Classifications

• • 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
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
• • 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
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular

Definitions

• the present invention relates to a method for producing a viscoelastic body containing hot-melt tetrafluoroethylene-based polymer particles and the viscoelastic body.
• the present invention also relates to a method for producing a dispersion using the viscoelastic material.
• Tetrafluoroethylene-based polymers such as polytetrafluoroethylene (hereinafter also referred to as "PTFE") are excellent in physical properties such as electrical properties, water and oil repellency, chemical resistance, and heat resistance, and are used in various applications such as printed circuit boards. are used for industrial purposes.
• a dispersion containing particles of a tetrafluoroethylene-based polymer is known as a coating agent used for imparting the above physical properties to the substrate surface.
• materials with electrical properties such as a low dielectric constant and a low dielectric loss tangent and excellent insulating performance are required.
• a dispersion liquid containing tetrafluoroethylene-based polymer particles has attracted attention as a material for forming dielectric layers of printed circuit boards that are excellent in electrical properties such as a low dielectric constant and a low dielectric loss tangent and that correspond to frequencies in the high frequency band.
• Patent Document 1 describes a resist ink dispersion containing particles of a tetrafluoroethylene-based polymer.
• Patent Document 2 discloses a dispersion containing PTFE particles and a ceramic inorganic filler.
• a tetrafluoroethylene-based polymer has extremely low affinity with other components due to its low surface tension. Therefore, a dispersion liquid containing tetrafluoroethylene-based polymer particles and other resins or inorganic fillers poses problems of thickening and aggregation of particles.
• the dispersions described in Patent Documents 1 and 2 are still insufficient in physical properties. As a result of intensive studies, the present inventors found that if a powder of a heat-melting tetrafluoroethylene-based polymer is dry pulverized and wet-mixed with a liquid composition containing an organic resin or inorganic particles, dispersibility and uniformity can be improved.
• An object of the present invention is to provide a method for producing a viscoelastic body containing particles of a tetrafluoroethylene polymer and having excellent physical properties such as dispersibility and uniformity, and dispersion stability, uniformity and rheology obtained from such a viscoelastic body. , a method for producing a dispersion having excellent liquid physical properties such as coatability and storage stability, and the provision of such a viscoelastic body.
• the present invention has the following aspects.
• Powder of a heat-meltable tetrafluoroethylene polymer is dry pulverized to form particles of the tetrafluoroethylene polymer, and the particles are wet-mixed with at least one of an organic resin and inorganic particles in the presence of a liquid substance. to obtain a viscoelastic body containing the particles and at least one of the organic resin and the inorganic particles.
• the dry pulverization is performed by a Henschel mixer, a pressure kneader, a Banbury mixer, a rotation-revolution mixer, a planetary mixer, a ball mill, an attritor, a basket mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a spike mill, and an agitator mill. , a microfluidizer, a nanomizer, an agitzer, a dissolver, a disper, and a high-speed impeller.
• the wet mixing includes a Henschel mixer, a pressure kneader, a Banbury mixer, a rotation-revolution mixer, a planetary mixer, a ball mill, an attritor, a basket mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a spike mill, an agitator mill, Any of the above [1] to [3] carried out using at least one mixer selected from the group consisting of a microfluidizer, a nanomizer, an articulzer, an ultrasonic homogenizer, a desolver, a disper, a high-speed impeller, and a thin-film swirling high-speed mixer.
• the manufacturing method according to [5] The production method according to any one of [1] to [4], wherein the wet mixing is performed at a temperature equal to or higher than the glass transition point of the tetrafluoroethylene-based polymer.
• [6] The production method according to any one of [1] to [5], wherein the tetrafluoroethylene-based polymer has a glass transition point of 60 to 150°C.
• the organic resin is a thermosetting resin.
• the organic resin is at least one selected from the group consisting of aromatic epoxy resins, phenolic resins, aromatic polyimide resins, precursors of aromatic polyimide resins, aromatic polyamideimide resins and precursors of aromatic polyamideimide resins.
• Powder of the heat-meltable tetrafluoroethylene polymer is dry pulverized to obtain particles of the tetrafluoroethylene polymer, and the particles and the varnish of the thermosetting resin are added to the mass of the tetrafluoroethylene polymer.
• a method for producing a viscoelastic body comprising wet-mixing a thermosetting resin at a mass ratio of 0.1 or more to obtain a viscoelastic body containing the particles and the thermosetting resin.
• It contains particles of a heat-meltable tetrafluoroethylene-based polymer and a thermosetting resin, wherein the ratio of the mass of the thermosetting resin to the mass of the tetrafluoroethylene-based polymer is 0.1 or more, and the tetrafluoroethylene-based polymer A viscoelastic body, wherein the total content of the mass of the fluoroethylene-based polymer and the mass of the thermosetting resin is 40% by mass or more.
• a method for producing a viscoelastic body containing heat-melting tetrafluoroethylene-based polymer particles and at least one of an organic resin and inorganic particles, and dispersibility and the like formed from the viscoelastic body A dispersion having excellent liquid properties is provided. Further, according to the present invention, there is provided a viscoelastic body containing heat-melting tetrafluoroethylene-based polymer particles and at least one of an organic resin and inorganic particles in a predetermined ratio.
• the “heat-melting tetrafluoroethylene-based polymer” is a polymer containing units (hereinafter also referred to as “TFE units”) based on tetrafluoroethylene (hereinafter also referred to as “TFE”), and having a load of 49 N.
• TFE units polymer containing units
• TFE tetrafluoroethylene
• TFE tetrafluoroethylene
• a load of 49 N means a melt-flowable polymer at which there is a temperature at which the melt flow rate is 1 to 1000 g/10 minutes under the conditions of "Polymer glass transition point (Tg)" is a value measured by analyzing a polymer by dynamic viscoelasticity measurement (DMA).
• DMA dynamic viscoelasticity measurement
• Polymer melting temperature (melting point) is the temperature corresponding to the maximum of the melting peak measured by differential scanning calorimetry (DSC).
• D50 is the average particle diameter of particles, which is the volume-based cumulative 50% diameter of particles determined by a laser diffraction/scattering method. That is, the particle size distribution of particles is measured by a laser diffraction/scattering method, and a cumulative curve is obtained with the total volume of the group of particles being 100%.
• D90 is the cumulative volume particle diameter of particles, and is the volume-based cumulative 90% diameter of particles determined in the same manner as “D50".
• viscosity is a value measured for a dispersion liquid using a Brookfield viscometer at room temperature (25°C) and a rotation speed of 30 rpm. The measurement is repeated 3 times, and the average value of the 3 measurements is taken.
• the “thixotropic ratio” is a value calculated by dividing the viscosity obtained by measuring the dispersion at a rotation speed of 30 rpm by the viscosity obtained by measuring the dispersion at a rotation speed of 60 rpm.
• a unit based on a monomer means an atomic group based on the monomer formed by polymerization of the monomer. The units may be units directly formed by a polymerization reaction, or may be units in which some of said units have been converted to another structure by treatment of the polymer.
• monomer a units are also simply referred to as "monomer a units".
• the production method of the present invention (hereinafter also referred to as “this method”) comprises dry pulverizing a powder of a heat-melting tetrafluoroethylene polymer (hereinafter also referred to as "F polymer”) to form F polymer particles ( In the presence of a liquid substance, F particles and at least one of organic resin and inorganic particles are wet-mixed to obtain a viscosity containing F particles and at least one of organic resin and inorganic particles.
