WO2005068362A1 - Particule fine composite et procede de fabrication associe - Google Patents

Particule fine composite et procede de fabrication associe Download PDF

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Publication number
WO2005068362A1
WO2005068362A1 PCT/JP2005/000255 JP2005000255W WO2005068362A1 WO 2005068362 A1 WO2005068362 A1 WO 2005068362A1 JP 2005000255 W JP2005000255 W JP 2005000255W WO 2005068362 A1 WO2005068362 A1 WO 2005068362A1
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fine particles
fluorine
group
polymer
monomer
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PCT/JP2005/000255
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English (en)
Japanese (ja)
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Norihide Sugiyama
Kazushi Kobayashi
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Asahi Glass Company, Limited
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Publication of WO2005068362A1 publication Critical patent/WO2005068362A1/fr

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    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/10—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to inorganic materials
    • 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
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment with inorganic compounds
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3072—Treatment with macro-molecular organic compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/405—High molecular weight materials, e.g. polymers
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/405—High molecular weight materials, e.g. polymers
    • C09C2200/406—High molecular weight materials, e.g. polymers comprising additional functional groups, e.g. -NH2, -C=C- or -SO3
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/407—Organosilicon materials, e.g. silanes, silicones
    • 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
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
    • C09C2200/407—Organosilicon materials, e.g. silanes, silicones
    • C09C2200/408—Organosilicon materials, e.g. silanes, silicones comprising additional functional groups, e.g. –NH2, -C=C- or -SO3
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0224—Conductive particles having an insulating coating

Definitions

  • the present invention relates to composite fine particles whose surface is coated with a specific fluorine-containing polymer and which can also serve as tabular silica fine particles, a method for producing the composite fine particles, and uses thereof.
  • it is used as a low dielectric constant insulating circuit board material for electronic parts and the like, and as a moisture-proof insulating sealing material.
  • the physical properties can be improved by blending a powder composed of particulate silica with an organic polymer.
  • a powder composed of particulate silica For example, by adding fine-particle silica, the thermal expansion coefficient of the organic polymer can be reduced, the heat resistance can be improved, the mechanical strength can be improved, and the hardness can be improved.
  • it is necessary to uniformly mix the fine silica particles with the organic polymer It is considered necessary to improve the affinity of the particulate silica.
  • Patent Document 1 JP-A-7-43728
  • Patent Document 2 JP-A-9-194208
  • Patent Document 3 JP-A-2001-98164
  • a fluorine-containing polymer having a high fluorine content is usually an organic polymer having a very high hydrophobicity, and a fluorine-containing monomer as a raw material thereof is also a monomer having a very high hydrophobicity. For this reason, it is difficult to produce good core Z-shell composite fine particles simply by applying the known seed polymerization method.
  • a fluorine-containing monomer in which a fluorine atom is bonded to a carbon atom of a polymerizable unsaturated group is used as the fluorine-containing monomer
  • core-shell composite fine particles having a fluorine-containing polymer as a shell are produced by a known seed polymerization method. You can't.
  • tabular silica has a large contact area between particles due to its shape characteristics, and thus is more likely to aggregate than spherical ones. Therefore, it is extremely difficult to suppress secondary aggregation and disperse and composite in a fluoropolymer.
  • the present invention provides nano-sized flat silica fine particles whose surface is coated with a fluorine-containing polymer having a high fluorine content, composite fine particles, a method for producing the composite fine particles by a radical polymerization method in an aqueous medium, And it aims at providing the use of the composite fine particles.
  • the present invention relates to composite fine particles comprising nano-sized tabular silica fine particles whose surface is coated with a specific fluorine-containing polymer, a method for producing the same, a molding material containing the composite particles, and a molding material containing the composite particles.
  • the gist of the present invention relates to a molded product of the molding material described above.
  • Composite fine particles composed of nano-sized tabular silica fine particles whose surface is coated with a fluoropolymer (A), wherein the fluoropolymer (A) has a fluorine atom at the carbon atom of the polymerizable unsaturated group.
  • a fluorine-containing polymer containing a unit derived from a fluorine-containing monomer and the ratio of flat silica fine particles in the composite fine particles is 70% by mass. .
  • the composite fine particles according to the above (1) which is a fluorine-containing polymer containing a unit derived from a fluorine-containing monomer having a sum group (where R represents a fluorine atom, a fluoroalkyl group or a fluoroalkoxy group).
  • the surface of the following fluorine-containing polymer (A) is obtained by radical polymerization of a fluorine-containing monomer in a polymerization system in which nano-sized tabular silica fine particles are dispersed in an aqueous medium in the presence of a surfactant.
  • a method for producing composite fine particles which comprises producing composite fine particles comprising nano-sized tabular silica fine particles covered with a fine particle.
  • Fluorine-containing polymer (A) a fluorine-containing polymer containing a unit derived from a fluorine-containing monomer in which a fluorine atom is bonded to a carbon atom of a polymerizable unsaturated group.
  • core / shell composite particles having nano-sized flat silica fine particles as a core and a highly hydrophobic fluorine-containing polymer as a shell are provided.
  • the powder comprising the composite particles of the present invention is excellent as a molding material for producing a fluoropolymer molded product in which tabular silica fine particles are uniformly dispersed, and even if the content of the silica fine particles in the molded product is relatively small. The effect of reducing the coefficient of thermal expansion is exhibited. At the same time, the low dielectric constant of the Matritas fluoropolymer is maintained due to its low silica content.
  • the powder of the present invention which also has a composite particle strength, can be used as an additive for various polymer materials, and the molding material containing the powerful powder can reduce the amount of addition necessary for exerting the effect of adding inorganic fine particles.
  • the disadvantages caused by blending a large amount of additives can be eliminated.
  • FIG. 1 is a graph showing the relationship between the silica content of a molded product and the coefficient of thermal expansion in examples and comparative examples.
  • the composite fine particles in the present invention are core Z-shell composite fine particles, and the core part also has a nano-sized tabular silica fine particle power, and the shell part is made of the fluoropolymer (A).
  • the ratio of the tabular silica fine particles in the composite fine particles is 170% by mass
  • the fluorine-containing polymer (A) is a unit derived from a fluorine-containing monomer in which a fluorine atom is bonded to a carbon atom of a polymerizable unsaturated group. Is a fluorine-containing polymer.
  • the nano-sized tabular silica fine particles of the present invention are flaky silica fine particles having a maximum length of less than 200 nm and a thickness of 5 nm or less.
  • the flat silica fine particles preferably have a maximum length of 100 nm or less on average and substantially do not include a maximum length of 200 nm or more.
  • the average of the maximum length is preferably 10-100 ⁇ m.
  • the shape of the surface including the maximum length is a shape close to a circle or a polygon, and the length in the direction perpendicular to the direction having the maximum length is 1 to 50 nm (but not more than the maximum length) and linear.
  • the average thickness of the tabular silica fine particles is preferably 0.1 to 1 nm.
  • the ratio of the maximum length Z to the thickness is preferably 10 or more, particularly preferably 20 or more.
  • the above-mentioned powder of the flat silica fine particles is stably dispersed in an organic solvent, and the fine silica particles in the organic solvent solution can pass through a filter having a pore size of 0.2 ⁇ m.
  • the plate-like silica fine particles as the starting material in the present invention are obtained by subjecting a tetrafunctional hydrolyzable silane compound to a hydrolysis-condensation polymerization reaction in water in the presence of a cationic surfactant, and in the course of the reaction.
  • Solid silica fine particles obtained by terminating the reaction with a monofunctional hydrolyzable organosilane compound are preferred.
  • flat silica fine particles can be obtained by subjecting a silica sol obtained by dealkalizing an alkali silicate aqueous solution to hydrothermal treatment (see JP-A-11-29317).
  • the former method for producing tabular silica fine particles will be described.
  • Carohydrolysis-condensation polymerization (hereinafter also simply referred to as condensation polymerization) of the tetrafunctional hydrolyzable silani conjugate in water in which a cationic surfactant is present forms flat silica particles. Is done. The mechanism by which the plate is formed is not clear, but during the condensation polymerization reaction, two-dimensional assembly occurs due to the hydrophobic interaction of the long chain alkyl group of the cationic surfactant and the complex formation due to electrostatic attraction between N + and SiO— It is considered that the condensation polymerization reaction proceeds while the reaction proceeds.
  • the molecular weight of the generated silica fine particles is controlled, and tabular silica fine particles having an appropriate molecular weight can be obtained.
  • a tabular sheet can be obtained.
  • the surface properties (such as affinity for organic solvents) of the Jamaica fine particles can be changed.
  • the obtained tabular silica fine particle powder can be stably dispersed in an organic solvent. It can pass through a 0.2 ⁇ m filter. Since it can pass through a filter having a pore size of 0.2 m, this flat silica fine particle powder does not include fine particles having a maximum length of 200 nm or more.
  • a filter having a pore size of 0.2 m a filter made of polytetrafluoroethylene (PTFE) manufactured by A DVANTEC (trade name: DISMIC-25JP020AN) was used.
  • PTFE polytetrafluoroethylene
  • a DVANTEC trade name: DISMIC-25JP020AN
  • the shape of the tabular silica fine particles is based on observation of the particle shape by a transmission electron microscope (TEM).
