[go: up one dir, main page]

WO2020085444A1 - Composite material - Google Patents

Composite material Download PDF

Info

Publication number
WO2020085444A1
WO2020085444A1 PCT/JP2019/041758 JP2019041758W WO2020085444A1 WO 2020085444 A1 WO2020085444 A1 WO 2020085444A1 JP 2019041758 W JP2019041758 W JP 2019041758W WO 2020085444 A1 WO2020085444 A1 WO 2020085444A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
layered
mass
resin
flaking
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/041758
Other languages
French (fr)
Japanese (ja)
Inventor
智秋 斉木
横田　英之
大介 澤本
矢野　亨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Adeka Corp
Original Assignee
Adeka Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Adeka Corp filed Critical Adeka Corp
Priority to JP2020552598A priority Critical patent/JPWO2020085444A1/en
Priority to KR1020217009391A priority patent/KR102747045B1/en
Priority to CN201980066615.5A priority patent/CN112823189A/en
Publication of WO2020085444A1 publication Critical patent/WO2020085444A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation
    • C01B32/225—Expansion; Exfoliation
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/46—Graphite
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds

Definitions

  • the present invention relates to a composite material in which the surface of a flaky stratified material is coated with a polysiloxane compound having an organic group.
  • Exfoliated graphite such as graphene obtained by exfoliating graphite, which is a laminated substance, is a conductive auxiliary agent for an electrode of a secondary battery (see, for example, Patent Document 1), a conductive ink (see, for example, Patent Document 2).
  • a filler of resin or elastomer see, for example, Patent Documents 3 to 4
  • a gas barrier material see, for example, Patent Documents 5 to 6
  • the layered substance becomes flaked and becomes thinner, and the smaller the number of layers, the more likely it is to aggregate. Therefore, there is a problem that it is difficult to disperse in the matrix, and sufficient physical properties may not be obtained in some cases.
  • exfoliated graphite whose surface is coated with a polymer such as polyvinyl alcohol (see, for example, Patent Document 7) has been studied, but it has been blended with a silicone resin or the like. In this case, the effect of improving dispersibility was not sufficient.
  • a method of treating the surface of the layered substance with a silane coupling agent to improve the dispersibility in the resin is also known, but the silane coupling agent is relatively expensive. Yes, there is a need for an inexpensive method.
  • An object of the present invention is to provide a flaky layered material that has good dispersibility and a large effect of improving physical properties when blended with a silicone resin or the like.
  • the present invention is a composite material in which the surface of a fragmentation layered material is coated with a coating material, the coating material is a polysiloxane compound having an organic group, and a coating material for 100 parts by mass of the flaking layered material is provided. It is a composite material having a content of 0.1 to 100 parts by mass.
  • the present invention also provides a resin composition containing the above composite material and a synthetic resin.
  • the layered material which is the raw material of the flaky layered material used in the present invention has a layered structure in which unit layers formed by strong bonds such as covalent bonds and ionic bonds are mainly laminated via weak Van der Waals forces.
  • Examples of the layered substance include graphites, boron nitrides, transition metal dichalcogenides, group 13 chalcogenides, group 14 chalcogenides, bismuth chalcogenides, layered metal halides, layered transition metal oxides, layered perovskite oxides, clay minerals or layered silicic acid. Salt etc. are mentioned.
  • Graphites are layered compounds having a unit layer made of carbon.
  • Examples of graphites include, in addition to graphite, expanded graphite obtained by expanding graphite layers, and oxidized graphite obtained by oxidizing graphite with an oxidizing agent.
  • Boron nitrides are layered substances containing nitrogen and boron as constituent elements, such as boron nitride (BN) and carbon nitride boron (BCN).
  • a transition metal dichalcogenide is a layered substance composed of a transition metal and a chalcogen, and is represented by the formula MX 2 , where M is a transition metal and X is a chalcogen.
  • M is a transition metal
  • X is a chalcogen.
  • the transition metal include titanium, zirconium, hafnium, vanadium, niobium, chromium, monibden, tungsten, technetium, rhenium, nickel, tin, palladium or platinum.
  • Chalcogens include sulfur, selenium or tellurium.
  • transition metal dichalcogenide examples include TiS 2 , TiSe 2 , TiTe 2 , HfS 2 , HfSe 2 , HfTe 2 , VTe 2 , VSe 2 , NbS 2 , NbSe 2 , NbTe 2 , MoS 2 , MoSe 2 , WTe 2 , and MoTe 2 .
  • WSe 2 , WTe 2 TcS 2 , ReSe 2 , ReS 2 , ReTe 2 , TaS 2 , TaSe 2 , TaTe 2 , PtTe 2, and the like.
  • Group 13 chalcogenide is a layered substance composed of group 13 element gallium or indium and chalcogen, and examples thereof include GaS, GaSe, GaTe, InSe and the like.
  • Group 14 chalcogenide is a layered substance composed of chalcogen and germanium, tin or lead, which is a group 14 element, and examples thereof include GeS, SnS 2 , SnSe 2 , and PbO.
  • Bismuth chalcogenide is a layered substance composed of bismuth and chalcogen, and examples thereof include Bi 2 , Se 3 , and Bi 2 Te 3 .
  • the layered metal halide is a layered substance composed of a metal element and halogen, and examples thereof include MgBr 2 , CdCl 2 , CdI 2 , AgF 2 , AsI 3 , and AlCl 3 .
  • the layered transition metal oxide is a layered substance composed of an oxide or an oxyacid salt of a transition metal such as titanium, manganese, molybdenum, niobium, vanadium, MoO 3 , Mo 18 O 52 , V 2 O 5 , LiNbO 2 , Examples thereof include K 2 Ti 2 O 5 , K 2 Ti 4 O 9 and KTiNbO 5 .
  • the layered metal phosphate is a layered phosphate of titanium, zirconium, selenium, tin, zirconium, aluminum, etc., and is Ti (HPO 4 ) 2 , Ce (HPO 4 ) 2 , Zr (HPO 4 ) 2 , AlH 2 P 3 O 10 and the like.
  • Examples of the layered perovskite oxide include KCa 2 Nb 3 O 10 , KSr 2 Nb 3 O 10 and KLaNb 2 O 7 .
  • clay minerals or layered silicates include smectites such as montmorillonite, nontronite, and saponite; kaolin, pyrophyllite, talc, vermiculite, mica, brittle mica, chlorite, sepiolite, palygorskite, imogolite, allophane, Hisingelite, magadiite, kanemite and the like can be mentioned.
  • the flaked layered material used in the present invention is a material obtained by flaking the above layered material and having a layered structure in which one to several thousand unit layers of the layered material are laminated.
  • the stripped layered substance has a larger effect of improving the physical properties as the number of layers decreases and the thickness decreases, but it tends to aggregate.
  • the average thickness is preferably 0.3 nm to 1200 nm, more preferably 1.5 nm to 400 nm, and most preferably 3 nm to 200 nm. .
  • the present invention is preferably applied to a flaky layered material that has high cohesiveness and is difficult to disperse in a resin or the like.
  • exfoliated layered substances include exfoliated graphite and exfoliated boron nitride.
  • the present invention is preferably applied to exfoliated graphite and exfoliated boron nitride.
  • the thickness of the flaking layered material is the thickness in the direction perpendicular to the laminated surface of the flaking layered material, and the average thickness is the thickness of any 30 or more flaking layered materials. It is an average value.
  • the thickness of the flaked layered material can be measured using, for example, an SEM image of the flaked layered material taken by a scanning electron microscope.
  • the thickness of the flaking layered material is thinnest when it is composed of only one unit layer, but the thickness varies depending on the flaking layered material and is about 1 nm.
  • a substance composed of one unit layer is called graphene, and theoretically has a thickness of about 0.335 nm.
  • the area of the flaking layered material is small, a sufficient effect of improving the physical properties may not be obtained, so that the area of the flaking layered material is preferably large. However, if too large, it takes much labor to flakes of average area of flakes of layered material in the present invention is preferably 0.1 ⁇ m 2 ⁇ 500 ⁇ m 2, 0.5 ⁇ m 2 ⁇ 300 ⁇ m 2 Gayori It is preferably 1.0 ⁇ m 2 to 130 ⁇ m 2 .
  • the area of the flaking layered material is a projected area when the flaking layered material is viewed in a plane, and the average area is an average value of the areas of any 50 or more flaking layered materials. .
  • the area of the flaking layered material can be measured, for example, using an image obtained by dropping a dilute dispersion of the flaking layered material on a filter paper and photographing the flaking layered material with a microscope.
  • the method for exfoliating the layered substance is not particularly limited, and the layered substance may be exfoliated by applying shearing force, ultrasonic vibration, cavitation, etc. to the layered substance using a known device.
  • Examples of such an apparatus include a medium agitating mill such as a sand mill, an attritor and a bead mill; a container drive type mill such as a rotary mill, a vibration mill and a planetary mill that uses balls and rods as a medium; a jet mill, a roll mill, a hammer mill, a pin mill. , A high-pressure emulsifying machine, an ultrasonic emulsifying machine and the like.
  • Examples of the high pressure emulsifier include a through type high pressure emulsifier and a collision type high pressure emulsifier.
  • Examples of the penetration type of the penetration type high pressure emulsifying machine include a single nozzle type and a slit nozzle type.
  • Examples of the collision type of the collision type high pressure emulsifier include a method of causing a liquid containing a raw material to collide with a flat surface such as a valve or a spherical surface of a ball, a type of causing liquids containing the raw material to collide with each other, and the like.
  • either a wet flaking method using a solvent or a dry flaking method not using a solvent may be used, and the method may be selected according to the flaking method of each device.
  • alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, methoxyethanol
  • ketone solvents such as acetone and methyl ethyl ketone
  • pyridine Heterocyclic solvents such as piperidine, morpholine, tetrahydrofuran, dioxane
  • ionic liquids such as 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, dimethylformamide, N- Methylpyrrolidone, dimethyl sulfoxide, water and the like are preferable.
  • a water-soluble salt When a layered material is flaked, a water-soluble salt may be used together.
  • the water-soluble salt functions as a medium that promotes flaking in the solid-state peeling step, and the water-soluble salt dissolved in the solvent acts between the layers of the layered substance to promote flaking.
  • the water-soluble salt can be easily removed by washing with water.
  • Preferred water-soluble salts include sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, potassium sulfate, calcium sulfate, sodium acetate and the like.
  • the polysiloxane compound having an organic group is a general term for polymers or oligomers having a siloxane bond (Si—O—Si bond) as a main skeleton and having an organic group bonded to a silicon atom.
  • Examples of the organic group of the polysiloxane compound having an organic group used in the composite material of the present invention include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group and an aralkyl group.
  • the organic group may have a substituent such as a hydroxyl group, an ether group, an ester group, an epoxy group, a (meth) acryloxy group, a carbonyl group, a carboxyl group, an amino group, a thiol group and a thioether group.
  • a substituent such as a hydroxyl group, an ether group, an ester group, an epoxy group, a (meth) acryloxy group, a carbonyl group, a carboxyl group, an amino group, a thiol group and a thioether group.
  • a methyl group, an ethyl group, a butyl group, a vinyl group, a 2-cyclohexylethyl group, a 2-cyclohexenylethyl group, a phenyl group, a 2-phenylethyl group, and 2 are easy to obtain raw materials.
  • the organic group of the polysiloxane compound having an organic group is preferably an aryl group such as a phenyl group or an aralkyl group such as a 2-phenylethyl group or a 2-phenylpropyl group from the viewpoint of dispersibility in a resin.
  • the organic group may be only one type or a combination of two or more types, but in the case of a combination of two or more types, one type is preferably an aryl group or an aralkyl group from the viewpoint of dispersibility in a resin.
  • the content of the phenyl group in the compound is preferably 5% by mass to 70% by mass, more preferably 6% by mass to 70% by mass, and 8% by mass to 60% by mass. % Is most preferred.
  • the content of the phenyl group in the compound can be calculated from the content of the repeating units constituting the polysiloxane compound and the content ratio of the repeating units.
  • the organic group has an aryl group or an aralkyl group other than the phenyl group, only the benzene ring portion is included in the content of the phenyl group.
  • the phenyl group content is a mass average value in consideration of the mass ratio of the polysiloxane compound having an organic group to be used.
  • the silicon substituents may be organic groups, and if the number of organic substituents is small, some of the organic groups are hydrogen atoms, halogen atoms, hydroxyl groups, alkoxy groups, etc. May be substituted with.
  • the polysiloxane compound having an organic group is likely to volatilize when it has a low molecular weight, the polysiloxane compound having an organic group preferably has at least 5 silicon atoms, and more preferably has 10 or more silicon atoms.
  • the molecular shape of the polysiloxane compound having an organic group may be linear, cyclic, branched, cage-like, ladder-like (ladder-like), etc., and a combination thereof may be used. May have a molecular shape in which they are linked by a hydrocarbon group or the like.
  • the surface of the flaky layered material is coated with a polysiloxane compound having an organic group.
  • the polysiloxane compound having an organic group may cover a part of the surface of the flaked layered material or may cover the entire surface thereof, but at least a majority of the surface may be covered. preferable.
  • the polysiloxane compound having an organic group may continuously or intermittently cover the surface of the flaking layered material.
  • the content of the polysiloxane compound having an organic group is 100 parts by mass to 100 parts by mass with respect to 100 parts by mass of the flaked layered material.
  • the content of the polysiloxane compound having an organic group is less than 0.1 parts by mass, the coating with the polysiloxane compound having an organic group may be insufficient, and when it is more than 100 parts by mass, use Not only the effect of increasing the amount corresponding to the amount cannot be obtained, but when the composite material of the present invention is used by adding it to a resin or the like, it may adversely affect the physical properties of the resin or the like.
  • the content of the polysiloxane compound having an organic group is preferably 0.2 parts by mass to 70 parts by mass, more preferably 0.5 parts by mass to 60 parts by mass, and further preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the flaking layered material. Parts are most preferred.
  • Method of manufacturing composite material for example, a method of dispersing and mixing a polysiloxane compound having an organic group and a flaking layered material in a solvent, and coating (hereinafter, Mixed coating method), an organic group produced by adding a hydrolyzable silane compound to an aqueous dispersion of flaky layered material and subjecting the hydrolyzable silane compound to a hydrolysis / condensation reaction (so-called sol-gel reaction). And the like (hereinafter referred to as sol-gel coating method).
  • a dispersing device As a dispersing device therefor, a high-speed rotary shearing type agitator such as a homomixer; a medium agitating mill such as a sand mill, an attritor, or a bead mill; Mill; colloid mill, high-pressure emulsifying machine, ultrasonic emulsifying machine and the like.