• F polymer heat-melting tetrafluoroethylene polymer
• the present viscoelastic body is excellent in dispersibility and uniformity, and a dispersion having excellent liquid physical properties such as dispersion stability can be obtained from the present viscoelastic body.
• the reason is not necessarily clear, but is presumed as follows, for example.
• the tetrafluoroethylene-based polymer Since the tetrafluoroethylene-based polymer has a low surface tension and easily fibrillates, its particles tend to aggregate or adhere to each other, and the polymer itself is in a state of easily deteriorating. Therefore, when the particles are dispersed in a liquid and mixed with other materials such as organic resins and inorganic particles, aggregation and deterioration of the tetrafluoroethylene polymer particles are induced, and the dispersion has sufficient liquid physical properties. Liquid is difficult to obtain. In this method, powder, which can be said to be an aggregate of F particles, is first dry pulverized.
• the powder of the F polymer is highly pulverized while suppressing deterioration. That is, by dry pulverization, the F polymer powder becomes F particles in a state close to aggregates of primary particles in which aggregation and mutual adhesion are eliminated.
• the F particles in such a state and at least one of the organic resin and the inorganic particles are wet-mixed in the presence of a liquid substance, the fine F particles and the organic resin or the inorganic particles are likely to interact with each other.
• Making the mixture a viscoelastic body by wet mixing enhances the interaction, resulting in a composite in which the surface of the F particles is coated with an organic resin or inorganic particles, or a composite in which one material is highly mixed with the other material. It is believed to promote the formation of dispersed compositions. It is believed that this mechanism of action makes the viscoelastic material excellent in dispersibility and uniformity, and thus a dispersion liquid excellent in liquid physical properties such as dispersion stability can be obtained.
• the melting temperature of the F polymer is preferably 200° C. or higher, more preferably 260° C. or higher.
• the melting temperature of the F polymer is preferably 325° C. or lower, more preferably 320° C. or lower.
• the glass transition point of F polymer is preferably 60° C. or higher, more preferably 75° C. or higher.
• the glass transition point of the F polymer is preferably 150° C. or lower, more preferably 125° C. or lower.
• the fluorine content of the F polymer is preferably 70% by mass or more, more preferably 72 to 76% by mass.
• the surface tension of the F polymer is preferably 16 to 26 mN/m. The surface tension of the F polymer can be measured by placing a droplet of a wetting index reagent (manufactured by Wako Pure Chemical Industries, Ltd.) on a flat plate made of the F polymer.
• F polymers are based on PTFE, polymers containing TFE units and ethylene-based units, polymers containing TFE units and propylene-based units, TFE units and perfluoro(alkyl vinyl ether) (hereinafter also referred to as “PAVE”).
• units hereinafter also referred to as “PAVE units”
• PFA polymers including TFE units and units based on hexafluoropropylene
• FEP hexafluoropropylene
• PFA and FEP are more preferred
• PFA is even more preferred.
• These polymers may also contain units based on other comonomers.
• the F polymer preferably has an oxygen-containing polar group, more preferably a hydroxyl group-containing group or a carbonyl group-containing group, even more preferably a carbonyl group-containing group.
• an oxygen-containing polar group more preferably a hydroxyl group-containing group or a carbonyl group-containing group, even more preferably a carbonyl group-containing group.
• the hydroxyl group-containing group is preferably a group containing an alcoholic hydroxyl group, more preferably -CF 2 CH 2 OH and -C(CF 3 ) 2 OH.
• a 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)-), an imide Residues (--C(O)NHC(O)--, etc.) and carbonate groups (--OC(O)O--) are preferred, with anhydride residues being more preferred.
• the number of oxygen-containing polar groups in the F polymer is preferably 10 to 5,000, more preferably 100 to 3,000 per 1 ⁇ 10 6 carbon atoms in the main chain.
• the number of oxygen-containing polar groups in the F polymer can be quantified by the composition of the polymer or the method described in WO2020/145133.
• the oxygen-containing polar group may be contained in a unit based on a monomer in the F polymer, or may be contained in a terminal group of the main chain of the F polymer, the former being preferred.
• Examples of the latter embodiment include an F polymer having an oxygen-containing polar group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and an F polymer obtained by subjecting the F polymer to plasma treatment or ionizing radiation treatment.
• the monomer having a carbonyl group-containing group is preferably itaconic anhydride, citraconic anhydride and 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"), more preferably NAH.
• the F polymer is preferably a polymer having carbonyl-containing groups containing TFE units and PAVE units, comprising units based on monomers containing TFE units, PAVE units and carbonyl-containing groups, for all units: More preferred are polymers containing 90 to 99 mol %, 0.99 to 9.97 mol % and 0.01 to 3 mol % of these units in this order. Specific examples of such F polymers include the polymers described in WO2018/16644.
• F polymer powder is an aggregate of F particles. As described above, F particles tend to agglomerate, so F polymer powder usually exists as an agglomerate of F particles.
• D50 which is the average particle diameter of F particles constituting the F polymer powder, is preferably 0.1 ⁇ m or more, more preferably more than 0.3 ⁇ m, and even more preferably 1 ⁇ m or more.
• D50 of the F particles is preferably 25 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 8 ⁇ m or less.
• the specific surface area of the F particles constituting the F polymer powder is preferably 1 to 25 m 2 /g.
• the F particles constituting the F polymer powder may be of one type or two or more types.
• the F polymer powder may also be dry ground in a mixture containing particles of other resins or inorganic particles.
• Other resins include resin particles similar to organic resins described later, or inorganic particles similar to inorganic particles described later.
• Particles of PTFE are preferred as the particles of other resin.
• Such particles may be contained as a powder that is an aggregate of particles.
• the F polymer powder and the PTFE powder can be pulverized while suppressing the denaturation of the PTFE particles.
• the proportion of the former particles in the mixture is preferably 50% by mass or less, more preferably 25% by mass or less.
• the ratio is preferably 5% by mass or more, more preferably 10% by mass or more.
• the D50 of the F particles is preferably from 1 to 4 ⁇ m, and the D50 of the PTFE particles is preferably from 0.1 to 1 ⁇ m.
• the F particles are particles containing an F polymer, preferably consisting of an F polymer.
• the F particles may contain a resin or an inorganic compound other than the F polymer, and may form a core-shell structure in which the F polymer is the core and the shell is a resin or inorganic compound other than the F polymer, and the F polymer may be may form a core-shell structure in which a resin or an inorganic compound other than the F polymer is used as a core.
• Resins other than the F polymer include aromatic polyesters, polyamideimides, polyimides, and maleimides.
• examples of inorganic compounds include silica and boron nitride.
• the F polymer powder which is an aggregate of F particles, is dry pulverized to obtain F particles that are in a state close to an aggregate of primary particles.
• the dry pulverization may be carried out without adding a liquid substance such as a solvent to pulverize the aggregates of the F particles so as to eliminate agglomeration or adhesion of the F particles.
• the shearing force applied to the F polymer powder in dry pulverization may be applied so that the F polymer powder is pulverized into individual particles.
• Devices used to achieve the dry pulverization include, for example, Henschel mixer, pressure kneader, Banbury mixer, rotation/revolution mixer, planetary mixer, ball mill, attritor, basket mill, sand mill, sand grinder, dyno mill, At least one mixer selected from the group consisting of dispermat, SC mill, spike mill, agitator mill, microfluidizer, nanomizer, agitzer, dissolver, disper and high speed impeller.