  • a tetrafunctional hydrolyzable silane compound is a compound in which four hydrolyzable groups are bonded to a silicon atom.
  • the hydrolyzable group include an alkoxy group having 6 or less carbon atoms, an alkoxyalkyloxy group having 6 or less carbon atoms, an alkoxyloxy group having 6 or less carbon atoms, an acyloxy group having 6 or less carbon atoms, a chlorine atom, an amino group, Examples include dialkylamino, oxime, and isocyanate groups having 6 or less carbon atoms.
  • the tetrafunctional hydrolyzable silani conjugate is a conjugate having one or more of these carohydrate decomposable groups bonded to a silicon atom.
  • a compound bonded to a silicon atom having an alkoxy group having 4 or less carbon atoms that is, a tetraalkoxysilane is preferable.
  • the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, tetra (n-butoxy) silane, and tetra (t-butoxy) silane.
  • the hydrolyzable group in the tetrafunctional hydrolyzable silane compound reacts with water to form a silanol group, and the silanol groups undergo dehydration condensation polymerization to produce silica.
  • the partially hydrolyzed condensation polymer of the tetrafunctional hydrolyzable silane conjugate in the course of this reaction can also be used as a raw material for producing silica.
  • the partially hydrolyzed condensation polymer has an average molecular weight of 500 or less.
  • the tabular silica fine particles in the present invention are preferably silica fine particles formed from a tetraalkoxysilane monomer which is not a partially hydrolyzed condensation polymer.
  • the tabular silica fine particles By terminating the condensation polymerization reaction with the monofunctional hydrolyzable organosilane conjugate, the tabular silica fine particles have a triorganosilyl group on the surface thereof, At least a part of the silanol group generated by hydrolysis of the hydrolyzable group of the decomposable silane conjugate may be blocked with this triorganosilyl group.
  • the blockade by the triorganosilyl group controls the molecular weight during the formation of the tabular silica fine particles, thereby suppressing the generation of high molecular weight molecules exceeding a predetermined size, and has an affinity for organic solvents and surface reactivity. This is performed in order to exhibit the surface characteristics.
  • the above-mentioned tabular silica fine particles are stably dispersed in an organic solvent and exist as a single molecule in the organic solvent without aggregation.
  • the dispersibility with respect to the type of the organic solvent varies depending on the type and amount of the triorganosilyl group on the surface of the flat silica fine particles.
  • the surface characteristics of the tabular silica fine particles can be changed by using a bifunctional or trifunctional hydrolyzable organosilane conjugate together with the monofunctional hydrolyzable organosilane conjugate. It is considered that the use of the di- or tri-functional hydrolyzable organosilane conjugate produces tabular silica fine particles having a diorganosilyl group or a monoorganosilyl group bonded to the surface.
  • the affinity of the tabular silica fine particles with respect to the type of the organic solvent can be changed depending on the type and amount of the above-mentioned organosilyl group (general term for monolith organosilyl groups).
  • organosilyl group generally term for monolith organosilyl groups.
  • silica fine particles having trialkylsilyl groups bonded have high affinity for polar organic solvents such as alcohol and THF (tetrahydrofuran), and have a high fluorine content.
  • Flat plate with organosilyl groups having fluoroalkyl groups bonded Silica fine particles have high affinity for fluorine-based organic solvents.
  • the above-mentioned tabular silica fine particles are subjected to a hydrolysis-condensation polymerization reaction of a tetrafunctional carohydrate-decomposable silani conjugate in water in the presence of a cationic surfactant to form predetermined silica particles.
  • a monofunctional hydrolyzable organosilane conjugate is added to the reaction system to stop the condensation polymerization reaction.
  • the addition of a monofunctional hydrolyzable organosilane conjugate to the reaction system simultaneously blocks silanol groups and terminates the reaction.
  • the surface modification of the silica fine particles is performed by adding the 2-3 functional hydrolyzable organosilane conjugate to the reaction system.
  • You can also. Obtained as monofunctional hydrolyzable organosilane compound It is possible to introduce various organic groups into the surface of the silica fine particles to change the surface characteristics by using a 2-3 functional hydrolyzable organosilane conjugate having various organic groups which is difficult to carry out. it can. Examples of such an organic group include an organic group having a reactive group and a hydrophobic polyfluoroalkyl group.
  • the mono-functional hydrolyzable organosilane compound is reacted with the mono-functional hydrolyzable organosilane compound.
  • the hydrolysis-condensation polymerization reaction is terminated by reacting a soluble organosilane compound.
  • the condensation polymerization reaction is performed in the presence of a cationic surfactant to cause two-dimensional SiO chain growth accompanied by complex formation, and the plate has a flat shape. It is considered that silica fine particles are generated. In the absence of a cationic surfactant, plate-like fine particles are not generated under the conditions, and it is considered that spherical fine particles are generated.
  • the cationic surfactant is preferably a cationic surfactant such as an amine salt, an ester-bonded amine, an amide-bonded amine, an ether-bonded amine, a quaternary ammonium salt, or a pyridium salt.
  • the cationic surfactant contains a hydrophobic group, and the hydrophobic group is preferably a monovalent organic group such as a long-chain hydrocarbon group, a long-chain fluoroalkyl group, or a phenyl group.
  • the hydrophobic group a long-chain alkyl group or a fluoroalkyl group-containing monovalent organic group is particularly preferred.
  • an alkyl group having 6 or more carbon atoms, particularly 8 to 20 carbon atoms is preferable.
  • a perfluoroalkyl group having 4 to 20 carbon atoms is preferable! /.
  • Examples of the monovalent organic group having a perfluoroalkyl group include, for example, CF (CF) — (CH)
  • a surfactant having such a fluoroalkyl group-containing monovalent organic group is hereinafter referred to as a cationic fluorine-based surfactant.
  • cationic surfactant examples include the following cationic surfactants (R 1 represents an alkyl group or hydroxyalkyl group having 4 or less carbon atoms, and X— represents an acid residue).
  • Examples of the trifunctional hydrolyzable organosilane conjugate include a hexorganodisiloxane represented by the following formula (1) (monofunctional hydrolyzable organosilane conjugate).
  • Hexaorganodisilazane (monofunctional hydrolyzable organosilane compound) represented by the following formula (2)
  • 113-functional hydrolyzable organosilane silyl compound represented by the following formula (3)
  • Compounds are preferred.
  • Hexaorganodisiloxane and hexorganodisilazane are formed into two molecules of monosilanolyl conjugate by hydrolysis. It is.
  • R 2 , R 3 and R 4 each independently represent a monovalent non-hydrolysable organic group
  • Y represents a monovalent hydrolysable group
  • n represents an integer of 13 to 13.
  • each R 4 may be different.
  • R 2 , R 3 , and R 4 are each a monovalent organic group in which a bond bonding to a silicon atom is a bond of a carbon atom, and particularly an alkyl group, an alkyl group, a cycloalkyl group, and an aryl group.
  • an alkyl group having 20 or less carbon atoms is preferable, and an alkyl group having 4 or less carbon atoms (hereinafter, referred to as a lower alkyl group) is particularly preferable.
  • An alkenyl group is an alkenyl group having 4 or less carbon atoms, such as a butyl group or a aryl group.
  • a cycloalkyl group is a cyclohexyl group.
  • a aryl group is a phenyl group or a substituted with a lower alkyl group.
  • -Alkyl group Lower alkyl group-containing alkyl group such as benzyl group is preferred as the aralkyl group.
  • haloalkyl group a fluoroalkyl group having 16 or less carbon atoms is preferable.
  • the functional group-containing alkyl group include a hydroxyl group, an epoxy group, a glycidyloxy group, and an epoxy group.
  • An alkyl group having a carbon number of 6 or less having a functional group such as a xycycloalkyl group, an amino group, an N-aminoalkylamino group, an N-phenylamino group, a methacryloyloxy group, and a mercapto group is preferable.
  • all of the organic groups are lower alkyl groups or one of them. Is preferably an organic group other than a lower alkyl group.
  • one R 4 is preferably an organic group other than a lower alkyl group.
  • the organic group other than the lower alkyl group an alkyl group having 5 or more carbon atoms, a phenyl group, a monoalkyl organic group containing a fluoroalkyl group, and an alkyl group containing a functional group are preferable.
  • the fluoroalkyl group-containing monovalent organic group a monovalent organic group having a perfluoroalkylene group having 412 carbon atoms is preferable. In particular, CF (CF) — (CH) C
  • Fluoroalkyl group-containing monovalent organic groups having at least one moiety are preferred (P is an integer of 3-10, q is an integer of 216).
  • the hydrolyzable organosilane conjugate having a fluoroalkyl group-containing monovalent organic group is hereinafter referred to as a fluorine-based hydrolyzable organosilane conjugate.
  • Y is a monovalent hydrolyzable group.
  • the number of Ys (ie, 4n) attached to the silicon atom indicates the functionality of the hydrolyzable organosilane conjugate.
  • Y is the above-mentioned hydrolyzable group such as an alkoxy group, and preferred Y is a lower alkoxy group. Particularly preferred Y is methoxy and ethoxy. When the number of Y is 2 or 3, a plurality of Ys may be different, but are usually the same group.
  • Hexamethyldisiloxane is preferred as the compound represented by the formula (1).
