WO2022149551A1

WO2022149551A1 - Method for producing tetrafluoroethylene-based polymer composition, composition, metal-clad laminate, and stretched sheet

Info

Publication number: WO2022149551A1
Application number: PCT/JP2021/048874
Authority: WO
Inventors: 蔵藤岡; 渉笠井
Original assignee: Ａｇｃ株式会社
Priority date: 2021-01-06
Filing date: 2021-12-28
Publication date: 2022-07-14
Also published as: TW202235498A; KR20230129373A; JPWO2022149551A1

Abstract

Provided are a composition comprising particles of a tetrafluoroethylene-based polymer and inorganic-oxide particles and having excellent dispersion stability and a method for producing the composition.　The composition production method comprises mixing inorganic-oxide particles with particles of a tetrafluoroethylene-based polymer (1) having a carbonylated group and/or a hydroxylated group to give a mixture and mixing the mixture with particles of a tetrafluoroethylene-based polymer (2), which is different from the tetrafluoroethylene-based polymer (1).

Description

Methods for Producing Tetrafluoroethylene Polymer Compositions, Compositions, Metallic Laminates and Stretched Sheets

The present invention relates to a method for producing a composition containing tetrafluoroethylene polymer particles and inorganic oxide particles, the composition, a metal-clad laminate, and a stretched sheet.

Tetrafluoroethylene polymers have been attracting attention as materials for printed circuit boards in recent years because they have excellent electrical properties such as low dielectric constant and low dielectric loss tangent. Patent Document 1 describes a high-frequency printed circuit board in which a molded product formed from a composition containing a plurality of types of tetrafluoroethylene polymers and inorganic particles has high thermal conductivity, low dielectric loss tangent, and a wide range of dielectric constants. Have been described.

Japanese Unexamined Patent Publication No. 2020-050860

However, in the composition described in Patent Document 1, the interaction between the components is not sufficient, and the dispersion stability is not sufficient. Therefore, the molded product formed from the molded product has a problem that not only the physical properties of the molded product are not sufficiently exhibited due to the aggregation of the inorganic particles, but also the inorganic particles are easily peeled off.
Further, further improvement of the adhesiveness between the molded product and other resins or metals and further reduction of the linear expansion property of the molded product are required for the printed circuit board material, particularly the rigid printed circuit board material for high frequency. ing.

The present inventors have prepared a composition containing a tetrafluoroethylene polymer and inorganic oxide particles, which have excellent dispersion stability, excellent adhesiveness to other resins and metals, and can form a molded product having a low linear expansion rate. We have found a method for producing the same and a metal-clad laminate having the composition. An object of the present invention is to provide such a composition, a method for producing the same, and a metal-clad laminate and a stretched sheet which are particularly useful as a rigid printed circuit board material.

The present invention has the following aspects.
[1] Particles of the tetrafluoroethylene-based polymer (1) having at least one of a carbonyl group-containing group and a hydroxyl group-containing group and inorganic oxide particles are mixed to form a mixture, and further, the tetrafluoroethylene-based polymer (1) is prepared. A method for producing a composition, wherein the particles of the tetrafluoroethylene polymer (2) different from the above) and the mixture are mixed.
[2] The production method according to [1], wherein the dispersion liquid in which the particles of the tetrafluoroethylene polymer (2) are dispersed in water is mixed with the mixture.
[3] The above-mentioned [1] or [2], wherein the tetrafluoroethylene polymer (1) is a polymer having 10 to 5000 carbonyl group-containing groups per 1 × 10 ⁶ main chain carbon atoms. Production method.
[4] The production method according to any one of [1] to [3], wherein the tetrafluoroethylene polymer (2) is polytetrafluoroethylene.
[5] The production method according to any one of [1] to [4], wherein the inorganic oxide is silicon oxide.

[6] Particles of a tetrafluoroethylene-based polymer (1) having at least one of a carbonyl group-containing group and a hydroxyl group-containing group, particles of a tetrafluoroethylene-based polymer (2) different from the tetrafluoroethylene-based polymer, and inorganic particles. The inorganic oxide particles contain the oxide particles, and the average particle size of the inorganic oxide particles is in the range of 1 to 1000% with respect to the average particle size of the particles of the tetrafluoroethylene polymer (1). The composition has a content of 5 to 75% by mass with respect to the total mass of the particles of the tetrafluoroethylene-based polymer (1), the particles of the tetrafluoroethylene-based polymer (2), and the inorganic oxide particles. ..
[7] The composition according to [6], further comprising an aromatic polymer.
[8] The composition according to [6] or [7], further comprising water.
[9] The composition according to any one of [6] to [8], wherein the tetrafluoroethylene polymer (2) is polytetrafluoroethylene.
[10] The composition according to any one of [6] to [9], wherein the inorganic oxide is silicon oxide.
[11] The mass of the tetrafluoroethylene polymer (2) is 25% by mass or more with respect to the total mass of the tetrafluoroethylene polymer (1) and the tetrafluoroethylene polymer (2), [6] to The composition according to any one of [10].

[12] A metal-clad laminate having a metal foil and a polymer layer formed on the surface of at least one of the metal foils, wherein the polymer layer is at least one of a carbonyl group-containing group and a hydroxyl group-containing group. It contains a tetrafluoroethylene-based polymer (1) having one of them, polytetrafluoroethylene and inorganic oxide particles, and the content of the inorganic oxide particles is the tetrafluoroethylene-based polymer (1) and the polytetrafluoroethylene. A metal-clad laminate that is 5 to 75% by mass with respect to the total mass of the inorganic oxide particles.
[13] The metal-clad laminate according to [12], wherein the polymer layer further contains an aromatic polymer.
[14] The metal-clad laminate according to [12] or [13], wherein the polymer layer has a thickness of 50 μm or more.
[15] A tetrafluoroethylene-based polymer (1) having at least one of a carbonyl group-containing group and a hydroxyl group-containing group, polytetrafluoroethylene, and inorganic oxide particles are contained, and the content of the inorganic oxide particles is the above. A stretched sheet obtained by stretching the inorganic oxide particles in an amount of 5 to 75% by mass based on the total mass of the tetrafluoroethylene polymer (1), the polytetrafluoroethylene and the inorganic oxide particles.

According to the present invention, there is provided a composition containing tetrafluoroethylene polymer particles and inorganic oxide particles and having excellent dispersion stability, and a method for producing the same. Such a composition has the physical characteristics of each of a tetrafluoroethylene polymer and an inorganic oxide, is excellent in adhesiveness and low linear expansion property, and can form a molded product in which exfoliation of components is suppressed. INDUSTRIAL APPLICABILITY According to the present invention, a metal-clad laminate and a stretched sheet useful as a printed circuit board material, particularly a rigid printed circuit board material, are provided.

The following terms have the following meanings.
The "tetrafluoroethylene-based polymer" is a polymer containing a unit based on tetrafluoroethylene (hereinafter, also referred to as "TFE").
The “polymer melting temperature (melting point)” is the temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
The "glass transition point (Tg) of the polymer" is a value measured by analyzing the polymer by the dynamic viscoelasticity measurement (DMA) method.
"D50 of particles" is the average particle size of the object, and is the volume-based cumulative 50% diameter of the particles obtained by the laser diffraction / scattering method. That is, the particle size distribution of the particles is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the particle population as 100%, and the particle size is the point where the cumulative volume is 50% on the cumulative curve.
“D90 of particles” is the volume-based cumulative 90% diameter of particles obtained in the same manner as “D50”.
The "viscosity of a liquid substance" is a value measured for an object at room temperature (25 ° C.) and at 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.
A "monomer-based unit" in a polymer is an atomic group formed directly from one molecule of a monomer by polymerization, and an atomic group obtained by processing a polymer produced to convert a part of the atomic group into another structure. Means. 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 this method) is also referred to as a tetrafluoroethylene-based polymer (1) having at least one of a carbonyl group-containing group and a hydroxyl group-containing group (hereinafter, also referred to as “F polymer (1)”). ) Particles (hereinafter, also referred to as “main particles (1)”) and inorganic oxide particles (hereinafter, also referred to as “main inorganic particles”) are mixed to form a mixture, and the tetrafluoroethylene polymer is further prepared. A mixture of particles of a tetrafluoroethylene polymer (2) (hereinafter, also referred to as “F polymer (2)”) different from (1) (hereinafter, also referred to as “main particles (2)”) and the above mixture. Is a method for producing a composition. Hereinafter, the F polymer (1) and the F polymer (2) are collectively referred to as "F polymer".
According to this method, a composition having excellent dispersion stability can be obtained. The reason is not always clear, but its mechanism of action is presumed to be as follows.

