WO2021095662A1 - 非水系分散液、積層体の製造方法及び成形物 - Google Patents

非水系分散液、積層体の製造方法及び成形物 Download PDF

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WO2021095662A1
WO2021095662A1 PCT/JP2020/041572 JP2020041572W WO2021095662A1 WO 2021095662 A1 WO2021095662 A1 WO 2021095662A1 JP 2020041572 W JP2020041572 W JP 2020041572W WO 2021095662 A1 WO2021095662 A1 WO 2021095662A1
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polymer
filler
powder
less
inorganic filler
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PCT/JP2020/041572
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English (en)
French (fr)
Japanese (ja)
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敦美 山邊
渉 笠井
創太 結城
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Ａｇｃ株式会社
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Priority to KR1020227017077A priority Critical patent/KR20220101640A/ko
Priority to JP2021556073A priority patent/JPWO2021095662A1/ja
Priority to CN202080073346.8A priority patent/CN114599712A/zh
Publication of WO2021095662A1 publication Critical patent/WO2021095662A1/ja

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    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
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    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Definitions

  • the present invention relates to a method for producing a laminate having a non-aqueous dispersion liquid containing a predetermined tetrafluoroethylene-based polymer and an inorganic filler and a polymer layer formed from the non-aqueous dispersion liquid, and molding having predetermined minute voids. Regarding things.
  • Tetrafluoroethylene-based polymers such as polytetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene and perfluoro (alkyl vinyl ether) (PFA), and a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP) are releasable. It has excellent physical properties such as electrical properties, water and oil repellency, chemical resistance, weather resistance, and heat resistance, and is used in various industrial applications.
  • a non-aqueous dispersion containing PTFE powder is known as a coating agent used to impart these physical properties to the surface of a base material.
  • Patent Document 1 from the viewpoint of improving the dispersion stability, at least one selected from the group consisting of Al 2 O 3 , SiO 2 , CaCO 3 , ZrO 2 , SiC, Si 3 N 4 and Zn O
  • a non-aqueous dispersion containing an inorganic filler of an inorganic compound is described.
  • Patent Documents 2 and 3 disclose non-aqueous dispersions (thermosetting compositions) containing an epoxy resin before curing as a main component and a PTFE powder and a silica filler as filling components. These patent documents describe the physical characteristics (viscosity, dispersibility, etc.) of the non-aqueous dispersion liquid based on the epoxy resin before curing, which is the main component, and the physical characteristics (linear expansion, adhesion, etc.) of the polymer layer formed from the non-aqueous dispersion. Electrical characteristics, etc.) are described. However, these patent documents do not describe any embodiment in which various polymers are used in place of the epoxy resin.
  • a molded product having a high degree of physical properties based on a tetrafluoroethylene polymer (electrical properties, heat resistance, etc.) and an inorganic filler (low linear expansion, electrical properties, etc.) can be obtained from such a non-aqueous dispersion liquid. There was a problem that it could not be formed.
  • non-aqueous dispersion liquid containing the epoxy resin described in Patent Documents 2 and 3 if various polymers are used instead of the epoxy resin, in addition to the physical characteristics based on the tetrafluoroethylene polymer, the polymer and silica to be added It was thought that the basic physical properties could be imparted to the polymer layer to be formed. In order to satisfactorily express the physical characteristics based on each component in the polymer layer, it is preferable to increase the content of each of the three components in the non-aqueous dispersion as much as possible.
  • the present inventors can obtain dispersion stability and other components such as an aromatic polymer even if the contents of both are high. It was found that a non-aqueous dispersion having excellent blendability with a polymer can be obtained, and that a molded product having highly physical properties of a tetrafluoroethylene polymer and an inorganic filler can be obtained from such a non-aqueous dispersion. did. Furthermore, the present inventors have also found that when the non-aqueous dispersion liquid contains another polymer, the molded product has a high degree of physical characteristics of the other polymer. An object of the present invention is to provide such a non-aqueous dispersion liquid and to provide a dense molded product having excellent physical properties (electrical characteristics, low linear expansion, heat resistance, etc.).
  • a tetrafluoroethylene polymer powder having a melt viscosity at 380 ° C. of 1 ⁇ 10 6 Pa ⁇ s or less, an inorganic filler having an average particle size of more than 0.10 ⁇ m, and a liquid dispersion medium are included.
  • the inorganic filler is a substantially spherical inorganic filler having an average particle size of more than 0.10 ⁇ m and less than 10 ⁇ m and substantially free of particles having a particle size of 25 ⁇ m or more, or has an average major axis.
  • the tetrafluoroethylene polymer having a melt viscosity at 380 ° C. of 1 ⁇ 10 6 Pa ⁇ s or less contains a powder having an average particle size of 10 ⁇ m or less, an aromatic polymer, and an inorganic filler.
  • the inorganic filler is a filler containing at least one inorganic compound selected from the group consisting of boron nitride, aluminum nitride, beryllium oxide, silicon oxide, cerium oxide, aluminum oxide, magnesium oxide, zinc oxide and titanium oxide.
  • the non-aqueous dispersion liquid according to any one of [8] to [11] which contains at least one non-aqueous dispersion medium selected from the group consisting of aromatic hydrocarbons, amides, ketones and esters.
  • the non-aqueous dispersion liquid according to any one of [1] to [12] is applied to the surface of the base material and heated to form a polymer layer, and the base material and the polymer layer are formed in this order.
  • a method for producing a laminated body which obtains a laminated body having the same.
  • the molded product of [14] wherein the mass ratio of the content of the inorganic filler to the content of the tetrafluoroethylene polymer is 1.5 or less.
  • a molded product having a high degree of physical properties of a tetrafluoroethylene polymer and an inorganic filler can be molded, the content of both is high, and the dispersion stability and the blendability with other polymers are excellent.
  • a non-aqueous dispersion can be obtained.
  • a molded product having such physical characteristics can be obtained.
  • the "average particle size (D50)" is an object obtained by dispersing an object (powder or inorganic filler) in water and using a laser diffraction / scattering type particle size distribution measuring device (LA-920 measuring device manufactured by HORIBA, Ltd.).
  • the volume-based cumulative 50% diameter of the object That is, the particle size distribution of the object is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the powder particle population as 100%, and the particle diameter at the point where the cumulative volume is 50% on the cumulative curve. Is.
  • “98% cumulative volume particle size (D98)”, “90% cumulative volume particle size (D90)” and “10% cumulative volume particle size (D10)” are the volume-based cumulative 98 of the powder or inorganic filler obtained in the same manner. % Diameter and volume standard cumulative 10% diameter.
  • the “particle size distribution” is a distribution shown by a curve plotting the amount of particles (%) in each particle size interval obtained in the same manner.
  • the “melting temperature (melting point)” is the temperature corresponding to the maximum value of the melting peak obtained by analyzing the polymer by the differential scanning calorimetry (DSC) method.
  • the "glass transition point” is a value measured by analyzing a polymer by a dynamic viscoelasticity measurement (DMA) method.
  • the “specific surface area” is a value obtained by analyzing an inorganic filler by a gas adsorption method (BET method).
  • the "substantially spherical inorganic filler” is an inorganic particle in which the ratio of the minor axis to the major axis is 0.7 or more and the proportion of spherical particles is 95% or more when observed with a scanning electron microscope (SEM). Means a filler.
  • the “aspect ratio of the inorganic filler” is a ratio obtained by dividing the average particle size (D50) by the minor axis length (length in the lateral direction) of the inorganic filler.
  • the aspect ratio of the scaly anisotropic filler is obtained by dividing its D50 by its average minor axis (average value of its lateral diameter).
  • “Viscosity” is the viscosity of a liquid material measured using a B-type viscometer under the conditions of 25 ° C. and a rotation speed of 30 rpm.
  • the "thixotropy” is a value calculated by dividing the viscosity of a liquid material measured under the condition of a rotation speed of 30 rpm by the viscosity of the liquid material measured under the condition of a rotation speed of 60 rpm.
  • “Porosity” is the percentage (%) of the area of the void portion in the cross section of the molded product observed using a scanning electron microscope (SEM). "Ten-point average roughness (Rzjis)” is specified in Annex JA of JIS B 0601: 2013. "Dissipation factor” is a value measured by the SPDR method at a frequency of 10 GHz in an environment of 24 ° C. and 50% RH.
  • the "monomer-based unit” means an atomic group based on the above-mentioned monomer formed by polymerization of the monomer. The unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the above unit is converted into another structure by processing a polymer. Hereinafter, the unit based on the monomer a is also simply referred to as a “monomer a unit”.
  • the non-aqueous dispersion liquid of the present invention (hereinafter, also referred to as “the present dispersion liquid”) is a tetrafluoroethylene-based polymer having a melt viscosity at 380 ° C. of 1 ⁇ 10 6 Pa ⁇ s or less (hereinafter, also referred to as “F polymer”). Includes a powder (hereinafter, also referred to as “F powder”) and an inorganic filler.
  • the first aspect of the dispersion liquid (hereinafter, also referred to as “the dispersion liquid (1)”) contains F powder and an inorganic filler having an average particle size of more than 0.10 ⁇ m.
  • the F polymer is also referred to as F polymer (1)
  • the F powder is referred to as F powder (1)
  • the inorganic filler is also referred to as filler (1).
  • the content of the F polymer (1) and the content of the filler (1) in the dispersion liquid (1) are each more than 5% by mass. In this dispersion liquid (1), the F powder (1) and the filler (1) are dispersed.
  • the dispersion liquid (1) contains a large amount of each of the F polymer (1) and the filler (1), is excellent in dispersion stability, and has a high degree of physical properties of each of the F polymer (1) and the filler (1).
  • a molded product (a molded product of the present invention described later, etc.) can be formed. The reason is not always clear, but it can be considered as follows.
  • the F polymer (1) has a low melt viscosity at 380 ° C., and is affected by physical stress (shear stress, etc.) and state changes over time as compared with non-thermally meltable tetrafluoroethylene-based polymers. It is difficult, and F powder (1) has high dispersion stability.
  • the dispersion liquid (1) contains a large amount of the F powder (1), and the interaction between the filler (1) having an average particle size exceeding a predetermined value and the F powder (1) is relatively likely to increase. It can be said that. That is, if a large amount of inorganic filler having an average particle size of a predetermined value or less is contained, the cohesive action between the inorganic fillers is simply enhanced and the dispersibility is impaired. However, if the filler (1) is used, the F powder contained in a large amount It is considered that the loose aggregating action (interaction) with (1) is relatively enhanced, and pseudo secondary particles are formed in at least a part of both to stabilize. As a result, it is considered that the present dispersion liquid (1) is excellent in dispersion stability and blendability when other components are added.
