Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/22—Expanded, porous or hollow particles
  • C08K7/24—Expanded, porous or hollow particles inorganic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

• the present invention is a dispersion containing a tetrafluoroethylene polymer powder, an inorganic filler, a compound P composed of a polymer having an ester bond, an imide bond or an amide bond, or a precursor of such a polymer, and a predetermined liquid dispersion medium. And a method for producing the same, and a method for producing a laminate having a polymer layer formed from such a dispersion.
• 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. As a coating agent for imparting these physical properties to the surface of the base material, a dispersion liquid containing a powder of a tetrafluoroethylene polymer is known.
• Patent Document 1 from the viewpoint of improving the state stability, in addition to the powder of PTFE, it is 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 liquid in which an inorganic filler composed of at least one kind of ceramics (inorganic compound) is blended is described (see Patent Document 1).
• the dispersion liquid of the tetrafluoroethylene polymer contains an inorganic filler, there is a problem that it is difficult to obtain a molded product having sufficient properties. Such a problem is remarkable when another component (various components described in paragraph 0019 of Patent Document 1 and the like) is further blended with the dispersion liquid. According to the studies by the present inventors, the state stability of the dispersion is remarkable when a polymer having an ester bond, an imide bond or an amide bond or a compound P composed of a precursor of such a polymer is blended as another component. It has decreased. Specifically, due to the foaming of the dispersion liquid and the decrease in dispersibility, a molded product having excellent surface smoothness could not be obtained.
• An object of the present invention is to provide such a dispersion liquid and a method for producing the same, and a method for producing a laminate having a polymer layer formed from the dispersion liquid.
• the present invention has the following aspects.
• Compound P composed of a tetrafluoroethylene polymer powder, an inorganic filler, a polymer having an ester bond, an imide bond or an amide bond, or a precursor of such a polymer, a liquid amide, a ketone, an ester, and an aromatic.
• the dispersion liquid of [1] or [2], wherein the content of the tetrafluoroethylene polymer is 5% by mass or more.
• the liquid amide is N-methyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N, N-dimethylacetamide or dimethylformamide.
• the dispersion liquid according to any one of [1] to [8], wherein the liquid compound is cyclohexanone, cyclopentanone, ⁇ -butyrolactone or toluene.
• the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing a unit based on perfluoro (alkyl vinyl ether) or a unit based on hexafluoropropene, or a polytetrafluoroethylene having a number average molecular weight of 200,000 or less.
• [14] The method for producing a dispersion according to any one of [1] to [13], wherein a liquid composition containing the compound P, the inorganic filler, the liquid amide and the liquid compound, and the tetrafluoroethylene system.
• a method for producing a dispersion which comprises mixing a polymer powder and a liquid composition containing the liquid amide to obtain the dispersion.
• the dispersion liquid according to any one of [1] to [13] is applied to the surface of the base material and heated to form a polymer layer containing the tetrafluoroethylene-based polymer, which is composed of the base material.
• a method for producing a laminate which comprises obtaining a laminate having a base material layer and the polymer layer.
• a dispersion liquid containing a tetrafluoroethylene polymer powder, an inorganic filler, and the compound P and having excellent state stability can be obtained.
• the "average particle size (D50)” is a volume-based cumulative 50% diameter of the object (powder or filler) determined by the laser diffraction / scattering method. That is, the particle size distribution of the object is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the group of particles of the object as 100%, and the particles at the point where the cumulative volume is 50% on the cumulative curve.
• the diameter. “D90” is the volume-based cumulative 90% diameter of the object, measured in the same manner.
• the "specific surface area” is a value obtained by analyzing an inorganic filler by a gas adsorption method (BET method).
• the “melting temperature (melting point)” is the temperature corresponding to the maximum value of the melting peak of the polymer measured 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.
• a "unit" in a polymer is an atomic group formed directly from one molecule of a monomer by a polymerization reaction, and an atom obtained by processing the polymer obtained by the polymerization reaction by a predetermined method to convert a part of its structure. It may be a group.
• the unit based on monomer A contained in the polymer is also simply referred to as "monomer A unit".
• the dispersion liquid of the present invention is a powder of a tetrafluoroethylene-based polymer (hereinafter, also referred to as “F polymer”) (hereinafter, also referred to as “F powder”).