Since a tetrafluoroethylene polymer has high rigidity and extremely low affinity with other components, it is recommended to improve the dispersibility by shearing when preparing a composition such as a dispersion liquid. It is common. However, the tetrafluoroethylene polymer tends to deteriorate the dispersion stability of the composition due to alteration such as fibrillation and aggregation due to shearing. In particular, when the F polymer (2) is polytetrafluoroethylene, or when the composition is a liquid composition (dispersion liquid), particularly a dispersion liquid using water as a dispersion medium, which is highly polar, such a tendency is remarkable. Will be.
Therefore, in this method, the present particles (1) and the present inorganic particles are mixed in advance, and then the present particles (2) are further mixed to produce a composition. The F polymer (1) has a predetermined functional group, tends to form microspherulites at the molecular aggregate level, and tends to have a fine concavo-convex structure on its surface. Therefore, when the particles (1) and the inorganic particles are mixed, the characteristics of the particles (1) are not impaired, and the mixture forms a pseudo coalescence of the particles (1) and the inorganic particles. It is also considered that it is. The hard coalescence containing the present inorganic particles has a high affinity with the F polymer (2) while cushioning the shearing force at the time of mixing the present particles (2) and suppressing the alteration of the F polymer (2). Therefore, it is considered that a composition containing the F polymer (1), the F polymer (2) and the present inorganic particles having excellent dispersion stability was obtained.

The F polymer (1) in this method has at least one of a carbonyl group-containing group and a hydroxyl group-containing group.
A carbonyl group-containing group is a group containing a carbonyl group (> C (O)). Examples of the carbonyl group-containing group include a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH ₂ ), an acid anhydride residue (-C (O) OC (O)-), and the like. An imide residue (-C (O) NHC (O)-etc.) and a carbonate group (-OC (O) O-) are preferable, and an acid anhydride residue is more preferable.
As the hydroxyl group-containing group, a group containing an alcoholic hydroxyl group is preferable, and —CF ₂ CH ₂ OH and —C (CF ₃ ) ₂ OH are more preferable.

When the F polymer (1) has a carbonyl group-containing group, the number of carbonyl group-containing groups in the F polymer is preferably 10 to 5000, more preferably 50 to 4000 per 1 × 10 ⁶ main chain carbon atoms. , 100-2000 pieces are more preferable. In this case, the F polymer (1) easily interacts with the present inorganic particles or the F polymer (2), and the composition tends to be excellent in processability and stability. 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.

When the F polymer (1) has a carbonyl group-containing group, the carbonyl group-containing group may be contained in the unit contained in the polymer, or may be contained in the terminal group of the polymer backbone. Examples of the latter polymer include a polymer having a carbonyl group-containing group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and a polymer having a carbonyl group-containing group prepared by plasma treatment, ionization line treatment, or radiation treatment. Can be mentioned.

The fluorine content of the F polymer (1) is preferably 70 to 76% by mass. The F polymer (1) having a high fluorine content is excellent in physical properties such as electrical properties of the F polymer (1), but has a low polarity, so that it tends to aggregate. Therefore, for example, when a dispersion is prepared, its dispersibility tends to decrease. According to this method, even in such a dispersion liquid, the physical characteristics of the entire F polymer (1) are not impaired, and a composition having excellent dispersibility can be obtained. Further, the exfoliation of the present inorganic particles from the molded product formed from the composition is also suppressed, and a molded product having excellent low linear expansion property can be obtained.

The melting temperature of the F polymer (1) is preferably 200 ° C. or higher, more preferably 260 ° C. or higher. The melting temperature of the F polymer (1) is preferably 325 ° C or lower, more preferably 320 ° C or lower. The melting temperature of the F polymer (1) is particularly preferably 260 ° C. or higher and 325 ° C. or lower.
The glass transition point of the F polymer (1) is preferably 50 ° C. or higher, more preferably 75 ° C. or higher. The glass transition point of the F polymer (1) is preferably 150 ° C. or lower, more preferably 125 ° C.

The F polymer (1) includes a polymer containing TFE units and ethylene units, and a polymer containing TFE units and units based on perfluoro (alkyl vinyl ether) (hereinafter, also referred to as PAVE) (hereinafter, also referred to as PAVE units) (hereinafter, PFA). Also referred to as), and a polymer containing TFE and hexafluoropropylene units (hereinafter, also referred to as FEP) are preferable, PFA and FEP are more preferable, and PFA is further preferable. These polymers may further contain units based on other comonomeres.
As the PAVE, CF ₂ = CFOCF ₃ , CF ₂ = CFOCF ₂ CF ₃ and CF ₂ = CFOCF ₂ CF ₂ CF ₃ (hereinafter, also referred to as PPVE) are preferable, and PPVE is more preferable.

The F polymer (1) is preferably a polymer having a carbonyl group-containing group containing a TFE unit and a PAVE unit, and is a polymer containing a unit based on a monomer having a TFE unit, a PAVE unit and 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. When such a polymer is contained, the adhesiveness with the present inorganic particles is likely to be excellent. In addition, the molded product formed from the composition becomes dense and tends to have excellent low-line expandability.
As the monomer having a carbonyl group-containing group, itaconic anhydride, citraconic anhydride and 5-norbornen-2,3-dicarboxylic acid anhydride (hereinafter, also referred to as “NAH”) are preferable.
Specific examples of such an F polymer (1) include the polymers described in International Publication No. 2018/16644.

The particles (1) are particles containing the F polymer (1), and the amount of the F polymer (1) in the particles is preferably 80% by mass or more, more preferably 100% by mass. ..
The D50 of the particles (1) is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The D50 of the particles (1) is preferably 0.1 μm or more, more preferably 0.5 μm or more. Further, the D90 of the present particle (1) is more preferably 50 μm or less. If D50 and D90 of the main particle (1) are in such a range, the surface area thereof becomes large, and the dispersibility of the main particle (1) is likely to be further improved.

The particles (1) may contain a polymer different from the F polymer.
Specific examples of the polymer different from the F polymer include heat-resistant resins such as aromatic polyester, aromatic polyimide, aromatic polymaleimide, polyamideimide, polyphenylene ether, polyphenylene oxide, and polymaleimide.

The present inorganic particles are particles of an inorganic oxide used for improving the physical properties of a molded product obtained from the composition, and the type thereof is appropriately selected according to the purpose of the molded product. The inorganic particles may be fired ceramic particles.
For example, for the purpose of improving the dielectric constant of a molded product, inorganic oxide particles having a high dielectric constant are used. The dielectric constant of the high dielectric constant inorganic oxide particles at 25 ° C. is 10 or more, preferably 25 or more, and more preferably 50 or more.
As such inorganic oxide particles, perovskite-type ferroelectric particles and bismuth layered perovskite-type ferroelectric particles are preferable.
Examples of the perovskite-type ferroelectric substance include barium titanate, lead zirconate titanate, lead titanate, zirconium oxide, and titanium oxide. On the other hand, examples of the bismuth layered perovskite type ferroelectric substance include bismuth strontium tantalate, bismuth strontium niobate, and bismuth titanate.

For example, for the purpose of reducing the dielectric constant and dielectric loss tangent or linear expansion factor of a molded product, inorganic oxide particles having low dielectric constant and low dielectric loss tangent or low linear expansion factor are used.
As such inorganic oxide particles, beryllium oxide particles (berilia particles), silicon oxide particles (silica particles), wollastonite particles, and magnesium metasilicate particles (steatite particles) are preferable.

For example, metal oxide particles are used for the purpose of improving the thermal conductivity or scratch resistance of the molded product.
As the metal oxide, aluminum oxide, lead oxide, iron oxide, tin oxide, magnesium oxide, titanium oxide, zinc oxide, antimony pentoxide, zirconium oxide, lanthanum oxide, neodium oxide, cerium oxide and niobium oxide are preferable, and aluminum oxide is preferable. Is more preferable. These metal oxides, particularly alumnium oxide, are preferable because of their high thermal conductivity.

As the present inorganic particles, silica particles and magnesium metasilicate particles are preferable, and silica particles are more preferable.
When the inorganic particles are silica particles or magnesium metasilicate particles, the content of silica or magnesium metasilicate is preferably 80% by mass or more, more preferably 95% by mass. The content of silica or magnesium metasilicate is preferably 100% by mass or less, more preferably 90% by mass or less.

The shape of the inorganic particles is appropriately selected according to the purpose, and is spherical, scale-like, layered, flat plate-like, leaf-like, apricot kernel-like, columnar, chicken crown-like, equiaxed, leaf-like, mica-like, block-like, flat plate. It may be scaly, wedge-shaped, rosette-shaped, mesh-shaped, or prismatic, and is preferably scaly or spherical, and more preferably spherical. When the spherical present inorganic particles are used, the composition tends to be excellent in dispersibility and stability, and the molded product formed from the composition tends to be excellent in low linear expansion.
The D50 of the inorganic particles is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less. The D50 of the particles is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more.

When the inorganic particles are spherical, it is preferably substantially spherical. In this case, the ratio of the minor axis to the major axis is preferably 0.5 or more, more preferably 0.8 or more. The above ratio is preferably less than 1. By using such highly spherical present inorganic particles, the composition tends to be excellent in stability and dispersibility. In addition, the molded product formed from the composition tends to have excellent adhesiveness and low line expansion property.