  • the F polymer (1) can be said to be a crystalline polymer containing TFE units, and tends to form fine spherulites in a molded product. Due to the micro-concavo-convex structure on the surface of the spherulite, the filler (1) and the spherulite are not completely adhered to each other in the molded product, and at least a part thereof is uniformly distributed through minute voids. it is conceivable that.
  • such minute voids serve as a buffer and highly express the physical characteristics of both (F polymer (1) and filler (1)) in the molded product.
  • the filler (1) is an inorganic filler having a low linear expansion coefficient such as a silica filler
  • the molded product is less likely to be warped by the filler (1) and has various physical properties due to the F polymer (1). It can have a high degree of heat resistance, electrical characteristics, etc.).
  • Such a molded product can be suitably used as a printed circuit board material or a member thereof.
  • the F polymer (1) in the dispersion liquid (1) is a polymer containing a unit (TFE unit) based on tetrafluoroethylene (TFE) and having a melt viscosity at 380 ° C. of 1 ⁇ 10 6 Pa ⁇ s or less. ..
  • the F polymer (1) may consist of only TFE units, or may contain TFE units and other units.
  • Melt viscosity at 380 ° C. of F polymer (1) is preferably not more than 5 ⁇ 10 5 Pa ⁇ s, more preferably at most 1 ⁇ 10 5 Pa ⁇ s.
  • the melt viscosity is preferably 1 ⁇ 10 2 Pa ⁇ s or more, and more preferably 1 ⁇ 10 3 Pa ⁇ s or more.
  • the affinity between the F powder (1) and the filler (1) tends to be improved.
  • the F polymer (1) a polymer containing TFE units and PAVE units is preferable.
  • the melting temperature (melting point) of the F polymer (1) is preferably 260 to 320 ° C, more preferably 285 to 320 ° C.
  • the glass transition point of the F polymer (1) is preferably 75 to 125 ° C, more preferably 80 to 100 ° C.
  • the F polymer (1) preferably further has a monomer-based unit other than the TFE unit and the PAVE unit.
  • the monomer include olefins (ethylene, propylene, etc.), chlorotrifluoroethylene, fluoroolefins (hexafluoropropylene, fluoroalkylethylene, etc.), and monomers having an oxygen-containing polar group described later.
  • the F polymer (1) preferably has an oxygen-containing polar group.
  • the oxygen-containing polar group may be contained in the unit contained in the F polymer (1), or may be contained in the terminal group of the polymer main chain.
  • the latter F polymer (1) has an F polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like, or an oxygen-containing polar group prepared by plasma treatment or ionization line treatment. F polymer can be mentioned. If the F polymer (1) has an oxygen-containing polar group, the dispersibility of the F powder (1) in the present dispersion is excellent.
  • the oxygen-containing polar group is preferably a hydroxyl group-containing group, a carbonyl group-containing group, or a phosphono group-containing group, and the hydroxyl group-containing group or the carbonyl group-containing group is preferable from the viewpoint of the dispersibility of the dispersion and the adhesiveness of the surface of the molded product. More preferably, a carbonyl group-containing group is particularly preferable.
  • the hydroxyl group-containing group is preferably an alcoholic hydroxyl group-containing group, more preferably -CF 2 CH 2 OH, -C (CF 3 ) 2 OH or 1,2-glycol group (-CH (OH) CH 2 OH).
  • the carbonyl group-containing group includes 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 an imide. Residues (-C (O) NHC (O) -etc.) or carbonate groups (-OC (O) O-) are preferred.
  • the F polymer (1) having an oxygen-containing polar group preferably has a unit based on a monomer having an oxygen-containing polar group.
  • the F polymer (1) tends to improve the adhesiveness and heat resistance of the molded product.
  • the monomer preferably has a hydroxyl group-containing group or a carbonyl group-containing group, and more preferably a monomer having a carbonyl group-containing group.
  • Monomers having a carbonyl group-containing group include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (also known as hymic anhydride; hereinafter also referred to as "NAH”) or maleic anhydride.
  • NAH is more preferred.
  • the F polymer (1) is preferably a polymer containing TFE units and PAVE units, containing 1 to 10 mol% of PAVE units with respect to all units, and having a melting temperature of 260 to 320 ° C., preferably TFE units, PAVE units and Includes polymers containing units based on monomers with oxygen-containing polar groups, polymers consisting of 95.0-98.0 mol% TFE units and 2.0-5.0 mol% PAVE units, TFE units and PMVE units. Polymers are more preferred.
  • polymers are particularly susceptible to physical stress and changes of state over time and are more dispersible. Further, since the interaction with the filler (1) tends to be relatively enhanced, the dispersion stability of the dispersion liquid is likely to be improved. Further, it is easy to form dense spherulites in the molded product, and it is easy to improve the physical properties of the molded product. Specifically, a molded product having various physical properties (heat resistance, electrical properties, etc.) due to the F polymer (1) and various physical properties (low linear expansion rate, dielectric properties, etc.) due to the filler (1) is formed. It is easy and such a molded product can be suitably used as a printed circuit board material or a member thereof.
  • the F powder (1) in the present dispersion liquid (1) may contain components other than the F polymer (1), and is preferably composed of the F polymer (1).
  • the components other than the F polymer (1) include liquid crystal polyester, polyamideimide, polyimide, polyphenylene ether, and polyphenylene oxide.
  • the F powder (1) may form a complex with an inorganic substance.
  • oxides, nitrides, simple metals, alloys and carbons are preferable, and silicon oxide (silica) and metal oxides (beryllium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.) are preferable.
  • silicon oxide (silica) and metal oxides beryllium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.
  • Boron nitride, and magnesium metasilicate (steatite) are more preferred, silica and boron nitride are even more preferred, and silica is particularly preferred. In this case, the dispersibility of the present dispersion liquid (1) is likely to be improved.
  • the complex of the F powder (1) and the inorganic substance preferably has the F polymer (1) as a core, and particles having the inorganic substance on the surface of the core. Such particles are obtained, for example, by coalescing (collision, agglomeration, etc.) the powder of the F polymer (1) and the powder of an inorganic substance.
  • the inorganic substance may be contained in the filler (1). In other words, the F powder (1) and the filler (1) may form a complex.
  • the F powder (1) may be used alone or as a mixture of two types.
  • the F powder (1) contains 90 to 98 mol% of TFE units, 1 to 9.97 mol% of PAVE units, and 0.01 to 3 mol of units based on a monomer having an oxygen-containing polar group, based on all the units. %, Each of which may be a mixture of a polymer powder and a PTFE powder.
  • the PTFE in this case is preferably low molecular weight PTFE.
  • the D50 of the F powder (1) is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, and even more preferably 1 ⁇ m or more.
  • the D50 of the F powder (1) is preferably 6 ⁇ m or less, more preferably 4 ⁇ m or less, and even more preferably 3 ⁇ m or less. In this case, the interaction between the F powder (1) and the filler (1) is enhanced, and the dispersion stability of the present dispersion liquid (1) is likely to be further improved.
  • the F powder (1) preferably contains substantially no coarse particles.
  • the particle size of the coarse particles in the F powder (1) is preferably 10 ⁇ m or more, more preferably 6 ⁇ m or more.
  • the 98% particle size of the F powder (1) is preferably less than 10 ⁇ m, more preferably less than 6 ⁇ m. If the dispersion liquid (1) does not contain coarse particles, the interaction between the F powder (1) and the filler (1) is enhanced, and the dispersion stability is likely to be further improved.
  • the content of the F powder (1) in the dispersion liquid (1) is more than 5% by mass, preferably 7% by mass or more, more preferably 10% by mass or more, and further preferably 25% by mass or more.
  • the content of the F powder (1) is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. In this case, the dispersibility of the F powder (1) in the present dispersion liquid (1) is excellent.
  • the content of the F powder (1) is within such a range, the interaction between the F powder (1) and the filler (1) is relatively enhanced, and the dispersion stability thereof is likely to be further improved.
  • the physical characteristics of the F polymer (1) in the molded product are likely to be remarkably expressed.
  • the filler (1) in the dispersion liquid (1) is preferably a nitride filler or an inorganic oxide filler, and is preferably a boron nitride filler, a berylium oxide filler (berilia filler), a silicon oxide filler (silica filler), or a metal oxide (oxidation). Cerium, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.) filler or magnesium metasilicate filler (steatite filler) is more preferable, and silica filler or magnesium metasilicate filler (steatite filler) is further preferable. These fillers may be fired ceramic fillers.
  • Such a filler (1) tends to enhance the interaction with the F powder (1), and the dispersion stability of the present dispersion (1) tends to be further improved. Further, in the molded product, the physical characteristics based on the filler (1) are likely to be remarkably developed.
  • the filler (1) preferably contains silicon oxide or magnesium metasilicate (steatite).
  • the interaction of silicon oxide and steatite with the F polymer (1) is likely to be enhanced, and the filler (1) containing the silicon oxide and steatite is likely to further improve the dispersion stability of the dispersion liquid (1).
  • the physical properties of silicon oxide or steatite are likely to be remarkably expressed in the molded product.
  • the content of silicon oxide or magnesium metasilicate in the filler (1) is preferably 50% by mass or more, more preferably 75% by mass.
  • the content of silicon oxide or magnesium metasilicate is preferably 100% by mass or less, more preferably 90% by mass or less.
  • the pH of the water may be acidic, neutral or alkaline, and preferably neutral or alkaline.
  • the surface of the filler (1) is surface-treated.
  • the surface treatment agent used for such surface treatment include polyhydric alcohols (trimethylolethane, pentaeristol, propylene glycol, etc.), saturated fatty acids (stearic acid, lauric acid, etc.), esters thereof, alkanolamines, amines (trimethylamine, etc.). Triethylamine etc.), paraffin wax, silane coupling agent, silicone, polysiloxane, aluminum, silicon, zirconium, tin, titanium, antimony and other oxides, their hydroxides, their hydrated oxides, their phosphoric acid Examples include salt.
  • the filler (1) is preferably an inorganic filler surface-treated with a silane coupling agent.
  • a filler (1) has an excellent affinity with the F powder (1), and easily improves the dispersibility of the present dispersion liquid (1). Further, in the melt firing of the F polymer (1) when forming a molded product from the present dispersion liquid (1) containing the same, the flow of the filler (1) is promoted by thermal decomposition to generate gas, and the molding is performed. It is considered that the uniformity of objects is likely to be improved.
  • the silane coupling agent is preferably a silane coupling agent having a functional group, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -Methoxyloxypropyltriethoxysilane or 3-isocyanatepropyltriethoxysilane is more preferable.