  • Hexamethyldisilazane is preferred as the compound represented by (2).
  • the compound represented by the formula (3) the following compounds are preferable.
  • Monofunctional compounds trimethylchlorosilane, t-butyldimethylchlorosilane, triphenylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylacetoxysilane, n-xyldimethylmethoxysilane, n-xyldimethylmethoxysilane, triphenylaminosilane , 3- (perfluoro-n-butyl) propyldimethylmethoxysilane, 3- (perfluoro-n-xyl) propyldimethylmethoxysilane, 3- (perfluoro-n- Hexoxysilur)) ppropropirpirdidimethytylethoxyethoxysilicranane, 33 —— ((Paperfurfurooloololo-nn-kixsilyl)) propropipirul djetitytyllmethoxoxysilic
  • 22-functional functional compound :: dimethymethyiludidicchlorochlorosilosilane, dijetityl ludicichlorochlorosirolane, ffe-lelumethitylyl didichlorochloro Sicilalane, Dimethicino-resinmethytoxymethoxysilicane, Didetichtinoresimi-methotoxisicilan, Meetochino-silicone ,, Didimethytyl rudijetetoxysicilan iran, nn xysilylmethityl didimethiethoxy thixisishiranan, nn-de-desicillumethityl didimethytoxysisiranylane, didiffee Luludjetetoxysicilsilalanne, 33 Dimethotoxoxysicillaran, 33—Gugurylisidodoxycypropropipyrurmetimetyl
  • Trifunctional compounds methyltrichlorosilane, ethyltrichlorosilane, n-trioctadecyltrichlorosilane, ethyltrimethoxysilane, nxyltrimethoxysilane, ndecyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) ) Silane, 3 methacryloxytrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N-phenol 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3,3,3-trifluoroprop
  • the amount of the cationic surfactant with respect to water is based on 100 parts by mass of water. V, preferably 3 to 5 parts by mass, particularly 10 to 10 parts by mass. If the amount of the cationic surfactant is too small, there are problems such as low solubility such as spheres and particles of a shape are formed. If the amount is too large, the viscosity becomes high, and the tetrafunctional hydrolyzable silane conjugate is used. Are difficult to mix uniformly.
  • the amount of the tetrafunctional hydrolyzable silani conjugate relative to water is preferably 5 to 20 parts by mass per 100 parts by mass of water, particularly 10 to 15 parts by mass. Parts are preferred.
  • the amount of the tetrafunctional hydrolyzable silani conjugate is too small, there is a problem that the time for growing the particles is too long.
  • reaction conditions such as a reaction temperature, a PH, and a reaction time are controlled in addition to the amounts of the cation-based surfactant and the raw material compound in order to form the above-mentioned tabular silica fine particles. Do it. If the reaction temperature is too high, if the PH is too high, or if the reaction time is too long, silica with too high a molecular weight will be produced, and a gelling component will be produced, producing tabular silica fine particles that can be dispersed in the intended solvent. Shina.
  • the reaction temperature is preferably from room temperature to about 100 ° C, but more preferably from room temperature to 60 ° C from the viewpoints of suppression of gelling and reaction time.
  • Acids or bases are usually used to promote the hydrolysis-condensation polymerization reaction.
  • the reaction rate is controlled using an appropriate amount of acid, which is preferred to use an acid.
  • the amount of acid used is preferably adjusted by adjusting the pH of the aqueous solution.
  • the pH is preferably 2-5, but pH 4-5 is preferable from the viewpoint of suppression of gelling and reaction time. For example, when the reaction temperature is 40 ° C and the pH is 4, the reaction time is 10 to 40 hours, and when the reaction temperature is 40 ° C and the pH is 4.5, the reaction time is 5 to 20 hours.
  • Adjustment of the pH is usually performed by adding an acid such as hydrochloric acid.
  • an acid such as hydrochloric acid.
  • the above hydrolysis reaction is stopped, and the silanol groups of the generated tabular silica fine particles are blocked.
  • the condensation polymerization reaction is stopped by reacting a monofunctional hydrolyzable organosilane conjugate.
  • a catalyst such as an acid and raising the Z or reaction temperature to quickly stop the reaction.
  • concentrated hydrochloric acid is particularly preferred as the acid to be added.
  • a method in which an aqueous solution containing a reaction product is added to a solution of a monofunctional hydrolyzable organosilane conjugate to perform a termination reaction can be used.
  • a bifunctional or trifunctional hydrolyzable organosilane conjugate is used in addition to a monofunctional hydrolyzable organosilane conjugate.
  • a hydrophobic group, a reactive group, or the like into the silica surface, use of only a monofunctional hydrolyzable organosilane conjugate may be insufficient. Therefore, it is preferable to use a di- or tri-functional hydrolyzable organosilane conjugate for specific surface modification, and a mono-functional hydrolyzable organosilane conjugate to terminate the reaction.
  • the hydrolysis reaction does not stop and the molecular weight of silica continues to increase.Therefore, in order to stop the reaction at a predetermined target molecular weight, it is necessary to first perform surface modification. For this purpose, it is preferable to react the bifunctional or trifunctional hydrolyzable organosilane conjugate and then react the monofunctional hydrolyzable organosilane conjugate to terminate the hydrolysis-condensation polymerization reaction. Good.
  • the silica fine particles may be formed by hydrolysis of the tetrafunctional hydrolyzable organosilane conjugate.
  • a bi- or trifunctional hydrolyzable organosilane conjugate is added to the reaction system. It is preferable that the average molecular weight of the silica fine particles at the time of the addition of calories is 1,000 or more. After the addition, it is preferable to dilute it 2-5 times with alcohol so that growth of the molecular weight does not substantially occur. If not diluted, rapid gelation is likely to occur because the overall silanol concentration is increased by the amount of silanol derived from the organosilane compound.
  • ingredients 4-functional hydrolyzable silani conjugate 1 mol of 2- or 3-functional hydrolyzable
  • the amount of the luganosilane conjugate is not particularly limited, but is preferably 0.8 mol or less, particularly preferably 0.3 mol or less. However, it is not necessary to react all the used amounts.
  • the monofunctional hydrolyzable organosilane conjugate is reacted to cause condensation polymerization. Stop the reaction.
  • the amount of the monofunctional hydrolyzable organosilane conjugate may be determined by the amount of silanol groups (unreacted hydrolyzable groups remaining on the surface of the silica fine particles after the reaction is stopped!
  • silanol groups (unreacted hydrolysable groups may remain on the surface of the flat silica fine particles before the reaction is stopped) ) Must be in an amount that can be blocked by a triorganosilyl group.
  • the amount of the monofunctional hydrolyzable organosilane conjugate used per mole of the tetrafunctional hydrolyzable silane conjugate is usually at least 0.1 mol based on the average molecular weight of the generated silica. In particular, it is preferable that the amount is 0.5 mol or more and the above amount becomes an excess amount.
  • the plate-like silica fine particles obtained by the reaction in water are insoluble in water, and therefore, the solid can be separated hydraulically by filtration, precipitate collection, or the like, so that the reaction system can be separated.
  • a solution of the monofunctional hydrolyzable organosilane conjugate is used, an appropriate amount of the silica fine particles is insoluble in a mixed solvent of this solvent and water. It is preferable to add water or to select the type and amount of the solvent.
  • a solvent in the solution of the monofunctional hydrolyzable organosilane compound a solvent such as isopropyl alcohol, which has a water-compatible power S and has a too high solubility of the flat silica fine particles, is preferable. Thereafter, if necessary, it can be purified by washing with an insoluble solvent such as water.
  • the obtained powder is an aggregate of tabular silica fine particles, and this powder can be dispersed in an organic solvent to form a dispersion as described above.
  • the organic solvent used in the organic solvent dispersion of the tabular silica fine particles includes alcohols such as methanol, ethanol, isopropanol, and ethylene glycolone monomethinoleether.
  • Esters such as toluene, ethyl acetate, and butyl acetate; ketones such as acetone and methyl ethyl ketone; liquid hydrocarbons such as benzene, toluene, and hexane; and hexafluorometaxylene dichloropentafluoropropane and hexafluoro.
  • fluorinated organic solvents such as benzene.
  • a mixed solvent of a water-soluble alcohol and a water-insoluble organic solvent is preferable.
  • the type and amount of the organosilyl group used for the hydrophobic treatment of the surface of the tabular silica fine particles were used as the organic solvent. It is desirable to use a mixture of an alcohol and a water-insoluble solvent depending on the conditions.
  • the affinity will be poor, and if it is too high, the dispersion in the aqueous solution containing the surfactant will decrease, so mixing according to the type and amount of the organosilyl group used in the hydrophobic treatment Adjusting the ratio is preferred.
  • the tabular silica fine particles as a raw material for producing the composite fine particles of the present invention described below are tabular silica fine particles obtained by using a cationic fluorine-based surfactant as the cationic surfactant. preferable. It is considered that the cationic surfactant used in the production is not contained in the obtained tabular silica fine particles, but actually, a trace amount of the cationic surfactant is present on the surface of the fine particles. it is conceivable that. If the cationic surfactant contained in the fine particles is a hydrocarbon-based cationic surfactant, the polymerization of a fluorine-containing monomer described later may be inhibited.