  • a high-speed rotary shearing type agitator such as a homomixer
  • a medium agitating mill such as a sand mill, an attritor, or a bead mill
  • Mill colloid mill
  • high-pressure emulsifying machine ultrasonic emulsifying machine and the like.
  • the high pressure emulsifier include a through type high pressure emulsifier and a collision type high pressure emulsifier.
  • the penetration type of the penetration type high pressure emulsifying machine include a single nozzle type.
  • Examples of the collision type of the collision type high pressure emulsifier include a method of causing a liquid containing a raw material to collide with a flat surface such as a valve or a spherical surface of a ball, a type of causing liquids containing the raw material to collide with each other, and the like.
  • a strong shearing force is applied to the exfoliated layered material, the number of layers, the thickness, the particle size, etc. of the exfoliated layered material may be lower than before coating.
  • the dispersal device used for disintegration may be used as it is after disintegrating the flaky layered material.
  • the solvent used in the mixed coating method is not only a solvent capable of dissolving the polysiloxane compound having an organic group, but also a polysiloxane compound having an organic group if it is dispersible and soluble using a dispersing device.
  • a solvent that does not dissolve the siloxane compound can also be used, and may be selected in consideration of ease of removal, safety (toxicity, flammability, chargeability, etc.).
  • Examples of the solvent used in the mixed coating method include alcohol solvents such as methanol, ethanol, isopropanol, and methoxyethanol; ketone solvents such as acetone and methylethylketone; and water.
  • the ratio of the flaking layered material to the solvent or the solution of the polysiloxane compound having an organic group varies depending on the pulverizing device, the solution of the polysiloxane compound having a solvent or an organic group to 100 parts by mass of the flaking layered material 200 It is preferable that the amount is about from 5,000 to 5,000.
  • the solvent is removed to obtain the composite material of the present invention.
  • the method of removing the solvent is not particularly limited, and heat drying, reduced pressure drying, spray drying, freeze drying, or the like, or a combination of these methods may be applied.
  • the polysiloxane compound having an excess organic group and a part of the solvent may be removed by filtration or centrifugation, and then the remaining solvent may be removed.
  • the composite material of the present invention may be pulverized and granulated if necessary.
  • the disperser used for the crushing include the dispersers exemplified in the mixed coating method.
  • the sol-gel coating method when a strong shearing force is applied to the exfoliated layered material by cleavage, the number of layers and the thickness of the exfoliated layered material are larger than those before the coating. The particle size may decrease.
  • a hydrolyzable silane compound is a silane compound having a group in which a silanol (Si-OH) group is formed by hydrolysis, and a silanol group is dehydrated and condensed to form a siloxane group.
  • the hydrolyzable silane compound may be selected in consideration of the structure of the polysiloxane compound having a hydrolyzable group and an organic group in addition to the organic group introduced into the polysiloxane compound having an organic group.
  • hydrolyzable group of the hydrolyzable silane compound examples include an alkoxysilyl group such as a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a methoxyethoxysilyl group; a halosilyl group such as a chlorosilyl group and a bromosilyl group; and an acetyloxysilyl group.
  • an alkoxysilyl group is preferable, and a methoxysilyl group and an ethoxysilyl group are more preferable, because they are less corrosive to the apparatus, have a rapid hydrolysis reaction, and are easily industrially available.
  • a hydrolyzable silane compound is an M-type silane compound having three organic groups and one hydrolyzable group, and a hydrolyzable silane compound having two organic groups depending on the number of organic groups and hydrolyzable groups.
  • a compound having two groups is called a D-type silane compound
  • a compound having one organic group and three hydrolyzable groups is called a T-type silane compound
  • a compound having four hydrolyzable groups is called a Q-type silane compound.
  • the structure of the polysiloxane compound having an organic group obtained by the sol-gel reaction is greatly influenced by the number of hydrolyzable groups of the hydrolyzable silane compound used.
  • a polysiloxane compound having a high molecular weight and linear organic group is obtained, and when only the T-type silane compound is used, a cage-shaped organic group is obtained.
  • a D-type silane compound is preferable because a film of a polysiloxane compound having a high-molecular weight organic group can be formed on the flaky stratified material, and a hydrolyzable silane compound having a different type is used.
  • at least one type is preferably a D-type silane compound.
  • Examples of preferable D-type silane compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like.
  • the flaky layered material is separated into water in which secondary particles are crushed and dispersed in the state of primary particles, to which a hydrolyzable silane compound is added to cause a sol-gel reaction to cause flaking.
  • a film of a polysiloxane compound having an organic group is formed on the surface of the layered material.
  • the water used may be water alone or water containing a water-soluble solvent such as methanol, ethanol, or isopropanol.
  • the water used is, as a catalyst, inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid to accelerate the reaction; organic acids such as formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, and benzenesulfonic acid; Inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia may be contained.
  • the temperature of the sol-gel reaction varies depending on the type of hydrolyzable silane compound, the type and amount of catalyst, etc., but is preferably 5 to 50 ° C., more preferably 8 to 30 ° C.
  • drying is not particularly limited, and methods such as heat drying, reduced pressure drying, spray drying, and freeze drying are used. Alternatively, these methods may be applied in combination. Further, the composite material of the present invention may be pulverized and granulated, if necessary.
  • the surface of the flaking layered material is coated with the polysiloxane compound having an organic group, so that the flaking layered material does not aggregate and the dispersibility in the substrate is significantly improved.
  • the effect of improving the physical properties of the flaking layered material such as conductivity, heat dissipation, mechanical properties (impact resistance, bending strength, compressive strength, etc.) can be improved.
  • the composite material of the present invention can be suitably used for applications such as resins such as synthetic resins, additives such as elastomers and paints; conductive additives for battery electrodes.
  • the resin composition of the present invention contains the composite material of the present invention and a synthetic resin.
  • the synthetic resin that can be preferably used in the resin composition of the present invention include phenol resin, epoxy resin, melamine resin, urea resin, alkyd resin, PET resin, PBT resin, polycarbonate resin, polyacetal resin, modified polyphenylene ether resin, polyurethane, and polyimide.
  • the composite material of the present invention is particularly Good dispersibility in silicone resin.
  • the composite material of the present invention may be blended in the step of kneading the resin and the additive, as in the case of other additives.
  • the resin may be cured after blending the composite material of the present invention with the uncured resin.
  • the composite material of the present invention is added to an uncured silicone resin composition together with other additives, and then cured by a method such as heating. You can do it.
  • the uncured silicone resin composition is, for example, an addition-curable composition containing a polysiloxane compound having a hydrosilyl group (SiH group), a polysiloxane compound having a vinyl group (CH 2 ⁇ CH-group), and a hydrosilylation catalyst.
  • the amount of the composite material of the present invention added varies depending on the type of resin and the required physical properties, but is preferably 1 to 150 parts by mass of the composite material of the present invention with respect to 100 parts by mass of the synthetic resin. It is more preferably 100 parts by mass.
  • a resin composition using a silicone resin as a resin is preferable. Since such a resin composition has excellent heat resistance, it can be suitably used as, for example, a sealing material for semiconductors, a heat dissipation sheet, or the like.
  • the average thickness of the flaking layered material is an average value of the thickness of any 30 pieces of the flaking layered material measured using an SEM image taken by a scanning electron microscope. Further, the average area of the flaking layered material was measured by using a thin dispersion of the flaking layered material dropped on a filter paper and measuring the flaking layered material with an image taken by a microscope. It is the average value of the area of the layered material.
  • a flaked layered material A1 was prepared from natural graphite. That is, 74 parts by mass of 1-butyl-3-methylimidazolium hexafluorophosphate and 26 parts by mass of polyethylene glycol (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd., product name: polyethylene glycol 20000) are mixed, heated and dissolved to give a natural mixture. 10 parts by mass of graphite (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was dispersed.
  • 0.6 g of this dispersion was collected in a 0.5 cm 3 vial, and after covering with a lid, a microwave of 2450 MHz was applied to the dispersion at 170 ° C. using a microwave synthesizer (Initiator + manufactured by Biotage Japan). For 30 minutes. Then, the dispersion was filtered, washed with acetone, and dried by heating in an oven to obtain a flaked layered material A1 derived from natural graphite.
  • the exfoliated layered material A1 had an average thickness of 123 nm and an average area of 11.6 ⁇ m 2 .
  • Exfoliated layered material A2 derived from expanded graphite was obtained by performing the same operation as in Production Example 1 except that expanded graphite (manufactured by Ito Graphite Industry Co., Ltd., product name: EC1500) was used instead of natural graphite. .
  • the exfoliated layered material A2 had an average thickness of 30 nm and an average area of 1.4 ⁇ m 2 .
  • Examples 1 to 9 and Comparative Example 1 The above flaked layered substance, the following coating substance and solvent were charged into a bead mill (manufactured by Kotobuki Kogyo, trade name: UAM-015) at the mass ratio shown in Table 1, and the secondary particles of the flaked layered substance were crushed. Then, the solvent was removed by heating under reduced pressure, and the composite materials of Examples 1 to 9 and Comparative Example 1 were manufactured.
  • Table 1 the numbers in parentheses represent mass ratios, and MEK of the solvent represents methyl ethyl ketone.
  • Comparative Example 1 is an experimental example in which polyvinyl alcohol was used as the coating substance, but only water was used as the solvent because it was powdery and did not dissolve in methyl ethyl ketone.
  • B1 Diphenylsiloxane-dimethylsiloxane copolymer (phenyl group content: 31% by mass, Gelest, trade name: PDM-1922)
  • B2 Phenylmethylsiloxane-dimethylsiloxane copolymer (phenyl group content: 10% by mass, manufactured by Gelest, trade name: PMM-1015)
  • B3 Phenylmethylsiloxane polymer (phenyl group content: 56% by mass, Gelest, trade name: PMM-0021)
  • B4 Silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer (phenyl group content: 26% by mass, Gelest, trade name: PDS-1615)
  • B5 Vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer (phenyl group content: 22% by mass, manufactured by AB Specialty Silicones, trade name: Andis
  • Example 10 70 parts by mass of the flaked layered substance A1 and 1400 parts by mass of water were subjected to a crushing treatment of secondary particles of the flaked layered substance using a bead mill (manufactured by Kotobuki Industries, trade name: UAM-015). A glass container was charged with 147 parts by mass of the exfoliated layered material dispersion, 4 parts by mass of dimethyldiethoxysilane, 1.2 parts by mass of diphenyldimethoxysilane, and 0.05 parts by mass of 85% phosphoric acid. The composite material of Example 10 was prepared by stirring for an hour and then at 30 ° C. for an hour. The phenyl group content of the polysiloxane compound having an organic group of Example 10 was 25% by mass.
  • an addition-curable silicone resin manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KE-109E-A / B
  • the produced resin sheet was cut using a cryomicrotome, the central portion of the cross section was photographed using a microscope, and the number of aggregates per 300 ⁇ m ⁇ 300 ⁇ m and the aggregate ratio were measured by image analysis software.
  • the number of aggregates is the number when particles having an area of 40 ⁇ m 2 or more are aggregates, and the aggregate ratio is the ratio (%) of the total area of aggregates to the total area of all particles. The larger the number of aggregates and the larger the ratio of aggregates, the larger the proportion of aggregates.
  • Table 2 The results are shown in Table 2.
  • the resin sheets of Comparative Examples 4 and 5 are exfoliated layered substances A1, and the resin sheets of Examples 11 to 19 and Comparative Examples 2 to 3 are examples using composite materials derived from the exfoliated layered substances A1.
  • the resin sheet is an example using the flaking layered material A2, and the resin sheet of Example 21 is an example using a composite material derived from the flaking layered material A3.
  • the resin sheets of Examples 11 to 19 in which the exfoliated layered material A1 was coated with a polysiloxane compound having an organic group have improved dispersibility as compared with Comparative Examples 4 to 5 in which they were not coated.
  • the resin sheets of Comparative Examples 2 to 3 coated with polyvinyl alcohol have lower dispersibility than the resin sheets of Comparative Examples 4 to 5 not coated, and the dispersibility is significantly different depending on the coating substance. I understand.
  • the resin sheets of Examples 13 to 18 in which the surface of the graphite-based exfoliated layered material is coated with a polysiloxane compound having an organic group are the resin sheets of Comparative Example 3 coated with polyvinyl alcohol and Comparative Example 5 not coated. Has a larger tensile strain and a lower surface resistivity. It is presumed that this is due to the effect of dispersibility on the resin.
  • the resin sheet of Example 21 in which the surface of the boron nitride-based exfoliated layered material is coated with the polysiloxane compound having an organic group has a larger tensile strain than the resin sheet of Comparative Example 6 which is not coated. It is presumed that this is due to the effect of dispersibility on the resin. Although there is no difference in the surface resistivity, it is presumed that the conductivity of boron nitride is originally low.
  • the dispersibility of the flaking layered material in a resin or the like is improved, and the physical properties of the obtained resin composition such as toughness, stretchability and impact resistance are significantly improved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The present invention addresses the problem of providing an exfoliated lamellar substance which, when incorporated into silicone resins, etc., has satisfactory dispersibility and is highly effective in improving physical properties. The present invention is a composite material comprising an exfoliated lamellar substance and a coating substance with which the surface of the exfoliated lamellar substance has been coated, wherein the coating substance is a polysiloxane compound having an organic group and the content of the coating substance is 0.1-100 parts by mass per 100 parts by mass of the exfoliated lamellar substance. It is preferable that the exfoliated lamellar substance have an average thickness of 1,200 nm or less and have an average area of 0.1 μm2 to 500 μm2.