• F polymer tetrafluoroethylene-based polymer
• At least one liquid selected from the group consisting of an inorganic filler, a polymer having an ester bond, an imide bond or an amide bond, or a compound P consisting of a precursor of such a polymer, a liquid amide, and a ketone, an ester and an aromatic hydrocarbon. Includes with compounds.
• the liquid compound selected from the group consisting of ketones, esters and aromatic hydrocarbons is also referred to as "liquid compound Q”.
• the F polymer and the compound P are different compounds, and the compound P is a compound different from both the liquid amide and the liquid compound Q.
• This dispersion is a dispersion in which F powder and an inorganic filler are dispersed in a liquid dispersion medium containing a liquid amide and a liquid compound Q, and compound P is highly dissolved.
• This dispersion is excellent in state stability. From this dispersion, it is easy to form a molded product having a high degree of physical characteristics of each of the F polymer, the inorganic filler and the compound P (hereinafter, also referred to as “three components”). The reason is not always clear, but it can be considered as follows.
• the liquid amide has high wettability in all three components and functions as a good dispersion medium or solvent for the three components in the dispersion liquid. Due to this function, in the dispersion liquid containing the liquid amide, the liquid amide and the F polymer having a low surface tension are highly wetted, so that the apparent concentration of the other two components, particularly the compound P, is considered to increase. As a result, it is considered that the interaction of the compound P is excessively enhanced, the viscosity of the dispersion liquid is increased, and the aggregation and sedimentation of the three components are induced, so that the state stability of the entire dispersion liquid is rather lowered.
• This dispersion further contains the liquid compound Q in addition to the above liquid amide.
• the liquid compound Q has the same solubility in the compound P as the liquid amide, the wettability to the inorganic filler and the F polymer, particularly the F polymer, is lower than that of the liquid amide. Therefore, if the dispersion liquid further contains the liquid compound Q, it is considered that it selectively functions as a solvent for the compound P and stabilizes the state.
• this dispersion is excellent in state stability such as foaming and homogeneity because the dispersibility or solubility of the three components is balanced by the inclusion of the two liquid dispersion media.
• a molded product having excellent surface smoothness and having a high degree of physical characteristics of the three components can be easily formed from the dispersion liquid.
• the F powder in this dispersion contains an F polymer.
• the content of the F polymer in the F powder is preferably 80% by mass or more, more preferably 100% by mass.
• Other components that can be contained in the F powder include polymers and inorganic substances different from the F polymer.
• the polymer different from the F polymer include aromatic polyester, polyamide-imide, thermoplastic polyimide, polyphenylene ether, and polyphenylene oxide.
• the inorganic substance include silicon oxide (silica), metal oxides (beryllium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite).
• the F powder containing the other component preferably has a core-shell structure having the F polymer as a core and the other component in the shell, or a core-shell structure having the F polymer as the shell and the other component in the core. ..
• Such F powder is obtained, for example, by coalescing (collision, agglomeration, etc.) the powder of the F polymer and the powder of the other components.
• the D50 of the F powder is preferably 10 ⁇ m or less, more preferably 6 ⁇ m or less, and even more preferably 4 ⁇ m or less.
• the D50 of the F powder is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and even more preferably 1 ⁇ m or more.
• the D90 of the F powder is more preferably 10 ⁇ m or less.
• the content of the F polymer in this dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 25% by mass or more.
• the content of the F polymer is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. Due to the above-mentioned mechanism of action, the dispersion liquid tends to be excellent in state stability even when the content of the F polymer is high.
• the F polymer in this dispersion is a polymer containing a unit (TFE unit) based on tetrafluoroethylene (TFE).
• TFE tetrafluoroethylene
• examples of the F polymer include polytetrafluoroethylene having a number average molecular weight of 200,000 or less (hereinafter, also referred to as “low molecular weight PTFE”), and a unit (PAVE unit) or hexafluoro based on perfluoro (alkyl vinyl ether) (PAVE).
• Polymers containing units based on propene (HFP) (HFP units) are preferred.
• the latter F polymer may contain both PAVE and HFP units.
• the number average molecular weight of the low molecular weight PTFE is preferably 100,000 or less, more preferably 50,000 or less.