  • a cationic fluorine-based surfactant has no risk of inhibiting the polymerization of the fluorine-containing monomer, and therefore, if there is a possibility that the cationic surfactant may remain in the fine particles, the cationic fluorine-based surfactant is used. Is preferred U ⁇ .
  • the flat silica fine particles as a raw material for producing the composite fine particles of the present invention need to have a hydrophobic surface.
  • a highly hydrolyzable, hydrolyzable organosilane conjugate as at least a part of the hydrolyzable organosilane conjugate.
  • a fluorine-based hydrolyzable organosilane compound is particularly preferred. It is often difficult to easily obtain a monofunctional compound as a fluorine-containing hydrolyzable organosilane compound.
  • the amount of the bifunctional or trifunctional fluorine-based hydrolyzable onoleganosilane conjugate used per mole of the starting material 4-functional hydrolyzable silane conjugate is 0.05 to 0.8 monoles, particularly 0. 1— 0.3 Monoreca Further, the amount of the fluorinated hydrolyzable organosilane conjugate with respect to the tabular silica fine particles is preferably from 1 to 50% by mass, particularly preferably from 5 to 30% by mass.
  • the surface of the tabular silica fine particles is treated with a trifunctional fluorine-based hydrolyzable organosilane conjugate. It is also possible to obtain hydrophobic fine plate-like silica fine particles by treating and hydrophobizing. In this case, it is considered necessary that the surface of the tabular silica fine particles have a certain level of active sites (usually silanol groups), and the monofunctional hydrolyzable organosilane coupling in the production of the tabular silica fine particles is considered to be necessary. It is preferable that the amount of material used is such that some reaction points remain!
  • a method of adding a fluorine-based hydrolyzable organosilane conjugate to a dispersion of the tabular silica fine particles and reacting the dispersion is usually used. . At that time, it is preferable to promote hydrolysis by a method such as acidifying the dispersion.
  • the liquid medium in the dispersion liquid of the tabular silica fine particles is preferably an organic solvent such as alcohol. It is preferable to add a small amount of an acidic aqueous solution to the organic solvent dispersion of the fine silica particles, add a hydrolyzable fluorosilane-based organosilane compound, and heat and stir to modify the surface.
  • the composite fine particles in the present invention are core Z-shell-shaped composite fine particles, the core portion also having a nano-sized tabular silica fine particle force, and the shell portion being made of the fluoropolymer (A).
  • the composite fine particles can be produced by dispersing tabular silica fine particles in an aqueous medium in the presence of a surfactant and radically polymerizing a fluorine-containing monomer in a polymerization system.
  • a fluoromonomer is dispersed in an aqueous dispersion in which hydrophobically rendered nanosized tabular silica fine particles are uniformly dispersed with a surfactant, and then core / shell polymerization is performed, and a fluoropolymer is formed on the surface of the tabular silica fine particles. It is manufactured by forming (A).
  • the aqueous dispersion in which the plate-like silica fine particles are uniformly dispersed is the dispersion of the plate-like silica fine particles in an organic solvent.
  • the hydraulic power is also produced by solvent replacement.
  • an aqueous dispersion is obtained by dispersing an organic solvent dispersion in an aqueous medium and then distilling off the organic solvent.
  • a surfactant is usually required.
  • the aqueous dispersion containing the surfactant is preferably obtained by solvent replacement from the organic solvent dispersion containing the surfactant.
  • the surfactant as will be described later, anionic surfactants and nonionic surfactants are preferred, and fluorine-based surfactants are particularly preferred.
  • the fluorine-containing monomer is polymerized on the surface of the tabular silica fine particles serving as the core, and a layer of the fluoropolymer (A) is formed on the surface of the tabular silica fine particles.
  • Surfactants have a hydrophobic surface in aqueous media! / Coordinates to the surface of the flat silica fine particles to form surfactant-coordinated flat silica fine particles (hereinafter referred to as “coordinate fine particles”), and the fluorine-containing monomer is coplanar with the surfactant of the coordinating fine particles. It is taken into the interface of the silica fine particles and polymerized there.
  • the flat silica fine particles have a polar group even when the surface is hydrophobicized, hydrophobic fluorine-containing monomers are less likely to be incorporated into the coordinating fine particles.
  • the affinity between the flat silica fine particles and the fluorine-containing monomer is low.
  • the stability of the coordinating fine particles incorporating the fluorine-containing monomer is low.
  • fluorine-containing monomers have much higher hydrophobicity than ordinary monomers, so that it is difficult for ordinary surfactants to form good coordinating fine particles. Due to these problems, the surfactant is preferably a surfactant having a much higher hydrophobic group than usual. Further, as described above, it is preferable that the surface of the tabular silica fine particles is previously highly hydrophobicized, and the degree of hydrophobicity is much higher than usual.
  • a surfactant is usually used to disperse the tabular silica fine particles in an aqueous medium and polymerize the fluorine-containing monomer on its surface.
  • an a-ionic surfactant ⁇ a non-ionic surfactant is preferred ⁇ .
  • the hydrophilic group of the a-one-based surfactant include a carboxylate, a sulfate, a phosphate, and a phosphonate, and a carboxylate is preferred.
  • the counter ion include an alkali metal ion and an ammonium ion. In the present invention, an ammonium ion is particularly preferred.
  • Metal ions remain in the composite particles If it is present, it may adversely affect the physical properties of the fluoropolymer, and may cause inconvenience depending on the application (for example, in a semiconductor-related application, the residual alkali metal ion in the material is not preferable).
  • the surfactant is preferably a surfactant having a much higher hydrophobic group than usual.
  • a surfactant there is a surfactant having a fluorine-containing hydrophobic group, and particularly, an anionic fluorosurfactant and a nonionic fluorosurfactant are preferable.
  • These fluorine-based surfactants are surfactants having a fluorinated hydrocarbon group as a hydrophobic group, and the above-mentioned monovalent organic group containing a fluoroalkyl group is preferred as such a hydrophobic group.
  • a salt of sulfonic acid having a fluoroalkyl group-containing monovalent organic group or a nonionic surfactant having a fluoroalkyl group-containing monovalent organic group and a polyoxyethylene chain is preferable.
  • Particularly preferred fluorinated surfactants are amine salts such as a carboxylic acid having a fluoroalkyl group-containing monovalent organic group, such as an ammonium salt and a alkanolamine salt.
  • Specific examples of these fluorine-based surfactants include the following compounds (where r is an integer of 1 or more).
  • the amount of the surfactant to be used generally depends on the amount of the tabular silica fine particles used. However, it is not always the case that flat silica particles have a different surface area depending on the particle diameter of the flat silica particles. It is not limited only to the usage amount of the fine particles. An amount is used which is at least equal to or more than an amount at which stable coordinating fine particles are formed, and which contains tabular silica fine particles and minimizes micelles. Usually 10- 75 mass% is preferable with respect to the tabular silica particles, preferably it is especially ⁇ This 20- 50 mass 0/0.
  • the fluorinated monomer is added to the aqueous medium in which the tabular silica fine particles are dispersed as described above, and the fluorinated monomer is polymerized on the surface of the flat silica fine particles to coat the surface with the fluorinated polymer (A).
  • a fluorine-containing monomer is usually polymerized by radical polymerization, a radical polymerization initiator is used as a polymerization initiator.
  • a water-soluble inorganic peroxide such as sodium persulfate or ammonium persulfate, or an oil-soluble peroxide or azoi-conjugate is used.
  • accelerators such as redox agents such as sulfites and ferrous salts may be used in combination.
  • the oil-soluble radical polymerization initiator include, for example, organic peroxides such as peroxycarbonates, hydroxides at the mouth, disilver oxides, and ketone peroxides; And azo compounds such as azobis (2,4-dimethylvale-tolyl).
  • fluorine-containing peroxides such as polyfluorosilyl peroxides can also be used.
  • organic peroxides such as peroxycarbonates, hide-opened peroxides, and disilver oxides are used.
  • the fluorine-containing monomer is incorporated into the interface between the coordinating fine particle surfactant and the tabular silica fine particles in the aqueous medium and needs to be polymerized in situ.
  • the fluorinated monomer was sufficiently brought into contact with the tabular silica fine particles, and the number of fluorinated monomer droplets not containing the flat silica fine particles was small and droplets containing a large number of flat silica particles were not generated. It is necessary to disperse the fluorine-containing monomer in the aqueous medium. For this purpose, it is necessary to disperse the fluorine-containing monomer in an aqueous medium so as to be sufficiently fine particles.
  • the aqueous medium to which the fluorine-containing monomer has been added is used in the aqueous medium.
  • dispersing means such as stirring vigorously enough to form fine particles, dispersing the fluorine-containing monomer by irradiating ultrasonic waves, and dispersing with a high-pressure emulsifier.
  • the gaseous fluorine-containing monomer is incorporated into the surface of the tabular silica fine particles if a hydrophobic layer such as a liquid fluorine-containing monomer exists on the surface of the silica fine particles, so a special means for dispersing the gaseous fluorine-containing monomer. Is usually not needed.
  • the polymerization is carried out at a temperature in which the polymerization initiator does not react. It is preferred to do so.
  • the fluorinated monomer is polymerized.