It is preferable that at least a part of the surface of the inorganic particles is surface-treated. In this case, the particles (1) and the inorganic particles are likely to form composite particles, and the composition obtained by this method is likely to be excellent in dispersibility and stability. Further, it is considered that during heating when forming a molded product from the composition, the surface treatment agent is thermally decomposed to generate gas to promote the flow of the inorganic particles, and the uniformity of the molded product is likely to be improved.
Examples of the surface treatment agent used for surface treatment include polyhydric alcohols such as trimethylolethane, pentaeristol, and propylene glycol, saturated fatty acids such as stearic acid and lauric acid, and esters thereof, and amines such as alkanolamine, trimethylamine, and triethylamine. , Paraffin wax, silane coupling agent, silicone, polysiloxane, and silane coupling agent is preferable.

As the silane coupling agent, a silane coupling agent having a functional group is preferable, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-Methyloxypropyltriethoxysilane, phenylaminosilane and 3-isocyandiapropyltriethoxysilane are more preferred.

As the present inorganic particles, one kind of inorganic oxide particles may be used alone, or two or more kinds of inorganic oxide particles may be used in combination.
Suitable specific examples of the inorganic particles include silica particles (“Admafine (registered trademark)” series manufactured by Admatex Co., Ltd.) and zinc oxide particles surface-treated with an ester such as propylene glycol dicaprate (Sakai Chemical Industry Co., Ltd.). "FINEX (registered trademark)" series manufactured by Denka Co., Ltd.), spherical molten silica particles ("SFP (registered trademark)" series manufactured by Denka Co., Ltd.), titanium oxide particles coated with polyhydric alcohol and inorganic substances (Ishihara) "Typake (registered trademark)" series manufactured by Sangyo Co., Ltd.), rutile-type titanium oxide particles surface-treated with alkylsilane ("JMT (registered trademark)" series manufactured by Teika Co., Ltd.), hollow silica particles (Pacific cement) "E-SPHERES" series manufactured by Nittetsu Mining Co., Ltd., "Sirinax" series manufactured by Nittetsu Mining Co., Ltd., "Ecocos Fire" series manufactured by Emerson & Cumming Co., Ltd., talc particles ("SG" series manufactured by Nippon Tarku Co., Ltd., etc.) , Steatite particles (“BST” series manufactured by Nippon Tarku Co., Ltd., etc.).

The F polymer (2) is a tetrafluoroethylene-based polymer different from the F polymer (1), and a tetrafluoroethylene-based polymer that does not contain the carbonyl group-containing group and the hydroxyl group-containing group is preferable.

As the F polymer (2), non-heat-meltable polytetrafluoroethylene (hereinafter, also referred to as “non-heat-meltable PTFE”) is more preferable.
The non-heat-meltable PTFE is polytetrafluoroethylene (PTFE), and in addition to the homopolymer of TFE, also includes a so-called modified PTFE which is a copolymer of TFE and a comonomer such as PAVE, HFP, FAE, etc. in a trace amount. Will be done. The ratio of TFE units in the non-hot melt PTFE is preferably 99.5 mol% or more, more preferably 99.9 mol% or more, out of all the units.

The non-heat-meltable PTFE is preferably fibrilable. The non-heat-meltable PTFE having a fibril property means a PTFE that can paste-extrude unfired polymer powder, and is a poly having a number average molecular weight, Mn, calculated based on the following formula (1) of 200,000 or more. Tetrafluoroethylene is preferred.
Mn = 2.1 × 10 ¹⁰ × ΔHc- ^5.16 ... (1)
In the formula (1), Mn indicates the number average molecular weight of PTFE, and ΔHc indicates the calorie of crystallization of PTFE measured by the differential scanning calorimetry method (cal / g).
The particles (2) are particles containing the F polymer (2), and the amount of the F polymer (2) in the particles (2) is preferably 80% by mass or more, preferably 100% by mass. Is more preferable.
The D50 of the particles (2) is preferably 20 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less. The D50 of the particles (2) is preferably 0.1 μm or more, more preferably 0.2 μm or more. Further, the D90 of the present particle (2) is more preferably 20 μm or less. If D50 and D90 of the particles (2) are in such a range, the surface area thereof becomes large, and the dispersibility of the particles is likely to be further improved.

The particles (2) may contain a polymer or an inorganic substance different from the F polymer as in the particles (1).
Specific examples of polymers and inorganic substances different from the F polymer include the same compounds as described above.

In this method, first, the particles (1) and the inorganic particles are mixed. The mixture of both is usually a powder which is an aggregate of the present particles (1) (hereinafter, also referred to as “powder (1)”) and a powder which is an aggregate of the present inorganic particles (hereinafter, “the present inorganic”). It is also described as "powder").
The mixing method using the powder is not particularly limited as long as the powder (1) and the present inorganic powder are uniformly mixed. The powder (1) and the present inorganic powder may be mixed at once, one of them may be added in a plurality of times and mixed, or the powder (1) and the present inorganic powder may be continuously added and mixed. Examples of the mixer used for mixing include a mixer with a stirring blade, a Henshell mixer, a ribbon blender, a swing type mixer, and a vibration type mixer.

When the powder (1) and the inorganic powder are mixed, the particles (1) are used as the core, and the inorganic particles are attached to the surface of the core, or the inorganic particles are used as the core of the core. It is preferable to mix the particles (1) so that the particles (1) are attached to the surface.
In order to achieve such an embodiment, it is preferable to mix the particles (1) and the inorganic particles so as to collide, aggregate, or the like so that the particles coalesce.

The mixing of the particles (1) and the inorganic particles in this method can also be performed in the presence of a liquid medium. Further, the particles (1) and the inorganic particles can be mixed by using a dispersion liquid such as a dispersion liquid in which the particles (1) are dispersed in a liquid medium. In this case, the obtained mixture is a mixture containing a liquid medium. Also in this case, similarly to the above, it is preferable to mix the particles (1) and the inorganic particles so as to collide, aggregate, or the like so that the particles coalesce.
Specific examples of mixing in the presence of a liquid medium include simultaneous mixing of the powder (1) with the present inorganic powder and the liquid medium, and mixing the liquid medium with the mixture of the powder (1) and the present inorganic powder. Examples thereof include mixing, mixing of the dispersion liquid in which the particles (1) are dispersed in the liquid medium, and the present inorganic powder.
Water is preferable as the liquid medium. Since water has high polarity and poor affinity with F polymer, it was considered that the dispersibility of the particles (1) in such a mixture was low, but the above-mentioned mechanism of action gave a mixture with excellent dispersion stability. Be done.

When water is used, it is preferable to knead the particles (1), the inorganic particles, and the mixture containing water. After mixing the powder (1) and the inorganic powder, water is further added and kneaded. Is more preferable. For example, it is preferable to mix the powder (1) and the present inorganic powder in advance using various mixers such as a tumbler or a Henschel mixer, and then add water to the mixture to further knead.

When kneading, it is preferable to knead in a closed system.
For kneading, it is preferable to use a kneader equipped with a stirring tank and uniaxial or multiaxial stirring blades. The number of stirring blades is preferably two or more in order to obtain a high kneading action. The kneading method may be either a batch method or a continuous method.

As the kneader used for the batch type kneading, a Henschel mixer, a pressurized kneader, a Banbury mixer and a planetary mixer are preferable, and a planetary mixer is more preferable.
Examples of the continuous kneader include a twin-screw extrusion kneader and a stone mill type kneader.

When the kneading is performed in the presence of water, a slurry-like or sol-like mixture containing the main particles (1) and the main inorganic particles in a liquid state can be obtained. In the presence of water, the amount of water in the mixture is preferably 10-70% by weight, more preferably 20-50% by weight.
The slurry-like or sol-like mixture thus obtained is highly viscous and is usually semi-solid. Its viscosity is usually 10,000 mPa · s or more, and in some cases 25,000 mPa · s or more. The viscosity is preferably 100,000 mPa · s or less, more preferably 80,000 mPa · s.

In this method, the mixture containing the particles (1) and the inorganic particles is then mixed with the particles (2) to obtain a composition. The method of mixing the mixture and the present particles (2) and the mixer used are the same as when mixing the present particles (1) and the present inorganic particles. The particles (2) may be mixed with the mixture as a powder, or may be mixed with the mixture as a dispersion liquid previously dispersed in a liquid medium. Water is preferable as the liquid medium.
When mixing the mixture and the main particles (2), it is preferable to use the aqueous dispersion of the main particles (2). When the aqueous dispersion of the particles (2) is mixed, the mixture may contain water. When the aqueous dispersion of the particles (2) is mixed, it is preferable to knead the mixture and the dispersion. Examples of the kneading method and the kneading machine include the same method and the kneading machine as described above.
Since water has high polarity and poor affinity with F polymer, it was considered that the dispersibility of the particles (2) would decrease in such mixing, but the composition having excellent dispersion stability due to the above-mentioned mechanism of action. Is obtained.
When a dispersion liquid in which the particles (2) are dispersed in water is used, the amount of water in the dispersion liquid is preferably 20 to 80% by mass, more preferably 40 to 70% by mass.