  • the D50 of the filler (1) is more than 0.10 ⁇ m, preferably 0.15 ⁇ m or more, and more preferably 0.30 ⁇ m or more.
  • the D50 of the filler (1) is preferably less than 10 ⁇ m, more preferably 1.8 ⁇ m or less, still more preferably 1.5 ⁇ m or less. In this case, the dispersibility of the F powder (1) in the present dispersion liquid (1) is excellent. If the D50 of the filler (1) is in such a range and is close to the D50 of the F powder (1), the interaction between the two is relatively enhanced, and the dispersion stability thereof is likely to be further improved.
  • the filler (1) preferably contains substantially no coarse particles.
  • the particle size of the coarse particles in the filler (1) is preferably 25 ⁇ m or more, more preferably 20 ⁇ m or more, still more preferably 10 ⁇ m or more.
  • the 98% particle size of the filler (1) is preferably less than 25 ⁇ m, more preferably less than 20 ⁇ m, and even more preferably less than 10 ⁇ m.
  • the dispersibility of the filler (1) in the present dispersion (1) is excellent. If the dispersion liquid (1) does not contain coarse particles, the interaction between the F powder (1) and the filler (1) is enhanced, and the dispersion stability is likely to be further improved.
  • the D50 of the filler (1) is preferably D50 or less of the F powder (1).
  • the interaction between the two is relatively enhanced, and the dispersion stability is likely to be further improved.
  • the filler (1) is more likely to be distributed more uniformly, and its physical properties are likely to be remarkably exhibited.
  • the D50 of the filler (1) is more than 0.10 ⁇ m and 1 ⁇ m or less
  • the D50 of the F powder (1) is 1 ⁇ m or more and 3 ⁇ m or less.
  • the specific surface area of the filler (1) is preferably 1 ⁇ 20 m 2 / g, more preferably 5 ⁇ 8m 2 / g.
  • the filler (1) is likely to get wet in the dispersion liquid (1), and the interaction with the F powder (1) is likely to be enhanced. Further, in the molded product formed from the present dispersion liquid (1), the filler (1) and the F polymer (1) are more likely to be distributed more uniformly, and the physical properties of both are easily expressed in a well-balanced manner.
  • the shape of the filler (1) is preferably substantially spherical.
  • the ratio of the minor axis to the major axis is preferably 0.8 or more, more preferably 0.9 or more. The above ratio is preferably less than 1. If the filler (1) is highly spherical, the filler (1) tends to get wet in the dispersion liquid (1), and the interaction with the F powder (1) tends to be enhanced. Further, in the molded product, the filler (1) and the F polymer (1) are more likely to be distributed more uniformly, and the physical properties of both are easily expressed in a well-balanced manner.
  • the shape of the filler (1) is preferably scaly.
  • the aspect ratio of the scaly filler (1) is preferably 5 or more, and more preferably 10 or more.
  • the aspect ratio is preferably 1000 or less.
  • the average major axis (average value of the diameter in the longitudinal direction) of the scaly filler (1) is preferably 1 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • the average major axis is preferably 20 ⁇ m or less, and more preferably 10 ⁇ m or less.
  • the average minor axis is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the average minor axis is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less.
  • the filler (1) is likely to get wet in the dispersion liquid (1), and the interaction with the F powder (1) is likely to be enhanced. Further, in the molded product, the filler (1) and the F polymer (1) are more likely to be distributed more uniformly, and the physical properties of both are easily expressed in a well-balanced manner.
  • the scaly filler (1) may have a single-layer structure or a multi-layer structure.
  • the internal structure of the filler (1) may be a dense shape, a hollow shape, or a honeycomb shape.
  • the hollow ratio (average value of the volume ratio of voids per particle) of the hollow filler (1) is preferably 40 to 80%.
  • the particle strength of the hollow filler (1) is preferably 20 MPa or more. The particle strength is the particle strength when the residual ratio of the hollow filler after pressure pressing is 50%. The particle strength can be calculated from the apparent density of the hollow filler and the apparent density of the pellets obtained by press-pressing the medium spherical filler.
  • the filler (1) is preferably a sintered inorganic filler (sintered inorganic filler). In other words, it is preferable to form ceramics.
  • the water content of the filler (1) is preferably 0.3% by mass or less, more preferably 0.1% by mass or less.
  • the water content is preferably 0% by mass or more. In this case, the filler (1) is likely to get wet in the dispersion liquid (1), and the interaction with the F powder (1) is likely to be enhanced. Further, in the molded product, the filler (1) and the F polymer (1) are more likely to be distributed more uniformly, and the physical properties of both are easily expressed in a well-balanced manner.
  • Suitable specific examples of the filler (1) include silica fillers having a D50 of more than 0.10 ⁇ m (such as the “Admafine” series manufactured by Admatex) and D50 surface-treated with an ester such as propylene glycol dicaprate.
  • Zinc oxide with a thickness of more than 0.10 ⁇ m (“FINEX” series manufactured by Sakai Chemical Industry Co., Ltd., etc.), a substantially spherical molten silica filler with a D50 of more than 0.10 ⁇ m and 0.5 ⁇ m or less and a 98% particle size of less than 1 ⁇ m.
  • Rutyl-type titanium oxide filler with a D50 coated with polyhydric alcohol and inorganic substances of more than 0.10 ⁇ m and 0.5 ⁇ m or less (Tipeke” series manufactured by Ishihara Sangyo Co., Ltd.) Etc.), rutile type titanium oxide filler with D50 surface-treated with alkylsilane exceeding 0.10 ⁇ m (“JMT” series manufactured by Teika Co., Ltd., etc.), steatite filler with D50 exceeding 0.10 ⁇ m (manufactured by Nippon Tarku Co., Ltd.) "BST” series, etc.), boron nitride fillers with a D50 of more than 0.10 ⁇ m (“UHP” series manufactured by Showa Denko Co., Ltd., "HGP” series, “GP” series manufactured by Denka, etc.).
  • a preferred embodiment of the inorganic filler contained in the dispersion liquid (1) includes a filler (1) (hereinafter, also referred to as “filler (11)”), and further, a D50 of less than 1 ⁇ m and a filler.
  • An embodiment including an inorganic filler having a D50 smaller than that of (11) (hereinafter, also referred to as “different filler”) can be mentioned.
  • the improvement of the dispersion stability of the present dispersion liquid (1) by the filler (11) and the ability to form a dense molded product by different fillers are balanced, and various physical properties (water resistance, low) of the obtained molded product are obtained. Linear expandability, electrical characteristics, etc.) are more likely to be improved.
  • the different fillers may be inorganic fillers having a D50 smaller than that of the filler (11), and the material thereof may be the same as or different from that of the filler (11).
  • the D50 of the filler (11) is preferably 1 ⁇ m or more, and more preferably 1 ⁇ m or more and less than 10 ⁇ m. Further, when the D50 of the different filler is more than 0.10 ⁇ m, it is preferable that the different filler has a D50 smaller than that of the filler (11), and more preferably a silica filler. When the D50 is 0.10 ⁇ m or less, it is preferably a silica filler. The D50 of the different fillers is preferably 0.01 ⁇ m or more and less than 1 ⁇ m.
  • the filler (1) in such a preferred embodiment may have a multimodal particle size distribution.
  • the peak caused by the filler (11) is the highest among the peaks in the particle size distribution.
  • the filler (1) is preferably contained in a state having a bimodal particle size distribution having peaks in a region of 0.8 ⁇ m or less and a region of 1 ⁇ m or more, respectively. It is more preferable that the latter peak is contained in a state having a bimodal particle size distribution higher than that of the former peak.
  • the filler (1) in such a preferred embodiment is contained by at least a part thereof adhering to the surface of the F powder (1) or at least a part of the F powder (1) adhering to the surface thereof. May be.
  • the present dispersion liquid (1) contains a composite body of the F powder (1) and the filler (1), and the dispersion stability thereof is further improved, and various physical properties of the molded product formed from the composite body (1). Water resistance, low line expansion, electrical characteristics, etc.) are likely to be further improved.
  • the mass ratio of the contents of different fillers to the content of the filler (11) is preferably 0.1 or more, more preferably 0.4 or more.
  • the mass ratio is preferably 1 or less, more preferably 0.8 or less. In this case, the dispersion stability of the dispersion liquid (1) and the physical properties of the molded product are easily balanced.
  • the content of the filler (1) in the dispersion liquid (1) is more than 5% by mass, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more.
  • the content of the filler (1) is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. When the content of the filler (1) is within such a range, the interaction between the F powder (1) and the filler (1) is relatively enhanced, and the dispersion stability thereof is likely to be further improved. In addition, the physical characteristics of the filler (1) are likely to be remarkably exhibited in the molded product.
  • the content of the filler (1) in the dispersion liquid (1) is preferably equal to or less than the content of the F polymer (1).
  • the F polymer (1) in the molded product, is used as a matrix, and the molded product in which the filler (1) is uniformly distributed is easily formed, and the physical properties of both are easily expressed in a well-balanced manner.
  • the content of the filler (1) is 5% by mass or more and 25% by mass or less, and the content of the F polymer (1) is more than 25% by mass and 50% by mass or less.
  • the dispersion liquid (1) preferably further contains another resin (polymer) different from the F polymer (1).
  • the other resin may be a thermosetting resin or a thermoplastic resin.
  • examples of other resins include epoxy resins, maleimide resins, urethane resins, fluororesins, elastomers, polyimides, polyamic acids, polyamideimides, polyphenylene ethers, polyphenylene oxides, liquid crystal polyesters, and fluoropolymers other than F polymers.
  • the other resin polyimide or polyamic acid is preferable, and thermoplastic polyimide is more preferable.
  • the porosity of the molded product is reduced to make it denser, and the physical properties of the F polymer (1) and the filler (1) are likely to be remarkably developed.
  • the content of the polyimide or polyamic acid in the dispersion liquid (1) is preferably 1 to 30% by mass, more preferably 5 to 25% by mass.
  • the mass ratio of the polyimide content to the F polymer (1) content is preferably 1.0 or less, more preferably 0.1 to 0.7.
  • the present dispersion (1) when containing another resin may be produced by mixing the present dispersion (1) with powder of another resin, and the present dispersion (1) and the other resin may be mixed. It may be produced by mixing with the containing varnish.
  • the other resin is preferably an aromatic polymer.
  • the definition and scope of the aromatic polymer, including its preferred embodiment, are the same as those of the aromatic polymer (AR polymer) in the present dispersion (2) described later.
  • the liquid dispersion medium in the present dispersion (1) is a non-aqueous liquid dispersion medium, which is an inert liquid compound at 25 ° C. that functions as a dispersion medium for the F powder (1) and the filler (1).