  • the polymerization is carried out at a temperature equal to or higher than the reaction temperature of the polymerization initiator, that is, at a temperature equal to or higher than the temperature at which the radical polymerization initiator is cleaved to generate radicals.
  • the polymerization is preferably performed at a temperature at which the half-life of the radical polymerization initiator is about 3 to 10 hours.
  • the polymerization can be carried out under normal pressure, or under pressure or under reduced pressure.
  • the polymerization temperature is not particularly limited, and a force of 0 to 100 ° C is appropriate, and 20 to 95 ° C is preferable.
  • a particularly preferred polymerization temperature is 30 to 80 ° C.
  • the new monomer is a liquid monomer
  • the monomer in which the polymerization initiator is dissolved is dispersed in an aqueous medium so as to be sufficiently fine particles as described above. It is preferable to form a second polymer layer by incorporating a new monomer into the surface of the fine particles and performing polymerization. By repeating the same polymerization, tabular silica fine particles having three or more polymer layers can be obtained.
  • the polymer-coated flat silica fine particles before the formation of a new polymer layer be stably dispersed in an aqueous medium.
  • the diameter of the polymer-coated tabular silica fine particles increases, the dispersion stability tends to decrease, and the polymer coating having low dispersion stability tends to decrease. It is difficult to carry out a new polymerization in an aqueous medium in which the finely coated silica particles are dispersed. Therefore, when finally producing composite fine particles having a large diameter, it is preferable to increase the thickness of the outermost polymer layer.
  • the fluoropolymer (A) in the present invention is a fluoropolymer containing a unit derived from a fluoromonomer in which a fluorine atom is bonded to a carbon atom of a polymerizable unsaturated group.
  • the fluorine-containing monomer must have at least one fluorine atom bonded to at least one of the two carbon atoms of the polymerizable unsaturated group.
  • the fluorine-containing monomer may have two or more polymerizable unsaturated groups.In this case, at least one of the two or more polymerizable unsaturated groups has the above fluorine atom. It must have a polymerizable unsaturated group.
  • the fluorine-containing monomer must be a monomer having one polymerizable unsaturated group (hereinafter, also referred to as monoene! Or a monomer having two polymerizable unsaturated groups (hereinafter, also referred to as Jen). Is preferred.
  • a crosslinkable fluorine-containing monomer described later a monomer having three or more polymerizable unsaturated groups (hereinafter also referred to as polyene) can be used.
  • the crosslinkable fluorine-containing monomer is preferably a fluorine-containing gen.
  • there are two types of fluorine-containing gens ie, crosslinkable fluorinated gens and non-crosslinkable fluorinated gens. Monomer). Fluorinated polyenes are usually crosslinkable.
  • Fluorine-containing monoenes are compounds having any of these polymerizable unsaturated groups.
  • the fluorinated gen or fluorinated polyene has at least one of these polymerizable unsaturated groups, and the other polymerizable unsaturated groups may be polymerizable unsaturated groups other than these polymerizable unsaturated groups.
  • the fluorinated gen / fluorinated polyene has two or more of these polymerizable unsaturated groups.
  • a fluorine-containing monomer having a high fluorine content is preferable.
  • the number of fluorine atoms is preferably at least 75%, more preferably at least 80%, based on the total number of fluorine atoms and hydrogen atoms bonded to carbon atoms in the fluorine-containing monomer.
  • Most preferred Fluorine monomers are fluorinated monomers that have substantially no hydrogen atoms bonded to carbon atoms.
  • a fluorine-containing monomer having substantially no hydrogen atom bonded to a carbon atom is referred to as a perfluoromonomer.
  • fluorine atoms bonded to carbon atoms in the perfluoromonomer may be replaced by chlorine atoms.
  • the number of chlorine atoms relative to the total number of fluorine atoms and chlorine atoms in the perfluoromonomer is preferably 25% or less, particularly preferably 20% or less.
  • the most preferred perfluoromonomer is a perfluoromonomer having substantially no chlorine atom bonded to a carbon atom.
  • the fluorine-containing polymer (A) in the present invention is a homopolymer of a fluorine-containing monomer, a copolymer of two or more fluorine-containing monomers, one or more fluorine-containing monomers and one or more monomers other than the fluorine-containing monomers. And the like.
  • a fluorine-containing polymer with a high fluorine content (A) a homopolymer of a fluorine-containing monomer or a copolymer of two or more fluorine-containing monomers is preferred. Preferably not.
  • fluorine-containing polymer (A) in the present invention Pafuru Oromonoma 50 mole 0/0 or more relative to the total monomers, in particular 75 mol 0/0 above, fluorine-containing polymers obtained by polymerizing a monomer of the preferred.
  • fluorine-containing polymer obtained by polymerizing a monomer consisting essentially of a perfluoromonomer hereinafter, also referred to as a perfluoropolymer.
  • the fluoropolymer (A) in the present invention is preferably a fluoropolymer having a high fluorine content.
  • the fluorine content of the fluorine-containing polymer (A) is preferably at least 30% by mass, more preferably 50 to 76% by mass.
  • the shell part of the core / shell composite fine particles of the present invention is made of a fluoropolymer (A), and the shell part may be made of a multi-layered fluoropolymer (A).
  • the layer strength of two or more fluoropolymers (A) may also be provided). It is preferable that at least a part of the fluoropolymer (A) is a crosslinked fluoropolymer.
  • the fluoropolymer (A) is preferably a crosslinked fluoropolymer.
  • the shell part is composed of two or more layers of the fluoropolymer (A), at least the inner layer (the layer in contact with the surface of the flat silica fine particles) is crosslinked.
  • the shell portion is made of a fluorine-containing polymer.
  • Layers other than the inner layer may be crosslinked to form a substantially linear fluorine-containing polymer.
  • the shell portion is relatively thick, the shell portion has a structure of two or more layers, the inner layer is a cross-linked fluoropolymer layer, and the layers other than the inner layer are substantially linear fluoropolymer layers.
  • the substantially linear fluoropolymer (A) will be referred to as the fluoropolymer (A-1), and the crosslinked fluoropolymer (A) will be referred to as the fluoropolymer (A-2).
  • part of the polymer layer is made of a polymer other than the fluoropolymer (A).
  • the polymer other than the fluoropolymer (A) may be a fluoropolymer other than the fluoropolymer (A).
  • the polymer layer as a whole is preferably a polymer mainly composed of the fluoropolymer (A).
  • the proportion of the fluoropolymer (A) to the polymer in the entire polymer layer is 50% by mass or more. It is preferably at least 80% by mass.
  • all the polymers in the polymer layer are made of a fluorine-containing polymer, and the ratio of the fluorine-containing polymer (A) to the total polymer is 80% by mass or more.
  • the substantially linear fluorine-containing polymer (A), that is, the fluorine-containing polymer (A-1) is a homopolymer / copolymer of a fluorine-containing monoene or a homopolymer / copolymer of a cyclopolymerizable fluorogen. Or a copolymer of a fluorinated monoene and a cyclopolymerizable fluorinated gen is preferred.
  • the crosslinked fluorine-containing polymer (A), that is, the fluorine-containing polymer (A-2) is preferably a copolymer obtained by copolymerizing a crosslinkable fluorine-containing diene with a fluorine-containing monoene or a cyclopolymerizable fluorine-containing diene.
  • the amount of a crosslinkable monomer such as a crosslinkable fluorogen is usually 50 mol% or less, preferably 20 mol% or less based on all monomers.
  • the fluoropolymer (A-2) may become brittle, and unreacted polymerizable unsaturated groups may remain to lower the heat resistance of the polymer.
  • the lower limit of the amount of the crosslinkable monomer is not particularly limited, but is preferably 0.1 mol%.
  • R in the polymerizable unsaturated group of the fluoromonomer is a fluorine atom, a perfluoroalkyl group having 4 or less carbon atoms or a perfluoroalkyl group. And a perfluoroalkoxy group having 4 or less carbon atoms is preferred.
  • fluorine-containing monomer the following fluorine-containing monomers (a) to (e) are preferable.
  • fluorinated olefins (a) fluorinated olefins having 2 to 4 carbon atoms are preferred.
  • fluorinated olefins having 2 to 4 carbon atoms are preferred.
  • tetrafluoroethylene, trifluoroethylene, chlorofluoroethylene, vinylidene fluoride And hexafluoropropylene, and perfluoromonomers such as tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene are preferred.
  • a compound represented by the following formula (1) is preferred as the fluorinated methylene dioxolane-based monomer (b), and a fluorinated dioxole-based monomer (c) is represented by the following formula (2) Compounds are preferred.
  • R 11 — R 14 and R lb — R 18 each independently represent a fluorine atom, a fluoroalkyl group having 8 or less carbon atoms or a fluoroalkoxy group having 8 or less carbon atoms.
  • R 11 and R 13 are preferably each a fluorine atom.
  • R 12 and R 14 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
  • R lb is fluorine atom
  • per full O b alkoxycarbonyl is preferably alkoxy is a group member R 17 and R 18 of Pafuruo port alkyl group or a C 1 one 4 number 1 one 4 carbon independently Is preferably a fluorine atom or a perfluoroalkyl group having 6 or less carbon atoms.
  • fluorine-containing methylene dioxolane-based monomer (b) represented by the formula (1) include the following compounds.
