table 1.

Furthermore, the sheet obtained from the laminated body 2-3 was superior in bending property to the sheet obtained from the laminated body 2-1 and was excellent in sheet strength.

2-5. Production Example of Laminated Film By roll-to-roll process, liquid composition 2-7 is applied to one surface of polyimide film 1 by the small-diameter gravure reverse method, and placed in a ventilation drying oven (furnace temperature 150 ° C.) in 3 minutes. It was allowed to pass and water was removed to form a dry film. Further, the liquid composition 2-7 was similarly applied to the other surface of the polyimide film 1 and dried to form a dry film.
Next, the polyimide film 1 having the dry film formed on both sides is passed through a far-infrared furnace (a furnace temperature of 300 ° C. near the inlet and outlet of the furnace and a furnace temperature of 360 ° C. near the center) in 5 minutes, and the F particles 1 are passed. Was melt-fired.
As a result, a polymer layer (thickness: 25 μm) containing the melt-fired product of F particles 1 and PAI1 is formed on both sides of the polyimide film 1, and the polymer layer, the polyimide film layer, and the polymer layer are directly formed in this order. (Laminated film 2-1) was obtained by a roll-to-roll process.
A rectangular (length 100 mm, width 10 mm) test piece is cut out from the laminated film 2-1 and fixed at a position 50 mm from one end in the length direction of the test piece, with a tensile speed of 50 mm / min and from one end in the length direction. The polymer layer and the polyimide film layer were peeled off at 90 ° to the test piece. The maximum load applied at that time was 15 N / cm or more, and the laminated film 2-1 was excellent in interlayer adhesion.
A 180 mm square test piece was cut out from the laminated film 2-1 and the linear expansion coefficient of the test piece was measured by the measuring method specified in JIS C 6471: 1995. As a result, it was less than 20 ppm / ° C., and the laminated film 2-1. Was excellent in low line expansion.

<< Examples and Evaluations of Aspect 3 >>
3-1. Production Example of Liquid Composition [Example 3-1]
First, a powder mixture of F particles 1 and particles 1 and NMP were put into a pot and mixed to prepare a composition. Subsequently, the prepared composition is put into a planetary mixer, kneaded, and kneaded powder 3-1 containing F particles 1 (20 parts by mass), particles 1 (20 parts by mass) and NMP (30 parts by mass). Got The kneaded powder 3-1 was lumpy and clay-like.
NMP is added to the kneaded powder 3-1 in a plurality of times and stirred, and has a cylindrical stirring tank and a cylindrical portion having a plurality of holes formed which rotates inside the inner wall surface of the stirring tank. It was placed in a stirring tank of a stirrer equipped with a rotating portion, and the rotating portion was rotated at a high speed of 7500 rpm for 30 seconds to mix. As a result, a liquid composition 3-1 (viscosity: 500 mPa · s) containing F particle 1 (20 parts by mass), particle 1 (20 parts by mass) and NMP (60 parts by mass) was obtained.

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

[Example 3-4]
F particle 2 (20 parts by mass), particle 2 (20 parts by mass) and the same as in Example 3-1 except that F particle 1 was changed to F particle 2 and particle 1 was changed to particle 2. A liquid composition 3-4 (viscosity: 2000 mPa · s) containing NMP (60 parts by mass) was obtained.
[Example 3-5]
F particle 2, particle 1 and NMP were put into the pot, and zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to form a liquid composition 3-5 (viscosity: 3000 mPa · s) containing F particle 2 (20 parts by mass), particle 1 (20 parts by mass) and NMP (60 parts by mass). ) Was obtained.

3-2. Production Example of Laminated Liquid Composition 3-1 was applied to the surface of a long copper foil having a thickness of 18 μm using a bar coater to form a wet film. Next, the copper foil on which the wet film was formed was dried by passing it through a drying oven at 110 ° C. for 5 minutes to form 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, and pressed the dry film.
The substrate was then further heated in a nitrogen oven at 380 ° C. for 3 minutes. As a result, a laminate 3-1 having a copper foil and a polymer layer having a thickness of 200 μm as a molded product containing a melt-fired product of F particles 1 and particles 1 on the surface thereof was produced.
Laminated bodies 3-2 to 3-5 were obtained in the same manner as in laminated body 3-1 except that the liquid composition 3-1 was changed to liquid compositions 3-2 to 3-5.

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 at 25 ° C. for 14 days. 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, the dispersion layer ratio was calculated by the following formula, and the dispersion stability was evaluated according to the following criteria.
[Evaluation criteria]
〇: The dispersed layer ratio is 80% or more.
Δ: The dispersed layer ratio is 60% or more and less than 80%.
X: The dispersed layer ratio is less than 60%.

3-4. Evaluation of laminated body 3-4-1. Linear Expansion of Laminates For each laminate, the copper foil of the laminate was removed by etching with an aqueous ferric chloride solution to prepare a sheet as a single polymer layer. A 180 mm square test piece is cut out from the prepared sheet, and the coefficient of linear expansion of the test piece is measured in the range of 25 ° C. or higher and 260 ° C. or lower according to the measurement method specified in JIS C 6471: 1995. Evaluated according to.
[Evaluation criteria]
〇: The coefficient of linear expansion is 50 ppm / ° C or less.
Δ: The coefficient of linear expansion is more than 50 ppm / ° C and 75 ppm / ° C or less.
X: The coefficient of linear expansion is over 75 ppm / ° C.