  • a liquid compound one kind may be used alone, or two or more kinds may be mixed.
  • the boiling point of the liquid compound is preferably 125 to 250 ° C. In this case, when the molded product is formed from the present dispersion liquid (1), the F powder (1) and the filler (1) can be easily packed densely, and the physical properties of the molded product can be easily improved.
  • liquid compound at least one selected from the group consisting of amides, ketones and esters is preferable.
  • Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, and N-methyl-2-.
  • Examples thereof include pyrrolidone, ⁇ -butyrolactone, cyclohexanone, cyclopentanone, butyl acetate and methyl isopropyl ketone.
  • the liquid compound when the dispersion liquid (1) further contains an aromatic polymer, particularly when it contains an aromatic thermoplastic polyimide, the liquid compound preferably contains an amide and a ketone or ester, and 3-methoxy-. More preferably, it contains N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide or N-methyl-2-pyrrolidone, and cyclohexanone, cyclopentanone, ⁇ -butyrolactone or butyl acetate.
  • the content of the liquid dispersion medium in the dispersion liquid (1) is preferably 25% by mass or more, more preferably 30% by mass or more.
  • the content of the liquid dispersion medium is preferably 70% by mass or less, more preferably 60% by mass or less.
  • the dispersion liquid (1) further preferably contains a surfactant, and more preferably contains a nonionic surfactant.
  • the nonionic surfactant preferably has an alcoholic hydroxyl group and an oxyalkylene group (hereinafter, also referred to as "AO group”) as hydrophilic moieties, and more preferably has an alcoholic hydroxyl group and an AO group as hydrophilic moieties. preferable.
  • AO group oxyalkylene group
  • Such a surfactant further improves the affinity (interaction) with the liquid dispersion medium via the AO group, and tends to enhance the dispersibility of the present dispersion liquid (1).
  • the AO group may be composed of one kind of AO group or two or more kinds of AO groups. In the latter case, different types of AO groups may be randomly arranged or may be arranged in blocks.
  • the hydrophobic moiety of the surfactant is preferably an acetylene-containing group, a perfluoroalkyl group, or a perfluoroalkenyl group.
  • the surfactant is preferably an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant.
  • F powder (1) and the filler (1) and the surfactant interact with each other to a high degree, not only the dispersion stability of the dispersion liquid (1) can be more easily improved, but also both (F polymer)
  • the physical properties of (1) and the filler (1)) are likely to be remarkably expressed in the molded product.
  • the weight average molecular weight of the nonionic surfactant is preferably 1000 to 80,000.
  • the content of the AO group is preferably 10% by mass or more, more preferably 20% by mass or more.
  • the content of AO groups is preferably 50% by mass or less.
  • the affinity of the nonionic surfactant with respect to the liquid dispersion medium is further improved, and the dispersibility of the F powder (1) and the filler (1) in the present dispersion (1) is likely to be further enhanced.
  • the nonionic surfactant has an alcoholic hydroxyl group
  • the hydroxyl value thereof is preferably 100 mgKOH / g or less, more preferably 50 mgKOH / g or less.
  • the hydroxyl value is preferably 10 mgKOH / g or more.
  • the fluorine content thereof is more preferably 20 to 50% by mass.
  • a copolymer of a compound represented by the following formula (F) and a compound represented by the following formula (H) is preferable.
  • CH 2 CHR F- C (O) O-Q F- X F ... (F)
  • CH 2 CHR H -C (O ) - (Q H) m -OH ⁇ (H)
  • RF represents a hydrogen atom or a methyl group.
  • Q F represents an alkylene group or an oxyalkylene group.
  • X F represents a perfluoroalkyl group or perfluoroalkenyl group.
  • RH represents a hydrogen atom or a methyl group.
  • Q H represents an oxyalkylene group.
  • m represents an integer from 1 to 120.
  • the amount of each compound (monomer) used in the production of the above-mentioned copolymer should be appropriately determined according to the type and the physical characteristics (fluorine content, AO group content, hydroxyl value, etc.) of the above-mentioned surfactant. Just do it.
  • nonionic surfactants include “Futergent” series (manufactured by Neos), “Surflon” series (manufactured by AGC Seimi Chemical Co., Ltd.), “Megafuck” series (manufactured by DIC), and “Unidyne” series.
  • “Futergent” series manufactured by Neos
  • “Surflon” series manufactured by AGC Seimi Chemical Co., Ltd.
  • Megafuck manufactured by DIC
  • Unidyne Manufactured by Daikin Industries, Ltd.
  • BYK-347 "BYK-349", “BYK-378”, “BYK-3450”, “BYK-3451”, “BYK-3455”, “BYK-3456” (Big Chemie) -Japan
  • “KF-6011”, “KF-6043” manufactured by Shin-Etsu Chemical Co., Ltd.
  • the content of the surfactant in the dispersion liquid (1) is preferably 1 to 15% by mass.
  • the content of the surfactant is within such a range, the interaction between the F powder (1) and the filler (1) is enhanced, and the dispersion stability of the present dispersion (1) is likely to be further improved.
  • the dispersion liquid (1) contains a viscosity-imparting agent, a defoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weather resistant agent, an antioxidant, a heat stabilizer, a lubricant, and an antistatic agent. It may contain additives such as agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, flame retardants, and organic fillers.
  • the dispersion liquid (1) has excellent dispersion stability even when it contains such an additive, and the physical properties of the F polymer (1) and the filler (1) in the molded product formed from the dispersion liquid (1). Is highly expressed.
  • the water content of the dispersion liquid (1) is preferably 20000 ppm or less, more preferably 8000 ppm or less, and further preferably 5000 ppm or less.
  • the water content of the dispersion liquid (1) is preferably 0 ppm or more. In this case, the dispersion stability of the dispersion liquid (1) is likely to be further improved.
  • the viscosity of the dispersion liquid (1) is preferably 50 mPa ⁇ s or more, and more preferably 100 mPa ⁇ s or more.
  • the viscosity of the dispersion liquid (1) is preferably 1000 m ⁇ Pa or less, more preferably 800 m ⁇ Pa or less. In this case, the dispersion stability of the dispersion liquid (1) is likely to be further improved.
  • the thixotropy ratio of the dispersion liquid (1) is preferably 1.0 or more.
  • the thixotropy ratio of the dispersion liquid (1) is preferably 3.0 or less, more preferably 2.0 or less.
  • the dispersion liquid (1) can easily form such a liquid composition having excellent thixotropy property by the above-mentioned action mechanism.
  • the present dispersion (1) can be produced by mixing an F powder (1), a filler (1), and a liquid dispersion medium, and is a non-aqueous dispersion containing the F powder (1) and a non-aqueous dispersion containing the filler (1). It is preferable to prepare each of the dispersion liquid and mix the two for production. In this case, the interaction between the F powder (1) and the filler (1) is enhanced, and it is easy to prepare the present dispersion liquid (1) having excellent dispersion stability. Further, in this case, each non-aqueous dispersion liquid preferably contains the above-mentioned surfactant.
  • the F powder (1) is added at the same time as the liquid dispersion medium in advance, or the F powder (1) ) Is preferably added in advance to the liquid dispersion medium before being dispersed.
  • the production method of the dispersion liquid (1) include a production method in which an F powder (1), a filler (1), a different filler, and a liquid dispersion medium are mixed.
  • the F powder (1) and the liquid dispersion medium may be mixed in advance to form a non-aqueous dispersion liquid, or the filler (11) and the above-mentioned different filler may be mixed in advance.
  • the second aspect of the present dispersion (hereinafter, also referred to as “the dispersion (2)”) is a powder having an average particle size of F polymer of 10 ⁇ m or less and an aromatic polymer (hereinafter, “AR polymer”). Also referred to as), an inorganic filler, and a liquid dispersion medium.
  • the F polymer is also referred to as F polymer (2)
  • the F powder is referred to as F powder (2)
  • the inorganic filler is also referred to as filler (2).
  • the F powder (2) and the filler (2) are each dispersed, and the AR polymer is dissolved or highly dispersed.
  • the content of the F polymer (2), the content of the AR polymer, and the content of the filler (2) are each more than 5% by mass.
  • the dispersion liquid (2) is a non-aqueous system having a large content of each of the three components (three components of the F polymer (2), AR polymer and filler (2); the same applies hereinafter) and has excellent dispersibility. It is a dispersion liquid, and the polymer layer (molded product) obtained from the dispersion has a high degree of good physical properties based on the three components and is excellent in rigidity. The reason is not always clear, but it can be considered as follows.
  • AR polymers and inorganic fillers themselves exhibit predetermined dispersibility or solubility in non-aqueous dispersions, their stability and properties of non-aqueous dispersions tend to deteriorate as their content increases. .. Specifically, when the content of the AR polymer is high, the viscosity and thixotropy of the non-aqueous dispersion liquid are increased, and the stability of the non-aqueous dispersion is likely to be impaired. Further, when the content of the inorganic filler is high, the inorganic filler itself is likely to aggregate or settle, and the stability of the non-aqueous dispersion liquid is likely to be impaired.
  • the F polymer (2) has a melt viscosity within a predetermined range and has plasticity, and the powder thereof is not easily affected by physical stress and has excellent dispersibility.
  • the dispersion liquid (2) contains a high content of the fine granular powder of the F polymer (2).
  • the dispersion liquid (2) contains the F polymer (2) densely (at a high density), the interaction between the three components tends to gradually increase. Therefore, the present dispersion liquid (2) is considered to be excellent in dispersion stability and handleability. Further, in the polymer layer formed from the polymer layer, the three components are likely to be densely and uniformly filled.
  • the molded product (polymer layer, etc.) formed from the present dispersion liquid (2) has excellent rigidity such as folding resistance and low linear expansion property while having a high degree of physical characteristics of the three components. ..
  • the above effects are more prominently exhibited in the preferred embodiment of the present dispersion (2), which will be described later.
  • F-polymer (2) and F-powder (2) are similar to those of F-polymer (1) and F-powder (1), including preferred embodiments.
  • the F polymer (2) may be polytetrafluoroethylene having a number average molecular weight of 10,000 to 200,000 (hereinafter, also referred to as “low molecular weight PTFE”).
  • the number average molecular weight of the low molecular weight PTFE is a value calculated based on the following formula (1).
  • Mn 2.1 ⁇ 10 10 ⁇ ⁇ Hc- 5.16 ...
  • Mn indicates the number average molecular weight of low molecular weight PTFE
  • ⁇ Hc indicates the amount of heat of crystallization (cal / g) of low molecular weight PTFE measured by differential scanning calorimetry.