  • fluorinated dioxol-based monomer (c) represented by the formula (2) include the following compounds.
  • R 21 has a substituent such as a fluoroalkyl group having 16 or less carbon atoms, which may have an etheric oxygen atom between carbon atoms, a fluorine atom having 418 carbon atoms in the ring, Alternatively, a fluorocycloalkyl group having a total of 16 or less carbon atoms, the above-mentioned fluoroalkyl group substituted with this fluorocycloalkyl group, or R 22 — X group (where R 22 is an etheric oxygen atom between carbon atoms) A fluoroalkylene group having 16 or less carbon atoms, and X represents a functional group).
  • a fluoroalkyl group having 16 or less carbon atoms which may have an etheric oxygen atom between carbon atoms, a fluorine atom having 418 carbon atoms in the ring
  • a fluorocycloalkyl group having a total of 16 or less carbon atoms the above-mentioned
  • a perfluoroalkyl group having 8 or less carbon atoms, an etheric oxygen atom between carbon atoms, or a ring having 5 or 6 carbon atoms and a ring having 4 or less carbon atoms Having a perfluoroalkyl group of A fluorocycloalkyl group having 10 or less, a YX, group (R 2d may have an etheric oxygen atom between carbon atoms, and a perfluoroalkylene group having 8 or less carbon atoms, Y is a single bond or an alkylene group having 1 to 4 carbon atoms, X 'is — SO F, one COOR 26
  • H represents -SIR 27 (OR 28 ).
  • R 26 is a hydrogen atom or an alkyl having 4 or less carbon atoms.
  • R 27 is an alkyl group having 4 or less carbon atoms
  • R 28 is an alkyl group or an alkoxyalkyl group having 4 or less carbon atoms
  • m is an integer of 0-2. Is preferred.
  • Particularly preferred R 21 is a perfluoroalkyl group having 6 or less carbon atoms
  • R 24 — X group (R 24 is a perfluoroalkylene group having 6 or less carbon atoms, in which X, represents SO F or COOR 26 )).
  • a fluorine-containing diene having a compatible unsaturated group wherein the length of the linking group for bonding the both polymerizable unsaturated groups is within a specific range.
  • a fluorinated gen having a linking group length outside the specified range becomes a crosslinkable fluorinated gen. Cyclopolymerizable fluorine-containing gen
  • R 31 and R 32 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a trifluoromethyl group
  • R 33 and R 34 each independently represent a hydrogen atom
  • Q 1 represents a linking group.
  • R 31 and R 32 are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom
  • both R 33 and R 34 are preferably a fluorine atom.
  • Q 1 is a linking group, and its length in atoms (excluding side chain atoms) is 2-4, preferably 2 or 3, and more preferably 3. Most preferred.
  • the linking group preferably comprises a carbon atom or a carbon atom and an oxygen atom. When an oxygen atom is present, it is preferably present at one or both ends of the linking group.
  • the carbon atom must be bonded to an alkyl group having 4 or less carbon atoms such as a hydrogen atom, a fluorine atom, a chlorine atom, or a methyl group, or a haloalkyl group having 4 or less carbon atoms such as a trifluoromethyl group or a trifluoromethyl group.
  • U which is preferred.
  • the cyclopolymerizable fluorine-containing gen (e) is preferably a compound represented by the following formula (41) or (42)! / !. More preferred! /,
  • the cyclopolymerizable fluorine-containing gen (e) is represented by the following formula (4-1) Compound.
  • the most preferred conjugated product is a cyclopolymerizable fluorine-containing gen represented by the formula (41) and having a perfluoro opening (that is, having no hydrogen atom bonded to a carbon atom).
  • R 41 represents an alkylene group, a fluoroalkylene group or a fluoroalkylene group having 1 or 2 carbon atoms excluding the side chain and having a total carbon number of not more than 1, and R 42 represents a hydrogen atom, R 43 represents a hydrogen atom, a fluorine atom, a chlorine atom, a fluoroalkyl group having 2 or less carbon atoms or a fluoroalkyl group having 2 or less carbon atoms.
  • Examples of specific compounds of the cyclopolymerizable fluorine-containing diene (e) include the following compounds.
  • the fluorinated polymer (A) also has the fluorinated monomer power of the above (a) to (e) or the power of one or more copolymers selected from the above.
  • a monomer other than these monomers can be copolymerized with the above-mentioned (a) -one (e) fluorine-containing monomer.
  • the other monomer is a non-crosslinkable monomer, usually a monoene.
  • examples of other monomers include, for example, fluorine-containing monomers having no fluorine atom in a polymerizable unsaturated group such as (perfluoroalkyl) butyl ether, ore fins such as ethylene and propylene, and alkylbutyl ether.
  • butyl ether monomers unsaturated carboxylic esters such as alkyl acrylates and alkyl methacrylates, and vinyl esters such as butyl acetate. If these other monomers are used, the other monomers are preferably less than 50 mol%, especially less than 20 mol%, based on the total monomers.
  • the fluorine-containing polymer (A-1) obtained from the various monomers described above is a substantially linear polymer, and is usually thermoplastic. It is often solvent-soluble.
  • cyclopolymerizable fluorine-containing gen ( e ) one of the carbon atoms of one of the two polymerizable unsaturated groups and one of the carbon atoms of the other polymerizable unsaturated group are used.
  • the two bond together to form a ring, and the two carbon atoms that are not involved in ring formation form a bond to form a divalent monomer unit. Since the monomer unit formed from the cyclopolymerizable fluorinated gen (e) is divalent, a linear polymer is formed from this monomer, similarly to the divalent monomer unit formed from a monoene.
  • a polymer having a ring structure in the main chain is obtained.
  • the main chain of a polymer obtained from a monomer having a polymerizable unsaturated group has a chain force of carbon atoms.
  • the carbon atoms of this main chain are formed from the carbon atoms of the polymerizable unsaturated groups, and even in the polymer of cyclopolymerizable gen, the main chain is formed from the four carbon atoms of the two polymerizable unsaturated groups.
  • Having a ring structure in the main chain means that at least one of the carbon atoms constituting the ring is a carbon atom in the main chain.
  • the ring is preferably a carbocyclic ring having one or two oxygen atoms.
  • Fluorinated methylene di In the monomer unit formed from the oxolane-based monomer (b), one carbon atom in the dioxolane ring becomes the carbon atom in the main chain, and in the monomer unit formed from the fluorinated dioxole-based monomer (c), two carbon atoms in the dioxole ring are used. Carbon atoms become carbon atoms in the main chain.
  • Cyclopolymerizable fluorinated gen (e) force In the monomer units formed, 2 to 4 of the 4 carbon atoms of the polymerizable unsaturated group are ring carbon atoms.
  • the linking group Q 1 that have a oxygen atom is formed is ring comprising an oxygen atom and a carbon atom, when consisting of only carbon atoms to form a carbon ring.
  • the fluoropolymer (A) is preferably a fluoropolymer having an aliphatic ring in the main chain. That is, both the fluoropolymer (A-1) and the fluoropolymer (A-2) are preferably fluoropolymers having an aliphatic ring in the main chain.
  • the proportion of the monomer unit having an aliphatic ring to all the monomer units in the fluoropolymer is preferably 20 mol% or more, particularly preferably 50 mol% or more.
  • the fluoropolymer (A) is preferably a crosslinked fluoropolymer.
  • the fluorine-containing polymer (A-2), which is a crosslinked fluorine-containing polymer, is a monomer having a linear polymer as described above and a monomer having two or more polymerizable unsaturated groups (however, it has a cyclopolymerizability).
  • a polymer obtained by copolymerizing a monomer is preferred.
  • a crosslinkable fluorine-containing gen is preferable!
  • a polyene having a fluorine atom and having a fluorine atom may be used.
  • the compound represented by the following formula (5) is preferable as the crosslinkable fluorine-containing diene.
  • Such fluorine-containing diene is cyclic polymerization is difficult for Jen than the length of the linking group Q 2 is too short or too long. As a result, the two polymerizable unsaturated groups are bonded to other monomer molecules, respectively, to form a crosslinked structure.
  • R 51 and R 52 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a trifluoromethyl group
  • R 53 and R 54 each independently represent a hydrogen atom.
  • Q 2 represents a linking group.
  • R 51 and R 52 are respectively Independently, a hydrogen atom, a fluorine atom or a chlorine atom is preferred, and both R 53 and R 54 are preferably a fluorine atom.
  • Q 2 is a linking group, and its length in terms of the number of atoms (excluding side chain atoms) is 1 or 5 or more, preferably 5-16, and more preferably 6-12 Is most preferred.
  • the linking group preferably comprises a carbon atom or a carbon atom and an oxygen atom. When an oxygen atom is present, it is preferably present at one or both ends of the linking group.
  • the carbon atom is preferably bonded to an alkyl group having 2 or less carbon atoms such as a hydrogen atom, a fluorine atom, a chlorine atom and a methyl group, and a haloalkyl group having 2 or less carbon atoms such as a trifluoromethyl group and a trichloromethyl group.
  • a preferred compound represented by the formula (5) is a compound having a perfluorinated mouth, and a compound represented by the formula (5) is particularly preferably a compound represented by the following formula (5-1) (where n is 4 or less). (An integer of 10).