Description

複合材料Composite material

　本発明は、剥片化層状物質の表面が有機基を有するポリシロキサン化合物により被覆された複合材料に関する。 The present invention relates to a composite material in which the surface of a flaky stratified material is coated with a polysiloxane compound having an organic group.

　積層物質である黒鉛を剥離して得られるグラフェン等の剥片化黒鉛は、二次電池の電極の導電助剤（例えば、特許文献１を参照）、導電性インク（例えば、特許文献２を参照）、樹脂やエラストマーのフィラー（例えば、特許文献３～４を参照）、ガスバリア材（例えば、特許文献５～６を参照）等として使用されている。層状物質は、剥片化されて薄くなり、層数が少ないほど凝集を起こしやすくなるため、マトリックスに分散しにくいという問題があり、充分な物性が得られない場合があった。凝集性や溶媒等への分散性を向上させるため、ポリビニルアルコール等の高分子で表面を被覆した剥片化黒鉛（例えば、特許文献７を参照）が検討されているが、シリコーン樹脂等に配合した場合の分散性の改善効果は充分ではなかった。また、樹脂への分散性を向上させるために層状物質の表面をシランカップリング剤で処理する方法（例えば、特許文献８を参照）も知られているが、シランカップリング剤は比較的高価であり、安価な方法が求められている。 Exfoliated graphite such as graphene obtained by exfoliating graphite, which is a laminated substance, is a conductive auxiliary agent for an electrode of a secondary battery (see, for example, Patent Document 1), a conductive ink (see, for example, Patent Document 2). , A filler of resin or elastomer (see, for example, Patent Documents 3 to 4), a gas barrier material (see, for example, Patent Documents 5 to 6), and the like. The layered substance becomes flaked and becomes thinner, and the smaller the number of layers, the more likely it is to aggregate. Therefore, there is a problem that it is difficult to disperse in the matrix, and sufficient physical properties may not be obtained in some cases. In order to improve cohesiveness and dispersibility in a solvent or the like, exfoliated graphite whose surface is coated with a polymer such as polyvinyl alcohol (see, for example, Patent Document 7) has been studied, but it has been blended with a silicone resin or the like. In this case, the effect of improving dispersibility was not sufficient. A method of treating the surface of the layered substance with a silane coupling agent to improve the dispersibility in the resin (see, for example, Patent Document 8) is also known, but the silane coupling agent is relatively expensive. Yes, there is a need for an inexpensive method.

特開２０１６－０６０８８７号公報JP, 2016-06088, A ＵＳ２０１７０１７９４９０US20170179490 ＷＯ２０１１／０８６３９１WO2011 / 086391 ＷＯ２０１３／１６５６７７WO2013 / 165677 ＵＳ２０１４０２７２３５０US20140227350 ＷＯ２０１６／１１５３７７WO2016 / 115377 ＵＳ２０１６０２００５８０US201602005580 特開２０１５－０４０２１１号公報Japanese Unexamined Patent Publication No.

　本発明の課題は、シリコーン樹脂等に配合した場合に、分散性が良好で、物性改良効果の大きな剥片化層状物質を提供することにある。 An object of the present invention is to provide a flaky layered material that has good dispersibility and a large effect of improving physical properties when blended with a silicone resin or the like.

　本発明者らは上記課題について鋭意検討を行った結果、剥片化層状物質の表面を特定の物質で被覆することにより、上記課題を解決できることを見出し、本発明を完成させた。即ち、本発明は、片化層状物質の表面が被覆物質により被覆された複合材料であって、被覆物質が、有機基を有するポリシロキサン化合物であり、剥片化層状物質１００質量部に対する被覆物質の含量が０．１質量部～１００質量部である複合材料である。 As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by coating the surface of the flaky stratified material with a specific substance, and have completed the present invention. That is, the present invention is a composite material in which the surface of a fragmentation layered material is coated with a coating material, the coating material is a polysiloxane compound having an organic group, and a coating material for 100 parts by mass of the flaking layered material is provided. It is a composite material having a content of 0.1 to 100 parts by mass.

　また、本発明は、上記複合材料と合成樹脂とを含有する樹脂組成物を提供する。 The present invention also provides a resin composition containing the above composite material and a synthetic resin.

〔剥片化層状物質〕
　本発明で用いる剥片化層状物質の原料である層状物質は、共有結合やイオン結合のような強い結合により形成されている単位層が、主に弱いファンデルワールス力を介して積層した層状構造を持つ。層状物質としては、黒鉛類、窒化ホウ素類、遷移金属ジカルコゲナイド、１３族カルコゲナイド、１４族カルコゲナイド、ビスマスカルコゲナイド、層状ハロゲン化金属、層状遷移金属酸化物、層状ペロブスカイト酸化物、粘土鉱物又は層状ケイ酸塩等が挙げられる。 [Peeled layered material]
The layered material which is the raw material of the flaky layered material used in the present invention has a layered structure in which unit layers formed by strong bonds such as covalent bonds and ionic bonds are mainly laminated via weak Van der Waals forces. To have. Examples of the layered substance include graphites, boron nitrides, transition metal dichalcogenides, group 13 chalcogenides, group 14 chalcogenides, bismuth chalcogenides, layered metal halides, layered transition metal oxides, layered perovskite oxides, clay minerals or layered silicic acid. Salt etc. are mentioned.

　黒鉛類は、炭素からなる単位層を有する層状化合物である。黒鉛類としては、黒鉛の他に、黒鉛の層間を膨張させた膨張化黒鉛や、黒鉛を酸化剤で酸化した酸化黒鉛が含まれる。 Graphites are layered compounds having a unit layer made of carbon. Examples of graphites include, in addition to graphite, expanded graphite obtained by expanding graphite layers, and oxidized graphite obtained by oxidizing graphite with an oxidizing agent.

　窒化ホウ素類は、窒素とホウ素を構成元素として含む層状物質であり、窒化ホウ素（ＢＮ）及び窒化炭素ホウ素（ＢＣＮ）等である。 Boron nitrides are layered substances containing nitrogen and boron as constituent elements, such as boron nitride (BN) and carbon nitride boron (BCN).

　遷移金属ジカルコゲナイドは、遷移金属とカルコゲンとからなる層状物質であり、式ＭＸ2で表され、式中、Ｍは遷移金属であり、Ｘはカルコゲンである。遷移金属としてはチタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、クロム、モニブデン、タングステン、テクネチウム、レニウム、ニッケル、スズ、パラジウム又は白金が挙げられる。カルコゲンとしては、硫黄、セレン又はテルルが挙げられる。遷移金属ジカルコゲナイドとしては、ＴｉＳ2、ＴｉＳｅ2、ＴｉＴｅ2、ＨｆＳ2、ＨｆＳｅ2、ＨｆＴｅ2、ＶＴｅ2、ＶＳｅ2、ＮｂＳ2、ＮｂＳｅ2、ＮｂＴｅ2、ＭｏＳ2、ＭｏＳｅ2、ＭｏＴｅ2、ＷＳ2、ＷＳｅ2、ＷＴｅ2、ＴｃＳ2、ＲｅＳｅ2、ＲｅＳ2、ＲｅＴｅ2、ＴａＳ2、ＴａＳｅ2、ＴａＴｅ2、ＰｔＴｅ2等が挙げられる。 A transition metal dichalcogenide is a layered substance composed of a transition metal and a chalcogen, and is represented by the formula MX 2 , where M is a transition metal and X is a chalcogen. Examples of the transition metal include titanium, zirconium, hafnium, vanadium, niobium, chromium, monibden, tungsten, technetium, rhenium, nickel, tin, palladium or platinum. Chalcogens include sulfur, selenium or tellurium. Examples of the transition metal dichalcogenide include TiS 2 , TiSe 2 , TiTe 2 , HfS 2 , HfSe 2 , HfTe 2 , VTe 2 , VSe 2 , NbS 2 , NbSe 2 , NbTe 2 , MoS 2 , MoSe 2 , WTe 2 , and MoTe 2 . 2 , WSe 2 , WTe 2 , TcS 2 , ReSe 2 , ReS 2 , ReTe 2 , TaS 2 , TaSe 2 , TaTe 2 , PtTe 2, and the like.

　１３族カルコゲナイドは、第１３族元素であるガリウム又はインジウムとカルコゲンとからなる層状物質であり、ＧａＳ、ＧａＳｅ、ＧａＴｅ、ＩｎＳｅ等が挙げられる。 Group 13 chalcogenide is a layered substance composed of group 13 element gallium or indium and chalcogen, and examples thereof include GaS, GaSe, GaTe, InSe and the like.

　１４族カルコゲナイドは、第１４族元素であるゲルマニウム、スズ又は鉛とカルコゲンとからなる層状物質であり、ＧｅＳ、ＳｎＳ2、ＳｎＳｅ2、ＰｂＯ等が挙げられる。 Group 14 chalcogenide is a layered substance composed of chalcogen and germanium, tin or lead, which is a group 14 element, and examples thereof include GeS, SnS 2 , SnSe 2 , and PbO.

　ビスマスカルコゲナイドは、ビスマスとカルコゲンとからなる層状物質であり、Ｂｉ2、Ｓｅ3、Ｂｉ2Ｔｅ3等が挙げられる。 Bismuth chalcogenide is a layered substance composed of bismuth and chalcogen, and examples thereof include Bi 2 , Se 3 , and Bi 2 Te 3 .

　層状ハロゲン化金属は、金属元素とハロゲンとからなる層状物質であり、ＭｇＢｒ2、ＣｄＣｌ2、ＣｄＩ2、ＡｇＦ2、ＡｓＩ3、ＡｌＣｌ3等が挙げられる。 The layered metal halide is a layered substance composed of a metal element and halogen, and examples thereof include MgBr 2 , CdCl 2 , CdI 2 , AgF 2 , AsI 3 , and AlCl 3 .

　層状遷移金属酸化物は、チタン、マンガン、モリブデン、ニオブ、バナジウム等の遷移金属の酸化物又はオキシ酸塩からなる層状物質であり、ＭｏＯ3、Ｍｏ18Ｏ52、Ｖ2Ｏ5、ＬｉＮｂＯ2、Ｋ2Ｔｉ2Ｏ5、Ｋ2Ｔｉ4Ｏ9、ＫＴｉＮｂＯ5等が挙げられる。 The layered transition metal oxide is a layered substance composed of an oxide or an oxyacid salt of a transition metal such as titanium, manganese, molybdenum, niobium, vanadium, MoO 3 , Mo 18 O 52 , V 2 O 5 , LiNbO 2 , Examples thereof include K 2 Ti 2 O 5 , K 2 Ti 4 O 9 and KTiNbO 5 .

　層状金属リン酸塩は、チタン、ジリコニウム、セレン、スズ、ジルコニウム、アルミニウム等の層状リン酸塩であり、Ｔｉ(ＨＰＯ4)2、Ｃｅ(ＨＰＯ4)2、Ｚｒ(ＨＰＯ4)2、ＡｌＨ2Ｐ3Ｏ10等が挙げられる。 The layered metal phosphate is a layered phosphate of titanium, zirconium, selenium, tin, zirconium, aluminum, etc., and is Ti (HPO 4 ) 2 , Ce (HPO 4 ) 2 , Zr (HPO 4 ) 2 , AlH 2 P 3 O 10 and the like.