  • the melting temperature of the F polymer (2) is preferably 280 to 325 ° C, more preferably 285 to 320 ° C.
  • the F polymer (2) contains TFE units and PAVE units, and preferably contains 1 to 5 mol% of PAVE units with respect to all units and has a melting temperature of 260 to 320 ° C., preferably TFE units, PAVE units and oxygen.
  • the polymer (2) having no oxygen-containing polar group is more preferable.
  • the polymer (1) contains 90 to 98 mol% of TFE units, 1 to 9.97 mol% of PAVE units, and 0.01 to 3 mol% of units based on a monomer having a polar functional group, based on all the units. It is preferable to contain each of them.
  • Specific examples of the polymer (1) include the polymers described in International Publication No. 2018/16644.
  • the content of PAVE units in the polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, based on all the units.
  • the polymer (2) is composed of only TFE units and PAVE units, and contains 95.0 to 98.0 mol% of TFE units and 2.0 to 5.0 mol% of PAVE units with respect to all the units. preferable.
  • the polymer (2) does not have oxygen-containing polar groups when the number of oxygen-containing polar groups contained in the polymer is less than 500 per 1 ⁇ 10 6 carbon atoms constituting the polymer main chain. It means that there is.
  • the number of the oxygen-containing polar groups is preferably 100 or less, more preferably 50 or less.
  • the lower limit of the number of oxygen-containing polar groups is usually 0.
  • the polymer (2) may be produced by using a polymerization initiator, a chain transfer agent or the like that does not generate an oxygen-containing polar group as the terminal group of the polymer chain, and is an F polymer having an oxygen-containing polar group (polymerization initiator).
  • F polymer, etc., which has an oxygen-containing polar group derived from the above in the terminal group of the main chain of the polymer may be fluorinated to produce the polymer.
  • Examples of the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314, etc.).
  • the D50 of the F powder (2) is preferably 8 ⁇ m or less, more preferably 4 ⁇ m or less.
  • the D50 of the powder is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the D90 of the F powder (2) is preferably 10 ⁇ m or less, more preferably 6 ⁇ m or less. In D50 and D90 in this range, the fluidity and dispersibility of the F powder (2) become good, and the electrical characteristics (low dielectric constant, etc.) and heat resistance of the obtained polymer layer are most likely to be exhibited.
  • the AR polymer in the dispersion liquid (2) is a polymer other than the F polymer (2), and is preferably a polymer having an aromatic ring in the main chain or a prepolymer forming such a polymer.
  • the AR polymer is preferably thermoplastic.
  • the dielectric loss tangent of the AR polymer is preferably 0.005 or less, more preferably 0.003 or less.
  • the dielectric loss tangent of a polymer that is a precursor of another aromatic polymer such as an aromatic polyamic acid, which will be described later, is the dielectric loss tangent of an aromatic polymer formed from the precursor.
  • the AR polymer examples include at least one selected from the group consisting of aromatic polyimide, aromatic polyamic acid, aromatic polyamideimide, aromatic polyester, polyphenylene ether, phenol resin and diallyl phthalate resin.
  • the AR polymer is preferably aromatic polyimide, aromatic polyamic acid, aromatic polyester or polyphenylene ether, and more preferably aromatic polyimide or aromatic polyamic acid.
  • aromatic polyesters include liquid crystal polyesters.
  • the liquid crystal polyester include the polymers described in paragraphs [0010] to [0015] of JP-A-2000-248506.
  • Specific examples of aromatic polyesters include dicarboxylic acids (terephthalic acid, isophthalic acid, diphenyl ether-4,4'-dicarboxylic acid, acetic anhydride, etc.), dihydroxy compounds (4,4'-biphenol, etc.), aromatic hydroxycarboxylic acids. Examples thereof include polymers of acids (4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 2-hydroxy-6-naphthoic acid, etc.), aromatic diamines, aromatic hydroxyamines, aromatic aminocarboxylic acids and the like.
  • aromatic polyester examples include a reaction product of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a reaction product of 6-hydroxy-2-naphthoic acid, terephthalic acid and acetaminophen, and 4 Reaction product of -hydroxybenzoic acid, terephthalic acid and 4,4'-biphenol, reaction product of 2-hydroxy-6-naphthoic acid, 4,4'-dihydroxybiphenyl, terephthalic acid and 2,6-naphthalenedicarboxylic acid Can be mentioned.
  • the liquid crystal polyester may be a solvent-soluble type or a solvent-insoluble type.
  • the melting point of the liquid crystal polyester is preferably 280 to 340 ° C.
  • Aromatic polyimide is a unit based on carboxylic acid dianhydride and diamine, and a unit formed by an imidization reaction of both compounds (a unit having an imide structure; hereinafter, also referred to as "imide unit”).
  • the aromatic polyimide may consist of only an imide unit, and is a unit formed by the amidation reaction of the imide unit and both of the above compounds (unit having an amic acid structure; hereinafter, also referred to as "amic acid unit”. It may have.) And.
  • the aromatic polyamic acid is an aromatic polyimide precursor consisting only of the amic acid unit.
  • aromatic polyimides or aromatic polyamic acids (hereinafter, these are also collectively referred to as "PIs")
  • at least one of the carboxylic acid dianhydride and the diamine, and at least a part thereof are aromatic. It is a sex compound.
  • one kind of each of the carboxylic acid dianhydride and the diamine may be used, or a plurality of kinds of each may be used.
  • the carboxylic acid dianhydride it is preferable to use at least one aromatic carboxylic acid dianhydride.
  • PIs include a unit based on an acid dianhydride of an aromatic tetracarboxylic dian and an aromatic diamine having a structure in which two or more arylene groups are linked via a linking group, or an aliphatic diamine. preferable.
  • Such PIs tend to have a higher affinity for the F polymer (2), which not only enhances the dispersibility of the present dispersion (2) but also tends to improve the adhesiveness of the molded product formed from the dispersion liquid (2). .. That is, such PIs easily function as a dispersant in the present dispersion (2) and as an adhesive component in the polymer layer.
  • the acid dianhydride of the aromatic tetracarboxylic acid is preferably a compound represented by the following formulas AN1 to AN6.
  • the structure of the aromatic diamine is preferably a structure in which 2 to 4 arylene groups are linked. In this case, the polarities of the PIs are balanced, and the above tendency is more likely to be exhibited.
  • the arylene group is preferably a phenylene group.
  • the hydrogen atom of the arylene group may be substituted with a hydroxyl group, a fluorine atom or a trifluoromethyl group.
  • the linking group in the aromatic diamine is preferably an ethereal oxygen atom, a propane-2,2-diyl group or a perfluoropropane-2,2-diyl group.
  • the linking group may be one kind or two or more kinds, and it is more preferable that an ether oxygen atom is essential. In this case, the PIs are more likely to show the above tendency due to the steric effect.
  • the aromatic diamine is preferably a compound represented by the following formulas DA1 to DA6.
  • Aliphatic diamines include alicyclic diamines (1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,2-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2). , 2-Bis (4-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) hexafluoropropane, isophorone diamine, norbornane diamine, etc.).
  • the AR polymer is preferably a liquid crystal polymer (such as the liquid crystal polyester described above).
  • the molded product formed from the present dispersion (2) containing the three components densely has a high content of the three components and is easily filled uniformly, and has the original physical characteristics (strength, elasticity, vibration absorption, etc.) of the liquid crystal polymer. It is easy to suppress the decrease in tensile strength and thermal expansion due to its anisotropy while having mechanical physical characteristics and electrical characteristics such as dielectric properties).
  • the F polymer (2) is the above-mentioned polymer (1) or (2), such a tendency is likely to be enhanced due to its adhesion.
  • the AR polymer may be a polymer that dissolves in a liquid dispersion medium to form a solution, or may be a polymer that is dispersed in a liquid dispersion medium to form a dispersion liquid.
  • the D50 of the AR polymer particles is preferably 1 to 40 ⁇ m, more preferably 5 to 20 ⁇ m.
  • the solubility of the AR polymer at 25 ° C. is preferably 10 g or less, more preferably 5 g or less, with respect to 100 g of the liquid dispersion medium.
  • the solubility is preferably 1 g or more.
  • the AR polymer is partially dispersed in the form of particles during the preparation and storage of the dispersion liquid (2) performed in a low temperature range such as room temperature.
  • the interaction is enhanced, and the dispersion stability and physical properties of the present dispersion (2) are likely to be improved.
  • the solubility of the AR polymer at the boiling point of the liquid dispersion medium is preferably 20 g or more, more preferably 25 g or more, with respect to 100 g of the liquid dispersion medium.
  • the solubility is preferably 10 g or less.
  • the solubility of the AR polymer at 150 ° C. is preferably 20 g or more, more preferably 25 g or more with respect to 100 g of the liquid dispersion medium. preferable.
  • the filler (2) in the present dispersion liquid (2) may be determined according to the physical properties imparted to the molded product formed from the present dispersion liquid (2).
  • the definition and scope of the filler (2) is similar to that of the filler (1), including preferred embodiments.
  • the dielectric loss tangent of the filler (2) is 0.005 or less, preferably 0.003 or less, and more preferably 0.001 or less.
  • a silica filler is preferable.
  • the shape of the filler (2) may be granular (granular, spherical), non-granular (scaly, layered), or fibrous.
  • the D50 of the spherical filler (2) is preferably 0.01 to 10 ⁇ m. In this case, the filler (2) is more excellent in dispersibility in the present dispersion (2) and is more likely to be more uniformly distributed in the molded product.
  • the length is the fiber length and the diameter is the fiber diameter.
  • the fiber length is preferably 1 to 10 ⁇ m.
  • the fiber diameter is preferably 0.01 to 1 ⁇ m.
  • the filler (2) is preferably a spherical filler.
  • the definition and scope of the liquid dispersion medium contained in the dispersion liquid (2) are the same as those of the liquid dispersion medium contained in the dispersion liquid (1), including preferred embodiments.
  • the dispersion liquid (2) preferably contains a surfactant from the viewpoint of improving dispersion stability.
  • the definition and scope of the surfactant contained in the dispersion liquid (2) are the same as those of the surfactant contained in the dispersion liquid (1), including preferred embodiments.
  • the dispersion liquid (2) preferably contains water in an amount of 50 ppm or more. A small amount of water can be expected to have an effect of increasing the affinity between the components contained in the dispersion liquid (2).
  • the water content is more preferably 100 ppm or more.
  • the upper limit of the water content (ratio) in the dispersion liquid (2) is preferably 5000 ppm or less, more preferably 1000 ppm or less.