• the number average molecular weight of the PTFE is preferably 10,000 or more.
• the number average molecular weight is a value calculated based on the following equation (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.
• CF 2 CFOCF 3
• the melting temperature (melting point) of the F polymer is preferably 200 ° C. or higher, more preferably 260 ° C. or higher, further preferably 280 to 325 ° C., and particularly preferably 285 to 320 ° C.
• the glass transition point of the F polymer is preferably 75 to 125 ° C, more preferably 80 to 100 ° C.
• the F polymer preferably has a polar functional group.
• the polar functional group may be contained in a unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer.
• Examples of the latter aspect include an F polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and an F polymer having a polar functional group obtained by plasma-treating or ionizing the F polymer. Be done.
• the polar functional group is preferably a hydroxyl group-containing group or a carbonyl group-containing group, and a carbonyl group-containing group is more preferable from the viewpoint of enhancing the state stability of the dispersion.
• the hydroxyl group-containing group is preferably an alcoholic hydroxyl group-containing group, preferably -CF 2 CH 2 OH or -C (CF 3 ) 2 OH.
• the carbonyl group-containing group is a group containing a carbonyl group (> C (O)), and is a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH 2 ), and an acid anhydride residue.
• a group (-C (O) OC (O)-), an imide residue (-C (O) NHC (O)-etc.) or a carbonate group (-OC (O) O-) is preferred.
• the number of carbonyl group-containing groups in the F polymer is preferably 10 to 5000, more preferably 100 to 3000, and even more preferably 50 to 1500, per 1 ⁇ 10 6 carbon atoms in the main chain.
• the number of carbonyl group-containing groups in the F polymer can be quantified by the composition of the polymer or the method described in International Publication No. 2020/145133.
• the F polymer a polymer containing TFE units and PAVE units, containing 1.5 to 5.0 mol% of PAVE units with respect to all units, and having a melting temperature of 285 to 320 ° C. is preferable, and TFE units, PAVE units and A polymer having a polar functional group (1) containing a unit based on a monomer having a polar functional group, and containing 2.0 to 5.0 mol% of PAVE units with respect to all units including TFE units and PAVE units.
• the polymer (2) having no polar functional group is more preferable.
• these F polymers are more likely to be more densely and uniformly distributed in the molded product formed from the present dispersion.
• microspherulites are likely to be formed in the molded product, and adhesion with other components is likely to be enhanced. As a result, it is easier to obtain a molded product having a high degree of physical characteristics of the three components.
• the TFE unit is 90 to 98 mol%
• the PAVE unit is 1.5 to 9.97 mol%
• the unit based on the monomer having a polar functional group is 0.01 to 3 with respect to all the units. It is preferable to contain each in mol%.
• the monomer having a polar functional group itaconic anhydride, citraconic anhydride and 5-norbornene-2,3-dicarboxylic acid anhydride (also known as hymic anhydride; hereinafter, also referred to as “NAH”) are preferable.
• Specific examples of the polymer (1) include the polymers described in International Publication No. 2018/16644.
• the polymer (2) is composed of only TFE units and PAVE units, and 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. Is preferable.
• 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 fact that the polymer (2) does not have polar functional groups means that the number of polar functional groups contained in the polymer is less than 500 with respect to 1 ⁇ 10 6 carbon atoms constituting the polymer main chain. Means that The number of the polar functional groups is preferably 100 or less, more preferably less than 50. The lower limit of the number of polar functional 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 a polar functional group as the terminal group of the polymer chain, and is an F polymer having a polar functional group (derived from the polymerization initiator).
• An F polymer having a polar functional group at the terminal group of the main chain of the polymer may be fluorinated to produce the polymer.
• the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314, etc.).
• the content of the inorganic filler in this dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more.
• the content of the inorganic filler is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.
• the ratio (mass ratio) of the content of the inorganic filler to the content of the F polymer in the present dispersion is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more.
• the above ratio is preferably 2.0 or less, more preferably 1.8 or less, and even more preferably 1.6 or less. Due to the above-mentioned action mechanism, the dispersion liquid tends to be excellent in state stability even when the inorganic filler is contained in a high concentration.
• a nitride filler and an inorganic oxide filler are preferable, and boron nitride filler, beryllia filler (verylium oxide filler), silicate filler (silica filler, wollastonite filler, talc filler), and talc filler.