　層状ペロブスカイト酸化物としては、ＫＣａ2Ｎｂ3Ｏ10、ＫＳｒ2Ｎｂ3Ｏ10、ＫＬａＮｂ2Ｏ7等が挙げられる。 Examples of the layered perovskite oxide include KCa 2 Nb 3 O 10 , KSr 2 Nb 3 O 10 and KLaNb 2 O 7 .

　粘土鉱物又は層状ケイ酸塩としては、モンモリロナイト、ノントロナイト、サポナイト等のスメクタイト類；カオリン、パイロフィライト、タルク、バーミキュライト、雲母類、脆雲母類、クロライト、セピオライト、パリゴルスカイト、イモゴライト、アロフェン、ヒシンゲライト、マガディアイト、カネマイト等が挙げられる。 Examples of clay minerals or layered silicates include smectites such as montmorillonite, nontronite, and saponite; kaolin, pyrophyllite, talc, vermiculite, mica, brittle mica, chlorite, sepiolite, palygorskite, imogolite, allophane, Hisingelite, magadiite, kanemite and the like can be mentioned.

　本発明で用いる剥片化層状物質は、上記のような層状物質が剥片化された物質であって、層状物質の単位層が１層～数千層積層した層状構造を有する物質をいう。剥片化層状物質は、層数が少なくなり、厚さが薄くなるほど物性改良効果は大きくなるが、凝集しやすくなる。このこと及び経済性の点から、本発明においては、平均厚さが０．３ｎｍ～１２００ｎｍであることが好ましく、１．５ｎｍ～４００ｎｍであることが更に好ましく、３ｎｍ～２００ｎｍであることが最も好ましい。 The flaked layered material used in the present invention is a material obtained by flaking the above layered material and having a layered structure in which one to several thousand unit layers of the layered material are laminated. The stripped layered substance has a larger effect of improving the physical properties as the number of layers decreases and the thickness decreases, but it tends to aggregate. From the viewpoint of this and economical efficiency, in the present invention, the average thickness is preferably 0.3 nm to 1200 nm, more preferably 1.5 nm to 400 nm, and most preferably 3 nm to 200 nm. .

　本発明は、凝集性が高く樹脂等への分散が困難な剥片化層状物質に対して適用されることが好ましい。このような剥片化層状物質としては、剥片化黒鉛類、剥片化窒化ホウ素類が挙げられる。中でも本発明は、剥片化黒鉛、剥片化窒化ホウ素に適用されることが好ましい。 The present invention is preferably applied to a flaky layered material that has high cohesiveness and is difficult to disperse in a resin or the like. Examples of such exfoliated layered substances include exfoliated graphite and exfoliated boron nitride. Above all, the present invention is preferably applied to exfoliated graphite and exfoliated boron nitride.

　本発明において、剥片化層状物質の厚さとは、剥片化層状物質の積層面に対して垂直方向の厚さであり、平均厚さとは、任意の３０個以上の剥片化層状物質の厚さの平均値である。剥片化層状物質の厚さは、例えば、剥片化層状物質を走査型電子顕微鏡により撮影したＳＥＭ画像を用いて測定できる。なお、剥片化層状物質の厚さが最も薄くなるのは、単位層１層のみからなる場合であるが、その厚さは剥片化層状物質によって異なり、１ｎｍ前後とされている。例えば、黒鉛の剥片化層状物質のうち、単位層１層からなる物質はグラフェンと呼ばれ、厚さは理論上、約０．３３５ｎｍである。 In the present invention, the thickness of the flaking layered material is the thickness in the direction perpendicular to the laminated surface of the flaking layered material, and the average thickness is the thickness of any 30 or more flaking layered materials. It is an average value. The thickness of the flaked layered material can be measured using, for example, an SEM image of the flaked layered material taken by a scanning electron microscope. The thickness of the flaking layered material is thinnest when it is composed of only one unit layer, but the thickness varies depending on the flaking layered material and is about 1 nm. For example, among the exfoliated layered substances of graphite, a substance composed of one unit layer is called graphene, and theoretically has a thickness of about 0.335 nm.

　剥片化層状物質の面積が小さいと、充分な物性改良効果が得られない場合があることから、剥片化層状物質の面積は大きいことが好ましい。しかし、あまりに大きい場合には、剥片化に多大の労力を要することから、本発明における剥片化層状物質の平均面積は、０．１μｍ2～５００μｍ2が好ましく、０．５μｍ2～３００μｍ2がより好ましく、１．０μｍ2～１３０μｍ2が更に好ましい。本発明において、剥片化層状物質の面積とは、剥片化層状物質を平面視した場合の投影面積であり、平均面積とは、任意の５０個以上の剥片化層状物質の面積の平均値である。剥片化層状物質の面積は、例えば、剥片化層状物質の希薄分散液を濾紙上に滴下し、剥片化層状物質をマイクロスコープにより撮影した画像を用いて測定できる。 If the area of the flaking layered material is small, a sufficient effect of improving the physical properties may not be obtained, so that the area of the flaking layered material is preferably large. However, if too large, it takes much labor to flakes of average area of flakes of layered material in the present invention is preferably 0.1μm 2 ~ 500μm 2, 0.5μm 2 ~ 300μm 2 Gayori It is preferably 1.0 μm 2 to 130 μm 2 . In the present invention, the area of the flaking layered material is a projected area when the flaking layered material is viewed in a plane, and the average area is an average value of the areas of any 50 or more flaking layered materials. . The area of the flaking layered material can be measured, for example, using an image obtained by dropping a dilute dispersion of the flaking layered material on a filter paper and photographing the flaking layered material with a microscope.

　層状物質を剥片化する方法は、特に限定されず、公知の装置により層状物質に対して剪断力、超音波振動、キャビテーション等を加えて剥片化すればよい。このような装置としては、サンドミル、アトライター、ビーズミル等の媒体撹拌ミル；回転ミル、振動ミル、遊星ミル等のボールやロッドを媒体とする容器駆動型ミル；ジェットミル、ロールミル、ハンマーミル、ピンミル、高圧乳化機、超音波乳化機等が挙げられる。高圧乳化機としては、例えば、貫通型高圧乳化機及び衝突型高圧乳化機が挙げられる。貫通型高圧乳化機の貫通形式としては、シングルノズル形式、スリットノズル形式等が挙げられる。衝突型高圧乳化機の衝突形式としては、原料を含む液を、バルブ等の平面やボール等の球面に衝突させる形式、原料を含む液同士を衝突させる形式等が挙げられる。 The method for exfoliating the layered substance is not particularly limited, and the layered substance may be exfoliated by applying shearing force, ultrasonic vibration, cavitation, etc. to the layered substance using a known device. Examples of such an apparatus include a medium agitating mill such as a sand mill, an attritor and a bead mill; a container drive type mill such as a rotary mill, a vibration mill and a planetary mill that uses balls and rods as a medium; a jet mill, a roll mill, a hammer mill, a pin mill. , A high-pressure emulsifying machine, an ultrasonic emulsifying machine and the like. Examples of the high pressure emulsifier include a through type high pressure emulsifier and a collision type high pressure emulsifier. Examples of the penetration type of the penetration type high pressure emulsifying machine include a single nozzle type and a slit nozzle type. Examples of the collision type of the collision type high pressure emulsifier include a method of causing a liquid containing a raw material to collide with a flat surface such as a valve or a spherical surface of a ball, a type of causing liquids containing the raw material to collide with each other, and the like.

　層状物質を剥片化する場合は、溶媒を用いる湿式剥片化方法、溶媒使用しない乾式剥片化方法のいずれの方法であってもよく、それぞれの装置の剥片化方法に合わせて、選択すればよい。 When flaking a layered material, either a wet flaking method using a solvent or a dry flaking method not using a solvent may be used, and the method may be selected according to the flaking method of each device.

　湿式剥片化方法に使用する溶媒としては、静電気が帯電しにくいことから、メタノール、エタノール、イソプロパノール、エチレングリコール、プロピレングリコール、メトキシエタノール等のアルコール系溶媒；アセトン、メチルエチルケトン等のケトン系溶媒；ピリジン、ピペリジン、モルホリン、テトラヒドロフラン、ジオキサン等の複素環式溶媒；１－エチル－３－メチルイミダゾリウムテトラフルオロボレート、１－ブチル－３－メチルイミダゾリウムヘキサフルオロフォスフェート等のイオン液体、ジメチルホルムアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド、水等が好ましい。 As the solvent used in the wet flaking method, since static electricity is less likely to be charged, alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, methoxyethanol; ketone solvents such as acetone and methyl ethyl ketone; pyridine; Heterocyclic solvents such as piperidine, morpholine, tetrahydrofuran, dioxane; ionic liquids such as 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, dimethylformamide, N- Methylpyrrolidone, dimethyl sulfoxide, water and the like are preferable.

　層状物質を剥片化する場合は、水溶性塩を併用してもよい。水溶性塩は、剥片化工程において、固体状の水溶性塩は剥片化を促進する媒体として機能し、溶媒に溶解した水溶性塩は層状物質の層間に作用して剥片化を促進する。剥片化後、水溶性塩は、水洗により容易に除去できる。好ましい水溶性塩としては、塩化ナトリウム、塩化カリウム、塩化マグネシウム、硫酸ナトリウム、硫酸カリウム、硫酸カルシウム、酢酸ナトリウム等が挙げられる。 When a layered material is flaked, a water-soluble salt may be used together. In the flaking step, the water-soluble salt functions as a medium that promotes flaking in the solid-state peeling step, and the water-soluble salt dissolved in the solvent acts between the layers of the layered substance to promote flaking. After the flaking, the water-soluble salt can be easily removed by washing with water. Preferred water-soluble salts include sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, potassium sulfate, calcium sulfate, sodium acetate and the like.

〔有機基を有するポリシロキサン化合物〕
　本発明において、有機基を有するポリシロキサン化合物とは、シロキサン結合（Ｓｉ－Ｏ－Ｓｉ結合）を主骨格とし、ケイ素原子に結合した有機基を有するポリマー又はオリゴマーの総称である。本発明の複合材料に用いられる有機基を有するポリシロキサン化合物の有機基としては、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、アリール基、アラルキル基等が挙げられ、これらの有機基は、水酸基、エーテル基、エステル基、エポキシ基、（メタ）クリロキシ基、カルボニル基、カルボキシル基、アミノ基、チオール基、チオエーテル基等の置換基を有してもよい。有機基としては、原料の入手が容易であることから、メチル基、エチル基、ブチル基、ビニル基、２－シクロヘキシルエチル基、２－シクロヘキセニルエチル基、フェニル基、２－フェニルエチル基、２－フェニルプロピル基、２－ノルボネニルエチル基、３－ヒドロキシプロピル基、２－（３．４－エポキシシクロヘキシル）エチル基、３－グリシドキシプロピル基、３－アクリロキシプロピル基、３－メタクリロキシプロピル基、３－（ポリオキシアルキレン）プロピル基等が好ましく、メチル基、エチル基、ビニル基、フェニル基が好ましい。また、有機基を有するポリシロキサン化合物の有機基は、樹脂への分散性の観点からは、フェニル基等のアリール基、２－フェニルエチル基、２－フェニルプロピル基等のアラルキル基が好ましい。有機基は１種のみでも、２種以上の組合せでもよいが、２種以上の組合せの場合には、樹脂への分散性の観点から、１種はアリール基又はアラルキル基であることが好ましい。有機基としてフェニル基を有する場合、化合物中のフェニル基の含量が５質量％～７０質量％であることが好ましく、６質量％～７０質量％であることが更に好ましく、８質量％～６０質量％であることが最も好ましい。化合物中のフェニル基の含量は、ポリシロキサン化合物を構成する繰り返し単位中の含量と、繰り返し単位の含有比率から計算することができる。なお、有機基が、フェニル基以外のアリール基やアラルキル基を有する場合には、ベンゼン環部分のみをフェニル基の含量に含めるものとする。フェニル基含量の異なる２種以上の有機基を有するポリシロキサン化合物を組み合わせて使用する場合、フェニル基含量は、使用する有機基を有するポリシロキサン化合物の質量比を勘案した質量平均値とする。有機基を有するポリシロキサン化合物は、ケイ素の置換基が全て有機基であってもよく、有機基に対して少数であれば、有機基の一部が水素原子、ハロゲン原子、水酸基、アルコキシ基等に置換されたものであってもよい。 [Polysiloxane Compound Having Organic Group]
In the present invention, the polysiloxane compound having an organic group is a general term for polymers or oligomers having a siloxane bond (Si—O—Si bond) as a main skeleton and having an organic group bonded to a silicon atom. Examples of the organic group of the polysiloxane compound having an organic group used in the composite material of the present invention include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group and an aralkyl group. The organic group may have a substituent such as a hydroxyl group, an ether group, an ester group, an epoxy group, a (meth) acryloxy group, a carbonyl group, a carboxyl group, an amino group, a thiol group and a thioether group. As the organic group, a methyl group, an ethyl group, a butyl group, a vinyl group, a 2-cyclohexylethyl group, a 2-cyclohexenylethyl group, a phenyl group, a 2-phenylethyl group, and 2 are easy to obtain raw materials. -Phenylpropyl group, 2-norbonenylethyl group, 3-hydroxypropyl group, 2- (3.4-epoxycyclohexyl) ethyl group, 3-glycidoxypropyl group, 3-acryloxypropyl group, 3-methacryl group Roxypropyl group, 3- (polyoxyalkylene) propyl group and the like are preferable, and methyl group, ethyl group, vinyl group and phenyl group are preferable. The organic group of the polysiloxane compound having an organic group is preferably an aryl group such as a phenyl group or an aralkyl group such as a 2-phenylethyl group or a 2-phenylpropyl group from the viewpoint of dispersibility in a resin. The organic group may be only one type or a combination of two or more types, but in the case of a combination of two or more types, one type is preferably an aryl group or an aralkyl group from the viewpoint of dispersibility in a resin. When the compound has a phenyl group as an organic group, the content of the phenyl group in the compound is preferably 5% by mass to 70% by mass, more preferably 6% by mass to 70% by mass, and 8% by mass to 60% by mass. % Is most preferred. The content of the phenyl group in the compound can be calculated from the content of the repeating units constituting the polysiloxane compound and the content ratio of the repeating units. In addition, when the organic group has an aryl group or an aralkyl group other than the phenyl group, only the benzene ring portion is included in the content of the phenyl group. When a polysiloxane compound having two or more kinds of organic groups having different phenyl group contents is used in combination, the phenyl group content is a mass average value in consideration of the mass ratio of the polysiloxane compound having an organic group to be used. In the polysiloxane compound having an organic group, all of the silicon substituents may be organic groups, and if the number of organic substituents is small, some of the organic groups are hydrogen atoms, halogen atoms, hydroxyl groups, alkoxy groups, etc. May be substituted with.