3-4-2. Thermal conductivity of the laminate For each laminate, the copper foil of the laminate was removed by etching with an aqueous solution of ferric chloride to prepare a sheet as a single polymer layer. A 10 mm × 10 mm square test piece was cut out from the center of the prepared 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: The thermal conductivity is 5 W / m · K or more.
X: The thermal conductivity is less than 5 W / m · K.
The results of each evaluation are summarized in Table 2.

Further, the sheet obtained from the laminated body 3-3 was superior in bending property as compared with the sheet obtained from the laminated body 3-1 and was excellent in sheet strength.

The liquid composition produced by the method of the present invention is excellent in dispersion stability, uniformity and handleability.
The liquid composition obtained by the production method of Aspect 1 is also useful as, for example, a solder resist composition, a filling material used for filling through holes or recesses in a multilayer printed wiring board.
From the liquid composition obtained by the method of Aspect 2 or Aspect 3, a molded product having excellent physical properties such as low linear expansion property, thermal conductivity, and electrical properties can be formed. Therefore, such a liquid composition can be easily processed into a film, a fiber reinforced film, a prepreg, a metal laminated plate (metal foil with resin), or the like. The obtained processed article can be used as a material for antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry supplies, slip bearings, and the like.

Claims

The particles of the tetrafluoroethylene polymer, at least one of the aromatic resin or the inorganic particles having a new moth hardness of 12 or less, and the liquid compound are provided with a stirring mechanism by thin film swirling or a stirring mechanism by rotation and revolution. A liquid composition obtained by mixing in a tank to obtain a liquid composition containing the particles of the tetrafluoroethylene polymer, at least one of an aromatic resin or an inorganic particle having a new Morse hardness of 12 or less, and the liquid compound. Production method.
A rotating portion having a cylindrical stirring tank and a cylindrical portion having a plurality of holes formed by rotating tetrafluoroethylene polymer particles and an aromatic resin varnish inside the inner wall surface of the stirring tank. The tetrafluoroethylene-based polymer and the aromatic The production method according to claim 1, wherein a liquid composition containing a sex resin is obtained.
The production 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).
The production method according to claim 2 or 3, wherein the ratio of the mass of the particles of the tetrafluoroethylene-based polymer to the mass of the aromatic resin is 0.5 to 10.
The total content of the tetrafluoroethylene polymer particles and the aromatic resin is 50% by mass or more, and the aromatic resin contains particles of the tetrafluoroethylene polymer and a varnish of the aromatic resin. A liquid composition used by mixing with an aromatic resin varnish in which the mass ratio of the particle content of the tetrafluoroethylene-based polymer to the sex resin is 0.5 to 10.
A stirring mechanism by thin film swirling or rotation of tetrafluoroethylene polymer particles, an aromatic resin, at least one thickening polymer selected from the group consisting of polar vinyl polymers and polysaccharides, and water. To obtain a liquid composition containing the tetrafluoroethylene polymer particles, the aromatic resin, the thickening polymer, and water by mixing in a tank equipped with a stirring mechanism by revolution. The manufacturing method described.
The tetrafluoroethylene polymer particles, the aromatic resin, the thickening polymer, and the water are mixed in a tank equipped with a stirring mechanism by thin film swirling or a stirring mechanism by rotation and revolution, and further water is added. The production method according to claim 6, wherein the liquid composition is obtained by mixing the above-mentioned liquid composition.
The production method according to claim 6 or 7, wherein the tetrafluoroethylene-based polymer particles include heat-meltable tetrafluoroethylene-based polymer particles and non-heat-meltable tetrafluoroethylene-based polymer particles.
The production method according to any one of claims 6 to 8, wherein the aromatic resin is aromatic polyimide, aromatic polyamideimide, aromatic polyetherimide or a precursor thereof.
The liquid composition is obtained by mixing the inorganic particles in a stirring mechanism by swirling a thin film or in a tank equipped with a stirring mechanism by rotation and revolution, according to any one of claims 6 to 9. Manufacturing method.
For the particles of the tetrafluoroethylene-based polymer, which comprises particles of the 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. A composition having a thickening polymer content ratio of 0.05 or less, a viscosity of 10000 Pa · s to 100,000 Pa · s as measured by a capillograph with a temperature of 25 ° C. and a shear rate of 1s -1 .
The tetrafluoroethylene polymer particles, the inorganic particles having a new moth hardness of 12 or less, and the liquid compound are mixed by swirling a thin film to obtain the tetrafluoroethylene polymer particles, the inorganic particles, and the liquid compound. The production method according to claim 1, wherein a liquid composition containing the above is obtained.
The production method according to claim 12, wherein the tetrafluoroethylene-based polymer particles include heat-meltable tetrafluoroethylene-based polymer particles and non-heat-meltable tetrafluoroethylene-based polymer particles.
The production method according to claim 12 or 13, wherein the inorganic particles are boron nitride particles or silica particles.
The production method according to any one of claims 12 to 14, wherein the viscosity of the liquid composition is 10,000 mPa · s or less.