• Metal oxide (cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.) fillers are more preferable.
• Such an inorganic filler makes it easy to balance the interaction between the components and further improves the state stability of the dispersion liquid. In addition, the physical properties of the molded product are likely to be remarkably exhibited.
• the inorganic filler preferably contains silica from the viewpoint of further improving the state stability of the dispersion liquid.
• the content of silica in the inorganic filler containing silica is preferably 50% by mass or more, more preferably 75% by mass or more, still more preferably 99% by mass or more.
• the upper limit of the silica content is 100% by mass.
• the surface of the inorganic filler 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, etc.
• Silane coupling agents include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane or 3-isocyanate. Propyltriethoxysilane is preferred.
• the average particle size of the inorganic filler is preferably 20 ⁇ m or less, more preferably 1 ⁇ m or less, further preferably 0.8 ⁇ m or less, and particularly preferably 0.6 ⁇ m or less.
• the average particle size is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and even more preferably 0.1 ⁇ m or more. Even when the dispersion liquid contains such an inorganic filler, which has a large specific surface area and is easily wetted, it tends to be excellent in state stability due to the above-mentioned action mechanism.
• the inorganic filler is a hollow inorganic filler, the average particle size described later is preferable.
• inorganic fillers include zinc oxide ("FINEX” manufactured by Sakai Chemical Industry Co., Ltd.) surface-treated with an ester such as silica filler ("Admafine” series manufactured by Admatex Co., Ltd.) and propylene glycol dicaprate. Series, etc.), spherical molten silica (Denka's "SFP” series, etc.), coated with polyhydric alcohol and inorganic substances (Ishihara Sangyo's "Typake” series, etc.), and surface-treated with alkylsilane.
• Type Titanium oxide (“JMT” series manufactured by Teika), talc filler ("SG” series manufactured by Nippon Tarku, etc.), Steatite filler (“BST” series manufactured by Nippon Tarku, etc.), Boron nitride filler (“BST” series, etc.)
• JMT Type Titanium oxide
• talc filler (“SG” series manufactured by Nippon Tarku, etc.)
• Steatite filler BST” series manufactured by Nippon Tarku, etc.
• Boron nitride filler (“BST” series, etc.)
• Examples include the “UHP” series manufactured by Showa Denko Co., Ltd. and the “Denka Boron Night Ride” series (“GP” and “HGP” grades) manufactured by Denka Co., Ltd.).
• the shape of the inorganic filler may be granular, needle-like (fibrous), or plate-like.
• Specific shapes of the inorganic filler include spherical, scaly, layered, leafy, apricot kernel, columnar, chicken crown, equiaxed, leafy, mica, block, flat, wedge, rosette, and mesh. Shape and prismatic shape.
• the shape of the inorganic filler is preferably hollow. Even when the dispersion liquid contains such an inorganic filler, which has a large specific surface area and is easily wetted, it tends to be excellent in state stability due to the above-mentioned action mechanism.
• the average particle size of the hollow inorganic filler is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
• the average particle size is preferably 100 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
• the specific surface area of the inorganic filler (BET method) is preferably 10 ⁇ 250m 2 / g, more preferably 40 ⁇ 100m 2 / g. Due to the above-mentioned action mechanism, the present dispersion tends to be excellent in state stability even when it contains an inorganic filler having a large average particle size and a large specific surface area.
• the average pore diameter of the pores of the hollow inorganic filler is preferably 10 to 1000 nm, more preferably 50 to 100 nm.
• the average pore diameter the pore diameters of a plurality of pores (100) are obtained by direct observation with a scanning electron microscope (SEM) or the like, and the average value is taken as the average pore diameter. In the case of irregularly shaped holes, the maximum diameter of the holes is the hole diameter.
• the apparent specific gravity of the hollow inorganic filler is preferably 100 g / L or less, more preferably 30 to 60 g / L, from the viewpoint of sufficiently increasing the porosity.
• the apparent specific gravity of the hollow inorganic filler is obtained from the mass and volume of the inorganic filler when it is charged into a graduated cylinder (capacity: 250 mL).
• the bulk density of the hollow inorganic filler is preferably from 5 g / cm 3 or less, preferably from 1 g / cm 3 or less.