• the powder of the F polymer is highly pulverized into F particles in a fine state while suppressing deterioration of the F polymer.
• the dry pulverization may be carried out by using one type of the above-mentioned mixer or by using a plurality of types. When multiple types of mixers are used, dry pulverization may be performed using different types of mixers sequentially. good too. Among these mixers, a rotation-revolution mixer is preferable.
• the dry pulverization may be carried out at room temperature or while heating or cooling, but is preferably carried out at a temperature below the glass transition point of the F polymer.
• a temperature below the glass transition point of the F polymer softening of the F polymer can be suppressed while pulverizing while maintaining the rigidity of the F particles. It can be crushed while maintaining the shape of
• the temperature is usually 10°C or higher, and does not need to be a constant temperature.
• the temperature may rise due to heat generated by shearing, or dry crushing is performed at a constant temperature while cooling to suppress the temperature rise. may Moreover, if necessary, you may heat.
• the dry pulverization is preferably carried out at a temperature lower than the glass transition point of the F polymer by 20°C or lower, more preferably at a temperature lower than the glass transition point of the F polymer by 30°C or lower.
• the dry crushing time is preferably 5 minutes or longer, more preferably 10 minutes or longer.
• the end point of the dry pulverization may be until the F polymer powder becomes individual F particles, which is usually 20 hours or less.
• the F polymer powder is dry pulverized to form F particles.
• the D50 and specific surface area of the F particles after dry pulverization may be the same as the D50 and specific surface area of the F particles constituting the powder of the F polymer, or may be fine particles, and the specific surface area may be changed.
• may D50 of F particles after dry crushing is preferably 0.1 ⁇ m or more, more preferably more than 0.3 ⁇ m, and still more preferably 1 ⁇ m or more.
• D50 of F particles after dry crushing is preferably 25 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 8 ⁇ m or less.
• the specific surface area of the F particles after dry crushing is preferably 1 to 25 m 2 /g. Except for the D50 after dry pulverization and the specific surface area, it is the same as the F particles constituting the F polymer powder.
• the F particles after dry pulverization and at least one of the organic resin and the inorganic particles are wet-mixed in the presence of a liquid substance.
• a liquid component is a component that is liquid at 25° C., and includes a solvent as described later.
• the organic resin may be wet-mixed as a liquid substance.
• a liquid composition containing at least one of an organic resin and inorganic particles (hereinafter also referred to as a "mixing component") is used to combine the F particles with the organic resin or inorganic particles. It is preferable from the viewpoint of interaction.
• a liquid composition containing a mixed component may be prepared in advance, and the F particles and the liquid composition may be mixed, or the F particles, the mixed component, and the solvent may be mixed.
• the liquid composition may be a composition containing a liquid organic resin as described above, a composition containing a mixed component and a solvent, or a composition containing a liquid organic resin and a solvent as described above.
• the mixed component is either an organic resin, an inorganic resin, or both.
• the organic resin (hereinafter, also referred to as "this organic resin"), which is one of the mixed components, is a resin different from the F polymer.
• the organic resin may be thermosetting, photocurable, or thermoplastic, but is preferably a thermosetting resin.
• the heat generated during mixing causes the thermosetting resin to partially harden and thicken while being mixed with the F particles, so that the surface of the F particles is It is considered that the material is effectively covered with a thermosetting resin and is easily stabilized, and the present viscoelastic material having excellent uniformity and dispersibility and the dispersion described later can be easily obtained.
• the thermosetting resin can be partially cured while softening the F polymer. It is easy to obtain the present viscoelastic body excellent in dispersibility.
• the organic resin examples include polyester resins such as liquid crystalline aromatic polyesters and polyarylate resins, amide resins, imide resins, epoxy resins, maleimide resins, urethane resins, polyphenylene ether resins, polyphenylene oxide resins, polyphenylene sulfide resins, and polyolefin resins. , polycarbonate resins, polyacetal resins, aromatic resins, and fluorine resins other than the F polymer.
• An aromatic resin is preferable as the organic resin. When the organic resin is an aromatic resin, it tends to interact with the F polymer, and the present viscoelastic body tends to be excellent in uniformity and dispersibility.
• aromatic resins include aromatic epoxy resins, phenolic resins, aromatic polyimide resins, precursors of aromatic polyimide resins, aromatic polyamideimide resins, and precursors of aromatic polyamideimide resins. At least one aromatic resin selected from the group consisting of resins, aromatic polyimide resins, precursors of aromatic polyimide resins, aromatic polyamideimide resins, and aromatic polyamideimide resins is preferred.
• aromatic epoxy resins examples include biphenyl novolak type epoxy resins, phenol novolak type epoxy resins, o-cresol novolak type epoxy resins, p-tert-butylphenol novolac type novolac type epoxy resins, bisphenol A type epoxy resins, and bisphenol F type epoxy resins.
• These epoxy resins may be solid, semi-solid, or liquid.
• the solid state means a solid state at 40°C
• the semi-solid state means a solid state at 20°C and a liquid state at 40°C
• the liquid state means a liquid state at 20°C.
• Phenol resins include phenol novolak resins, alkylphenol borak resins, bisphenol A novolac resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene-modified phenol resins, cresol resins or naphthol resins, polyvinylphenol resins, and ⁇ -naphthol skeletons.
• Precursors of aromatic polyimide resins include polyamic acids obtained by polymerizing tetracarboxylic dianhydrides and diamines and salts thereof.
• aromatic polyamideimide resins or precursors thereof include polyamideimide resins or precursors thereof obtained by reacting at least one of diisocyanate and diamine with tribasic acid anhydride.
• Tetracarboxylic dianhydrides include pyromellitic anhydride and biphenyltetracarboxylic anhydride.
• Diamines include phenylenediamine, 3,3'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl ether.
• Diisocyanates include 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, and 3,3'-diphenylmethane diisocyanate.
• aromatic polyimide resins aromatic polyamide resins, or precursors thereof include “Upia-AT” series (manufactured by Ube Industries, Ltd.), “Neoprim (registered trademark)” series (manufactured by Mitsubishi Gas Chemical Company, Inc.), “ Spixeria (registered trademark)” series (manufactured by Somar), “Q-PILON (registered trademark)” series (manufactured by PI Technical Research Institute), “WINGO” series (manufactured by Wingo Technology), “Tomide (registered trademark)” series (manufactured by T&K TOKA), “KPI-MX” series (manufactured by Kawamura Sangyo), "HPC-1000” and “HPC-2100D” (both manufactured by Showa Denko Materials).
• the aromatic resin may also be a modified aromatic resin having a carboxyl group and an ethylenically unsaturated double bond derived from a (meth)acryloyloxy group in the molecule.
• a (meth)acryloyloxy group is a generic term for an acryloyloxy group, a methacryloyloxy group, and both of them.
• Such a modified aromatic resin is a photosensitive resin with good photocurability and developability, and is an alkali-soluble resin.
• the modified aromatic resin is preferably a phenolic resin containing a carboxyl group.
• a polyfunctional phenolic resin such as a polyfunctional novolac type epoxy resin with (meth)acrylic acid
• the hydroxyl groups present in the side chains are treated with an organic polybasic acid.
• a carboxyl group-containing phenolic resin to which an anhydride is added is more preferred.