When at least one of the mixture or the particles (2) contains water, an ultrasonic homogenized baint shaker, a ball mill, an attritor, a basket mill, etc., from the viewpoint of dispersibility and dispersion stability of the obtained composition. Dispersers that use media such as sand mills, sand grinders, dyno mills, disperser mats, SC mills, spike mills, and agitator mills, and dispersers that do not use media such as ultrasonic homogenizers, nanomizers, resolvers, dispersers, and high-speed impeller dispersers. It is preferable to use it for kneading, and it is more preferable to use a disperser using media for kneading.

In this method, a third component other than the present particles (1), the present particles (2) and the present inorganic particles may be used. The third component may be mixed with a liquid medium such as water in advance and used. The third component can be used when mixing the present particles (1) and the present inorganic particles to prepare a mixture containing the third component, and the mixture containing the present particles (1) and the present inorganic particles and the present particles. A composition containing the third component can be produced by using it when mixing (2).
Examples of the third component include an ultraviolet absorber, a polymer different from the F polymer (hereinafter, also referred to as “other polymer”), a surfactant, a pH adjuster, a nonionic water-soluble polymer, and the like. ..

As the ultraviolet absorber, an ultraviolet absorber having a phenolic hydroxyl group and a nitrogen-containing heterocyclic structure is preferable, an ultraviolet absorber having a hydroxybenzophenone structure, and an ultraviolet absorber having a phenolic hydroxyl group and a triazine structure or a benzotriazole structure. Is more preferable. The latter UV absorber preferably has a hydroxyphenyltriazine structure or a structure in which various substituents are substituted in the hydroxyphenyl structure.

Other polymers include (meth) acrylic polymers and aromatic polymers. The (meth) acrylic polymer is a general term for polymers containing units based on acrylic acid, methacrylic acid, acrylate or methacrylate.
The glass transition point of the (meth) acrylic polymer is preferably 30 to 120 ° C, more preferably 40 to 110 ° C, and even more preferably 60 to 100 ° C. The (meth) acrylic polymer preferably has a hydroxy group. In this case, the interaction with the F polymer (1) or the F polymer (2) is also likely to be improved.

The (meth) acrylic polymer includes a (meth) acrylate-based polymer containing a unit based on a monomer having a hydroxy group, a chain transfer agent (alcanthiol, etc.) and an alcohol such as methanol, ethanol, propanol, etc. ( A (meth) acrylate-based polymer having a hydroxy group at the end of a polymer chain obtained by polymerizing a meta) acrylate is preferable.

Examples of the (meth) acrylate having a hydroxy group include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl ( Examples thereof include (meth) acrylate obtained by adding (meth) acrylate, monoglycidyl ether or glycidol and (meth) acrylic acid.

The (meth) acrylic polymers include methyl (meth) acrylate, ethyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobornyl (meth) acrylate, cyclopentyl (meth) acrylate, and cyclohexyl (meth). It preferably contains at least one (meth) acrylate-based unit selected from the group consisting of meta) acrylates and benzyl (meth) acrylates.

As the aromatic polymer, an aromatic imide-based polymer is preferable, and an aromatic polyimide, a polyamic acid or a salt thereof, an aromatic polyimide precursor, an aromatic polyamideimide, an aromatic polyamideimide precursor, an aromatic polyetherimide and an aroma are preferable. Group polyetherimide precursors are preferred, aromatic polyimide precursors and aromatic polyamideimides are more preferred. These aromatic polymers may be modified aromatic polymers into which acidic groups such as carboxylic acid groups and phenolic hydroxyl groups are further introduced.

When water is used in this method, the aromatic polymer is preferably water soluble. The water-soluble aromatic polymer can be prepared by adjusting the acid value thereof and the basicity of the composition obtained by this method. For example, if the aromatic polymer is an aromatic polyamic acid, a water-soluble aromatic polymer can be prepared by reacting the aromatic polyamic acid with an aqueous ammonia or an organic amine to form a polyamic acid salt.
Specifically, the water-soluble aromatic polymer preferably has an acid value of 20 to 100 mg / KOH, and more preferably 35 to 70 mgKOH / g. Further, in the case of a composition using a water-soluble aromatic polymer, the pH of the composition is preferably 5 to 10, and more preferably 7 to 9. If the acid value of the aromatic polymer and the pH of the obtained composition are within such a range, not only the dispersion stability of the obtained composition is improved, but also the aromatic polymer is formed from the dispersion liquid when the molded product is formed. Is highly dispersed, and it is easy to improve the physical properties of the polymer such as ultraviolet absorption, flexibility, and adhesion.
Specific examples of the aromatic polymer include "Ultem 1000F3SP" (manufactured by SABIC), "HPC-1000", and "HPC-2100D" (all manufactured by Showa Denko Materials Co., Ltd.).

When water is used in this method, a surfactant may be used as the third component from the viewpoint of improving the dispersion stability and handleability of the obtained liquid composition.
The surfactant is preferably nonionic.
The hydrophilic moiety of the surfactant preferably has a polyoxyalkylene chain or an alcoholic hydroxyl group.
The polyoxyalkylene chain may be composed of two or more kinds of oxyalkylene groups. In the latter case, different types of oxyalkylene groups may be randomly arranged or may be arranged in blocks.
As the oxyalkylene group, an oxyethylene group is preferable.

The hydrophobic moiety of the surfactant preferably has an acetylene group, a polysiloxane group, a perfluoroalkyl group or a perfluoroalkenyl group. In other words, as the surfactant, a polyoxyalkylene alkyl ether-based surfactant, an acetylene-based surfactant, a silicone-based surfactant and a fluorine-based surfactant are preferable, and a silicone-based surfactant is more preferable.
As the silicone-based surfactant, an organopolysiloxane having a polyoxyalkylene chain as a hydrophilic group and a polydimethylsiloxane structure as a hydrophobic group is preferable. When a silicone-based surfactant is used, a polyoxyalkylene alkyl ether-based surfactant may be used in combination from the viewpoint of improving the long-term storage stability of the liquid composition.

Specific examples of surfactants include the "Futergent" series (Futtergent 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 (DIC). Megafuck Co., Ltd. is a registered trademark), "Unidyne" series (Unidyne manufactured by Daikin Industries, Ltd. is a registered trademark), "BYK-347", "BYK-349", "BYK-378", "BYK-3450", Examples thereof include "BYK-3451", "BYK-3455", "BYK-3456" (manufactured by BIC Chemie Japan Co., Ltd.), "KF-6011", and "KF-6043" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
The polyoxyalkylene alkyl ether is available as a commercial product, and specifically, "Tergitol TMN-100X" (manufactured by Dow Chemical Co., Ltd.), "Lutensol TO8", "Lutensol XL70", "Lutensol XL80", "Lutensol XL90", "Lutensol XP80", "Lutensol M5" (above, manufactured by BASF), "Newcall 1305", "Newcol 1308FA", "Newcol 1310" (above, manufactured by Nippon Emulsifier), "Leocol TDN-90-80" , "Leocol SC-90" (above, manufactured by Lion Specialty Chemicals Co., Ltd.).
When a surfactant is contained, the content in the liquid composition is preferably 1 to 15% by mass. In this case, the affinity between the components is increased, and the dispersion stability of the composition obtained by this method is likely to be further improved.

When water is used in this method, a basic compound is used as a pH adjuster so that the pH of the liquid composition is 5 to 10 from the viewpoint of stability after long-term storage of the obtained liquid composition. May be.
Examples of the basic compound include ammonia, dimethylamine, diethylamine, diisopropylamine, diethanolamine, triethanolamine, tripropanolamine, triethylamine, triamylamine, pyridine and N-methylmorpholine.
In this case, a pH buffer may be further added to stabilize the pH of the liquid composition. Examples of the pH buffer include tris (hydroxymethyl) aminomethane, ethylenediaminetetraacetic acid, ammonium hydrogencarbonate, ammonium carbonate and ammonium acetate.

When water is used in this method, the resulting liquid composition may further contain a nonionic water-soluble polymer. In this case, the dispersion stability and rheological characteristics of the obtained liquid composition tend to be further improved, and the film-forming property tends to be improved. As a result, it is easier to form a thick molded product or the like from the present dispersion. In particular, if the water-soluble polymer has a nonionic hydroxyl group, not only this tendency becomes remarkable, but also the obtained molded product is likely to be improved. In particular, if the water-soluble polymer has a nonionic hydroxyl group, not only this tendency becomes remarkable, but also the obtained molded product is likely to be improved.
As the nonionic water-soluble polymer, a polyvinyl alcohol-based polymer, a polyvinylpyrrolidone-based polymer, and a polysaccharide are preferable.

The polyvinyl alcohol-based polymer may be a partially acetylated or partially acetalized polyvinyl alcohol.
Examples of the polysaccharide include glycogens, amicropectins, dextrins, glucans, fructans, chitins, amyloses, agaroses, amicropectins, and celluloses. Examples of celluloses include methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose.