• the lower limit of the bulk density is preferably 0.1 or more.
• a hollow silica filler is preferable.
• hollow silica fillers include hydrophobic AEROSIL series "RX200" (manufactured by Nippon Aerosil), E-SPHERES series (manufactured by Taiheiyo Cement), Sirinax series (manufactured by Nittetsu Mining Co., Ltd.), and eco-cosfier series. (Manufactured by Emerson & Cumming) and the like.
• Compound P in this dispersion is a polymer having an ester bond, an imide bond or an amide bond, or a precursor of such a polymer.
• the polymer precursor refers to an oligomer or a non-polymeric compound that becomes a polymer by polymerization, cross-linking, or the like.
• a compound P having an imide bond or an amide bond is preferable, a polymer having a unit containing an imide bond, a polymer having a unit containing an amide bond, and an N-substituted maleimide structure, an imide succinate structure or a phthalimide structure.
• a precursor having the above is more preferable.
• a compound having a polyimide, polyamideimide, polyamic acid, and N-substituted maleimide structure is preferable, and a polyimide and a maleimide compound are particularly preferable.
• the polymer-like compound P is a polymer different from the F polymer.
• the dispersion liquid preferably contains a polymerization initiator for polymerizing the polymer precursor and a curing agent for curing the polymer precursor together with the polymer precursor.
• Compound P is preferably aromatic.
• the aromatic compounds having high flatness are likely to be in a laminated state, so that the mechanical strength and heat resistance of the molded product are likely to be improved. Further, since the aromatic compound has an absorption property for ultraviolet rays having a wavelength of 355 nm, which is common in UV lasers, the UV processability of the obtained molded product is likely to be further improved.
• the polyimide is preferably an aromatic polyimide, and more preferably a thermoplastic aromatic polyimide.
• the plasticity of the compound P further improves the uniformity of the aromatic polyimide in the molded product formed from the present dispersion, and a dense molded product is likely to be formed.
• the physical properties of the aromatic polyimide are likely to be highly expressed in the molded product, and the adhesion of the molded product is also likely to be excellent.
• aromatic polyimide a semi-aromatic polyimide in which one of the tetracarboxylic dianhydride and the diamine has an aromatic ring, or a total aromatic polyimide in which both have an aromatic ring is more preferable.
• aromatic polyimides include "Neoprim” series (manufactured by Mitsubishi Gas Chemical Company), “Spixeria” series (manufactured by Somar), “Q-PILON” series (manufactured by PI Technology Research Institute), and “WINGO” series (manufactured by PI Technology Co., Ltd.). Wingo Technology Co., Ltd.), “Toimide” series (T & K TOKA Co., Ltd.), “KPI-MX” series (Kawamura Sangyo Co., Ltd.).
• the maleimide compound is likely to be uniformly and densely distributed in the molded product formed from the present dispersion, the physical properties of the maleimide compound are likely to be highly expressed, and the electrical characteristics and difficulties of the molded product are difficult. Flammability and adhesion are more likely to be improved.
• the dispersion further contains a component (radical polymerization initiator, imidazole-based curing agent, cationic curing agent, other copolymerizable crosslinkable monomer, etc.) that further promotes the reaction of the maleimide compound. Is preferable.
• a bismaleimide compound is more preferable.
• the bismaleimide compound may have an N-substituted maleimide structure only in the terminal group, or may have an N-substituted maleimide structure in both the terminal group and the side chain.
• Maleimide compounds include 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane. Examples thereof include bismaleimide, 4-methyl-1,3-phenylene bismaleimide, and 1,6'-bismaleimide- (2,2,4-trimethyl) hexane.
• the maleimide compound is a reaction product of a diamine such as diamine or a diamine having an alicyclic structure and a tetracarboxylic acid dianhydride having an aromatic ring, and maleic anhydride is added to a polyimide having an amino group as a terminal group.
• a diamine such as diamine or a diamine having an alicyclic structure and a tetracarboxylic acid dianhydride having an aromatic ring
• maleic anhydride is added to a polyimide having an amino group as a terminal group.
• Examples thereof include a bismaleimide compound obtained by reaction.
• These maleimide compounds are commercially available as BMI series manufactured by DESIGNER MOLECULES Inc.