　有機基を有するポリシロキサン化合物が低分子量であると揮発しやすいことから、有機基を有するポリシロキサン化合物は、少なくともケイ素原子を５個有することが好ましく、ケイ素原子を１０個以上有することが好ましい。有機基を有するポリシロキサン化合物の分子形状は、線状、環状、分枝状、カゴ状、はしご状（ラダー状）等のいずれでもよく、これらの組合せでもよく、有機基を有するポリシロキサン化合物同士が炭化水素基等で連結された分子形状でもよい。 Since the polysiloxane compound having an organic group is likely to volatilize when it has a low molecular weight, the polysiloxane compound having an organic group preferably has at least 5 silicon atoms, and more preferably has 10 or more silicon atoms. The molecular shape of the polysiloxane compound having an organic group may be linear, cyclic, branched, cage-like, ladder-like (ladder-like), etc., and a combination thereof may be used. May have a molecular shape in which they are linked by a hydrocarbon group or the like.

〔複合材料〕
　本発明の複合材料は、剥片化層状物質の表面が有機基を有するポリシロキサン化合物で被覆されている。本発明においては、有機基を有するポリシロキサン化合物が剥片化層状物質の表面の一部を覆っていてもよく、表面の全部を覆っていてもよいが、少なくとも表面の過半を覆っていることが好ましい。さらに、有機基を有するポリシロキサン化合物が剥片化層状物質の表面を連続的に覆っていてもよいし、断続的に覆っていてもよい。 [Composite material]
In the composite material of the present invention, the surface of the flaky layered material is coated with a polysiloxane compound having an organic group. In the present invention, the polysiloxane compound having an organic group may cover a part of the surface of the flaked layered material or may cover the entire surface thereof, but at least a majority of the surface may be covered. preferable. Furthermore, the polysiloxane compound having an organic group may continuously or intermittently cover the surface of the flaking layered material.

　本発明の複合材料において、剥片化層状物質１００質量部に対する有機基を有するポリシロキサン化合物の含量は０．１量部～１００質量部である。有機基を有するポリシロキサン化合物の含量が０．１質量部よりも少ない場合には、有機基を有するポリシロキサン化合物による被覆が不十分になる場合があり、１００質量部よりも多い場合は、使用量に見合う増量効果は得られないばかりか、本発明の複合材料を樹脂等に添加して用いる場合、樹脂等の物性に悪影響を及ぼすことがある。剥片化層状物質１００質量部に対する有機基を有するポリシロキサン化合物の含量は、０．２質量部～７０質量部が好ましく、０．５質量部～６０質量部が更に好ましく、１質量部～５０質量部が最も好ましい。 In the composite material of the present invention, the content of the polysiloxane compound having an organic group is 100 parts by mass to 100 parts by mass with respect to 100 parts by mass of the flaked layered material. When the content of the polysiloxane compound having an organic group is less than 0.1 parts by mass, the coating with the polysiloxane compound having an organic group may be insufficient, and when it is more than 100 parts by mass, use Not only the effect of increasing the amount corresponding to the amount cannot be obtained, but when the composite material of the present invention is used by adding it to a resin or the like, it may adversely affect the physical properties of the resin or the like. The content of the polysiloxane compound having an organic group is preferably 0.2 parts by mass to 70 parts by mass, more preferably 0.5 parts by mass to 60 parts by mass, and further preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the flaking layered material. Parts are most preferred.

〔複合材料の製造方法〕
　剥片化層状物質を、有機基を有するポリシロキサン化合物で被覆する方法としては、例えば、有機基を有するポリシロキサン化合物と剥片化層状物質を、溶媒中で分散、混合し、被覆する方法（以下、混合被覆法という。）、剥片化層状物質の水分散液に加水分解性シラン化合物を添加し、加水分解性シラン化合物を加水分解・縮合反応（いわゆるゾル－ゲル反応）させて、生成した有機基を有するポリシロキサン化合物により被覆する方法（以下、ゾル－ゲル被覆法という。）等が挙げられる。 [Method of manufacturing composite material]
As a method of coating the flaking layered material with a polysiloxane compound having an organic group, for example, a method of dispersing and mixing a polysiloxane compound having an organic group and a flaking layered material in a solvent, and coating (hereinafter, Mixed coating method), an organic group produced by adding a hydrolyzable silane compound to an aqueous dispersion of flaky layered material and subjecting the hydrolyzable silane compound to a hydrolysis / condensation reaction (so-called sol-gel reaction). And the like (hereinafter referred to as sol-gel coating method).

＜混合被覆法＞
　剥片化層状物質は、凝集して二次粒子を形成しやすいため、剥片化層状物質を、有機基を有するポリシロキサン化合物の溶液又は分散液に、単に浸漬するだけでは、被覆が不十分である。そのため、有機基を有するポリシロキサン化合物の溶液又は分散液中で、剥片化層状物質の二次粒子を解砕して被覆する、又は剥片化層状物質の二次粒子を解砕して得られた分散液に有機基を有するポリシロキサン化合物を添加することが好ましい。剥片化層状物質の二次粒子を解砕するためには、剥片化層状物質を含有する液に、分散装置を用いて、剪断力、超音波振動、キャビテーション等を加える必要がある。そのための分散装置としては、ホモミキサー等の高速回転剪断型撹拌機；サンドミル、アトライター、ビーズミル等の媒体撹拌ミル；回転ミル、振動ミル、遊星ミル等のボールやロッドを媒体とする容器駆動型ミル；コロイドミル、高圧乳化機、超音波乳化機等が挙げられる。高圧乳化機としては、例えば、貫通型高圧乳化機及び衝突型高圧乳化機が挙げられる。貫通型高圧乳化機の貫通形式としては、シングルノズル形式等が挙げられる。衝突型高圧乳化機の衝突形式としては、原料を含む液を、バルブ等の平面やボール等の球面に衝突させる形式、原料を含む液同士を衝突させる形式等が挙げられる。剥片化層状物質に強い剪断力が加わった場合には、被覆前よりも、剥片化層状物質の層数、厚さ、粒子径等が低下する場合がある。 <Mixed coating method>
Since the flaking layered material easily aggregates to form secondary particles, the coating is insufficient by simply immersing the flaking layered material in a solution or dispersion of a polysiloxane compound having an organic group. . Therefore, it was obtained by crushing and coating the secondary particles of the flaked layered material in a solution or dispersion of a polysiloxane compound having an organic group, or by crushing the secondary particles of the flaked layered material. It is preferable to add a polysiloxane compound having an organic group to the dispersion liquid. In order to disintegrate the secondary particles of the flaking layered material, it is necessary to apply shearing force, ultrasonic vibration, cavitation, etc. to the liquid containing the flaking layered material using a dispersion device. As a dispersing device therefor, a high-speed rotary shearing type agitator such as a homomixer; a medium agitating mill such as a sand mill, an attritor, or a bead mill; Mill; colloid mill, high-pressure emulsifying machine, ultrasonic emulsifying machine and the like. Examples of the high pressure emulsifier include a through type high pressure emulsifier and a collision type high pressure emulsifier. Examples of the penetration type of the penetration type high pressure emulsifying machine include a single nozzle type. Examples of the collision type of the collision type high pressure emulsifier include a method of causing a liquid containing a raw material to collide with a flat surface such as a valve or a spherical surface of a ball, a type of causing liquids containing the raw material to collide with each other, and the like. When a strong shearing force is applied to the exfoliated layered material, the number of layers, the thickness, the particle size, etc. of the exfoliated layered material may be lower than before coating.

　混合被覆法において、剥片化層状物質の二次粒子を解砕して得られた分散液に有機基を有するポリシロキサン化合物を添加する場合には、有機基を有するポリシロキサン化合物の溶解、分散が容易になることから、剥片化層状物質を解砕した後、解砕に用いた分散装置をそのまま用いてもよい。 In the mixed coating method, when the polysiloxane compound having an organic group is added to the dispersion obtained by crushing the secondary particles of the flaky layered material, the polysiloxane compound having an organic group is dissolved or dispersed. Since it becomes easy, the dispersal device used for disintegration may be used as it is after disintegrating the flaky layered material.

　混合被覆法に用いる溶媒は、有機基を有するポリシロキサン化合物を溶解可能な溶媒だけでなく、分散装置を用いて有機基を有するポリシロキサン化合物を分散可能で溶解であれば、有機基を有するポリシロキサン化合物を溶解できない溶媒も使用可能であり、除去のしやすさ、安全性（毒性、引火性、帯電性等）等を考慮して選択すればよい。混合被覆法に用いられる溶媒としては、メタノール、エタノール、イソプロパノール、メトキシエタノール等のアルコール系溶媒；アセトン、メチルエチルケトン等のケトン系溶媒；水等が挙げられる。剥片化層状物質と溶媒若しくは有機基を有するポリシロキサン化合物の溶液との比は、粉砕装置により異なるが、剥片化層状物質１００質量部に対して、溶媒若しくは有機基を有するポリシロキサン化合物の溶液２００質量部～５０００質量部程度であることが好ましい。 The solvent used in the mixed coating method is not only a solvent capable of dissolving the polysiloxane compound having an organic group, but also a polysiloxane compound having an organic group if it is dispersible and soluble using a dispersing device. A solvent that does not dissolve the siloxane compound can also be used, and may be selected in consideration of ease of removal, safety (toxicity, flammability, chargeability, etc.). Examples of the solvent used in the mixed coating method include alcohol solvents such as methanol, ethanol, isopropanol, and methoxyethanol; ketone solvents such as acetone and methylethylketone; and water. Although the ratio of the flaking layered material to the solvent or the solution of the polysiloxane compound having an organic group varies depending on the pulverizing device, the solution of the polysiloxane compound having a solvent or an organic group to 100 parts by mass of the flaking layered material 200 It is preferable that the amount is about from 5,000 to 5,000.

　剥片化層状物質と有機基を有するポリシロキサン化合物とを混合した後、溶媒を除去して本発明の複合材料が得られる。溶媒を除去する方法は、特に限定されず、加熱乾燥、減圧乾燥、噴霧乾燥、凍結乾燥等の方法、又はこれらの方法を組み合わせて適用すればよい。溶媒を除去する前に、必要に応じて、濾過や遠心分離等により、過剰の有機基を有するポリシロキサン化合物と溶媒の一部を除去してから、残りの溶媒を除去してもよい。本発明の複合材料は、必要に応じて、粉砕、造粒を行ってもよい。 After mixing the flaking layered material and the polysiloxane compound having an organic group, the solvent is removed to obtain the composite material of the present invention. The method of removing the solvent is not particularly limited, and heat drying, reduced pressure drying, spray drying, freeze drying, or the like, or a combination of these methods may be applied. Before removing the solvent, if necessary, the polysiloxane compound having an excess organic group and a part of the solvent may be removed by filtration or centrifugation, and then the remaining solvent may be removed. The composite material of the present invention may be pulverized and granulated if necessary.

＜ゾル－ゲル被覆法＞
　ゾル－ゲル被覆法の場合も、水を溶媒として剥片化層状物質の二次粒子を解砕してから、加水分解性シラン化合物をゾル－ゲル反応させる。解砕に用いる分散装置としては、混合被覆法で例示した分散装置が挙げられる。ゾル－ゲル被覆法の場合も、混合被覆法の場合と同様に、劈開で剥片化層状物質に強い剪断力が加わった場合には、被覆前よりも、剥片化層状物質の層数、厚さ、粒子径等が低下する場合がある。 <Sol-gel coating method>
Also in the case of the sol-gel coating method, the secondary particles of the flaked layered material are crushed using water as a solvent, and then the hydrolyzable silane compound is subjected to a sol-gel reaction. Examples of the disperser used for the crushing include the dispersers exemplified in the mixed coating method. Also in the case of the sol-gel coating method, as in the case of the mixed coating method, when a strong shearing force is applied to the exfoliated layered material by cleavage, the number of layers and the thickness of the exfoliated layered material are larger than those before the coating. The particle size may decrease.