  • the viscosity of the dispersion liquid (2) is preferably 10,000 mPa ⁇ s or less, and more preferably 10 to 1000 mPa ⁇ s.
  • the thixotropy ratio of the dispersion liquid (2) is preferably 1 to 2.
  • the dispersion liquid (2) may contain additives as long as the effects of the present invention are not impaired.
  • Examples of the additive include the same additives that may be contained in the present dispersion (1).
  • the content of the F polymer (2) in the dispersion liquid (2) is more than 5% by mass, preferably 10% by mass or more, and more preferably 12% by mass or more.
  • the upper limit of the content of the F polymer (2) is preferably 30% by mass.
  • the content of the AR polymer in the dispersion liquid (2) is more than 5% by mass, preferably 10% by mass or more, and more preferably 20% by mass or more.
  • the upper limit of the content of the AR polymer is preferably 40% by mass.
  • the content of the filler (2) in the dispersion liquid (2) is more than 5% by mass, preferably 10% by mass or more, and more preferably 12% by mass or more.
  • the upper limit of the content of the filler (2) is preferably 30% by mass.
  • the total content of the F polymer (2), the AR polymer and the filler (2) in the dispersion liquid (2) is preferably 30 to 75% by mass, more preferably 30 to 60% by mass. In this case, the dispersion stability of the dispersion liquid (2) is further improved, and the characteristics based on the three components are more easily balanced in the formed molded product. Further, the ratio of the content of the F polymer (2) to the content of the AR polymer is preferably 0.25 to 1.0, and the ratio of the content of the filler (2) to the content of the AR polymer is 0.25. ⁇ 1.0 is preferable.
  • the content of the liquid dispersion medium in the dispersion liquid (2) is preferably 10 to 70% by mass, more preferably 30 to 70% by mass. When the dispersion liquid (2) contains a surfactant, the content thereof is preferably 1 to 15% by mass. In this case, the original physical properties of the F polymer (2) are more likely to be improved in the molded product.
  • the dispersion liquid (2) include a mode in which the content of the F polymer (2) is lower than the content of the AR polymer, and a mode in which the content of the F polymer (2) is higher than the content of the AR polymer.
  • the contents of the F polymer (2), the AR polymer, the filler (2), and the liquid dispersion medium in the former aspect are, in this order, more than 5% by mass and 30% by mass or less, 10% by mass or more and 40% by mass or less, and 5% by mass. It is preferably more than% by 30% by mass and more than 0% by mass and less than 80% by mass.
  • the contents of the F polymer (2), the AR polymer, the filler (2), and the liquid dispersion medium in the latter aspect are, in this order, 10% by mass or more and 30% by mass or less, 5% by mass or more and 20% by mass or less, 5% by mass. It is preferably more than 30% by mass and 20% by mass or more and less than 80% by mass.
  • Examples of the method for producing the present dispersion (2) include the same method as the above-mentioned method for producing the present dispersion (1) when the AR polymer is contained.
  • the dispersion liquid is applied to the surface of a base material and heated to form a polymer layer as a molded product, and the base material and the polymer layer are formed.
  • this method a method for obtaining a laminate having the above in this order.
  • the dispersion liquid is applied to the surface of the base material to form a liquid film, and the liquid film is heated and dried, and then further fired to form a polymer layer.
  • the polymer layer is a layer containing at least an F polymer and an inorganic filler.
  • the AR polymer in the polymer layer may be the AR polymer itself contained in the dispersion liquid, and is an AR polymer in which the imidization reaction has proceeded by heating in the formation of the polymer layer.
  • 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 law and the comma coat method can be mentioned.
  • the heating temperature (atmospheric temperature) when drying the liquid film in this method is less than the melting temperature of the F polymer and may be set according to the boiling point of the solvent contained in the dispersion, and is 90 to 250 ° C. It is preferably 100 to 200 ° C., more preferably 100 to 200 ° C.
  • the heating time is preferably 0.1 to 10 minutes, more preferably 0.5 to 5 minutes.
  • the heating in drying may be carried out in one step, or may be carried out in two or more steps at different temperatures. In addition, a part of the polar solvent may remain in the dry film.
  • the temperature (atmosphere temperature) at which the dry film is fired in this method may be set at or above the melting temperature of the F polymer and according to the type of the F polymer, preferably 300 to 400 ° C, preferably 320 to 390 ° C. More preferably, 340 to 380 ° C. is further preferable.
  • the heating time is preferably 30 seconds to 5 minutes. Further, the heating in firing may be carried out in one step, or may be carried out in two or more steps at different temperatures.
  • Examples of the heating means for drying and firing include a method using a ventilation drying furnace and a method using a heat ray irradiation furnace such as infrared rays.
  • the state of the atmosphere at that time may be either under normal pressure or under reduced pressure.
  • the atmosphere at that time may be any of an oxidizing gas (oxygen gas, etc.) atmosphere, a reducing gas (hydrogen gas, etc.) atmosphere, and an inert gas (helium gas, neon gas, argon gas, nitrogen gas, etc.) atmosphere. ..
  • the base material in this method is preferably a metal foil or a heat-resistant resin film.
  • the ten-point average roughness of the surface of the metal foil is preferably 0.5 ⁇ m or less, more preferably less than 0.1 ⁇ m.
  • the ten-point average roughness of the surface of the metal foil is preferably 0.01 ⁇ m or more.
  • the polymer layer and the metal foil are in close contact with each other to a higher degree. Therefore, in the laminated body (metal foil with a polymer layer) or the printed circuit board obtained by processing the laminate, the dielectric loss tangent (Df) tends to decrease more remarkably.
  • the dielectric loss tangent of the laminate at a frequency of 10 GHz is preferably 0.0020 or less, more preferably 0.0015 or less.
  • the dielectric loss tangent is preferably 0.0001 or more.
  • 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 rolled copper foil or electrolytic copper foil.
  • the surface of the metal foil may be rust-proofed (formation of an oxide film such as chromate). Further, the surface of the metal foil may be treated with a silane coupling agent. The processing range at that time may be a part of the surface of the metal foil or the entire surface.
  • the thickness of the metal foil is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m.
  • the thickness of the polymer layer is preferably 1 to 20 ⁇ m, more preferably 2 to 18 ⁇ m, still more preferably 5 to 15 ⁇ m. In this case, the swelling of the interface between the polymer layer and the metal foil due to heating is suppressed, and the transmission loss in the high frequency region is significantly improved.
  • a metal foil with a carrier containing two or more layers of metal foil may be used.
  • the metal foil with a carrier includes a carrier copper foil (thickness: 10 to 35 ⁇ m) and an ultrathin copper foil (thickness: 2 to 5 ⁇ m) laminated on the carrier copper foil via a release layer. Copper foil can be mentioned.
  • a copper foil with a carrier it is possible to form a fine pattern by an MSAP (modified semi-additive) process.
  • the release layer a metal layer containing nickel or chromium or a multilayer metal layer in which the metal layers are laminated is preferable.
  • Specific examples of the metal leaf with a carrier include the trade name "FUTF-5DAF-2" manufactured by Fukuda Metal Leaf Powder Industry Co., Ltd.
  • the heat-resistant resin film is a film containing one or more of heat-resistant resins, and may be a single-layer film or a multilayer film. Glass fiber, carbon fiber, or the like may be embedded in the heat-resistant resin film.
  • the base material is a heat-resistant resin film
  • the absolute value of the coefficient of linear expansion of the laminate in this embodiment is preferably 1 to 25 ppm / ° C.
  • the heat-resistant resin examples include polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, liquid crystal polyester, and liquid crystal polyester amide.
  • Polyimide particularly aromatic polyimide
  • the aromatic ring of the AR polymer of the polymer layer and the aromatic ring of the aromatic polyimide of the heat-resistant resin film (base material) are stacked, the adhesion of the polymer layer to the heat-resistant resin film is improved. Conceivable.
  • the polymer layer and the heat-resistant resin film are not integrated with each other, but exist as independent layers. Therefore, it is considered that the low water absorption of the F polymer complements the high water absorption of the AR polymer, and the laminate exhibits low water absorption (high water barrier property).
  • the thickness (total thickness) of the laminate which is a heat-resistant resin film having polymer layers on both sides, is preferably 25 ⁇ m or more, more preferably 50 ⁇ m or more.
  • the thickness is preferably 150 ⁇ m or less.
  • the ratio of the total thickness of the two polymer layers to the thickness of the heat-resistant resin film is preferably 0.5 or more, more preferably 0.8 or more.
  • the above ratio is preferably 5 or less. In this case, the characteristics of the heat-resistant resin film (high yield strength, resistance to plastic deformation) and the characteristics of the polymer layer (low water absorption) are exhibited in a well-balanced manner.
  • the base material is a heat-resistant resin film
  • the heat-resistant resin film is a polyimide film having a thickness of 20 to 100 ⁇ m
  • the polymer layer, the polyimide film, and the polymer layer In this order, a three-layered film which is directly contacted and laminated can be mentioned.
  • the thickness of the two polymer layers is the same, preferably 15 to 50 ⁇ m.
  • the ratio of the total thickness of the two polymer layers to the thickness of the polyimide film is preferably 0.5 to 5.
  • the laminated body of such an embodiment is most likely to exhibit the effect of the above-mentioned laminated body.
  • the outermost surface of the polymer layer of the laminate may be further subjected to annealing treatment, corona treatment, plasma treatment, ozone treatment, excimer treatment, or silane coupling treatment in order to further improve its linear expansion property and adhesiveness.
  • Another substrate may be laminated on the outermost surface of the polymer layer of the laminated body.
  • substrates include a heat-resistant resin film, a prepreg which is a precursor of a fiber-reinforced resin plate, a laminate having a heat-resistant resin film layer, and a laminate having a prepreg layer.
  • the prepreg is a sheet-like substrate in which a base material (toe, woven cloth, etc.) of reinforcing fibers (glass fibers, carbon fibers, etc.) is impregnated with a thermosetting resin or a thermoplastic resin.
  • a base material toe, woven cloth, etc.
  • reinforcing fibers glass fibers, carbon fibers, etc.
  • thermosetting resin thermosetting resin
  • thermoplastic resin thermoplastic resin
  • the laminating method examples include a method of heat-pressing the laminated body and another substrate.
  • the hot press conditions are preferably such that the temperature is 120 to 300 ° C., the atmospheric pressure is a vacuum of 20 kPa or less, and the press pressure is 0.2 to 10 MPa.
  • the temperature of the hot press is preferably 310 to 400 ° C.
  • the laminate of the present invention has a polymer layer having excellent electrical properties, and is therefore suitable as a printed circuit board material.