• an aromatic polyester is preferable, and a liquid crystal aromatic polyester (liquid crystal polyester) is more preferable.
• the aromatic polyester also includes an aromatic polyester amide having an amide bond further introduced, and an aromatic polyester having an isocyanate-derived bond such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond introduced therein. Will be done.
• liquid crystal polyester examples 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 (4,4'-biphenol, etc.).
• dicarboxylic acids terephthalic acid, isophthalic acid, diphenyl ether-4,4'-dicarboxylic acid, acetic anhydride, etc.
• dihydroxy compounds (4,4'-biphenol, etc.
• aromatic hydroxycarboxylic acids (4,4'-biphenol, etc.).
• 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.
• the content of compound P in this dispersion is preferably 0.01% by mass or more, more preferably 0.1% by mass or more.
• the content of compound P is preferably 5% by mass or less, more preferably 1% by mass or less.
• the ratio (mass ratio) of the content of compound P to the content of F polymer in this dispersion by mass is preferably 0.001 or more, more preferably 0.01 or more.
• the above ratio is preferably 0.4 or less, more preferably 0.2 or less. Even when compound P is contained in such a ratio, the present dispersion is excellent in state stability due to the above-mentioned action mechanism.
• the liquid amide in this dispersion is a liquid compound inert at 25 ° C. that functions as a dispersion medium or solvent for the three components.
• the liquid amide is preferably an amide that is compatible with the liquid compound Q.
• the liquid amide may be used as a mixture of two or more of them.
• the boiling point of the liquid amide is preferably 125 to 250 ° C. In this case, when the molded product is formed from the present dispersion, the molded product tends to have excellent homogeneity.
• NMP N-methyl-2-pyrrolidone
• 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide are used from the viewpoint of ease of wetting with the three components.
• N, N-dimethylacetamide and dimethylformamide are preferred, with NMP being more preferred.
• the content of the liquid amide in this dispersion is preferably 40% by mass or more, more preferably 50% by mass or more.
• the content of the liquid amide is preferably 90% by mass or less, more preferably 80% by mass or less.
• the liquid compound Q in this dispersion is a liquid compound selected from the group consisting of ketones, esters and aromatic hydrocarbons, and is an inactive liquid compound at 25 ° C.
• the liquid compound Q is preferably a compound that is compatible with the liquid amide. Further, the liquid compound Q may be used in combination of two or more thereof.
• the liquid compound Q 4-methyl-2-pentanone, cyclohexanone, tetrahydrofuran, toluene, xylene, ⁇ -butyrolactone, cyclopentanone, butyl acetate and methyl isopropyl ketone are preferable from the viewpoint of enhancing the state stability of the dispersion.
• Cyclohexanone, cyclopentanone, ⁇ -butyrolactone and toluene are more preferred. Further, cyclohexanone, cyclopentanone and ⁇ -butyrolactone are more preferable as the liquid compound Q when the compound P is polyimide, and toluene is more preferable as the liquid compound Q when the compound P is a maleimide compound.
• the content of the liquid compound Q in this dispersion is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more.
• the content of the liquid compound Q is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.
• the content of the liquid amide in this dispersion is preferably higher than the content of the liquid compound Q.
• the above-mentioned mechanism of action balances the affinity between the three components (particularly between the inorganic filler and the compound P) without lowering the dispersibility of the three components (particularly the F polymer) itself. , It is easy to improve the state stability of this dispersion.
• the ratio (mass ratio) of the content of the liquid compound Q to the content of the liquid amide by mass is preferably 0.8 or less, more preferably 0.5 or less.
• the above ratio is preferably 0.1 or more, more preferably 0.2 or more.
• the dispersion liquid preferably further contains a surfactant from the viewpoint of improving state stability and handleability.
• the surfactant is preferably nonionic.
• the hydrophilic moiety of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group.
• the oxyalkylene group may be composed of one kind or two or more kinds. In the latter case, different types of oxyalkylene groups may be arranged in a random manner or in a block shape.
• As the oxyalkylene group an oxyethylene group is preferable.
• the hydrophobic moiety of the surfactant preferably has an acetylene group, a polysiloxane group, a perfluoroalkyl group or a perfluoroalkenyl group.
• the surfactant is preferably an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant.