• the number average molecular weight, Mn, of the aromatic resin is preferably from 5000 to 50000, and the acid value of the aromatic resin is preferably from 20 to 100 mg/KOH.
• the acid value of the aromatic resin was 0.5 g of the aromatic resin, 0.15 g of 1,4-diazabicyclo[2.2.2]octane, 60 g of N-methyl-2-pyrrolidone and ion-exchanged water. It is obtained by titrating 1 mL of the mixed solution with a potentiometric titrator using a 0.05 mol/L ethanolic potassium hydroxide solution.
• the aromatic resin has an acid anhydride group, the acid value obtained when the acid anhydride group is ring-opened is taken as the acid value of the aromatic resin.
• the organic resin may be a cyanate ester resin.
• cyanate ester resins include phenol novolac type cyanate ester resins, alkylphenol novolak type cyanate ester resins, dicyclopentadiene type cyanate ester resins, bisphenol A type cyanate ester resins, bisphenol F type cyanate ester resins, and bisphenol S type cyanate ester resins. mentioned. Also, a prepolymer partially triazined may be used. These cyanate ester resins may be used together as a curing agent for thermosetting resins such as the aromatic epoxy resins.
• the organic resin may be a non-heat-melting tetrafluoroethylene polymer, preferably PTFE.
• the PTFE is preferably particulate, more preferably particulate with a D50 of 0.1 to 1 ⁇ m.
• the organic resin that constitutes the present organic resin may be one kind, or two or more kinds.
• the present organic resin may be used in combination with an organic resin that functions as a curing agent for the thermosetting resin.
• the content thereof is 10% by mass or more when the total mass including the liquid substance, the present organic resin, and the inorganic particles described later, including the inorganic particles, is 100% by mass. is preferred, and 20% by mass or more is more preferred.
• the content is preferably 80% by mass or less, more preferably 60% by mass or less.
• the shape of the inorganic particles (hereinafter also referred to as "inorganic particles"), which is one of the mixed components, is preferably spherical, needle-like, fibrous or plate-like, preferably spherical, scale-like or layered, spherical or A scaly form is more preferred.
• the present spherical inorganic particles are preferably substantially spherical.
• substantially spherical means that the proportion of inorganic particles having a short diameter to long diameter ratio of 0.7 or more is 95% or more when the inorganic particles are observed with a scanning electron microscope (SEM). do.
• the non-spherical inorganic particles preferably have an aspect ratio of 2 or more, more preferably 5 or more. The aspect ratio is preferably 10000 or less.
• the present inorganic particles are preferably carbon fillers, inorganic nitride fillers or inorganic oxide fillers, such as carbon fiber fillers, boron nitride fillers, aluminum nitride fillers, beryllia fillers, silica fillers, wollastonite fillers, talc fillers, cerium oxide fillers. , aluminum oxide filler, magnesium oxide filler, zinc oxide filler or titanium oxide filler is more preferred, and boron nitride filler or silica filler is more preferred.
• D50 of the present inorganic particles is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less. D50 is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
• the specific surface area of the present inorganic particles is preferably 1 to 20 m 2 /g.
• the surface of the present inorganic particles may be surface-treated with a silane coupling agent.
• Silane coupling agents include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isocyanate.
• Silane coupling agents with functional groups such as propyltriethoxysilane are preferred.
• silica fillers include the “ADMAFINE” series (manufactured by Admatechs), the “SFP” series (manufactured by Denka), and the “E-SPHERES” series (manufactured by Taiheiyo Cement).
• zinc oxide fillers include the “FINEX” series (manufactured by Sakai Chemical Industry Co., Ltd.).
• titanium oxide fillers include the "Tipake” series (manufactured by Ishihara Sangyo Co., Ltd.) and the "JMT” series (manufactured by Tayca Corporation).
• talc filler include "SG” series (manufactured by Nippon Talc Co., Ltd.).
• a specific example of the steatite filler is the "BST” series (manufactured by Nippon Talc Co., Ltd.).
• Specific examples of the boron nitride filler include “UHP” series (manufactured by Showa Denko KK) and "GP” and “HGP” grades of the "Denka Boron Nitride” series (manufactured by Denka).
• the content thereof is 10% by mass or more based on 100% by mass of the total mass including the liquid substance, the present inorganic particles, and the present organic resin when the present organic resin is present. is preferred, and 20% by mass or more is more preferred.
• the content is preferably 80% by mass or less, more preferably 60% by mass or less.
• liquid composition containing at least one of the present organic resin and the present inorganic particles.
• liquid refers to a state in which the viscosity is 10000 mPa ⁇ s or less at 25° C., and may or may not contain a solvent.
• the solvent-free liquid composition includes, for example, a liquid composition containing the present liquid organic resin and containing no solvent.
• the solvent is preferably a compound that is liquid at 25°C under atmospheric pressure and has a boiling point of 50 to 240°C.
• One type of solvent may be used, or two or more types may be used.
• the two solvents are preferably compatible with each other.
• Solvents may be either water or non-aqueous solvents, and non-aqueous solvents include amides, ketones, esters, (meth)acrylates and glycol compounds.
• (meth)acrylate is a generic term for acrylate, methacrylate, and both of them.
• the F particles and the present organic resin or the present inorganic particles can interact via water or a non-aqueous solvent, thereby obtaining the present viscoelastic body excellent in uniformity and dispersibility.
• Cheap When water or a non-aqueous solvent is used as the liquid substance, the F particles and the present organic resin or the present inorganic particles can interact via water or a non-aqueous solvent, thereby obtaining the present viscoelastic body excellent in uniformity and dispersibility.
• Amides include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N ,N-dimethylpropanamide, N,N-diethylformamide, hexamethylphosphoric triamide and 1,3-dimethyl-2-imidazolidinone.
• Ketones include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone and cycloheptanone.
• Esters include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl 3-ethoxypropionate, ⁇ -butyrolactone and ⁇ -valero Lactones are mentioned.
• the viscosity of the (meth)acrylate is preferably 1 to 1000 mPa ⁇ s, more preferably 5 to 300 mPa ⁇ s.
• the (meth)acrylate preferably has a molecular weight of 100 to 1,000.
• the (meth)acrylate is preferably a polyfunctional (meth)acrylate or a mono(meth)acrylate having a hydroxyl group or an oxyalkylene group, more preferably a polyfunctional (meth)acrylate.
• Polyfunctional (meth)acrylates include glycol (meth)acrylate, alkylene glycol (meth)acrylate, glycerol (meth)acrylate, trimethylolpropane (meth)acrylate, ditrimethylolpropane (meth)acrylate, and pentaerythritol (meth)acrylate. , dipentaerythritol (meth)acrylate, erythritol (meth)acrylate and dierythritol (meth)acrylate are preferred.
• (Meth)acrylate is also available as a commercial product. Specifically, “A-DPH” (dipentaerythritol polyacrylate, 7500 mPa s (25 ° C.)), “A-9550” (dipentaerythritol polyacrylate, 6500 mPa s ( ⁇ NK Ester> series such as 25°C)).
• glycol-based compound is preferably liquid at 25°C.
• Glycol-based liquid compounds include glycol derivatives such as glycols, glycol ethers, glycol esters and glycol amides. Suitable glycol-based liquid compounds include ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, tripropylene glycol monobutyl ether, and propylene. Glycol monophenyl ether, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate are included.