　加水分解性シラン化合物は、加水分解によりシラノール（Ｓｉ－ＯＨ）基が生成する基を有するシラン化合物であり、シラノール基が脱水縮合してシロキサン基が生成する。加水分解性シラン化合物は、有機基を有するポリシロキサン化合物に導入する有機基の他に、加水分解性基及び有機基を有するポリシロキサン化合物の構造を考慮して選択すればよい。 A hydrolyzable silane compound is a silane compound having a group in which a silanol (Si-OH) group is formed by hydrolysis, and a silanol group is dehydrated and condensed to form a siloxane group. The hydrolyzable silane compound may be selected in consideration of the structure of the polysiloxane compound having a hydrolyzable group and an organic group in addition to the organic group introduced into the polysiloxane compound having an organic group.

　加水分解性シラン化合物の、加水分解性基としては、メトシキシリル基、エトシキシリル基、プロポキシシリル基、メトキシエトキシシリル基等のアルコキシシリル基；クロロシリル基、ブロモシリル基等のハロシリル基；アセチロキシシリル基等のアシロキシシリル基；ジメチルアミノシリル基、シクロヘキシルアミノシリル基等のアミノシリル基等が挙げられる。中でも、装置に対する腐食が少なく、加水分解反応が速く、工業的な入手が容易であることから、アルコキシシリル基が好ましく、メトシキシリル基、エトシキシリル基が更に好ましい。 Examples of the hydrolyzable group of the hydrolyzable silane compound include an alkoxysilyl group such as a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a methoxyethoxysilyl group; a halosilyl group such as a chlorosilyl group and a bromosilyl group; and an acetyloxysilyl group. An acyloxysilyl group; an aminosilyl group such as a dimethylaminosilyl group and a cyclohexylaminosilyl group. Of these, an alkoxysilyl group is preferable, and a methoxysilyl group and an ethoxysilyl group are more preferable, because they are less corrosive to the apparatus, have a rapid hydrolysis reaction, and are easily industrially available.

　本発明では、加水分解性シラン化合物を有機基と加水分解性基の数により、有機基が３つで加水分解性基が１つのものをＭ型シラン化合物、有機基が２つで加水分解性基が２つのものをＤ型シラン化合物、有機基が１つで加水分解性基が３つのものをＴ型シラン化合物、加水分解性基が４つのものをＱ型シラン化合物という。ゾル－ゲル反応により得られる有機基を有するポリシロキサン化合物の構造は、使用する加水分解性シラン化合物の加水分解性基の数により大きな影響を受ける。例えば、Ｄ型シラン化合物のみを用いた場合には、高分子量で直鎖状の有機基を有するポリシロキサン化合物が得られ、Ｔ型シラン化合物のみを用いた場合には、カゴ状の有機基を有するポリシロキサン化合物が得られる。ゾル－ゲル被覆法に使用する加水分解性シラン化合物としては、剥片化層状物質上に高分子量の有機基を有するポリシロキサン化合物の被膜が形成できることから、Ｄ型シラン化合物が好ましく、異なる型の加水分解性シラン化合物を組み合わせて使用する場合には、少なくとも１種はＤ型シラン化合物であることが好ましい。好ましいＤ型シラン化合物としては、ジメチルジメトキシシラン、ジメチルジエトキシシラン、メチルフェニルジメトキシシラン、メチルフェニルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン等が挙げられる。 In the present invention, a hydrolyzable silane compound is an M-type silane compound having three organic groups and one hydrolyzable group, and a hydrolyzable silane compound having two organic groups depending on the number of organic groups and hydrolyzable groups. A compound having two groups is called a D-type silane compound, a compound having one organic group and three hydrolyzable groups is called a T-type silane compound, and a compound having four hydrolyzable groups is called a Q-type silane compound. The structure of the polysiloxane compound having an organic group obtained by the sol-gel reaction is greatly influenced by the number of hydrolyzable groups of the hydrolyzable silane compound used. For example, when only the D-type silane compound is used, a polysiloxane compound having a high molecular weight and linear organic group is obtained, and when only the T-type silane compound is used, a cage-shaped organic group is obtained. A polysiloxane compound having is obtained. As the hydrolyzable silane compound used in the sol-gel coating method, a D-type silane compound is preferable because a film of a polysiloxane compound having a high-molecular weight organic group can be formed on the flaky stratified material, and a hydrolyzable silane compound having a different type is used. When a decomposable silane compound is used in combination, at least one type is preferably a D-type silane compound. Examples of preferable D-type silane compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like.

　ゾル－ゲル被覆法では、剥片化層状物質が、二次粒子が解砕されて一次粒子の状態で分散された水に、加水分解性シラン化合物を添加してゾル－ゲル反応が起こり、剥片化層状物質の表面に有機基を有するポリシロキサン化合物の被膜が形成される。使用する水は、水単独でもよいし、メタノール、エタノール、イソプロパノール等の水に可溶な溶媒を含む水でもよい。また、使用する水は、反応を促進するために、触媒として、塩酸、リン酸、硫酸等の無機酸類；ギ酸、酢酸、シュウ酸、クエン酸、メタンスルホン酸、ベンゼンスルホン酸等の有機酸類；水酸化ナトリウム、水酸化カリウム、水酸化リチウム、アンモニア等の無機塩基類等を含んでいてもよい。ゾル－ゲル反応の温度は、加水分解性シラン化合物の種類、触媒の種類及び量等により変わるが、５～５０℃が好ましく、８～３０℃が更に好ましい。 In the sol-gel coating method, the flaky layered material is separated into water in which secondary particles are crushed and dispersed in the state of primary particles, to which a hydrolyzable silane compound is added to cause a sol-gel reaction to cause flaking. A film of a polysiloxane compound having an organic group is formed on the surface of the layered material. The water used may be water alone or water containing a water-soluble solvent such as methanol, ethanol, or isopropanol. In addition, the water used is, as a catalyst, inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid to accelerate the reaction; organic acids such as formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, and benzenesulfonic acid; Inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia may be contained. The temperature of the sol-gel reaction varies depending on the type of hydrolyzable silane compound, the type and amount of catalyst, etc., but is preferably 5 to 50 ° C., more preferably 8 to 30 ° C.

　ゾル－ゲル反応が完了した後は、必要に応じて、濾過、洗浄を行った後、乾燥を行う、乾燥方法は、特に限定されず、加熱乾燥、減圧乾燥、噴霧乾燥、凍結乾燥等の方法、又はこれらの方法を組み合わせて適用すればよい。また、本発明の複合材料は、必要に応じて、粉砕、造粒を行ってもよい。 After the sol-gel reaction is completed, if necessary, filtration and washing are performed, and then drying is performed. The drying method is not particularly limited, and methods such as heat drying, reduced pressure drying, spray drying, and freeze drying are used. Alternatively, these methods may be applied in combination. Further, the composite material of the present invention may be pulverized and granulated, if necessary.

　本発明の複合材料は、剥片化層状物質の表面が有機基を有するポリシロキサン化合物により被覆されることにより、剥片化層状物質の凝集が起こらず、基材への分散性が大幅に改善される。これにより、剥片化層状物質による物性の改善効果、例えば、導電性、放熱性、機械物性（耐衝撃性、曲げ強度、圧縮強度等）等を向上することができる。本発明の複合材料は、合成樹脂等の樹脂、エラストマー、塗料等の添加剤；電池用電極の導電性添加剤等の用途に好適に使用できる。 In the composite material of the present invention, the surface of the flaking layered material is coated with the polysiloxane compound having an organic group, so that the flaking layered material does not aggregate and the dispersibility in the substrate is significantly improved. . As a result, the effect of improving the physical properties of the flaking layered material, such as conductivity, heat dissipation, mechanical properties (impact resistance, bending strength, compressive strength, etc.), can be improved. The composite material of the present invention can be suitably used for applications such as resins such as synthetic resins, additives such as elastomers and paints; conductive additives for battery electrodes.

〔樹脂組成物〕
　本発明の樹脂組成物は、本発明の複合材料と合成樹脂とを含有する。本発明の樹脂組成物に好ましく使用できる合成樹脂としては、フェノール樹脂、エポキシ樹脂、メラミン樹脂、ユリア樹脂、アルキッド樹脂、ＰＥＴ樹脂、ＰＢＴ樹脂、ポリカーボネート樹脂、ポリアセタール樹脂、変性ポリフェニレンエーテル樹脂、ポリウレタン、ポリイミド、ポリイミドアミド、ポリエーテルイミド、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリ酢酸ビニル、フッ素系樹脂、ＡＢＳ樹脂、ＡＳ樹脂、アクリル樹脂、シリコーン等が挙げられ、本発明の複合材料は、特に、シリコーン樹脂への分散性が良好である。 [Resin composition]
The resin composition of the present invention contains the composite material of the present invention and a synthetic resin. Examples of the synthetic resin that can be preferably used in the resin composition of the present invention include phenol resin, epoxy resin, melamine resin, urea resin, alkyd resin, PET resin, PBT resin, polycarbonate resin, polyacetal resin, modified polyphenylene ether resin, polyurethane, and polyimide. , Polyimide amide, polyether imide, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, fluorine resin, ABS resin, AS resin, acrylic resin, silicone, and the like. The composite material of the present invention is particularly Good dispersibility in silicone resin.

　本発明の樹脂組成物の樹脂が熱可塑性樹脂の場合には、他の添加剤と同様に、本発明の複合材料を、樹脂と添加剤を混練する工程で配合すればよく、熱硬化性樹脂の場合には、未硬化の樹脂に本発明の複合材料を配合してから樹脂を硬化させればよい。例えば、本発明の複合材料とシリコーン樹脂とを含有する樹脂組成物の場合、未硬化のシリコーン樹脂組成物に他の添加剤と共に本発明の複合材料を配合してから、加熱等の方法により硬化させればよい。未硬化のシリコーン樹脂組成物としては、例えば、ヒドロシリル基（ＳｉＨ基）を有するポリシロキサン化合物、ビニル基（ＣＨ2＝ＣＨ－基）を有するポリシロキサン化合物及びヒドロシリル化触媒を含む付加硬化型組成物；メチルシリル基（Ｓｉ－ＣＨ3基）を有するポリシロキサン化合物及び過酸化物触媒を含む縮合硬化型組成物；メチルシリル基を有するポリシロキサン化合物、ビニルシリル基を有するポリシロキサン化合物及び過酸化物触媒を含む縮合硬化型組成物；加水分解－縮合型ポリシロキサン化合物を含む湿気硬化型組成物、（メタ）アクリル基含有ポリシロキサン化合物を含む光硬化型組成物等が挙げられる。 When the resin of the resin composition of the present invention is a thermoplastic resin, the composite material of the present invention may be blended in the step of kneading the resin and the additive, as in the case of other additives. In this case, the resin may be cured after blending the composite material of the present invention with the uncured resin. For example, in the case of a resin composition containing the composite material of the present invention and a silicone resin, the composite material of the present invention is added to an uncured silicone resin composition together with other additives, and then cured by a method such as heating. You can do it. The uncured silicone resin composition is, for example, an addition-curable composition containing a polysiloxane compound having a hydrosilyl group (SiH group), a polysiloxane compound having a vinyl group (CH 2 ═CH-group), and a hydrosilylation catalyst. A condensation-curable composition containing a polysiloxane compound having a methylsilyl group (Si—CH 3 group) and a peroxide catalyst; a polysiloxane compound having a methylsilyl group, a polysiloxane compound having a vinylsilyl group, and a peroxide catalyst Condensation curable composition; a moisture curable composition containing a hydrolysis-condensation type polysiloxane compound, a photocurable composition containing a (meth) acrylic group-containing polysiloxane compound, and the like.

　本発明の複合材料の添加量は、樹脂の種類や求められる物性に応じて異なるが、合成樹脂１００質量部に対して、本発明の複合材料１～１５０質量部であることが好ましく、２～１００質量部であることがより好ましい。 The amount of the composite material of the present invention added varies depending on the type of resin and the required physical properties, but is preferably 1 to 150 parts by mass of the composite material of the present invention with respect to 100 parts by mass of the synthetic resin. It is more preferably 100 parts by mass.

　本発明の樹脂組成物においては、樹脂としてシリコーン樹脂を用いた樹脂組成物が好ましい。このような樹脂組成物は耐熱性が優れていることから、例えば、半導体の封止材料、放熱シート等として好適に使用できる。 In the resin composition of the present invention, a resin composition using a silicone resin as a resin is preferable. Since such a resin composition has excellent heat resistance, it can be suitably used as, for example, a sealing material for semiconductors, a heat dissipation sheet, or the like.