• a fluorine-based surfactant having a hydroxyl group (particularly an alcoholic hydroxyl group) or an oxyalkylene group and a perfluoroalkyl group or a perfluoroalkenyl group is preferable.
• Specific examples of surfactants include "Futergent” series (manufactured by Neos), “Surflon” series (manufactured by AGC Seimi Chemical Co., Ltd.), “Megafuck” series (manufactured by DIC), and "Unidyne” series (manufactured by Daikin Industries).
• the content of the surfactant in this dispersion is preferably 1 to 15% by mass. In this case, the affinity between the components is enhanced, and the state stability of the dispersion liquid is likely to be further improved.
• the viscosity of this dispersion is preferably 50 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more.
• the viscosity of this dispersion is preferably 10,000 mPa ⁇ s or less, more preferably 1000 mPa ⁇ s or less, and even more preferably 800 mPa ⁇ s or less.
• the thixotropy ratio of this dispersion is preferably 1.0 or more.
• the thixotropy of the dispersion is preferably 3.0 or less, more preferably 2.0 or less. This dispersion is easy to adjust to a viscosity or thixotropic property in such a range, and is excellent in handleability.
• the dispersion may further contain a resin (polymer) different from the F polymer or compound P.
• the other resin may be a thermosetting resin or a thermoplastic resin.
• other resins include epoxy resins, urethane resins, elastomers, polyphenylene ethers, polyphenylene oxides, and fluoropolymers other than F polymers.
• this dispersion contains a thioxogenic agent, a defoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weather resistant agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, and an increase. It may contain additives such as whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, and flame retardants.
• liquid composition N a liquid composition (hereinafter, also referred to as “liquid composition N”) is prepared by mixing the compound P dissolved in the liquid compound Q, the liquid amide, and the inorganic filler, and the liquid composition N is combined with the liquid composition N. It is preferably produced by a method of mixing a liquid composition containing F powder and a liquid amide (hereinafter, also referred to as “liquid composition F”) (hereinafter, also referred to as “method 1”).
• the liquid compound Q may be separately mixed to adjust its state stability.
• the content of the compound P in the liquid composition N is preferably 0.01% by mass or more, more preferably 0.1% by mass or more.
• the content is preferably 10% by mass or less.
• the content of the inorganic filler in the liquid composition N is preferably 5% by mass or more, more preferably 10% by mass or more.
• the content is preferably 50% by mass or less.
• the content of the liquid amide in the liquid composition N is preferably 50% by mass or more, more preferably 60% by mass or more. The content is preferably 90% by mass or less.
• the content of the liquid compound Q in the liquid composition N is preferably 1% by mass or more, more preferably 5% by mass or more. The content is preferably 40% by mass or less.
• the liquid composition N preferably further contains a dispersant.
• the mode of the dispersant in the liquid composition N is the same as that of the dispersant in the present dispersion, including the preferred mode.
• the liquid composition N may further contain a resin (polymer) different from the F polymer and the compound P, and other components other than the inorganic filler.
• the content of the F polymer in the liquid composition F is preferably 5% by mass or more, more preferably 10% by mass or more.
• the content is preferably 60% by mass or less.
• the content of the liquid amide in the liquid composition F is preferably 50% by mass or more, more preferably 60% by mass or more.
• the content is preferably 90% by mass or less.
• the liquid composition F preferably further contains a dispersant.
• the mode of the dispersant in the liquid composition F is the same as that of the dispersant in the present dispersion, including the preferred mode.
• the liquid composition F may further contain a resin (polymer) different from the F polymer and the compound P, and other components.
• This dispersion can be used for forming a molded product having a high degree of physical properties of three components.
• a laminate having the base material layer composed of the base material and the polymer layer can be obtained by a method of applying the dispersion liquid to the surface of the base material and heating to form a polymer layer containing the F polymer. ..
• This polymer layer is a layer containing an F polymer and an inorganic filler, and compound P or a reaction product thereof, and is a layer in which each component is uniformly and densely distributed.
• the base material examples include metal base materials (metal foils such as copper, nickel, aluminum, titanium, and alloys thereof), resin films (polyimide, polyarylate, polysulfone, polyallylsulfone, polyamide, polyetheramide, polyphenylene sulfide, etc.).