As the nonionic water-soluble polymer, nonionic polysaccharides are more preferable, and nonionic celluloses are particularly preferable. As the nonionic celluloses, hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.
Specific examples of such nonionic polysaccharides include "Sunrose (registered trademark)" series (manufactured by Nippon Paper Industries), "Metroise (registered trademark)" series (manufactured by Shin-Etsu Chemical Co., Ltd.), and "HEC CF grade" (manufactured by Shin-Etsu Chemical Co., Ltd.). Sumitomo Seika Co., Ltd.).

When the liquid composition obtained by this method contains a nonionic water-soluble polymer, the amount thereof is preferably 0.01% by mass or more, preferably 0.1% by mass or more, based on the total mass of the liquid composition. Is more preferable. The amount is preferably 5% by mass or less. The ratio of the mass of the water-soluble polymer to the total mass of the particles (1) and the particles (2) in the liquid composition is preferably 0.01 or more. Further, the previous ratio is preferably 0.1 or less.

In this method, the particles (1), the particles (2), the inorganic particles, and components other than the third component may be used. Other components include organic particles, organic pigments, metal soaps, lubricants, organic monomers, organic substances such as organic oligomers having a degree of polymerization of 50 or less, thioxogenic agents, viscosity modifiers, defoaming agents, silane coupling agents, and the like. Examples thereof include dehydrating agents, plasticizing agents, weather resistant agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, flame retardant agents and the like.

The composition of the present invention (hereinafter, also referred to as “the present composition”) contains the present particles (1), the present particles (2) and the present inorganic particles, and the average particle size of the present inorganic particles is the present particles (1). ) Is in the range of 1 to 1000% of the average particle size, and the content of the inorganic particles is 5 to 75% by mass with respect to the total mass of the particles (1), the particles (2) and the inorganic particles. Is a composition. The present composition is preferably the composition produced by the present method.
The types and average particle diameters of the particles (1), the particles (2) and the inorganic particles are as described above.
However, in the present composition, the average particle size of the present inorganic particles is in the range of 1 to 1000%, preferably 5 to 300%, and more preferably 10 to 100% of the average particle size of the present particles (1). It is in the range of%.
As a more preferable specific embodiment, the D50 of the particles (1) is 0.1 to 20 μm, the D50 of the inorganic particles is 0.01 to 20 μm, and the average particle size of the inorganic particles is 0.01 to 20 μm. Examples thereof include an embodiment in which the average particle size of the particles (1) is in the range of 20 to 100%.

The content of the particles (1) in the composition is preferably 5% by mass or more, preferably 10% by mass or more, based on the total mass of the particles (1), the particles (2) and the inorganic particles. More preferred. The content of the particles (1) is preferably 60% by mass or less, more preferably 30% by mass or less.
The content of the particles (2) in the composition is preferably 5% by mass or more, preferably 10% by mass or more, based on the total mass of the particles (1), the particles (2) and the inorganic particles. More preferred. The content of the particles (2) is preferably 60% by mass or less, more preferably 30% by mass or less.

The content of the F polymer (2) in the present composition is preferably 25% by mass or more, more preferably 50% by mass or more, based on the total mass of the F polymer (1) and the F polymer (2). The content of the F polymer (2) in the present composition is preferably 90% by mass or less, more preferably 80% by mass or less, based on the total mass of the F polymer (1) and the F polymer (2).
The content of the inorganic particles in the composition is preferably 40% by mass or more, and preferably 70% by mass or less, based on the total mass of the particles (1), the particles (2), and the inorganic particles.

When the present composition contains a liquid medium such as water, the components other than the liquid medium (hereinafter, referred to as "solid content") in the liquid present composition (hereinafter, also referred to as "the present liquid composition") , The present particles (1), the present particles (2) and the present inorganic particles are contained. The solid content in the liquid composition also includes the particles (1), the particles (2), and other components in the liquid composition other than the inorganic particles. From the viewpoint that a thick molded product can be easily obtained from the present liquid composition, the solid content concentration in the present liquid composition is preferably 20% by mass or more, more preferably 40% by mass. Further, from the viewpoint of dispersibility of the liquid composition, the solid content concentration is preferably 80% by mass or less, more preferably 60% by mass or less. The solid content may contain components other than the main particles (1), the main particles (2) and the main inorganic particles, and the total of the main particles (1), the main particles (2) and the main inorganic particles in the solid content. The amount is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total mass of the solid content.

Specific examples of other components in the present liquid composition include the above-mentioned third component, and more preferable specific examples include aromatic polyimides for the above-mentioned reasons, and in particular, aromatic polyimide precursors. Body and aromatic polyamide-imide precursors are preferred.

The viscosity of the liquid composition is preferably 50 mPa · s or more, more preferably 75 mPa · s or more, and even more preferably 100 mPa · s or more. The viscosity of the liquid composition is preferably less than 10,000 mPa · s, more preferably 5000 mPa · s or less, and even more preferably 1000 mPa · s or less. The present liquid composition having such a viscosity is excellent in coatability and homogeneity.
The thixotropy of the present liquid composition is preferably 1.0 to 2.2. This liquid composition having such a thixotropic ratio is excellent in coatability and homogeneity. The thixotropic ratio is calculated by dividing the viscosity of the present liquid composition measured under the condition of a rotation speed of 30 rpm by the viscosity of the present liquid composition measured under the condition of a rotation speed of 60 rpm.
From the viewpoint of reducing the uniformity of the component distribution of the molded product obtained from the present liquid composition and suppressing the voids, the foam volume ratio in the present liquid composition is preferably less than 10%, more preferably less than 5%. The foam volume ratio is preferably 0% or more.
The foam volume ratio was measured by measuring the volume ( _VN ) of the present liquid composition at standard atmospheric pressure and 20 ° C. and the combined volume ( _VV ) of the foam when the pressure was reduced to 0.003 MPa. It is a value obtained by the following formula.
Foam volume ratio [%] = 100 × ( _VV ₋ VN) / _VN .

The present liquid composition preferably has excellent long-term storage stability, and preferably has a dispersion ratio of 60% or more after long-term storage.
"Dispersion rate after long-term storage" means that when 20 mL of this liquid composition is placed in a vial with an internal volume of 30 mL and stored in a closed manner at 25 ° C for 30 days, the entire main liquid composition in the vial after sealed storage is used. It is a value calculated by the following formula from the height of the dispersion layer and the height of the dispersed layer. If the dispersed layer is not confirmed after the sealed storage and the state does not change, the height of the entire liquid composition does not change, and the dispersion rate is 100%. The larger the dispersion rate, the better the dispersion stability.
Dispersion rate (%) = (height of dispersion layer) / (height of the entire liquid composition) × 100

The present composition and the present liquid composition can be obtained by the above-mentioned method. In this method, the present composition and the present liquid composition can be obtained by using the present particles (1), the present particles (2) and the present inorganic particles, and, if necessary, a predetermined amount of a liquid medium such as water. can.
Further, by appropriately using the third component or the other component in this method, the present composition and the present liquid composition containing these components can be obtained.

When the composition does not contain a liquid medium such as water, the composition is in the form of powder. This powdery composition can be used for forming a coating film as a powder coating material or the like. Further, the powdery present composition can be melt-kneaded together with the third component and the other components, if necessary, and the obtained melt-kneaded product can be used as a molding material. Further, the powdery present composition can be made into a pellet-shaped or granular molding material by melt extrusion molding.
By melt-molding the powdery present composition and the molding material obtained from the same, a molded product such as a film containing the F polymer (1), the F polymer (2) and the present inorganic particles can be obtained. Examples of the melt molding include extrusion molding and injection molding, and extrusion molding is preferable. Extrusion molding can be performed using a single-screw screw extruder, a multi-screw screw extruder, or the like.

From the present composition, a laminate having a polymer layer containing the F polymer (1), the F polymer (2) and the present inorganic particles and a base material can be formed. When the composition does not contain a liquid medium such as water, a coextruder is used as the extruder, and the composition and the molding material obtained from the composition together with the raw material of the base material are used. A method of extruding the composition or a molding material obtained from the composition on the substrate, an extrusion molding of the composition or a molding material obtained from the composition, and the base thereof. An example is a method of heat-bonding to a material. Examples of the base material include the same base material as the base material in the laminate formed from the present liquid composition described later. Moreover, as a preferable embodiment of the said polymer layer, the F layer described later can be mentioned.

In the case of the present liquid composition, if the present liquid composition is applied to the surface of the base material and heated to form a polymer layer containing the F polymer (1), the F polymer (2) and the present inorganic particles, the present liquid composition may be formed. A laminate having a base material and a polymer layer can be produced. Preferable embodiments of the laminate include a metal-clad laminate having a metal foil and a polymer layer formed on at least one surface thereof, and a multilayer film having a resin film and a polymer layer formed on at least one surface thereof. Can be mentioned. The polymer layer is preferably the F layer, which will be described later.