  • the laminate of the present invention can be used as a flexible metal-clad laminate or a rigid metal-clad laminate for manufacturing a printed circuit board, and in particular, can be suitably used for manufacturing a flexible printed circuit board as a flexible metal-clad laminate. ..
  • a printed circuit board is obtained by etching a metal foil of a laminate (metal foil with a polymer layer) in which the base material is a metal foil to form a transmission circuit. Specifically, a method of etching a metal foil to process it into a predetermined transmission circuit, or a method of processing a metal foil into a predetermined transmission circuit by an electrolytic plating method (semi-additive method (SAP method), MSAP method, etc.). Can be used to manufacture printed circuit boards.
  • a printed circuit board manufactured from a metal leaf with a polymer layer has a transmission circuit formed from the metal leaf and a polymer layer in this order.
  • the configuration of the printed circuit board includes a transmission circuit / polymer layer / prepreg layer, and a transmission circuit / polymer layer / prepreg layer / polymer layer / transmission circuit.
  • an interlayer insulating film may be formed on the transmission circuit, a solder resist may be laminated on the transmission circuit, or a coverlay film may be laminated on the transmission circuit.
  • the present dispersion may be used as a material for these interlayer insulating films, solder resists and coverlay films.
  • a multi-layer printed circuit board in which the printed circuit board is multi-layered can be mentioned.
  • a preferred embodiment of the multilayer printed circuit board is a configuration in which the outermost layer of the multilayer printed circuit board is a polymer layer, and one or more of the metal foil or the transmission circuit, the polymer layer, and the prepreg layer are laminated in this order. Be done.
  • the number of the above configurations is preferably a plurality (2 or more).
  • a transmission circuit may be further arranged between the polymer layer and the prepreg layer.
  • the multilayer printed circuit board of such an embodiment is particularly excellent in heat resistance workability due to the outermost polymer layer.
  • a preferred embodiment of the multilayer printed circuit board also includes a configuration in which the outermost layer of the multilayer printed circuit board is a prepreg layer, and one or more of the metal foil or the transmission circuit, the polymer layer, and the prepreg layer are laminated in this order. Be done.
  • the number of the above configurations is preferably a plurality (2 or more).
  • a transmission circuit may be further arranged between the polymer layer and the prepreg layer.
  • the multilayer printed circuit board of this aspect is excellent in heat resistance workability even if the outermost layer has a prepreg layer. Specifically, even at 300 ° C., interface swelling between the polymer layer and the prepreg layer and interface peeling between the metal foil (transmission circuit) and the polymer layer are unlikely to occur.
  • the polymer layer is firmly adhered to the metal foil (transmission circuit), so that it is hard to warp and has excellent heat resistance workability. That is, according to the present invention, various configurations are provided in which the respective interfaces are firmly adhered to each other without various surface treatments, and interface swelling and interface peeling due to heating, particularly swelling and peeling in the outermost layer are suppressed. A printed circuit board to have can be easily obtained.
  • the molded product of the present invention contains an F polymer and an inorganic filler having an average particle size of more than 0.10 ⁇ m, and has a porosity of 5% by volume or less. It can be said that this molded product is a dense (solid) molded product in which an inorganic filler is highly filled in a polymer layer using F polymer as a matrix polymer.
  • a preferred embodiment of the molded product includes an F polymer (1), a filler (11), and a different filler, and has a porosity of 5% by volume or less. In such an embodiment, the voids of the polymer layer are filled with different fillers, and the porosity is more likely to be reduced. Examples of the form of this molded product include layered, film-shaped, plate-shaped, and lump-shaped.
  • the definitions and ranges of the F polymer and the inorganic filler in the molded product are the same as those in the dispersion liquid (1) and the dispersion liquid (2), including suitable embodiments.
  • the content of the F polymer and the content of the inorganic filler are preferably 30 to 70% by mass and 30 to 70% by mass in this order.
  • the mass ratio of the content of the inorganic filler to the content of the F polymer in this molded product is preferably 1.5 or less, more preferably 1 or less.
  • the content of the inorganic filler in the present molded product is preferably equal to or less than the content of the F polymer.
  • the above ratio is preferably 0.1 or more, more preferably 0.5 or more.
  • the mass ratio of the contents of the different fillers to the content of the filler (11) is preferably 0.1 to 1.
  • the content of the other resin is preferably 1 to 10% by mass.
  • the definition and scope of the other resins are the same as those of the other resins in the present dispersion (1), including their preferred embodiments.
  • an aromatic polymer is preferable, and an aromatic polyimide is more preferable.
  • the mass ratio of the content of the aromatic polyimide to the content of the F polymer is preferably 1.0 or less, more preferably 0.1 to 0.7.
  • the voids in the molded product preferably exist at the interface between the F polymer and the inorganic filler.
  • the porosity of the molded product is 5% by volume or less, preferably 4% by volume or less, and more preferably 3% by volume or less.
  • the porosity of the molded product is preferably 0.01% by volume or more, more preferably 0.1% by volume or more.
  • a molded product having various physical properties (heat resistance, electrical properties, etc.) due to the F polymer and various physical properties (low linear expansion rate, dielectric properties, etc.) due to the inorganic filler, and such a molded product.
  • various physical properties heat resistance, electrical properties, etc.
  • various physical properties low linear expansion rate, dielectric properties, etc.
  • inorganic filler low linear expansion rate, dielectric properties, etc.
  • the molded product is preferably formed from the dispersion liquid.
  • the method for forming the molded product from the dispersion liquid include the above-mentioned method.
  • the present molded product which is a polymer layer, can be easily formed on the surface of the base material.
  • the definition and scope of the laminate having the present molded product on the surface of the base material are the same as those of the laminate in the present method, including the preferred embodiment.
  • Powder 12 Powder (D50: 2.4 ⁇ m) composed of polymer 12 (melting temperature: 305 ° C.) containing 98.7 mol% and 1.3 mol% of TFE units and PPVE units in this order and having no oxygen-containing polar group.
  • Powder 13 Powder composed of polymer 12 and containing particles having a particle size of 10 ⁇ m or more (D50: 2.6 ⁇ m, D98: 10.5 ⁇ m)
  • Powder 14 Powder composed of PTFE (D50: 2.4 ⁇ m, 98% particle size: 6.3 ⁇ m)
  • the melt viscosities of the polymer 11 and the polymer 12 at 380 ° C. are 1 ⁇ 10 6 Pa ⁇ s or less, respectively.
  • Filler 11 A substantially spherical silica filler (D50: 0.4 ⁇ m, 98% particle size: 1.0 ⁇ m), which is composed of silicon oxide and has a specific surface area of 7 m 2 / g.
  • Filler 12 A substantially spherical silica filler (D50: 0.9 ⁇ m, 98% particle size: 3.1 ⁇ m), which is composed of silicon oxide and has a specific surface area of 5 m 2 / g.
  • Filler 13 A substantially spherical silica filler (D50: 0.08 ⁇ m, 98% particle size: 0.2 ⁇ m), which is composed of silicon oxide and has a specific surface area of 14 m 2 / g.
  • Filler 14 Scale-like steatite filler (D50: 4.8 ⁇ m, average major axis: 5.7 ⁇ m, average minor axis: 0.3 ⁇ m, aspect ratio: 20, “BST” manufactured by Nippon Talc Co., Ltd.)
  • Filler 15 A substantially spherical silica filler (D50: 1.5 ⁇ m, 98% particle size: 3.3 ⁇ m), which is composed of silicon oxide and has a specific surface area of 3 m 2 / g. The surface of each filler is surface-treated with vinyltrimethoxysilane.
  • NMP N-methyl-2-pyrrolidone
  • Varnish 11 Varnish in which thermoplastic polyimide (PI11) is dissolved in NMP
  • Example 1-1 Production example of dispersion liquid (Example 1-1) First, the powder 11, the varnish 11, the surfactant 11, and the NMP were put into the pot, and then the zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to prepare a liquid composition. Next, after the filler 11, the surfactant 11 and the NMP were put into the pot, the zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to prepare a liquid composition. Then, after putting both liquid compositions into the pot, zirconia balls were put into the pot.
  • the pot is rolled at 150 rpm for 1 hour to obtain powder 11 (11 parts by mass), filler 11 (11 parts by mass), PI11 (7 parts by mass), surfactant 11 (4 parts by mass) and NMP (67 parts by mass).
  • a dispersion liquid 1-1 (viscosity: 400 mPa ⁇ s) containing (part) was obtained.
  • Example 1-2 Powder 11 (7 parts by mass), powder 14 (4 parts by mass), filler 11 (11 parts by mass), PI11 (7 parts by mass) in the same manner as in Example 1-1 except that powder 14 was used in addition to powder 11. Part), a dispersion liquid 1-2 containing a surfactant 11 (4 parts by mass) and NMP (67 parts by mass) was obtained.
  • Example 1-3 Powder 12 (11 parts by mass), filler 11 (11 parts by mass), PI 11 (7 parts by mass), surfactant 1 (by mass), in the same manner as in Example 1-1, except that powder 12 was used instead of powder 11.
  • a dispersion 1-3 containing 4 parts by mass) and NMP (67 parts by mass) was obtained.
  • Example 1-4 First, the powder 12, the varnish 11, the surfactant 11, and the NMP were put into the pot, and then the zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to obtain a liquid composition. Next, the filler 11 is added to this liquid composition, and the pot is rolled at 150 rpm for 1 hour to obtain powder 12 (11 parts by mass), filler 11 (11 parts by mass), PI11 (7 parts by mass), and a surfactant. A dispersion liquid 1-4 containing 11 (4 parts by mass) and NMP (67 parts by mass) was obtained. (Example 1-5) The dispersion liquid 1-5 was obtained in the same manner as in Example 1-1 except that the powder 13 was used instead of the powder 11.
  • Example 1-6 The dispersion liquid 1-6 was obtained in the same manner as in Example 1-1 except that the powder 12 was used instead of the powder 11 and the filler 12 was used instead of the filler 11.
  • Example 1--7 A dispersion liquid 17 was obtained in the same manner as in Example 11 except that the powder 14 was used instead of the powder 11.
  • Example 1-8 The dispersion liquid 1-8 was obtained in the same manner as in Example 1-1 except that the powder 12 was used instead of the powder 11 and the filler 13 was used instead of the filler 11.
  • Example 1-9 Powder 14 (11 parts by mass), filler 11 (3 parts by mass), in the same manner as in Example 1-1, except that powder 14 was used instead of powder 11 and the amounts of filler 11 and NMP used were changed. A dispersion 1-9 containing PI 11 (7 parts by mass), surfactant 11 (4 parts by mass) and NMP (75 parts by mass) was obtained. (Example 1-10) Powder 11 (11 parts by mass), filler 11 (11 parts by mass), PI 11 (1 part by mass), surfactant 11 in the same manner as in Example 1-1, except that the amounts of varnish 11 and NMP used were changed. A dispersion liquid 1-10 containing (4 parts by mass) and NMP (73 parts by mass) was obtained.