• Glycol-based liquid compounds are also available as commercial products. Specifically, “Tergitol TMN-100X” (manufactured by Dow Chemical Co.), “Lutensol T08”, “Lutensol XL70”, “Lutensol XL80”, “Lutensol XL90”, “Lutensol XP80", “Lutensol M5" (above, BASF), “Newcole 1305", “Newcole 1308FA”, “Newcole 1310” (all from Nippon Emulsion Co., Ltd.), “Leocole TDN-90-80", “Lecole SC-90” (all from Lion ⁇ Specialty Chemicals), “Palmless NOB-25", “Palmless NOB-30” and “Palmless NOB-50” (all of which are manufactured by Three Palmless P&A).
• the F particles and the organic resin or the inorganic particles can highly interact with each other through the solvent, and the present viscoelastic body having excellent uniformity and dispersibility can be easily obtained.
• the liquid substance or liquid composition may contain a nonionic surfactant.
• the nonionic surfactant is preferably a glycol-based surfactant, an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant.
• One type of nonionic surfactant may be used, or two or more types may be used.
• the nonionic surfactants are preferably a silicone-based surfactant and a glycol-based surfactant.
• nonionic surfactants include “Futergent” series (manufactured by Neos), “Surflon” series (manufactured by AGC Seimi Chemical), “Megafac” series (manufactured by DIC), “Unidyne” series (manufactured by DIC). Daikin Industries, Ltd.), “BYK-347”, “BYK-349”, “BYK-378”, “BYK-3450”, “BYK-3451”, “BYK-3455”, “BYK-3456” (BYK-Chemie Japan), “KF-6011” and “KF-6043” (manufactured by Shin-Etsu Chemical Co., Ltd.).
• the content of the nonionic surfactant is preferably 1 to 15% by mass.
• the mixed component may contain a curing agent that is not a resin.
• the curing agent is appropriately selected in combination with the thermosetting resin.
• the curing agent may undergo a thermosetting reaction with the F polymer.
• curing agents include compounds having amine, imidazole, phenol, acid anhydride and maleimide groups.
• the curing agent is preferably selected so that the curing initiation temperature of the curable resin is 120 to 200°C.
• the curing initiation temperature is the temperature at which heat is first generated when the curable resin is heated, as confirmed by differential scanning calorimetry (DSC).
• Amines include aliphatic polyamines such as alkylenediamines, polyalkylenepolyamines, aliphatic polyamines having an aromatic ring, adduct compounds thereof, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, and bis(4-aminocyclohexyl).
• Alicyclic polyamines such as methane, norbornenediamine, 1,2-diaminocyclohexane, lalomine, and adduct compounds thereof can be mentioned.
• amines include "Fujicure FXR” series, “Fujicure FXR” series (both manufactured by Fuji Kasei Kogyo Co., Ltd.), “Ankamin” series, “Sunmide” series (both manufactured by Air Products Jean Co., Ltd.), jER Cure 113 (manufactured by Mitsubishi Chemical Corporation), Lalomin C-260 (manufactured by BASF), and the like.
• imidazole examples include 2-methylimidazole, 4-methyl-2-ethylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole and 2-isopropylimidazole. , 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, azine compound of imidazole, isocyanurate of imidazole, hydroxymethyl imidazole, or , adduct compounds thereof.
• Phenols include hydroquinone, resorcinol, and bisphenol A.
• Acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, and benzophenonetetracarboxylic acid.
• Compounds having a maleimide group include, for example, 4,4'-diphenylmethanebismaleimide, phenylmethanebismaleimide, m-phenylenebismaleimide, 3,3'-dimethyl-5,5'-dimethyl-4,4'-diphenylmethanebismaleimide.
• the present viscoelastic body is obtained by wet-mixing the F particles and the mixed component.
• the F particles and the present organic resin or the present inorganic particles, which are mixing components are mixed by shearing so that they are uniformly mixed.
• Apparatuses used for wet mixing include the mixers exemplified for the dry pulverization.
• an ultrasonic homogenizer and a thin-film swirling high-speed mixer can also be used for wet mixing.
• Wet mixers include Henschel mixers, pressure kneaders, Banbury mixers, rotation-revolution mixers, planetary mixers, ball mills, attritors, basket mills, sand mills, sand grinders, Dyno mills, Dispermat, SC mills, spike mills, agitator mills, micro It is preferable to use at least one mixer selected from the group consisting of a fluidizer, nanomizer, 8%zer, ultrasonic homogenizer, desolver, disper, high-speed impeller and thin-film swirling high-speed mixer.
• the F particles and the organic resin or inorganic particles can be well mixed while suppressing the modification of the F polymer, which is preferable.
• the wet mixing may be carried out using one of the mixers described above, or using a plurality of such mixers. When a plurality of types of mixers are used, different types of mixers may be used sequentially for wet mixing, or the wet-mixing may be performed in multiple batches using different mixers and then combined. Among these mixers, a rotation-revolution mixer is preferable.
• the wet mixing may be performed at room temperature or while heating or cooling, but is preferably performed at a temperature equal to or higher than the glass transition point of the F polymer.
• the temperature is usually 10° C. or higher, and does not need to be a constant temperature. The temperature may rise due to heat generation due to shearing, or wet mixing is performed at a constant temperature while cooling to suppress the temperature rise. good too.
• the wet mixing is preferably carried out at a temperature higher than the glass transition point of the F polymer, more preferably at a temperature higher than the glass transition point of the F polymer by 10°C.
• Wet mixing is preferably performed at 120° C. or lower, more preferably 100° C. or lower.
• the wet mixing time is preferably 5 minutes or longer, more preferably 10 minutes or longer.
• the end point of wet mixing may be regarded as the end point when the load applied to the mixer becomes constant, which is usually 20 hours or less.
• the surfactant or curing agent may be added during wet mixing.
• the F particles, the organic resin and the inorganic particles are wet-mixed, it is preferable to wet-mix the F particles and the inorganic particles, and then wet-mix the organic resin. In this case, it is easier to suppress the increase in viscosity and foamability of the present viscoelastic body and the dispersion obtained therefrom.
• the viscosity of the present viscoelastic body measured by a capillograph is preferably over 100 Pa ⁇ s, more preferably 1000 Pa ⁇ s or more, and even more preferably 3000 Pa ⁇ s or more.
• the viscosity of the present viscoelastic body measured by a capillograph is preferably 50000 Pa ⁇ s or less, more preferably 10000 Pa ⁇ s or less, and even more preferably 8000 Pa ⁇ s or less.
• the viscosity measured by the capillograph is defined by using a capillary with a capillary length of 10 mm and a capillary radius of 1 mm, a furnace body diameter of 9.55 mm, a load cell capacity of 2 t, a temperature of 25 ° C., and a shear rate of It is a value measured as 100 s ⁇ 1 .
• the compressive elastic modulus of the present viscoelastic body is preferably 0.4 MPa or more, more preferably 0.5 MPa or more.
• the compressive elastic modulus of the present viscoelastic body is preferably 1 MPa or less, more preferably 0.8 MPa or less.
• the compressive elastic modulus is the maximum load when the present viscoelastic body is compressed at 1 mm/min using a Strograph (manufactured by Toyo Seiki Co., Ltd.).
• a Strograph manufactured by Toyo Seiki Co., Ltd.
• the viscosity and compressive modulus of the present viscoelastic body measured by capillography are within such ranges, the interaction between the F particles and the present organic resin or the present inorganic particles is enhanced, which is preferable.