　以下に、実施例及び比較例により本発明を更に詳細に説明する。ただし、以下の実施例等により本発明は何ら制限されない。
　以下の実施例等において、剥片化層状物質の平均厚さは、走査型電子顕微鏡により撮影したＳＥＭ画像を用いて測定した、任意の３０個の剥片化層状物質の厚さの平均値である。また、剥片化層状物質の平均面積は、剥片化層状物質の希薄分散液を濾紙上に滴下し、剥片化層状物質をマイクロスコープにより撮影した画像を用いて測定した、任意の５０個の剥片化層状物質の面積の平均値である。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.
In the following examples and the like, the average thickness of the flaking layered material is an average value of the thickness of any 30 pieces of the flaking layered material measured using an SEM image taken by a scanning electron microscope. Further, the average area of the flaking layered material was measured by using a thin dispersion of the flaking layered material dropped on a filter paper and measuring the flaking layered material with an image taken by a microscope. It is the average value of the area of the layered material.

〔製造例１〕
　国際公開第２０１３／１７２３５０号に記載された実施例１に準じて、天然黒鉛から剥片化層状物質Ａ１を調製した。即ち、１－ブチル－３－メチルイミダゾリウムヘキサフルオロフォスフェート７４質量部と、ポリエチレングリコール（富士フイルム和光純薬製、製品名：ポリエチレングリコール２００００）２６質量部とを混合して加熱溶解し、天然黒鉛（富士フイルム和光純薬製）１０質量部を分散させた。この分散液０．６ｇを０．５ｃｍ3のバイアル瓶に採取し、フタをした後、マイクロウェーブ合成装置（バイオタージ・ジャパン製　Ｉｎｉｔｉａｔｏｒ＋）を用いて、分散液に２４５０ＭＨｚのマイクロ波を、１７０℃で３０分間照射した。この後、分散液を濾過してアセトンで洗浄し、オーブンで加熱乾燥することで、天然黒鉛由来の剥片化層状物質Ａ１を得た。剥片化層状物質Ａ１の平均厚さは１２３ｎｍ、平均面積は１１．６μｍ2であった。 [Production Example 1]
In accordance with Example 1 described in WO 2013/172350, a flaked layered material A1 was prepared from natural graphite. That is, 74 parts by mass of 1-butyl-3-methylimidazolium hexafluorophosphate and 26 parts by mass of polyethylene glycol (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd., product name: polyethylene glycol 20000) are mixed, heated and dissolved to give a natural mixture. 10 parts by mass of graphite (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was dispersed. 0.6 g of this dispersion was collected in a 0.5 cm 3 vial, and after covering with a lid, a microwave of 2450 MHz was applied to the dispersion at 170 ° C. using a microwave synthesizer (Initiator + manufactured by Biotage Japan). For 30 minutes. Then, the dispersion was filtered, washed with acetone, and dried by heating in an oven to obtain a flaked layered material A1 derived from natural graphite. The exfoliated layered material A1 had an average thickness of 123 nm and an average area of 11.6 μm 2 .

〔製造例２〕
　天然黒鉛の代わりに、膨張化黒鉛（株式会社伊藤黒鉛工業製、品名：ＥＣ１５００）を使用した以外は、製造例１と同様の操作を行い、膨張化黒鉛由来の剥片化層状物質Ａ２を得た。剥片化層状物質Ａ２の平均厚さは３０ｎｍ、平均面積は１．４μｍ2であった。 [Production Example 2]
Exfoliated layered material A2 derived from expanded graphite was obtained by performing the same operation as in Production Example 1 except that expanded graphite (manufactured by Ito Graphite Industry Co., Ltd., product name: EC1500) was used instead of natural graphite. . The exfoliated layered material A2 had an average thickness of 30 nm and an average area of 1.4 μm 2 .

〔製造例３〕
　天然黒鉛の代わりに、窒化ホウ素（アルドリッチ社製）を使用した以外は、製造例１と同様の操作を行い、窒化ホウ素由来の剥片化層状物質Ａ３を得た。剥片化層状物質Ａ３の平均厚さは１８３ｎｍ、平均面積は１０．３μｍ2であった。 [Production Example 3]
Except for using boron nitride (manufactured by Aldrich) instead of natural graphite, the same operation as in Production Example 1 was performed to obtain a flaked layered material A3 derived from boron nitride. The exfoliated layered material A3 had an average thickness of 183 nm and an average area of 10.3 μm 2 .

〔実施例１～９及び比較例１〕
　上記剥片化層状物質、下記被覆物質及び溶媒を、表１に示す質量比でビーズミル（寿工業製、商品名：ＵＡＭ－０１５）に仕込み、剥片化層状物質の二次粒子の解砕処理を行い、加熱減圧乾燥により溶媒を除去して、実施例１～９及び比較例１の複合材料を製造した。
　表１において、カッコ内の数字は質量比を表し、溶媒のＭＥＫはメチルエチルケトンを表す。比較例１は被覆物質としてポリビニルアルコールを用いた実験例であるが、粉状でメチルエチルケトンに溶解しないことから溶媒として水のみを用いた。 [Examples 1 to 9 and Comparative Example 1]
The above flaked layered substance, the following coating substance and solvent were charged into a bead mill (manufactured by Kotobuki Kogyo, trade name: UAM-015) at the mass ratio shown in Table 1, and the secondary particles of the flaked layered substance were crushed. Then, the solvent was removed by heating under reduced pressure, and the composite materials of Examples 1 to 9 and Comparative Example 1 were manufactured.
In Table 1, the numbers in parentheses represent mass ratios, and MEK of the solvent represents methyl ethyl ketone. Comparative Example 1 is an experimental example in which polyvinyl alcohol was used as the coating substance, but only water was used as the solvent because it was powdery and did not dissolve in methyl ethyl ketone.

＜被覆物質＞
　Ｂ１：ジフェニルシロキサン－ジメチルシロキサン共重合体
　（フェニル基含量：３１質量％、Ｇｅｌｅｓｔ社製、商品名：ＰＤＭ－１９２２）
　Ｂ２：フェニルメチルシロキサン－ジメチルシロキサン共重合体
　（フェニル基含量：１０質量％、Ｇｅｌｅｓｔ社製、商品名：ＰＭＭ－１０１５）
　Ｂ３：フェニルメチルシロキサン重合体
　（フェニル基含量：５６質量％、Ｇｅｌｅｓｔ社製、商品名：ＰＭＭ－００２１）
　Ｂ４：シラノール末端ジフェニルシロキサン－ジメチルシロキサン共重合体
　（フェニル基含量：２６質量％、Ｇｅｌｅｓｔ社製、商品名：ＰＤＳ－１６１５）
　Ｂ５：ビニル末端ジフェニルシロキサン－ジメチルシロキサン共重合体
　（フェニル基含量：２２質量％、ＡＢ　Ｓｐｅｃｉａｌｔｙ　Ｓｉｌｉｃｏｎｅｓ製、商品名:Ａｎｄｉｓｉｌ　ＳＦ２４３０ＣＶ）
　Ｃ１：ポリビニルアルコール（株式会社クラレ製、商品名：ＰＶＡ２１７） <Coating substance>
B1: Diphenylsiloxane-dimethylsiloxane copolymer (phenyl group content: 31% by mass, Gelest, trade name: PDM-1922)
B2: Phenylmethylsiloxane-dimethylsiloxane copolymer (phenyl group content: 10% by mass, manufactured by Gelest, trade name: PMM-1015)
B3: Phenylmethylsiloxane polymer (phenyl group content: 56% by mass, Gelest, trade name: PMM-0021)
B4: Silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer (phenyl group content: 26% by mass, Gelest, trade name: PDS-1615)
B5: Vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer (phenyl group content: 22% by mass, manufactured by AB Specialty Silicones, trade name: Andisil SF2430CV)
C1: Polyvinyl alcohol (Kuraray Co., Ltd., trade name: PVA217)

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

〔実施例１０〕
　剥片化層状物質Ａ１を７０質量部及び水１４００質量部を、ビーズミル（寿工業製、商品名：ＵＡＭ－０１５）を用いて、剥片化層状物質の二次粒子の解砕処理を行った。剥片化層状物質の分散液１４７質量部、ジメチルジエトキシシラン４質量部、ジフェニルジメトキシシラン１．２質量部、および８５％リン酸０．０５質量部をガラス製容器に仕込み、１０℃にて３時間、次いで３０℃で時間、撹拌して実施例１０の複合材料を製造した。なお、実施例１０の有機基を有するポリシロキサン化合物のフェニル基含量は２５質量％であった。 [Example 10]
70 parts by mass of the flaked layered substance A1 and 1400 parts by mass of water were subjected to a crushing treatment of secondary particles of the flaked layered substance using a bead mill (manufactured by Kotobuki Industries, trade name: UAM-015). A glass container was charged with 147 parts by mass of the exfoliated layered material dispersion, 4 parts by mass of dimethyldiethoxysilane, 1.2 parts by mass of diphenyldimethoxysilane, and 0.05 parts by mass of 85% phosphoric acid. The composite material of Example 10 was prepared by stirring for an hour and then at 30 ° C. for an hour. The phenyl group content of the polysiloxane compound having an organic group of Example 10 was 25% by mass.

〔樹脂組成物の作製〕
　表２に示す複合材料又は剥片化層状物質１０質量部もしくは３０質量部、付加硬化型シリコーン樹脂（信越化学工業製、商品名：ＫＥ－１０９Ｅ－Ａ／Ｂ）１００質量部を、遊星式撹拌脱泡装置を用いて混合した。この混合物を温度１００℃、圧力５ＭＰａで１時間加熱し、熱プレス硬化させて厚さ２ｍｍのシート状の樹脂組成物である、実施例１１～２１及び比較例２～５の樹脂シートを作製した。 [Preparation of resin composition]
10 parts by mass or 30 parts by mass of the composite material or flaking layered substance shown in Table 2 and 100 parts by mass of an addition-curable silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KE-109E-A / B) were removed by planetary stirring. Mix using a foam device. This mixture was heated at a temperature of 100 ° C. and a pressure of 5 MPa for 1 hour and heat-press-cured to prepare resin sheets in a sheet shape having a thickness of 2 mm, Examples 11 to 21 and Comparative Examples 2 to 5. .

〔分散性の評価〕
　作製した樹脂シートを、クライオミクロトームを用いて切断し、マイクロスコープを用いて断面の中央部を撮影し、画像解析ソフトにより、３００μｍ×３００μｍあたりの凝集物数と、凝集物比を測定した。なお、凝集物数は、面積４０μｍ2以上の粒子を凝集物とした場合の数、凝集物比は、全粒子の面積の合計に対する凝集物の面積の合計の比（％）である。凝集物数が多く、凝集物比が大きいほど凝集物の割合が多いことを示す。結果を表２に示す。 [Evaluation of dispersibility]
The produced resin sheet was cut using a cryomicrotome, the central portion of the cross section was photographed using a microscope, and the number of aggregates per 300 μm × 300 μm and the aggregate ratio were measured by image analysis software. The number of aggregates is the number when particles having an area of 40 μm 2 or more are aggregates, and the aggregate ratio is the ratio (%) of the total area of aggregates to the total area of all particles. The larger the number of aggregates and the larger the ratio of aggregates, the larger the proportion of aggregates. The results are shown in Table 2.

Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

　比較例４、５の樹脂シートは剥片化層状物質Ａ１、実施例１１～１９及び比較例２～３の樹脂シートは剥片化層状物質Ａ１由来の複合材料を用いた例であり、実施例２０の樹脂シートは剥片化層状物質Ａ２、実施例２１の樹脂シートは剥片化層状物質Ａ３由来の複合材料を用いた例である。剥片化層状物質Ａ１を、有機基を有するポリシロキサン化合物で被覆した実施例１１～１９の樹脂シートは、被覆していない比較例４～５よりも分散性が向上している。ポリビニルアルコールで被覆した比較例２～３の樹脂シートは、被覆していない比較例４～５の樹脂シートよりも、分散性が低下しておりしており、被覆物質により分散性が大きく異なることが分かる。 The resin sheets of Comparative Examples 4 and 5 are exfoliated layered substances A1, and the resin sheets of Examples 11 to 19 and Comparative Examples 2 to 3 are examples using composite materials derived from the exfoliated layered substances A1. The resin sheet is an example using the flaking layered material A2, and the resin sheet of Example 21 is an example using a composite material derived from the flaking layered material A3. The resin sheets of Examples 11 to 19 in which the exfoliated layered material A1 was coated with a polysiloxane compound having an organic group have improved dispersibility as compared with Comparative Examples 4 to 5 in which they were not coated. The resin sheets of Comparative Examples 2 to 3 coated with polyvinyl alcohol have lower dispersibility than the resin sheets of Comparative Examples 4 to 5 not coated, and the dispersibility is significantly different depending on the coating substance. I understand.

〔機械的物性の評価〕
　作製した樹脂シートをダンベル状（２号）に加工し、ＪＩＳ　Ｋ６２５１（加硫ゴムおよび熱可塑性ゴム－引張特性の求め方）に準じ、引張ひずみを測定した。結果を表３に示す。 [Evaluation of mechanical properties]
The produced resin sheet was processed into a dumbbell shape (No. 2), and the tensile strain was measured according to JIS K6251 (vulcanized rubber and thermoplastic rubber—method for determining tensile properties). The results are shown in Table 3.