The metal foil in the metal-clad laminate is preferably a copper foil. Such a metal-clad laminate is particularly useful as a printed circuit board material. The metal foil may be a low-roughened metal foil, and may be, for example, a metal foil having a surface average roughness of 0.01 to 0.1 μm.
The resin film in the multilayer film is preferably a polyimide film. Such a multilayer film is useful as an electric wire coating material and a printed circuit board material.

In the production of the above-mentioned laminate, the polymer layer may be formed on at least one side of the surface of the base material, the polymer layer may be formed on only one side of the base material, and the polymer layers are formed on both sides of the base material. You may. The surface of the base material may be surface-treated with a silane coupling agent or the like. When applying this liquid composition, spray method, roll coat method, spin coat method, gravure coat method, micro gravure coat method, gravure offset method, knife coat method, kiss coat method, bar coat method, die coat method, fountain Mayer bar. The coating method of the method and the slot die coating method can be used.

The polymer layer is preferably a layer formed by further heating the polymer after removing water by heating (hereinafter, also referred to as "F layer"). It is preferable to blow air in the process of removing water.

After removing the water, it is preferable to heat the substrate to a temperature range in which the F polymer is fired, and it is preferable to fire the polymer in the range of, for example, 300 to 400 ° C. The F layer preferably contains a fired product of at least one of the F polymer (1) and the F polymer (2).
The F layer is formed through the steps of coating, drying, and firing of the present liquid composition as described above. These steps may be performed once or twice or more. For example, the above liquid composition is applied and water is removed by heating to form a coating film. The liquid composition may be further applied onto the formed coating film to remove a liquid medium such as water by heating, and the polymer may be further fired by heating to form the coating film. From the viewpoint of easily obtaining a thick film having excellent smoothness, the steps of applying, drying and firing the present liquid composition may be performed a plurality of times.

The thickness of the F layer is preferably 0.1 μm or more, and more preferably 1 μm or more. The upper limit of the thickness is 200 μm. In this range, the F layer having excellent crack resistance can be easily formed.
The peel strength between the F layer and the base material layer is preferably 10 N / cm or more, more preferably 15 N / cm or more. The peel strength is preferably 100 N / cm or less. By using this liquid composition, such a laminate can be easily formed without impairing the physical characteristics of the F polymer in the F layer.
The porosity of the F layer is preferably 5% or less, more preferably 4% or less. The porosity is preferably 0.01% or more, more preferably 0.1% or more. The void ratio is determined by image processing to determine the void portion of the F layer from the SEM photograph of the cross section of the molded product observed using a scanning electron microscope (SEM), and the area occupied by the void portion is the area occupied by the F layer. It is the ratio (%) divided by the area. The area occupied by the void portion is obtained by approximating the void portion to a circle.

The material of the base material is copper, nickel, aluminum, titanium, metals such as alloys thereof, polyimide, polyarylate, polysulfone, polyallyl sulfone, polyamide, polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide. , Heat-resistant resin such as liquid crystal polyester and liquid crystal polyester amide, and glass. Examples of the shape of the base material include a planar shape, a curved surface shape, and an uneven shape, and may be any of a foil shape, a plate shape, a film shape, and a fibrous shape. Examples of the base material include a metal substrate such as a metal foil, a heat-resistant resin film, a heat-resistant resin sheet, a fiber-reinforced resin substrate, a prepreg sheet which is a precursor of the fiber-reinforced resin substrate, a glass film, and a glass sheet.
Specific examples of the laminate include a metal foil, a metal-clad laminate having an F layer on at least one surface of the metal foil, a polyimide film, and a multilayer film having an F layer on both surfaces of the polyimide film. Be done. These laminates are excellent in various physical properties such as electrical characteristics, and are suitable as a printed circuit board material or the like. Specifically, such a laminate can be used for manufacturing a flexible printed circuit board or a rigid printed circuit board.

One aspect of the laminated body is a laminated body of prepreg / F layer / metal foil. As the base material, a prepreg having a polymer layer on the surface of the glass cloth, which is obtained by impregnating the glass cloth with the heat-resistant resin or the tetrafluoroethylene-based polymer, is preferable. The polymer layer may be formed from a plurality of polymer layers, and in such cases, it is preferable that each polymer layer is formed from different polymers. It is preferable to have an F layer between the prepreg and the metal foil because the prepreg and the metal foil are not easily peeled off.

Such a laminate is used for impregnating an insulating layer of a printed wiring board, a thermal interface material, a substrate for a power module, a coil used in a power device such as a motor, and drying to form a thermally conductive heat-resistant coating layer. It can also be used for bonding ceramic parts and metal parts to each other in an in-vehicle engine, for imparting corrosion resistance to the fins or tubes constituting the heat exchanger, and for coating the inside and outside of a glass container. It is particularly suitable for coating to impart impact resistance. The laminate of the F layer and the base material is useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry supplies, heat dissipation parts, paints, cosmetics and the like. In the printed circuit board, in order to prevent the temperature of the printed circuit board on which electronic components are mounted at high density, it can be used as a new printed circuit board material in place of the conventional glass epoxy board.

Specifically, wire coating materials for aircraft electric wires, enamel wire coating materials used for motors for electric vehicles, etc., electrical insulating tapes, insulating tapes for oil drilling, materials for printed substrates, precision filtration membranes, limitations External filtration membranes, back-penetration membranes, ion exchange membranes, separation membranes such as dialysis membranes and gas separation membranes, electrode binders for lithium secondary batteries, fuel cells, copy rolls, furniture, automobile dashboards, home appliances, etc. Sliding members such as covers, load bearings, sliding shafts, valves, bearings, bushes, seals, thrust washers, wear rings, pistons, slide switches, gears, cams, belt conveyors and food transport belts, wear pads, wear strips, etc. Tools such as tube lamps, test sockets, wafer guides, worn parts of centrifugal pumps, hydrocarbons / chemicals and water supply pumps, shovels, shavings, cuttings, saws, boilers, hoppers, pipes, ovens, baking molds, chutes, dies, It is useful as a toilet bowl, container coating material, power device, transistor, thyristor, rectifier, transformer, power MOS FET, CPU, heat dissipation fin, and metal heat dissipation plate.
More specifically, sealing materials for processing machines, vacuum ovens, plasma processing equipment, etc. that heat-treat under low oxygen, such as housings for personal computers and displays, electronic device materials, interior and exterior of automobiles, spattering and various dry etching. It is useful as a heat dissipation component in a processing unit such as a device.

When the woven fabric is impregnated with the liquid composition and dried by heating, an impregnated woven fabric in which the F polymer and the inorganic particles are impregnated in the woven fabric can be obtained. The impregnated woven fabric can also be said to be a coated woven fabric in which the woven fabric is covered with an F layer. The woven fabric is preferably a glass fiber woven fabric, a carbon fiber woven fabric, an aramid fiber woven fabric or a metal fiber woven fabric, and more preferably a glass fiber woven fabric or a carbon fiber woven fabric. The woven fabric may be treated with a silane coupling agent from the viewpoint of enhancing the adhesiveness with the F layer. The total content of the F polymer in the main woven fabric is preferably 30 to 80% by mass. Examples of the method of impregnating the woven fabric with the present liquid composition include a method of immersing the woven fabric in the present liquid composition and a method of applying the present liquid composition to the woven fabric.

When the woven fabric is dried, the F polymer may be fired. Examples of the method of firing the F polymer include a method of passing the woven fabric through a ventilation drying oven in an atmosphere of 300 to 400 ° C. The drying of the woven fabric and the firing of the F polymer may be carried out in one step. This woven fabric has excellent characteristics such as high adhesion (adhesiveness) between the F layer and the woven fabric, high surface smoothness, and low distortion. By thermocompression bonding the main woven fabric and the metal foil, a metal-clad laminate having high peel strength and resistance to warping can be obtained, which can be suitably used as a printed circuit board material.

Further, in the production of the main woven fabric, the woven fabric impregnated with the present liquid composition is applied to the surface of the base material, heated and dried, whereby the impregnated woven fabric containing the F polymer, the present inorganic particles and the woven fabric is contained. A fabric layer may be formed to produce a laminated body in which the base material and the impregnated woven fabric layer are laminated in this order. The embodiment is also not particularly limited, and if a woven fabric impregnated with the present liquid composition is applied to a part or all of the inner wall surface of a member such as a tank, a pipe, or a container, and the member is heated while rotating. An impregnated woven fabric layer can be formed on a part or all of the inner wall surface of the member. This manufacturing method is also useful as a method for lining the inner wall surface of members such as tanks, pipes, and containers.