• the mass ratio of the F polymer and the present inorganic particles is preferably 0.05 or more, more preferably 0.1 or more, with the mass of the F polymer being 1.
• the above ratio is preferably 20 or less, more preferably 10 or less, and even more preferably 1 or less.
• the mass ratio of the F polymer and the present organic resin is preferably 0.05 or more, more preferably 0.1 or more, with the mass of the F polymer being 1.
• the above ratio is preferably 20 or less, more preferably 10 or less, and even more preferably 1 or less.
• the solid content in the present viscoelastic body means the total amount of substances forming the solid content in the present viscoelastic body or a molded article formed from the below-described dispersion.
• the present viscoelastic body contains the F polymer and the organic resin and/or inorganic particles, the total content of these components is the solid content in the present viscoelastic body.
• the solid content in the present viscoelastic body is preferably 20% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more.
• the solid content is 100% by mass or less, more preferably 80% by mass or less.
• the content of F particles in the solid content is preferably 20% by mass or more, more preferably 40% by mass or more. Moreover, the content of the F particles is preferably 90% by mass or less, more preferably 80% by mass or less.
• the content of the present inorganic particles in the solid content is preferably 10% by mass or more, more preferably 20% by mass or more.
• the content of the present inorganic particles is preferably 80% by mass or less, more preferably 60% by mass or less.
• the content of the present organic resin in the solid content is preferably 10% by mass or more, more preferably 20% by mass or more.
• the content of the organic resin is preferably 80% by mass or less, more preferably 60% by mass or less.
• at least one of the present inorganic particles or the present organic resin is preferably within the above range, more preferably both are within the above range.
• the content of the F particles, the present inorganic particles and the present organic resin in the solid content is 100% by mass of the solid content, the content of the F particles is 40% by mass or more, and the content of the present inorganic particles is 10% by mass.
• the content of the organic resin is preferably 10% by mass or more, or the content of the F particles is 40% by mass or more, and the content of the inorganic particles is 10% by mass, based on the solid content of 100% by mass. As described above, the content of the present organic resin is more preferably 10% by mass or more. Further, for example, the ratio of the F particles, the inorganic particles, and the organic resin in the viscoelastic body is such that the content of the F particles is 1 and the content of the inorganic particles is 0.05 to 1, or the content of the organic resin is The content is preferably 0.05 to 1, and the content of the F particles is 1, the content of the inorganic particles is 0.05 to 1, and the content of the organic resin is 0.05 to 1. more preferred.
• the composition of the mixed components and, if necessary, the components necessary for the wet mixing may be added.
• the viscosity and composition are within such ranges, the present viscoelastic body tends to be excellent in liquid physical properties such as dispersibility and uniformity.
• This viscoelastic material contains a thixotropic agent, a viscosity modifier, an antifoaming agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a brightener, a coloring agent, and a conductive agent. , release agents, surface treatment agents, flame retardants, various fillers, and other additives. These additives may be contained in the mixed components, and may be added during the wet mixing.
• the present organic resin is included as a mixing component, and the ratio of the mass of the present organic resin to the mass of the F polymer in wet mixing is 0.1 or more, and the mass of the F polymer in the obtained viscoelastic body and the mass of the present organic resin is preferably 40% by mass or more.
• the ratio of the present organic resin is within such a range, the F particles are less likely to aggregate again, and the present viscoelastic body having excellent uniformity and dispersibility can be easily obtained.
• the total content of the mass of the F polymer and the organic resin is in the range, the viscosity during wet mixing tends to increase, and the F particles and the organic resin are well mixed, resulting in excellent uniformity and dispersibility. Body is easy to obtain.
• the powder of the F polymer is dry pulverized to form the F particles, and the particles and the varnish of the thermosetting resin are mixed in the ratio of the mass of the thermosetting resin to the mass of the F polymer. It is preferable to use wet mixing as 0.1 or more.
• a thermosetting resin varnish is used as the organic resin, the thermosetting resin and the F particles are likely to interact with each other through the solvent. It is mixed with the F particles while being hardened and thickened.
• the present viscoelastic body contains a sufficient amount of the thermosetting resin relative to the F particles. As a result, the surface of the F particles is effectively covered with the thermosetting resin and is likely to be stabilized, and the present viscoelastic body tends to be excellent in uniformity and dispersibility.
• the viscoelastic body of the present invention comprises the F particles and the organic resin, which is the thermosetting resin, and the ratio of the mass of the thermosetting resin to the mass of the F polymer is 0.1 or more, and , the total content of the mass of the F polymer and the mass of the thermosetting resin is 40% by mass or more.
• a viscoelastic body contains a certain amount of F particles and a thermosetting resin at a high ratio, has a high viscosity, and is easy to effectively cover the surface of the F particles with the thermosetting resin, so that aggregation of the F particles is difficult to occur. Easy to be excellent in uniformity and dispersibility.
• the definitions and ranges of the F polymer, F particles, organic resin, and components that may be contained in the viscoelastic body are the same as those in the present method.
• the ratio of the mass of the thermosetting resin to the mass of the F polymer is preferably 0.2 or more.
• the ratio is preferably 20 or less, more preferably 10 or less, and even more preferably 1 or less.
• the total content of the mass of the F polymer and the mass of the thermosetting resin is preferably 60% by mass or more.
• the total content is 100% by mass or less, preferably 80% by mass or less.
• Such a viscoelastic body can be suitably produced by the present method.
• a dispersion having a viscosity of 10000 mPa ⁇ s or less can be obtained. Since this viscoelastic body is excellent in uniformity and dispersibility, it can be diluted to obtain a dispersion liquid with excellent liquid physical properties such as dispersion stability, uniformity, rheology, coatability, and storage stability (hereinafter referred to as “this (also referred to as “dispersion liquid”) is obtained.
• the non-aqueous solvent includes the same non-aqueous solvent as the non-aqueous solvent used in the wet mixing, and the preferred non-aqueous solvent is also the same.
• the viscoelastic body may be mixed with an organic resin or inorganic particles to form the dispersion. Since this viscoelastic body is excellent in uniformity and dispersibility, even if it is mixed with organic resin or inorganic particles, F particles are difficult to reaggregate, and dispersion stability, uniformity, rheology, coatability, storage stability, etc. A dispersion with excellent physical properties can be obtained.
• the organic resin and inorganic particles include the same organic resins and inorganic particles as the present organic resin and present inorganic particles, and preferred organic resins and inorganic particles are also the same.
• the organic resin and inorganic resin mixed with the viscoelastic body may be the same as or different from the organic resin and inorganic particles contained in the viscoelastic body.
• the content of F particles in the resulting dispersion is preferably 10% by mass or more, more preferably 20% by mass or more.
• the content of F particles is preferably 60% by mass or less, more preferably 50% by mass or less.
• the same mixer as described above may be used for dilution or mixing.
• a mixer to be used a rotation/revolution mixer or a thin-film swirling high-speed mixer is preferable.
• the viscosity of the present dispersion is preferably 10 mPa ⁇ s or more, more preferably 100 mPa ⁇ s or more.
• the viscosity of the present dispersion is preferably 5000 mPa ⁇ s or less, more preferably 3000 mPa ⁇ s or less.
• the thixotropic ratio of this dispersion is preferably from 1.0 to 3.0.
• the pH of the dispersion is preferably 5 to 10, more preferably 8 to 10.