  • crosslinkable fluorine-containing diene a crosslinkable fluorine-containing diene having another structure can be used.
  • a crosslinkable fluorine-containing gen in which the polymerizable unsaturated group in the above formula (5) is replaced with another polymerizable unsaturated group-containing organic group, and perfluorinated ether.
  • the size of the composite fine particles of the present invention is not particularly limited. However, since the composite fine particles are obtained by coating the surface of the tabular silica fine particles of a specific size with the fluoropolymer (A), the size is represented by the ratio of the tabular silica fine particles in the composite fine particles.
  • the ratio of the tabular silica fine particles in the composite fine particles is 117 to 70% by mass. More preferably, the proportion is 3-50% by mass.
  • the proportion exceeds 70% by mass, the surface of the inorganic fine particles is not sufficiently coated with the fluoropolymer (A), so that the composite fine particles are easily aggregated and the affinity with the organic polymer tends to be insufficient.
  • the proportion is less than 1% by mass, it is difficult to exhibit the properties derived from the tabular silica fine particles when using the composite fine particles.
  • the ratio of the flat silica fine particles in the composite fine particles is preferably 5 to 70% by mass. Particularly, 10 to 50% by mass is preferable.
  • Fluorine-containing polymer in composite fine particles In the case where (A) also has the fluorinated polymer (A-1) and fluorinated polymer (A-2) forces, the ratio of the flat silica fine particles in the composite fine particles is preferably 1 to 50% by mass, particularly 3 to 30%. % By mass is preferred.
  • the ratio of the fluoropolymer (A-1) to the fluoropolymer (A-2) in the composite fine particles is not particularly limited, but the total of the tabular silica fine particles and the fluoropolymer (A-2) It is preferable that the fluoropolymer (A-2) is contained in such an amount that the ratio of the tabular silica fine particles to 90% by mass or less is obtained.
  • the composite fine particles of the present invention can be used in various applications as a molding material in the form of a dispersion dispersed in an aqueous medium or another liquid medium. Further, it can be used in various applications as a molding material in the form of a powder obtained by separation from a liquid medium.
  • the dispersion in which the composite fine particles are dispersed in the liquid medium can be used as a coating agent by coating or cast molding by dispersing or dissolving other additive components as necessary.
  • Other additional components include a matrix polymer described later and a binder such as a curable resin that can be a matrix polymer.
  • the liquid medium is not limited to the aqueous medium used for producing the composite fine particles, and other liquid media can be used.
  • dispersions using various liquid media can be produced by a solvent replacement method or a method of dispersing powdered composite fine particles in a liquid medium.
  • a liquid medium having affinity for the polymer on the surface of the composite fine particles is preferable.
  • the polymer on the surface of the composite fine particles is a fluorinated polymer (A)
  • a highly hydrophobic liquid medium such as a fluorinated solvent is preferred.
  • liquid medium is a liquid medium that easily dissolves the fluoropolymer, if the polymer on the surface of the composite fine particles is a crosslinked polymer, there is no danger that the surface of the silica fine particles will be exposed.
  • the powder of the composite fine particles can be obtained by separating the composite fine particles from the composite fine particle-dispersed aqueous medium obtained by the above-mentioned production method. If necessary, the composite fine particles can be purified by washing or the like.
  • the powder of the composite fine particles can be used as various molding materials.
  • the ratio of silica in the composite fine particles is preferably from 50 to 50% by mass, more preferably from 110 to 20% by mass.
  • the composite fine particles have at least a polymer in the surface layer crosslinked, and most of the polymer except for the layer in contact with the surface of the flat silica fine particles, which is preferably a polymer in terms of moldability. Is a fluoropolymer (A-1) Is preferred.
  • the powder of the composite fine particles can also be used as various molding materials by compounding with other materials.
  • the molding material in which the composite fine particle powder and the matrix polymer are composited, the ratio of silica in the composite fine particles to the total of the composite fine particles and the matrix polymer is preferably 0.1 to 30% by mass. In particular, it is preferably 1 to 20% by mass.
  • various additives other than the composite fine particles and the matrix polymer can be mixed in the molding material. The amount of the additives is selected according to the type and purpose of the additives, and is not particularly limited.
  • the ratio of the tabular silica fine particles in the composite fine particles used in this application may be selected to be as high as 170% by mass depending on the ratio of the composite fine particles to the matrix polymer.
  • the composite fine particles having a relatively high silica fine particle ratio it is preferable to use the composite fine particles having a relatively high silica fine particle ratio.
  • substantially all of the fluorine-containing polymer (A) in the composite fine particles having a relatively high silica fine particle ratio is a fluorine-containing polymer (A-2).
  • the composite fine particles having a relatively high ratio of inorganic fine particles composite fine particles having a ratio of inorganic fine particles of 30 to 90% by mass, particularly 50 to 70% by mass are preferred.
  • fluorine-containing polymer as the matrix polymer examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene Z, and perfluoronooleanolequilby-noreether copolymer (PFA) and tetrafluoroethylene Z.
  • PTFE polytetrafluoroethylene
  • PFA perfluoronooleanolequilby-noreether copolymer
  • Xafluoropropylene-based copolymer FEP
  • PCTFE polychlorinated trifluoroethylene
  • PVDF polyvinylidene fluoride
  • ETFE ethylene Z tetrafluoroethylene copolymer
  • thermoplastic fluorine-containing elastomers and soft fluorine-containing polymers In addition to general-purpose fluorine-containing polymers such as Tylene Z-cloth trifluoroethylene copolymer (ECTFE), there are thermoplastic fluorine-containing elastomers and soft fluorine-containing polymers.
  • the powder of the composite fine particles can be blended with a fluorinated curable resin such as a fluorinated polyimide resin or a fluorinated epoxy resin.
  • fluorinated methylene dioxolane type monomer (b), fluorinated dioxol type monomer (c), cyclopolymerizable fluorinated gen It can also be blended with a fluorine-containing polymer containing a unit derived from a monomer such as (e), that is, a fluorine-containing polymer having an aliphatic ring in the main chain.
  • a fluorine-containing polymer containing a unit derived from a monomer such as (e), that is, a fluorine-containing polymer having an aliphatic ring in the main chain.
  • Preferred fluoropolymers are thermoplastic fluoropolymers.
  • the powder of the composite fine particles can also be used by being blended with a matrix polymer made of a thermoplastic or curable polymer other than the fluoropolymer. Further, it can be blended with a curable resin which can be cured to become a matrix polymer.
  • a matrix polymer made of a thermoplastic or curable polymer other than the fluoropolymer.
  • a curable resin which can be cured to become a matrix polymer.
  • the molding material containing the powder of the composite fine particles and the matrix polymer can be formed into a molded product by various molding methods such as heat molding, heat and pressure molding, extrusion molding, and injection molding.
  • the crosslinked polymer in the composite fine particles does not melt even in a molding method in which the matrix polymer is melted and molded. There is little possibility that the surface of the silica fine particles in the composite fine particles is exposed and comes into contact with the molten matrix polymer.
  • the composite fine particles function as a non-melting filler, and a molded product in which the flat silica fine particles in which aggregation and uneven distribution of the flat silica fine particles are eliminated are uniformly and monodispersed in the matrix polymer can be obtained.
  • affinity for a matrix polymer can be improved, and a polymer having no functional group on the composite fine particle surface and a matrix polymer can be used. Even when the affinity for the two is low, the affinity between the two can be improved and the two can be uniformly mixed without phase separation.
  • a fluorine-containing polymer having a functional group such as SOF or COOR 25 is used.
  • the polymer molded product of the present invention which also provides a molding material containing composite fine particles (comprising composite fine particles or composite fine particles and matrix polymer), exhibits a function derived from tabular silica fine particles.
  • the resulting polymer molded article is obtained. For example, it is effective in improving physical properties such as improvement in rigidity and strength of a polymer molded article, reduction in coefficient of thermal expansion, and improvement in heat resistance.
  • a fluorine-containing polymer which is not particularly crosslinked is preferable.
  • fluorinated olefins (a), fluorinated methylene dioxolane-based monomers (b), fluorinated dioxol-based monomers (c), fluorinated butyl ether-based monomers (d), cyclized polymerized fluorinated gens Fluorine-containing polymers containing units derived from monomers such as (e) are preferred.
  • the units derived from the fluorinated methylene dioxolane-based monomer (b), the fluorinated dioxol-based monomer (c) or the cyclopolymerizable fluorinated gen (e) are all repeating units of 20%.
  • a fluorine-containing polymer containing at least mol% (particularly at least 50 mol%) is preferred.
  • fluorinated olefins such as tetrafluoroethylene ( a ) or fluorinated vinyl ether monomers ( d ) are preferred, and fluorinated vinyl ether monomers ( d ) are preferred. May be a compound having a functional group! / ⁇ .
  • fluoropolymer (B) is a polymer known as a transparent fluororesin that has higher transparency than other fluoropolymers due to having an aliphatic ring structure in the main chain. It is a fluorine-containing polymer also used for.
  • -(B) is preferably substantially a perfluoropolymer.
  • tabular silica fine particles it has been difficult to uniformly mix tabular silica fine particles with perfluoropolymer without aggregation.
  • By blending the composite particles of the present invention it becomes possible to blend tabular silica fine particles uniformly into the perfluoropolymer without coagulation. Characteristics can be exhibited.