This liquid composition has excellent dispersion stability and can be efficiently impregnated into a porous or fibrous material. Examples of such porous or fibrous materials include materials other than the above-mentioned woven fabrics, specifically, plate-shaped, columnar or fibrous materials. These materials may be pretreated with a curable resin, a silane coupling agent, or the like, or may be further filled with inorganic oxide particles or the like. In addition, these materials may be twisted together to form a thread, a cable, or a wire. At the time of twisting, an intervening layer made of another polymer such as polyethylene may be arranged. As an embodiment of impregnating such a material with the present liquid composition to produce a molded product, there is an embodiment of impregnating the fibrous material on which the curable resin or the cured product thereof is carried with the present liquid composition.

Examples of the fibrous material include high-strength and low-elongation fibers such as carbon fiber, aramid fiber, and silicon carbide fiber. As the curable resin, a thermosetting resin such as an epoxy resin, an unsaturated polyester resin, or a thermosetting polyurethane resin is preferable. Specific examples of such an embodiment include a composite cable formed by impregnating a cable made by twisting carbon fibers carrying a thermosetting resin with the present liquid composition and further heating the cable to bake the F polymer. .. Such a composite cable is useful as a cable for large structures, ground anchors, oil drilling, cranes, cableways, elevators, agriculture, forestry and fisheries, and slinging cables.

A preferred embodiment of the laminate is a metal-clad laminate having a metal foil and the polymer layer formed on the surface of at least one of the metal foils, wherein the polymer layer is an F polymer ( 1), contains polytetrafluoroethylene and the present inorganic particles, and the content of the present inorganic particles is the total mass of the F polymer (1), polytetrafluoroethylene and the present inorganic particles (hereinafter, referred to as “total mass”. ), Which is 5 to 75% by mass, may be a metal-clad laminate (hereinafter, also referred to as “main laminate”).
In such a laminated body, the inclusion of the F polymer (1) not only enhances the adhesion between the polymer layer and the metal foil, but also tends to increase the uniformity between the polytetrafluoroethylene and the present inorganic particles in the polymer layer. It is useful as a printed circuit board material because it has electrical characteristics and mechanical properties such as warpage resistance and flexibility.

This tendency is more likely to be improved when the relationship between the contents of the F polymer (1), the polytetrafluoroethylene and the inorganic particles is in the range shown below.
That is, the content of the F polymer (1) in the polymer layer is more preferably 10% by mass or more with respect to the total mass. The content of the F polymer (1) is more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

The content of polytetrafluoroethylene in the polymer layer is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total mass. The content of polytetrafluoroethylene is preferably 60% by mass or less, more preferably 30% by mass or less.
The content of the present inorganic particles in the polymer layer is preferably 5% by mass or more, more preferably 40% by mass or more, based on the total mass. The content of the inorganic particles is preferably 80% by mass or less, more preferably 70% by mass or less.

Further, the mass of polytetrafluoroethylene in the polymer layer is preferably 50% by mass or more, more preferably more than 50% by mass, with respect to the total mass of F polymer (1) and polytetrafluoroethylene in the polymer layer. The mass of polytetrafluoroethylene in the polymer layer is preferably 90% by mass or less, more preferably 80% by mass or less, based on the total mass of the F polymer (1) and polytetrafluoroethylene in the polymer layer.

The thickness of the polymer layer in the present laminate is preferably 50 μm or more, more preferably 100 μm or more. The upper limit of the thickness is 1000 μm. Due to the above-mentioned tendency, the metal-clad laminate having such a thick polymer layer is particularly useful as a rigid printed circuit board material because it is less likely to warp due to the inclusion of the present inorganic particles.

The polymer layer in the present laminate preferably further contains an aromatic polymer, and more preferably contains an aromatic polyamide or an aromatic polyimide amide. In this case, the binder effect of the aromatic polymer enhances the denseness between the components and the adhesion between the metal foil and the polymer layer, and the powder falling of the components from the polymer layer and the warpage of the present laminate are more likely to be suppressed. Further, the UV absorption ability of the aromatic polymer improves the UV absorbability of the polymer layer, and the UV laser processability of the present laminate is likely to be improved. Therefore, this laminate is particularly useful as a rigid printed circuit board having a thick polymer layer.

Further, the composition may be extruded as described above and then stretched to form a stretched sheet, or the polymer layer obtained by removing the metal leaf of the laminated body may be subjected to the stretching treatment. A stretched sheet may be formed. Such a stretched sheet may be formed by molding the present composition in the case where the F polymer (2) is polytetrafluoroethylene into a sheet shape and further stretching treatment. Such a stretched sheet is a sheet having physical properties such as porosity and mechanical strength of stretched polytetrafluoroethylene on which the present inorganic particles are firmly supported by the action of the F polymer (1). Such a stretched sheet is also useful as a printed circuit board material having high adhesiveness and a low coefficient of linear expansion and excellent electrical characteristics.

In a preferred embodiment of the stretched sheet, the F polymer (1), polytetrafluoroethylene and the present inorganic particles are contained, and the content of the present inorganic particles is the F polymer (1), the lithotetrafluoroethylene and the present inorganic particles. Examples thereof include a stretched sheet (hereinafter, also referred to as “main stretched sheet”) which has been stretched and is 5 to 75% by mass with respect to the total mass of the above.
The relationship between the contents of the F polymer (1), the polytetrafluoroethylene and the inorganic particles in the stretched sheet is the same as the relationship between the contents in the laminated body.
Further, as a device for stretching, a biaxial stretching device can be mentioned, and as a stretching condition, a condition that the stretching ratio is 200% or more at a speed of 5 to 1000% / sec can be mentioned.

As described above, according to this method, a method for producing a composition containing F polymer particles and the present inorganic particles and having excellent stability and dispersibility and the composition are provided. Further provided are the present laminate and the present stretched sheet having the present composition useful as a printed circuit board material, which have electrical characteristics and mechanical properties such as warpage resistance and flexibility.

Although the present method, the present composition, the present laminated body and the present stretched sheet have been described above, the present invention is not limited to the configuration of the above-described embodiment.
For example, this method 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, the present composition, the present laminated body and the present stretched sheet may be added with any other configuration or may be replaced with any configuration exhibiting the same function in the configuration of the above embodiment.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
1. 1. Preparation of each component and each member [F polymer]
Powder A: 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. A powder dispersion B consisting of 1000 particles having a melting temperature of 300 ° C. and having a D50 of 2.1 μm: a non-thermally meltable PTFE F polymer (2) D50. An aqueous dispersion in which 0.3 μm PTFE particles are dispersed in water, and an aqueous dispersion containing 60% by mass of PTFE particles (AGC, “Product No. AD-911E”).
Powder C: Consists of an F polymer containing 98.5 mol% and 1.5 mol% of TFE units and PPVE units in this order, having no carbonyl group-containing group, and having a melting temperature of 300 ° C., and D50 is 2. Powder consisting of 4 μm particles [Inorganic oxide]
Powder G: Powder of spherical silica with D50 of 0.5 μm, which is surface-treated with phenylaminosilane [varnish of imide-based resin]
Varnish A: Water varnish containing a precursor of aromatic polyamide-imide (PAI, acid value: 50 mgKOH / g) [surfactant]
Surfactant A: Polyoxyalkylene-modified polydimethylsiloxane having a dimethylsiloxane unit in the main chain and an oxyethylene group in the side chain [water-soluble polymer]
Water-soluble polymer A: Hydroxyethyl cellulose, which is a nonionic polysaccharide Water-soluble polymer B: Carboxymethyl cellulose, which is an anionic polysaccharide

2. 2. Production Example of Liquid Composition (Part 1)
(Example 1-1)
Powder A and powder G were dry-blended to obtain a mixture. The mixture, water, and surfactant A are added to a planetary mixer and kneaded to form powder A particles (18.5 parts by mass), powder G particles (60 parts by mass), and a surfactant. A mixture containing A (1 part by mass) and water (40 parts by mass) and having a viscosity of 28,000 mPa · s was obtained.
The above mixture was put into a pot, and then the mixture of dispersion B and varnish A and water were added in a plurality of times and stirred, and the particles (18.5 parts by mass) of the F polymer (1) as a whole were added. , PTFE particles (20 parts by mass), spherical silica particles (60 parts by mass), PAI (1.5 parts by mass), surfactant (1 part by mass), water (100 parts by mass) with a viscosity of 400 mPa · s. A liquid composition P was obtained. The dispersion ratio of the obtained liquid composition P after long-term storage was 60% or more, and the redispersibility after the dispersion ratio measurement was also good.

(Example 1-2)
A mixture was obtained in the same manner as in Example 1-1 except that the powder A, the powder G, the water and the surfactant A were individually added to the planetary mixer, and then the liquid composition Q was prepared. The viscosity of the liquid composition Q was 600 mPa · s, and the dispersion rate of the liquid composition Q after long-term storage was 60% or more, but the redispersibility after the dispersion rate measurement was deteriorated.

(Example 1-3)
A liquid composition R was obtained in the same manner as in Example 1-1 except that the powder A was changed to the powder C. The dispersion ratio of the liquid composition R after long-term storage was less than 60%. In addition, it was difficult to redisperse the liquid composition R after measuring the dispersion rate.