• a pH adjuster or pH buffer may be added during preparation of the viscoelastic body or the dispersion.
• pH adjusters include amines, ammonia, and citric acid.
• pH buffers include tris(hydroxymethyl)aminomethane, ethylenediaminetetraacetic acid, ammonium bicarbonate, ammonium carbonate and ammonium acetate.
• the surfactant, the curing agent, or the additive may be added when preparing the dispersion from the viscoelastic material.
• the viscoelastic body and the dispersion obtained by the above method are useful as a coating material for imparting insulation, heat resistance, corrosion resistance, chemical resistance, water resistance, impact resistance, and thermal conductivity.
• the present viscoelastic material and the present dispersion are specifically used for printed wiring boards, thermal interface materials, substrates for power modules, coils used in power devices such as motors, in-vehicle engines, heat exchangers, vials, injections, etc.
• secondary batteries such as lithium ion batteries, primary batteries such as lithium batteries, radical batteries, solar batteries, fuel cells, lithium ion capacitors, hybrid capacitors, capacitors, aluminum electrolytic capacitors or tantalum It can be used for capacitors such as electrolytic capacitors, electrochromic elements, electrochemical switching elements, electrode binders, electrode separators, and positive or negative electrodes.
• the present viscoelastic body and present dispersion are also useful as an adhesive for bonding parts.
• the present viscoelastic material and the present dispersion are used for adhesion of ceramic parts, adhesion of metal parts, adhesion of electronic parts such as IC chips, resistors and capacitors on substrates of semiconductor elements and module parts, and heat dissipation from circuit boards. It can be used for bonding boards and bonding LED chips to substrates.
• the present viscoelastic body and dispersion containing a conductive filler can also be suitably used in applications requiring conductivity, such as the field of printed electronics. Specifically, it can be used to manufacture energization elements in printed circuit boards, sensor electrodes, and the like.
• the present viscoelastic body and present dispersion can be suitably used as a negative resist composition.
• the resist composition can be applied to the surface of the substrate by a coating method such as screen printing, bar coating, or blade coating. After coating, the coating film is dried, and the obtained dry film is exposed to light using an exposure mask having a predetermined exposure pattern. The dry film after exposure is developed with a developing solution and then cured by irradiating with ultraviolet rays to obtain a laminate having a substrate and a cured film on the surface of the substrate.
• the present viscoelastic body and present dispersion can also be suitably used as a filling material for filling through holes or recesses in multilayer printed wiring boards.
• Filling of the present viscoelastic body and dispersion into the through-holes or recesses can be carried out by screen printing, roll coating, die coating or vacuum printing. At this time, it is preferable to fill the composition to such an extent that it protrudes from the through holes or recesses.
• a laminate having a substrate layer and a layer containing F polymer on the surface of the substrate layer (hereinafter also referred to as "F layer") can be suitably produced.
• F layer a laminate having a substrate layer and a layer containing F polymer on the surface of the substrate layer
• a method for producing a laminate there is a method of coating the surface of a base material with this dispersion, removing the solvent by heating if necessary, and further heating to bake the F polymer to form the F layer. mentioned.
• the organic resin in the dispersion is a thermosetting resin or a photocurable resin
• the dispersion is coated on the surface of the base material, heated as necessary to remove the solvent, and then heated.
• the F layer may be formed by curing the present organic resin by light irradiation.
• metal substrates such as metal foils such as copper, nickel, aluminum, titanium and alloys thereof, polyimide, polyamide, polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystalline polyester, tetra
• a heat-resistant resin film such as a heat-resistant resin film such as a fluoroethylene polymer, a prepreg substrate that is a precursor of a fiber-reinforced resin substrate, a ceramic substrate such as a ceramic substrate such as silicon carbide, aluminum nitride, or silicon nitride, and a glass substrate. mentioned.
• the shape of the base material may be planar, curved, or uneven.
• the shape of the substrate may be any of foil, plate, film, and fiber.
• the ten-point average roughness of the substrate surface is preferably 0.01 to 0.05 ⁇ m.
• the surface of the substrate may be surface-treated with a silane coupling agent or plasma-treated.
• Coating methods for the present viscoelastic material and the present dispersion include a coating method, a droplet discharge method, and an immersion method, with roll coating, knife coating, bar coating, die coating, and spraying being preferred.
• Heating for solvent removal is preferably carried out at 50 to 200° C. for 0.1 to 30 minutes. In this heating, the solvent does not have to be completely removed, and may be removed to such an extent that the formed layer can maintain a self-supporting film. Also, during the heating, air may be blown to facilitate the removal of the liquid dispersion medium by air-drying.
• the heating for sintering the F polymer is preferably performed at a temperature equal to or higher than the sintering temperature of the F polymer, and more preferably at 360 to 400° C. for 0.1 to 30 minutes.
• a heating apparatus for each heating includes an oven and a ventilation drying oven.
• the heat source in the apparatus may be a contact heat source such as hot air or a hot plate, or a non-contact heat source such as infrared rays.
• each heating may be performed under normal pressure or under reduced pressure.
• the atmosphere in each heating may be an air atmosphere, an inert gas atmosphere such as helium gas, neon gas, argon gas, or nitrogen gas.
• the present viscoelastic body or the present dispersion contains a thermosetting resin or a photocurable resin as the present organic resin
• the present organic resin may be cured by a method suitable for the resin to form the F layer.
• the F layer is formed through the steps of coating the present viscoelastic material or the present dispersion, heating, or light irradiation. These steps may be performed once each, or may be repeated twice or more.
• the viscoelastic body or the dispersion is coated on the surface of a substrate and heated to form an F layer, and the surface of the F layer is coated with the viscoelastic body or the dispersion and heated or irradiated with light. You may form the F layer of the 2nd layer.
• the surface of the base material is coated with the present viscoelastic body or the present dispersion and heated to remove the solvent
• the surface is further coated with the present viscoelastic body or the present dispersion and heated or irradiated with light to obtain F Layers may be formed.
• the present viscoelastic body and present dispersion may be coated on only one surface of the substrate, or may be coated on both surfaces of the substrate.
• a laminate having a substrate layer and an F layer on one surface of the substrate layer is obtained, and in the latter case, the substrate layer and the F layer are provided on both surfaces of the substrate layer.
• a laminate is obtained.
• Preferred specific examples of the laminate include a metal foil and a metal-clad laminate having an F layer on at least one surface of the metal foil, a polyimide film, and a multilayer film having an F layer on both surfaces of the polyimide film. is mentioned.
• the thickness of the F layer is preferably 0.1 to 200 ⁇ m, more preferably 1 to 50 ⁇ m.
• the peel strength between the F layer and the substrate layer is preferably 10 to 100 N/cm. Further, the substrate layer may be removed from the laminate to obtain a film containing the F polymer.
• the laminate of the F layer and the base material is useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sporting goods, food products, heat dissipation parts, paints, cosmetics and the like.
• wire coating materials for aircraft wires enameled wire coating materials used for motors such as electric vehicles, electrical insulating tapes, insulating tapes for oil drilling, oil transport hoses, hydrogen tanks, and printed circuit boards.
• separation membranes such as microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, and gas separation membranes
• electrode binders for lithium secondary batteries and fuel cells copy rolls, furniture, Automobile dashboards, home appliance covers, load bearings, yaw bearings, slide shafts, valves, bearings, bushes, seals, thrust washers, wear rings, pistons, slide switches, gears, cams, belt conveyors, food conveyor belts, etc.