• metal base materials metal foils such as copper, nickel, aluminum, titanium, and alloys thereof
• resin films polyimide, polyarylate, polysulfone, polyallylsulfone, polyamide, polyetheramide, polyphenylene sulfide, etc.
• films such as polyallyl ether ketone, polyamideimide, liquid polyester, and liquid polyester amide
• prepreg a precursor of a fiber-reinforced resin base material
• the dispersion is applied by 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, etc. It can be done by the slot die coating method.
• the heating after the coating film is preferably carried out by heating by removing the liquid dispersion medium (liquid amide, liquid compound Q) and drying, and heating by melting and firing the F polymer.
• the former heating temperature is preferably 120 ° C to 200 ° C.
• the latter heating temperature is preferably 250 ° C. to 400 ° C., more preferably 300 to 380 ° C.
• the compound P is a polymer precursor
• Heating can be performed by a method using an oven, a method using a ventilation drying oven, or a method of irradiating heat rays such as infrared rays.
• the thickness of the polymer layer formed is preferably 0.1 to 150 ⁇ m.
• the thickness of the polymer layer is preferably 1 to 30 ⁇ m.
• the thickness of the polymer layer is preferably 1 to 150 ⁇ m, more preferably 10 to 50 ⁇ m.
• the polymer layer may be formed on only one surface of the base material or on both sides of the base material. In the former, a base material layer and a laminate having a polymer layer on one surface of the base material layer are obtained, and in the latter, a laminate having a polymer layer on both the surfaces of the base material layer and the base material layer. Is obtained. Since the latter laminate is less likely to warp, it is excellent in handleability during processing.
• the laminate include a metal foil layer, a metal-clad laminate having a polymer layer on at least one surface of the metal foil layer, a polyimide film layer, and a polymer layer on both surfaces of the polyimide film layer.
• Multilayer film can be mentioned.
• These laminates are suitable as a printed base material or the like because they have a high degree of physical characteristics of three components and are particularly excellent in electrical characteristics.
• such a laminate can be used in the production of a flexible printed base material or a rigid printed base material.
• [Inorganic filler] Filler 1: Hollow silica filler (D50: 0.5 ⁇ m, bulk specific density: 0.10 g / cm 3 )
• Filler 2 Crushed titanium oxide filler (D50: 2 to 6 ⁇ m, bulk specific density: 0.25 to 0.75 g / cm 3 )
• PI1 Thermoplastic aromatic polyimide
• BM1 Bismaleimide compound (“BMI-3000” manufactured by DESIGNER MOLECULES).
• BM1 further contains a heat-sensitive radical polymerization initiator for thermosetting it.
• Example 2 Production example of dispersion liquid (Example 1) First, the varnish in which PI1 was dissolved in CHN and NMP were put into the pot, then the zirconia balls were put into the pot, and the pot was rolled at 150 rpm for 1 hour. Subsequently, the surfactant 1 was added and the pot was rolled at 150 rpm for 1 hour, and further, the filler 1 was added and the pot was rolled at 150 rpm for 1 hour to prepare a liquid composition N1. Powder 1, surfactant 1 and NMP were put into another pot, and zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to prepare a liquid composition F1.
• the liquid compositions of both were charged, and zirconia balls were charged. Then, the pot was rolled at 150 rpm for 1 hour to add powder 1 (8 parts by mass), filler 1 (12 parts by mass), PI1 (0.1 parts by mass), and surfactant 1 (1 part by mass). , NMP (49 parts by mass) and CHN (27 parts by mass) were contained in a dispersion liquid 1 (viscosity: 700 mPa ⁇ s).
• the ratio of the content of the liquid compound Q to the content of the liquid amide in the dispersion 1 by mass was 0.6, and the ratio of the content of F polymer to the content of PI1 by mass was 0.01.
• the ratio of the content of F polymer to the content of inorganic filler by mass was 1.5.
• Example 2 to 7 Dispersions 2 to 7 were obtained in the same manner as in Example 1 except that the type and amount of the liquid dispersion medium were changed as shown in Table 1 below.
• This dispersion has excellent state stability and can be used for producing molded products (films, impregnated materials such as prepregs, laminated plates, etc.) having highly physical properties based on F-polymers, inorganic fillers and compound P.
• 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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• 2020
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