〔電気特性の評価〕
　ＪＩＳ　Ｋ７１９４（導電性プラスチックの４探針法による抵抗率試験方法）に準じ、４探針法により表面抵抗値を測定した。結果を表３に示す。 [Evaluation of electrical characteristics]
The surface resistance value was measured by the four-point probe method in accordance with JIS K7194 (Method for testing resistivity of conductive plastic by the four-point probe method). The results are shown in Table 3.

Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

　黒鉛系の剥片化層状物質の表面を、有機基を有するポリシロキサン化合物で被覆した実施例１３～１８の樹脂シートは、ポリビニルアルコールで被覆した比較例３及び被覆していない比較例５の樹脂シートよりも引張ひずみが大きく、表面抵抗率が低くなっている。これは樹脂への分散性の影響によるものと推定される。
　窒化ホウ素系の剥片化層状物質の表面を、有機基を有するポリシロキサン化合物で被覆した実施例２１の樹脂シートは、被覆していない比較例６の樹脂シートよりも引張ひずみが大きくなっている。これは樹脂への分散性の影響によるものと推定される。表面抵抗率には差がみられないが、窒化ホウ素の導電性が元々低いためと推定される。 The resin sheets of Examples 13 to 18 in which the surface of the graphite-based exfoliated layered material is coated with a polysiloxane compound having an organic group are the resin sheets of Comparative Example 3 coated with polyvinyl alcohol and Comparative Example 5 not coated. Has a larger tensile strain and a lower surface resistivity. It is presumed that this is due to the effect of dispersibility on the resin.
The resin sheet of Example 21 in which the surface of the boron nitride-based exfoliated layered material is coated with the polysiloxane compound having an organic group has a larger tensile strain than the resin sheet of Comparative Example 6 which is not coated. It is presumed that this is due to the effect of dispersibility on the resin. Although there is no difference in the surface resistivity, it is presumed that the conductivity of boron nitride is originally low.

　本発明によれば、剥片化層状物質の樹脂等への分散性が向上し、得られる樹脂組成物の靱性、伸縮性、耐衝撃性等の物性が大幅に向上する。
 
  According to the present invention, the dispersibility of the flaking layered material in a resin or the like is improved, and the physical properties of the obtained resin composition such as toughness, stretchability and impact resistance are significantly improved.

Claims (5)

　剥片化層状物質の表面が被覆物質により被覆された複合材料であって、被覆物質が、有機基を有するポリシロキサン化合物であり、剥片化層状物質１００質量部に対する被覆物質の含量が０．１質量部～１００質量部である複合材料。 A composite material in which the surface of a flaking layered material is coated with a coating material, wherein the coating material is a polysiloxane compound having an organic group, and the content of the coating material is 0.1 mass per 100 parts by mass of the flaking layered material. Parts to 100 parts by weight of the composite material. 　剥片化層状物質の平均厚さが１２００ｎｍ以下、剥片化層状物質の平均面積が０．１μｍ2～５００μｍ2である請求項１に記載の複合材料。 The composite material according to claim 1, wherein the exfoliated layered material has an average thickness of 1200 nm or less, and the exfoliated layered material has an average area of 0.1 μm 2 to 500 μm 2 . 　有機基を有するポリシロキサン化合物が、フェニル基を有するポリシロキサン化合物であり、フェニル基含量が５質量％～７０質量％である請求項１又は２に記載の複合材料。 The composite material according to claim 1 or 2, wherein the polysiloxane compound having an organic group is a polysiloxane compound having a phenyl group, and the phenyl group content is 5% by mass to 70% by mass. 　請求項１～３のいずれか１項に記載の複合材料と合成樹脂とを含有する樹脂組成物。 A resin composition containing the composite material according to any one of claims 1 to 3 and a synthetic resin. 　合成樹脂がシリコーン樹脂である請求項４に記載の樹脂組成物。
 
  The resin composition according to claim 4, wherein the synthetic resin is a silicone resin.

PCT/JP2019/041758 2018-10-26 2019-10-24 Composite material Ceased WO2020085444A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2020552598A JPWO2020085444A1 (en) 2018-10-26 2019-10-24 Composite material
KR1020217009391A KR102747045B1 (en) 2018-10-26 2019-10-24 Composite materials
CN201980066615.5A CN112823189A (en) 2018-10-26 2019-10-24 Composite material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-201472 2018-10-26
JP2018201472 2018-10-26

Publications (1)

Publication Number Publication Date
WO2020085444A1 true WO2020085444A1 (en) 2020-04-30

Family

ID=70331760

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/041758 Ceased WO2020085444A1 (en) 2018-10-26 2019-10-24 Composite material

Country Status (5)

Country Link
JP (1) JPWO2020085444A1 (en)
KR (1) KR102747045B1 (en)
CN (1) CN112823189A (en)
TW (1) TW202031795A (en)
WO (1) WO2020085444A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022032657A (en) * 2020-08-13 2022-02-25 株式会社Adeka Laminar graphite and resin composition
WO2023085322A1 (en) * 2021-11-10 2023-05-19 デンカ株式会社 Boron nitride powder

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54162741A (en) * 1978-06-14 1979-12-24 Mitsubishi Electric Corp Thermosetting resin composition
JPH03244645A (en) * 1990-02-22 1991-10-31 Matsushita Refrig Co Ltd Foamed thermal insulation material
JPH0733983A (en) * 1993-07-16 1995-02-03 Shin Etsu Chem Co Ltd Insulation heat dissipation sheet
JP2006001783A (en) * 2004-06-17 2006-01-05 Dokai Chemical Industries Co Ltd Monodispersed dry silica particle powder and method for producing the same
JP2009161707A (en) * 2008-01-10 2009-07-23 Toyo Ink Mfg Co Ltd COMPOSITE RESIN COMPOSITION AND MOLDED BODY USING THE SAME
JP2010242026A (en) * 2009-04-09 2010-10-28 Iwase Cosfa Kk Surface-treated powder
JP2016081922A (en) * 2014-10-15 2016-05-16 株式会社半導体エネルギー研究所 Electrode, power storage device, electronic equipment, and method for manufacturing electrode

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1392197A (en) * 1971-04-09 1975-04-30 Snam Progetti Hydrocarbon conversion catalyst and process for the production and use thereof
JP2005015344A (en) * 2003-06-23 2005-01-20 Nonogawa Shoji Kk Makeup cosmetic
US7531613B2 (en) * 2006-01-20 2009-05-12 Momentive Performance Materials Inc. Inorganic-organic nanocomposite
JP4860328B2 (en) * 2006-03-31 2012-01-25 株式会社コーセー Surface coating powder and cosmetics containing the same
GB201000743D0 (en) 2010-01-18 2010-03-03 Univ Manchester Graphene polymer composite
CN102952393A (en) * 2011-08-29 2013-03-06 奇菱科技股份有限公司 Organic modified layered composites
KR101437142B1 (en) 2011-10-28 2014-09-02 제일모직주식회사 Barrier film including graphene layer and flexible therof
US20130296479A1 (en) 2012-05-03 2013-11-07 Ppg Industries Ohio, Inc. Rubber formulations including graphenic carbon particles
JP2015040211A (en) 2013-08-20 2015-03-02 尾池工業株式会社 Graphene dispersion composition, and carbon-containing resin laminated body
JP5688669B1 (en) 2014-09-09 2015-03-25 グラフェンプラットフォーム株式会社 Graphite-based carbon material used as graphene precursor, graphene dispersion containing the same, graphene composite, and method for producing the same
JP6221022B2 (en) 2014-09-19 2017-10-25 康博 青木 Power generating composition and power generating element, power generating device and power storage device using the same
US10385189B2 (en) 2015-01-12 2019-08-20 Ningbo Morsh Technology Co., Ltd. Graphene composite powder form material and method for making the same
WO2016115377A1 (en) 2015-01-14 2016-07-21 Nitto Denko Corporation Graphene oxide barrier film
CN106752926B (en) * 2016-11-28 2019-07-05 复旦大学 A kind of graphene/polysiloxanes composite coating material and preparation method thereof
CN106752923A (en) * 2016-11-28 2017-05-31 复旦大学 A kind of damage resistant high, abrasion-resistant coatings material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54162741A (en) * 1978-06-14 1979-12-24 Mitsubishi Electric Corp Thermosetting resin composition
JPH03244645A (en) * 1990-02-22 1991-10-31 Matsushita Refrig Co Ltd Foamed thermal insulation material
JPH0733983A (en) * 1993-07-16 1995-02-03 Shin Etsu Chem Co Ltd Insulation heat dissipation sheet
JP2006001783A (en) * 2004-06-17 2006-01-05 Dokai Chemical Industries Co Ltd Monodispersed dry silica particle powder and method for producing the same
JP2009161707A (en) * 2008-01-10 2009-07-23 Toyo Ink Mfg Co Ltd COMPOSITE RESIN COMPOSITION AND MOLDED BODY USING THE SAME
JP2010242026A (en) * 2009-04-09 2010-10-28 Iwase Cosfa Kk Surface-treated powder
JP2016081922A (en) * 2014-10-15 2016-05-16 株式会社半導体エネルギー研究所 Electrode, power storage device, electronic equipment, and method for manufacturing electrode

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022032657A (en) * 2020-08-13 2022-02-25 株式会社Adeka Laminar graphite and resin composition
WO2023085322A1 (en) * 2021-11-10 2023-05-19 デンカ株式会社 Boron nitride powder
JPWO2023085322A1 (en) * 2021-11-10 2023-05-19
JP7389939B2 (en) 2021-11-10 2023-11-30 デンカ株式会社 boron nitride powder

Also Published As

Publication number Publication date
CN112823189A (en) 2021-05-18
JPWO2020085444A1 (en) 2021-10-07
TW202031795A (en) 2020-09-01
KR20210087019A (en) 2021-07-09
KR102747045B1 (en) 2024-12-26

Similar Documents

Publication Publication Date Title
Li et al. Polarization mechanism underlying strongly enhanced dielectric permittivity in polymer composites with conductive fillers
Huang et al. Boron nitride@ graphene oxide hybrids for epoxy composites with enhanced thermal conductivity
Tang et al. Rational design of graphene surface chemistry for high-performance rubber/graphene composites
Feng et al. High dielectric and mechanical properties achieved in cross-linked PVDF/α-SiC nanocomposites with elevated compatibility and induced polarization at the interface
Dang et al. Tailored dielectric properties based on microstructure change in BaTiO3-carbon nanotube/polyvinylidene fluoride three-phase nanocomposites
Ma et al. Enhanced electrical conductivity of nanocomposites containing hybrid fillers of carbon nanotubes and carbon black
Shrivastava et al. Development of electrical conductivity with minimum possible percolation threshold in multi-wall carbon nanotube/polystyrene composites
Li et al. Towards suppressing loss tangent: Effect of polydopamine coating layers on dielectric properties of core–shell barium titanate filled polyvinylidene fluoride composites
Zhang et al. Preparation and properties of styrene‐butadiene rubber nanocomposites blended with carbon black‐graphene hybrid filler
da Silva et al. Phosphonium–based ionic liquid as dispersing agent for MWCNT in melt-mixing polystyrene blends: Rheology, electrical properties and EMI shielding effectiveness
Grigorescu et al. Mechanical and dielectric properties of SEBS modified by graphite inclusion and composite interface
Hussein et al. Fabrication of EPYR/GNP/MWCNT carbon-based composite materials for promoted epoxy coating performance
AM et al. Improved dielectric and dynamic mechanical properties of epoxy/polyaniline nanorod/in situ reduced graphene oxide hybrid nanocomposites
Wang et al. Preparation and properties of octadecylamine modified graphene oxide/styrene‐butadiene rubber composites through an improved melt compounding method
Ismail et al. Multiwall carbon nanotube-filled natural rubber: the effects of filler loading and mixing method
Tan et al. Graphene nanoplatelets/barium titanate hybrid nanoparticles via ball milling for enhanced dielectric and mechanical properties of fluorosilicone rubber composites
Bhadra et al. Enhancement of the transport and dielectric properties of graphite oxide nanoplatelets‐polyvinyl alcohol composite showing low percolation threshold
Wondu et al. Improvement of dielectric properties and thermal conductivity of TPU with alumina-encapsulated rGO
González et al. Influence of ZnO and TiO 2 particle sizes in the mechanical and dielectric properties of vulcanized rubber
Lu et al. In‐situ thermal reduction and effective reinforcement of graphene nanosheet/poly (ethylene glycol)/poly (lactic acid) nanocomposites
Cai et al. Enhanced Electromechanical Properties of Three‐Phased Polydimethylsiloxane Nanocomposites via Surface Encapsulation of Barium Titanate and Multiwalled Carbon Nanotube with Polydopamine
KR20210035165A (en) Composite material
Thomas et al. Evaluation of mechanical, thermal, electrical, and transport properties of MWCNT‐filled NR/NBR blend composites
Wu et al. Latex co‐coagulation approach to fabrication of polyurethane/graphene nanocomposites with improved electrical conductivity, thermal conductivity, and barrier property
Nayak et al. Polydimethylsiloxane–PbZr0. 52Ti0. 48O3 nanocomposites with high permittivity: Effect of poling and temperature on dielectric properties

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19876090

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2020552598

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19876090

Country of ref document: EP

Kind code of ref document: A1