• sliding members tension ropes, wear pads, wear strips, tube ramps, test sockets, wafer guides, wear parts of centrifugal pumps, chemical and water supply pumps, tools such as shovels, files, awls and saws, boilers, Hoppers, pipes, ovens, baking molds, chutes, racket guts, dies, toilet bowls, container coverings, power devices, transistors, thyristors, rectifiers, transformers, power MOS FETs, CPUs, heat radiating fins, metal heat radiating plates, wind turbines and wind turbines.
• tools such as shovels, files, awls and saws, boilers, Hoppers, pipes, ovens, baking molds, chutes, racket guts, dies, toilet bowls, container coverings, power devices, transistors, thyristors, rectifiers, transformers, power MOS FETs, CPUs, heat radiating fins, metal heat radiating plates, wind turbines and wind turbines.
• Blades for power generation equipment and aircraft housings for personal computers and displays, electronic device materials, interior and exterior materials for automobiles, processing machines and vacuum ovens that perform heat treatment under low-oxygen conditions, sealing materials for plasma processing equipment, sputtering and various types of dry etching. It is useful as a heat radiating component in a processing unit such as a device and as an electromagnetic wave shield.
• a woven fabric is impregnated with the present viscoelastic material and the present dispersion and heated to obtain a woven fabric impregnated with the F polymer.
• the obtained woven fabric can also be said to be a coated woven fabric in which the woven fabric is coated with the F layer.
• the woven fabric is preferably a glass fiber woven fabric, a carbon fiber woven fabric, an aramid fiber woven fabric, or a metal fiber woven fabric.
• the woven fabric may be surface treated with a silane coupling agent.
• the content of the F polymer in the resulting woven fabric is preferably 30 to 80% by mass.
• the woven fabric When impregnating the woven fabric with the viscoelastic body and the dispersion, the woven fabric may be immersed in the viscoelastic body and the dispersion, and the viscoelastic body and the dispersion are applied to the woven fabric.
• the same heating method as that for obtaining the laminate can be used.
• the obtained woven fabric and the base material may be opposed to each other and thermocompressed to form a laminate in which the base material and the woven fabric are laminated in this order.
• the obtained woven fabric can be used for the same applications as the laminate.
• the woven fabric is also useful as a lining material for the inner walls of members such as tanks, pipes, and containers.
• the present invention is not limited to the configurations of the above-described embodiments.
• the present method and the method of obtaining the present dispersion from the viscoelastic body obtained by the present method may additionally have other arbitrary steps in the configuration of the above-described embodiments, and produce similar effects. Any step may be substituted.
• the viscoelastic body of the present invention and the viscoelastic body of the present invention may be added with any other configuration to the configurations of the above-described embodiments, or may be replaced with any configuration that exhibits similar functions.
• Mixed component 1 phenolic resin containing carboxyl group (acid value: 80 mgKOH/g, photocurable and thermosetting resin, hereinafter also referred to as “aromatic resin 1”) and liquid resin varnish containing toluene as solvent Composition.
• Mixed component 2 A slurry liquid composition containing silica particles (D50: 1.0 ⁇ m) and using toluene as a solvent.
• Example 1 Preparation of viscoelastic body and dispersion liquid
• Powder 1 was put into a rotation/revolution mixer, and then the mixer was operated for 5 minutes at 2000 rpm and 50° C. for dry pulverization. Further, the mixed component 1 is put into a rotation/revolution mixer, and the mixer is operated at a rotation speed of 2000 rpm and 100 ° C. for 5 minutes to perform wet mixing, and 60 parts by mass of F polymer 1 particles and 40 parts by mass of an aromatic resin.
• a viscoelastic body 1 containing 1 (viscosity measured by a capillograph: 5000 Pa ⁇ s, compression modulus: 0.6 MPa) was obtained.
• the viscoelastic body 1 and the resin varnish of the aromatic resin 1 are put into a rotation-revolution mixer, and then the mixer is operated for 5 minutes at a rotation speed of 2000 rpm to mix 20 parts by mass of powder 1 and 80 parts by mass of aromatic.
• Dispersion liquid 1 (viscosity: 300 mPa ⁇ s) containing group resin 1 was obtained.
• Viscoelastic body 2 (viscosity measured by capillograph: 7000 Pa s, compression modulus: 0.7 MPa) and dispersion liquid 2 (viscosity: 500 mPa ⁇ s) was obtained.
• Viscoelastic body 3 (viscosity measured by capillograph: 9000 Pa s, compression modulus: 0.9 MPa) and dispersion liquid 3 (viscosity: 800 mPa ⁇ s) was obtained.
• Viscoelastic body 4 (viscosity measured by capillograph: 10000 Pa s, compression modulus: 0.9 MPa) and dispersion liquid 4 (viscosity: 800 mPa) were prepared in the same manner as in Example 1 except that the wet mixing was performed at 70 ° C. ⁇ s) was obtained.
• Example 5 The powder 2 and the mixed component 1 are put into a rotation-revolution mixer, and then the mixer is operated for 5 minutes at a rotation speed of 2000 rpm to mix, and 60 parts by mass of the powder 2 and 40 parts by mass of the aromatic resin 1 are mixed.
• the viscoelastic body 5 and the aromatic resin 1 are put into a rotation-revolution mixer, and then the mixer is operated for 5 minutes at a rotation speed of 2000 rpm to obtain 20 parts by mass of the powder 2 and 80 parts by mass of the aromatic resin.
• a dispersion liquid 5 (viscosity: 1200 mPa ⁇ s) containing 1 was obtained.
• Evaluation 3-1 Homogeneity of Viscoelastic Body The homogeneity of each viscoelastic body was visually confirmed and evaluated according to the following criteria. [Evaluation criteria] ⁇ : It is in a uniform state, and cracks do not occur even when it is pressed. ⁇ : Uniform state, but cracks occur when pressed. x: A lump is visually recognized on the surface, and when it presses, it collapses.
• Adhesion of polymer layer Each dispersion is applied to an electrolytic copper foil (manufactured by Fukuda Metal Foil & Powder Co., Ltd., "CF-T49A-DS-HD2") to form a coating film, and the coating film is maintained at 80 ° C. for 10 minutes. After drying, a dry film (thickness: 50 ⁇ m) was obtained. Next, without using an exposure mask, the entire dry film is irradiated with ultraviolet rays, and the dry film is cured by heating at 150 ° C. for 50 minutes to form a polymer layer, and the polymer layer is formed on the surface of the electrolytic copper foil.
• an electrolytic copper foil manufactured by Fukuda Metal Foil & Powder Co., Ltd., "CF-T49A-DS-HD2
• Example 7 A viscoelastic body 7 and a dispersion liquid 7 were obtained in the same manner as in Example 6 except that the mixed component 1 was put into the rotation/revolution mixer first and then the mixed component 2 was put. Both Dispersions 6 and 7 had low viscosities, suppressed foaming, and had excellent handleability. However, when Dispersions 6 and 7 were compared, Dispersion 6 had lower viscosity, Foaming was also more suppressed. Dispersion 6 was more excellent in handleability.
• the viscoelastic material obtained by this method provides a dispersion with excellent liquid physical properties such as dispersion stability.
• the dispersion liquid obtained from the viscoelastic body is excellent in dispersibility, and the polymer layer of the obtained laminate is excellent in smoothness, adhesiveness and electrical properties.

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