  • Example 1-11 The dispersion liquid 1-11 was obtained in the same manner as in Example 1-1 except that the filler 14 was used instead of the filler 11.
  • Example 1-12 A dispersion liquid 1-12 was obtained in the same manner as in Example 1-1 except that 3 parts by mass of filler 11 and 8 parts by mass of filler 15 were used instead of 11 parts by mass of filler 11. Table 1 below summarizes the types of powder, polymer, and filler in each dispersion.
  • Laminates 1-2 to 1-12 were obtained in the same manner as in the laminate 1-1, except that the dispersions 1-2 to 1-12 were used instead of the dispersion 1-1.
  • the porosity of each polymer layer of the laminated body 1-1 and the laminated body 1-10 is 5% or less, and the porosity of the polymer layer of the laminated body 1-1 is based on the porosity of the laminated body 1-10. It was low.
  • Dispersion Stability of Dispersion Liquids 1-1 to 1-10 of each dispersion liquid were stored in a container at 25 ° C. for 1 week, the dispersibility was visually confirmed, and the dispersion stability was evaluated according to the following criteria. .. [Dispersion stability] ⁇ : Aggregates are not visible. ⁇ : Fine agglomerates are visually recognized on the side wall of the container. When lightly stirred, it was uniformly redispersed. ⁇ : Precipitation of agglomerates is also visible at the bottom of the container. When agitated with shearing, it redisperses uniformly. X: Precipitation of agglomerates is also visible at the bottom of the container. Redispersion is difficult even with shearing and stirring.
  • Dielectric Dissipation Factor of Polymer Layer (Molded Product)
  • the copper foil is etched with an aqueous ferric chloride solution to remove it to form a single polymer layer.
  • the polymer layer was prepared and the dielectric loss tangent (measurement frequency: 10 GHz) of the polymer layer was measured by the SPDR (split post dielectric resonance) method.
  • ⁇ The dielectric loss tangent is less than 0.0010.
  • the dielectric loss tangent is 0.0010 or more and 0.0019 or less.
  • ⁇ The dielectric loss tangent is more than 0.0019 and 0.0025 or less.
  • X The dielectric loss tangent is more than 0.0025.
  • Table 2 The evaluation results are summarized in Table 2 below.
  • the dispersion stability was " ⁇ ".
  • the surface smoothness was " ⁇ "
  • the coefficient of linear expansion was 26 ppm / ° C.
  • the dielectric constant was 2.2
  • the dielectric loss tangent was 0.0015. there were.
  • the porosity of the polymer layer of the laminated body 1-11 was 5% or less, and the porosity of the polymer layer of the laminated body 1-1 was lower than the porosity of the laminated body 1-11.
  • the permittivity was measured under the same equipment and conditions as the dielectric loss tangent.
  • the dispersion stability was " ⁇ ".
  • the surface smoothness was " ⁇ "
  • the coefficient of linear expansion was 25 ppm / ° C.
  • the dielectric constant was 2.2.
  • the porosity of the polymer layer of the laminated body 1-12 was 5% or less, which was lower than the porosity of the polymer layer of the laminated body 1-1.
  • [AR polymer] PI21 precursor solution (polyamic acid solution 21)
  • DMAc dimethylacetamide
  • p-PDA para-phenylenediamine
  • TPE-R 1,3-bis (4-aminophenoxy) benzene
  • the PI21 precursor solution was applied using a bar coater so that the thickness of the resin film after imidization on the roughened surface of the copper foil was 25 ⁇ m, and dried at 130 ° C. for 10 minutes. .. Further, the copper foil was cooled to 25 ° C. and then gradually heated to 360 ° C. (physical temperature) to obtain a film of PI21. After holding at 360 ° C. for 2 hours and then naturally cooling to 25 ° C., the copper foil was etched and removed to prepare a single film, and the dielectric loss tangent was measured and found to be 0.0037.
  • PI22 precursor solution (polyamic acid solution 22) A PI22 precursor solution was obtained in the same manner as the PI21 precursor solution except that only p-PDA and s-BPDA were used as the monomers. Then, a resin film containing PI22 was formed in the same manner as PI21, and the dielectric loss tangent thereof was measured and found to be 0.0075.
  • PES1 powder 100 g was added to N-methyl-2-pyrrolidone (NMP) and heated to 140 ° C. to dissolve it to obtain a brown transparent PES21 solution.
  • NMP N-methyl-2-pyrrolidone
  • the PES21 solution was cast on a copper foil using a film applicator, then heated to 100 ° C., further heated to 350 ° C. over 12 minutes from 250 ° C., and then allowed to cool to form a film.
  • the copper foil was removed by etching to obtain a PES21 film having a thickness of 25 ⁇ m, and the dielectric loss tangent was measured and found to be 0.0027.
  • -PES22 liquid crystal aromatic polyester 22
  • 2-Hydroxy-6-naphthoic acid, 4,4'-dihydroxybiphenyl, terephthalic acid, and 2,6-naphthalenedicarboxylic acid were added in this order to 60 mol%, 20 mol%, 15.5 mol%
  • the PES22 obtained by reacting at a ratio of 4.5 mol% was pulverized to obtain a powder of PES22 (D50: 16 ⁇ m). 100 g of PES22 powder was added to N-methyl-2-pyrrolidone (NMP) to obtain a dispersion of PES22 in which the PES22 powder was dispersed.
  • NMP N-methyl-2-pyrrolidone
  • the dispersion liquid of PES22 was cast on a copper foil using a film applicator, then heated to 100 ° C., further heated to 350 ° C. over 250 ° C. for 12 minutes, and then allowed to cool to form a film. ..
  • the copper foil was removed by etching to obtain a PES22 film having a thickness of 25 ⁇ m, and the dielectric loss tangent was measured and found to be 0.0007.
  • the solubility of PES22 in DMAc (boiling point: 165 ° C.) was 10 g or less at 25 ° C. and 20 g or more at 150 ° C.
  • powder-shaped PES22 was used.
  • polyphenylene ether 21 A polyphenylene ether resin (manufactured by SABIC, "Noyl 1640") was dissolved in toluene to prepare a PPE21 solution.
  • the PPE21 solution was cast on the surface of the copper foil using a film applicator, then heated to 100 ° C. and allowed to cool to form a PPE21 film.
  • the copper foil was removed by etching to obtain a PPE21 film having a thickness of 25 ⁇ m, and the dielectric loss tangent was measured and found to be 0.0040.
  • Dispersion liquids 2-2 to 2-9 were obtained in the same manner as the dispersion liquid 2-1 except that the types or amounts of the powder, the AR polymer, and the non-aqueous dispersion medium were changed as shown in Table 3 below. ..
  • the non-aqueous dispersion liquid of the present invention has excellent dispersion stability and can be used for producing molded products (films, impregnated materials such as prepregs, laminated plates, etc.) having physical characteristics based on F-polymer and characteristics based on inorganic filler. ..
  • the molded product of the present invention is useful as an antenna part, a printed substrate, an aircraft part, an automobile part, a sports tool, a food industry product, a paint, a cosmetic, and the like.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3909758A4 (en) * 2019-01-11 2022-09-28 Daikin Industries, Ltd. FLUORINE RESIN COMPOSITION, FLUORINE RESIN LAYER, MULTILAYER BODY AND SUBSTRATE FOR CIRCUIT CIRCUIT
WO2022259981A1 (ja) * 2021-06-11 2022-12-15 Ａｇｃ株式会社 組成物、並びに、金属張積層体及びその製造方法
WO2024004620A1 (ja) * 2022-07-01 2024-01-04 株式会社村田製作所 樹脂組成物、樹脂シート、導体層付き樹脂シート、積層基板、及び、樹脂シートの製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011225710A (ja) * 2010-04-19 2011-11-10 Daikin Industries Ltd フルオロポリマー非水系分散液
WO2016017801A1 (ja) * 2014-08-01 2016-02-04 旭硝子株式会社 樹脂パウダー、その製造方法、複合体、成形体、セラミックス成形体の製造方法、金属積層板、プリント基板及びプリプレグ
WO2019131809A1 (ja) * 2017-12-27 2019-07-04 Ａｇｃ株式会社 分散液、金属積層板及びプリント基板の製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6754999B2 (ja) 2015-03-05 2020-09-16 パナソニックＩｐマネジメント株式会社 樹脂組成物、低誘電率樹脂シート、プリプレグ、金属箔張り積層板、高周波回路基板および多層配線基板
JP6534848B2 (ja) 2015-04-01 2019-06-26 三菱鉛筆株式会社 ポリテトラフルオロエチレンの非水系分散体
JP6834155B2 (ja) 2016-03-16 2021-02-24 味の素株式会社 樹脂組成物
KR102353961B1 (ko) * 2016-07-22 2022-01-21 에이지씨 가부시키가이샤 액상 조성물, 그리고 그 액상 조성물을 사용한, 필름 및 적층체의 제조 방법
JP7151140B2 (ja) * 2018-04-11 2022-10-12 Ａｇｃ株式会社 フッ素樹脂シート、積層体及びそれらの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011225710A (ja) * 2010-04-19 2011-11-10 Daikin Industries Ltd フルオロポリマー非水系分散液
WO2016017801A1 (ja) * 2014-08-01 2016-02-04 旭硝子株式会社 樹脂パウダー、その製造方法、複合体、成形体、セラミックス成形体の製造方法、金属積層板、プリント基板及びプリプレグ
WO2019131809A1 (ja) * 2017-12-27 2019-07-04 Ａｇｃ株式会社 分散液、金属積層板及びプリント基板の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3909758A4 (en) * 2019-01-11 2022-09-28 Daikin Industries, Ltd. FLUORINE RESIN COMPOSITION, FLUORINE RESIN LAYER, MULTILAYER BODY AND SUBSTRATE FOR CIRCUIT CIRCUIT
US11963297B2 (en) 2019-01-11 2024-04-16 Daikin Industries, Ltd. Fluororesin composition, fluororesin sheet, laminate and substrate for circuits
WO2022259981A1 (ja) * 2021-06-11 2022-12-15 Ａｇｃ株式会社 組成物、並びに、金属張積層体及びその製造方法
WO2024004620A1 (ja) * 2022-07-01 2024-01-04 株式会社村田製作所 樹脂組成物、樹脂シート、導体層付き樹脂シート、積層基板、及び、樹脂シートの製造方法

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