(Example 1-4)
Powder A, dispersion B, varnish A, surfactant A and water are mixed to form F polymer (1) particles (18.5 parts by mass), PTFE particles (20 parts by mass), PAI (1.5 parts by mass). A liquid mixture containing (parts by mass), a surfactant (1 part by mass) and water (100 parts by mass). An attempt was made to prepare a liquid composition by adding powder G (60 parts by mass) to this mixture, but at that time, the composition thickened as the powder G was added, and its dispersion stability decreased. , A liquid composition having a viscosity of 1000 mPa · s or less, which contains water (100 parts by mass) as a whole, could not be directly formed.

3. 3. Example of Production of Laminate A wet film was formed by applying the liquid composition P produced in Example 1-1 to the surface of a long copper foil (thickness: 18 μm) using a bar coater. Next, the copper foil on which the wet film was formed was passed through a drying oven at 110 ° C. for 5 minutes and dried by heating to obtain a dry film. Then, the dry membrane was heated at 380 ° C. for 3 minutes in an oven in a nitrogen gas atmosphere. As a result, a laminate 1 having a copper foil and a polymer layer having a thickness of 100 μm as a molded product containing F polymer (1), PTFE, spherical silica particles and PAI on the surface thereof was produced.

The copper foil of the laminate 1 was removed by etching with an aqueous solution of ferric chloride to prepare a single polymer layer, and the dielectric tangent measured by the SPDR (split post dielectric resonance, measurement frequency: 10 GHz; the same applies hereinafter) method. Was 0.0010 or less.
The copper foil of the laminate 1 was removed by etching with an aqueous solution of ferric chloride to prepare a single polymer layer, and a 180 mm square test piece was cut out. The cut out test piece was measured in the range of 25 ° C. or higher and 260 ° C. or lower according to the measuring method specified in JIS C 6471: 1995. The coefficient of linear expansion of the test piece was 30 ppm / ° C. or less.

A rectangular test piece having a length of 100 mm and a width of 10 mm was cut out from the laminated body 1. The position 50 mm from one end in the length direction of the test piece was fixed, and the copper foil and the polymer layer were peeled off from one end in the length direction at a tensile speed of 50 mm / min at 90 ° to the test piece. The maximum load at the time of peeling was defined as the peel strength (N / cm). The peel strength was 10 N / cm or more. Further, the inorganic oxide particles 1 were firmly supported in the polymer layer 1 and did not fall off.

When the liquid composition P is changed to the liquid composition R to produce a laminate having a polymer layer having a thickness of 100 μm as a molded product, powder is severely removed from the polymer layer and is smooth. No laminate with a polymer layer was obtained.

4. Production example of liquid composition (Part 2)
(Example 2-1)
Powder A and powder G were dry-blended to obtain a mixture. The mixture, water, water-soluble polymer A, and surfactant A are added to a planetary mixer and kneaded to form powder A particles (18.5 parts by mass) and powder G particles (60 mass by mass). Part), a water-soluble polymer A (1 part by mass), a surfactant A (1 part by mass), and water (40 parts by mass) to obtain a mixture.
The above mixture is put into a pot, and then the mixture of dispersion B and varnish A and water are added in a plurality of times and stirred, and the particles (18.5 parts by mass) of the F polymer (1) as a whole are added. , PTFE particles (20 parts by mass), spherical silica particles (60 parts by mass), PAI (1.5 parts by mass), water-soluble polymer (1 part by mass), surfactant (1 part by mass), water (100 parts by mass) Part) was obtained as a liquid composition S having a viscosity of 500 mPa · s. The dispersion ratio of the liquid composition S after long-term storage was 60% or more, and the redispersibility after the dispersion ratio measurement was also good.

(Example 2-2)
A mixture was obtained in the same manner as in Example 1-1 except that the water-soluble polymer A was changed to the water-soluble polymer B, and the liquid composition T was prepared from the mixture.
5. Evaluation Example of Laminated Body In the above "3. Production Example of Laminated Body", the laminated body 2 is changed to the liquid composition P and the liquid composition P is changed to the liquid composition T in the same manner except that the liquid composition P is changed to the liquid composition S. The laminated bodies 3 were obtained in the same manner except for the above. The dielectric loss tangent of the single polymer layer prepared by removing the copper foil of the laminate 2 by etching with an aqueous solution of ferric chloride is 0.0010 or less, and the dielectric loss tangent of the single polymer layer prepared from the laminate 3 is 0. It was over 0010.

Further, the coating amount of the liquid composition in the above "3. Production example of laminated body" is prepared, and the thickness of the polymer layer that can be formed by the polymer layer forming process per one time is adjusted to the liquid composition P, the liquid composition S and the liquid composition S. As a result of evaluating the liquid composition T, the thickness of the polymer layer increased in the order of the liquid composition S, the liquid composition T, and the liquid composition P.

As is clear from the above results, the liquid composition prepared by this method has excellent dispersibility and stability, and the polymer layer obtained by applying it to the substrate has excellent electrical properties and low linear expansion. Was there. Further, the polymer layer and the base material had excellent adhesion, and the inorganic oxide particles were firmly supported in the F layer. Therefore, it is considered that the laminate using the composition obtained by this method is excellent in the uniformity of the component distribution and highly expresses the properties of the inorganic oxide particles. Further, it is considered that no voids are generated at the interface of the layer and the decrease in water resistance is suppressed. Such a laminate has electrical characteristics and mechanical properties such as warpage resistance and flexibility, and is considered to be useful as a printed circuit board material.
The entire specification, claims and abstracts of Japanese Patent Application No. 2021-001123 filed on January 06, 2021 and Japanese Patent Application No. 2021-038690 filed on May 18, 2021. The contents are cited here and incorporated as disclosure of the specification of the present invention.

Claims

Particles of a tetrafluoroethylene-based polymer (1) having at least one of a carbonyl group-containing group and a hydroxyl group-containing group and inorganic oxide particles are mixed to form a mixture, and the tetrafluoroethylene-based polymer (1) is further referred to as a mixture. A method for producing a composition, which comprises mixing particles of a different tetrafluoroethylene polymer (2) with the mixture.
The production method according to claim 1, wherein the dispersion liquid in which the particles of the tetrafluoroethylene polymer (2) are dispersed in water is mixed with the mixture.
The production method according to claim 1 or 2, wherein the tetrafluoroethylene polymer (1) is a polymer having 10 to 5000 carbonyl group-containing groups per 1 × 10 6 main chain carbon atoms.
The production method according to any one of claims 1 to 3, wherein the tetrafluoroethylene polymer (2) is polytetrafluoroethylene.
The production method according to any one of claims 1 to 4, wherein the inorganic oxide is silicon oxide.
Particles of a tetrafluoroethylene-based polymer (1) having at least one of a carbonyl group-containing group and a hydroxyl group-containing group, particles of a tetrafluoroethylene-based polymer (2) different from the tetrafluoroethylene-based polymer, and inorganic oxide particles. The average particle size of the inorganic oxide particles is in the range of 1 to 1000% with respect to the average particle size of the particles of the tetrafluoroethylene polymer (1), and the content of the inorganic oxide particles is , 5 to 75% by mass based on the total mass of the particles of the tetrafluoroethylene-based polymer (1), the particles of the tetrafluoroethylene-based polymer (2), and the inorganic oxide particles.
The composition according to claim 6, further comprising an aromatic polymer.
The composition according to claim 6 or 7, further comprising water.
The composition according to any one of claims 6 to 8, wherein the tetrafluoroethylene polymer (2) is polytetrafluoroethylene.
The composition according to any one of claims 6 to 9, wherein the inorganic oxide is silicon oxide.
Any of claims 6 to 10, wherein the mass of the tetrafluoroethylene polymer (2) is 25% by mass or more with respect to the total mass of the tetrafluoroethylene polymer (1) and the tetrafluoroethylene polymer (2). The composition according to item 1.
A metal-clad laminate having a metal foil and a polymer layer formed on the surface of at least one of the metal foils, wherein the polymer layer has at least one of a carbonyl group-containing group and a hydroxyl group-containing group. It contains a tetrafluoroethylene-based polymer (1), polytetrafluoroethylene, and inorganic oxide particles, and the content of the inorganic oxide particles is the tetrafluoroethylene-based polymer (1), the polytetrafluoroethylene, and the inorganic. A metal-clad laminate that is 5 to 75% by mass with respect to the total mass of the oxide particles.
The metal-clad laminate according to claim 12, wherein the polymer layer further contains an aromatic polymer.
The metal-clad laminate according to claim 12 or 13, wherein the polymer layer has a thickness of 50 μm or more.
It contains a tetrafluoroethylene-based polymer (1) having at least one of a carbonyl group-containing group and a hydroxyl group-containing group, polytetrafluoroethylene, and inorganic oxide particles, and the content of the inorganic oxide particles is the tetrafluoroethylene. A stretched sheet obtained by stretching the inorganic oxide particles in an amount of 5 to 75% by mass based on the total mass of the polymer (1), the polytetrafluoroethylene and the inorganic oxide particles.