  • Perfluoropolymers and fluorine-containing polymers having a high fluorine content have excellent properties such as low dielectric constant (low dielectric constant, low dielectric loss tangent), electrical insulation and heat resistance as insulating materials. Is known as a high frequency insulating material. Therefore, it is used as an insulating material in electronic circuit boards, LSI element boards, electronic components, wire coatings, and the like.
  • PTFE a typical perfluoropolymer, has poor mechanical properties such as low rigidity and high coefficient of thermal expansion! In order to improve the mechanical properties, it is necessary to incorporate a relatively large amount of an inorganic filler such as glass fiber or silica, and as a result, low dielectric properties are sacrificed.
  • a material in which the composite fine particles of the present invention are blended with a fluorine-containing polymer having a high fluorine content, particularly a perfluoropolymer, has a rigidity and a coefficient of thermal expansion due to the blending of a relatively small amount of tabular silica fine particles.
  • the mechanical properties such as the above are improved, and the lowering of the thermal expansion coefficient is exhibited with a smaller amount of blending compared to the spherical nano-sized silica fine particles. Therefore, it is characterized in that the lowering of the low dielectric properties due to the blending of silica is small.
  • there is little or no decrease in the inherent characteristics of the fluoropolymer such as mechanical properties, electrical properties, moldability, processability, heat resistance, chemical stability, and low water absorption.
  • the composite fine particles of the present invention containing the tabular silica fine particles have excellent characteristics particularly as a material for an electric insulating material having a low dielectric constant.
  • the powder of the composite fine particles of the present invention having a high proportion of the fluorinated polymer (A) can be used as a molding material as it is, and can be formed into sheets, films, and other molded products by hot press molding, extrusion molding, injection molding, or the like. Further, a similar molded product can be formed by using a molding material in which the powder of the composite fine particles of the present invention is blended with a perfluoropolymer such as a fluoropolymer (B) or a fluorine-containing high-V, fluoropolymer. .
  • the amount of silica derived from the composite fine particles in these molded products is preferably from 0.5 to 25% by mass, particularly preferably from 11 to 15% by mass, based on the entire fluoropolymer.
  • a molded product has excellent characteristics as an electronic circuit board.
  • a molded material useful for electronic circuit boards and the like is obtained from a molding material in which a composite fine particle having a fluoropolymer (A) having an aliphatic ring structure in the main chain and a matrix having a strong fluoropolymer (B) are combined. be able to.
  • the content ratio of the silica fine particles in the composite fine particles is the content ratio determined by thermogravimetric analysis (TGA) after measuring the residual weight force after heating at 600 ° C.
  • TGA thermogravimetric analysis
  • Fluoroalkylsilane A CF (CF) CH CH Si (OCH) (GE Toshiba Silicone
  • Fluorosurfactants A CF (CF) CONHC HN (CH) -HC1 0
  • Fluorosurfactant B CF (CF) COONH.
  • IPP ((CH) CHOCOO); diisopropyl peroxydicarbonate.
  • PBTHF Perfluoro (2-butyltetrahydrofuran).
  • TFE Tetrafluoroethylene
  • aqueous dispersion 60 g of pentafluoropropane in a mouth was prepared, and 0.2 g of a fluorosurfactant B was dissolved therein. This solution is added to water containing 0.3% of a fluorine-containing surfactant B, and the mixture is dispersed by irradiating ultrasonic waves with stirring, and then isopropyl alcohol is dispersed by a rotary evaporator. And dichloropentafluoropropane were distilled off. The resulting aqueous dispersion is bluish white and transparent.
  • the surface of flat silica fine particles of 10 to 50 nm in size and 15 to 15 nm in thickness was coated with two layers of fluororesin, and the inner layer was formed of PBVE cross-linked with HMDVE.
  • the outer layer is a homopolymer of PBVE.
  • the obtained powder was formed into tablets (diameter 12 mm, thickness 2.4 mm) at 300 ° C. using a press molding machine. It was suggested that this tablet-shaped molded product was translucent and had good dispersibility of silica fine particles.
  • TMA thermomechanical analyzer
  • the coefficient of thermal expansion was measured using a TMA (thermomechanical analyzer)
  • the thermal expansion coefficient of the PBVE polymer alone of 75 ppm Z ° C it was found that there was an effect of lowering the thermal expansion coefficient with a small silica content.
  • the dielectric constant Z dielectric loss tangent was measured using this sample, it was 2.1 / 0.001 at 100 MHz, confirming low dielectric properties.
  • Olg as a polymerization initiator obtained by adding ion-exchanged water to lOOg to add water to the aqueous dispersion of flat silica fine particles produced in the same manner as in Synthesis Example 1.
  • polymerization was carried out at 40 ° C. for 20 hours with stirring in a 200 cc glass reactor. Then cool to room temperature, PBVE A mixed solution of 1.5 g and IPPO.
  • Olg was added to the reactor, and a homogeneous solution was obtained by ultrasonic irradiation with stirring. Thereafter, the temperature was raised to 40 ° C again, and the reaction was carried out for 20 hours while stirring. After that, it was agglomerated and dried to obtain 1.lg of white powder.
  • the silica content determined from the heating residue by thermogravimetric analysis was 15%.
  • the PBVE polymer powder obtained by the emulsion polymerization and the fused silica fine particle powder (average particle size: 0.6 m) were mixed to adjust the silica content to 10 and 20%. These tablets were white and opaque.
  • the coefficient of thermal expansion was measured using TMA, the average value at 30-60 ° C was 62 ppmZ ° C (10% silica) and 51 ppmZ ° C (20% silica).
  • the molded product obtained from the composite particles of the present invention was compared with the CTE (average value at 30-60 ° C) of the fused silica composite of the comparative example, as shown in FIG. It can be seen that CTE can be reduced with smaller silica content of the particles.
  • Ion-exchanged water was added to a flat silica-containing aqueous solution prepared in the same manner as in Synthesis Example 1 to make 100 g of PBVE, and 2.0 g of PBVE was added. The mixture was sufficiently dispersed by ultrasonic irradiation for 5 minutes with stirring. . After adjusting the pH to 415 by adding a small amount of sodium hydrogen phosphate, 0.7 g of APS was added, and 0.7 g of TFE was introduced with stirring in a 200 cc stainless steel reactor. Polymerization was performed at 50 ° C for 20 hours. Thereafter, the mixture was cooled to room temperature, agglomerated and dried to obtain 2.6 g of a white powder. The silica content determined from the heating residue by thermogravimetric analysis was 4%.
  • the obtained powder was tableted at 320 ° C using a press molding machine (diameter 12 mm, thickness 2.4 mm). ). It was suggested that this tablet-shaped molded product was translucent and had good dispersibility of silica fine particles.
  • TMA coefficient of thermal expansion
  • Powder composed of Z-shell composite microparticles is used to produce a fluoropolymer molded product in which the tabular silica microparticles are uniformly dispersed. It is excellent as a molding material for producing the same, and the effect of adding silica particles is exhibited even when the content of the tabular silica fine particles in the molded product is relatively small.
  • the composite fine powder can be used as an additive for various polymer materials, and a molding material containing a strong powder can reduce the amount of silica particles required to exert the effect of adding silica particles.
  • the disadvantages caused by adding a large amount of additives can be eliminated.
  • the molding material made of a fluoropolymer containing a powder that also has a composite fine particle power is used particularly as a low dielectric constant insulating circuit board material and a moisture-proof insulating sealing material for electronic parts and the like.

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Abstract

L'invention concerne une particule composite à âme/enveloppe composée d'une âme d'une particule fine de silice semblable à une plaque de taille nanométrique et d'une enveloppe d'un polymère contenant du fluor contenant une unité issue d'un monomère contenant du fluor. L'invention porte aussi sur un procédé de fabrication de cette particule composite à âme/enveloppe et sur l'utilisation associée. Elle concerne notamment une particule fine composite composée d'une particule fine de silice semblable à une plaque de taille nanométrique dont la surface est recouverte d'un polymère contenant du fluor contenant une unité issue d'un monomère contenant du fluor. Dans cette particule fine composite, le rapport de la particule fine de silice semblable à une plaque est compris entre 1 et 70 % en poids. L'invention se rapporte également à un procédé de fabrication de cette particule fine composite, qui se caractérise par le fait qu'un monomère contenant du fluor est radicalement polymérisé dans un système de polymérisation dans lequel les particules fines de silice semblables à une plaque sont dispersées dans un solvant aqueux en présence d'un agent de surface. L'invention concerne aussi un matériau de formation contenant ces particules fines composites.
PCT/JP2005/000255 2004-01-13 2005-01-12 Particule fine composite et procede de fabrication associe WO2005068362A1 (fr)

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CN105153866A (zh) * 2015-10-20 2015-12-16 江苏丰彩新型建材有限公司 一种有机无机杂化超疏水涂层及其制备方法
CN112153839A (zh) * 2020-09-27 2020-12-29 黄杰 一种利用新材料对精密探测仪器进行防护的辅助装置
CN112153839B (zh) * 2020-09-27 2021-12-10 西安佰达菲仪器设备有限公司 一种利用新材料对精密探测仪器进行防护的辅助装置

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