WO2006101263A1 - Particule fine revetue, procede pour la fabriquer et particule fine conductrice - Google Patents

Particule fine revetue, procede pour la fabriquer et particule fine conductrice Download PDF

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Publication number
WO2006101263A1
WO2006101263A1 PCT/JP2006/306597 JP2006306597W WO2006101263A1 WO 2006101263 A1 WO2006101263 A1 WO 2006101263A1 JP 2006306597 W JP2006306597 W JP 2006306597W WO 2006101263 A1 WO2006101263 A1 WO 2006101263A1
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Prior art keywords
fine particle
mentioned
group
preferable
polymer
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PCT/JP2006/306597
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English (en)
Inventor
Tsuyoshi Yamashita
Mitsuo Kushino
Mamiko Kurosawa
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Nippon Shokubai Co., Ltd.
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Priority to JP2006517887A priority Critical patent/JP4950662B2/ja
Priority to CN2006800090393A priority patent/CN101146838B/zh
Publication of WO2006101263A1 publication Critical patent/WO2006101263A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • 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
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C09D161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • H05K2201/0212—Resin 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
    • H05K2201/0221—Insulating particles having an electrically conductive coating

Definitions

  • the present invention relates to a coated fine particle that have good adhesion to metals and the manufacturing method, and to a conductive fine particle using the coated fine particle.
  • Polymer particles are widely used in displays such as crystal displays, spacers for cell gaps (or panel gaps) such as touch panels, conductive adhesives for mounting microelements, and conductive gap fillers such as anisotropic conductive adhesives. In these applications, it is required to have nearly uniform particle shapes and to be flexible and excellent in elasticity. From such point of view, organic materials and organic and inorganic composite materials in which organic components and inorganic components are used together have been used as materials for the polymer particles.
  • organic resin particles consisting of amino resins (for example, urea resin, melamine resin, and guanamine -t ype resin) are disclosed. Because these amino resin fine particles have a number of functional groups on the surface of the fine particle, they have good adhesive to metals to be easy to form metal coated layer. Consequently, they are widely used as base material particles.
  • amino resins for example, urea resin, melamine resin, and guanamine -t ype resin
  • the above-mentioned amino resin fine particles have minute crosslinked structure, the particles are too hard to be compres s ively deformed, for example, when being used between electrodes as conductive fine particles, they could not broaden the contact area with the surfaces of the electrodes and the contact resistance was difficult to be reduced. Moreover, there was such a problem that when the compressive deformation volume is enlarged to broaden the contact area, the particles break down at which time the strain of particles becomes large and are, as a result, inferior for connecting reliability.
  • the present invention has been made in consideration of the above-mentioned circumstances, and the aims are to provide a coated fine particle that is excellent in. flexibility and have good adhesion to metals and the manufacturing method, and to provide a conductive fine particle having the coated fine particle as the core fine particle.
  • the coated fine particle of the present invention that could settle the above-mentioned problems have the essential points that the coated fine particle comprises a core fine particle containing an organic material or an organic and inorganic composite material, and a polymer coated layer on a surface of the core fine particle, wherein the polymer coated layer is formed by ring-opening reaction and/or polycondens at ion reaction on the surface of the core fine particle.
  • the present inventors have advanced the study of obtaining such fine particle that are excellent in flexibility and elasticity and have good adhesion to metals, and have repeated the process of trial and error based on their idea that getting the above-mentioned properties from different materials, respectively, and integrating them may lead to the effect of satisfying the settlement of the problems.
  • the above-mentioned properties cannot be sufficiently revealed by merely integrating such materials.
  • the essential point of the present invention is that the composition is made so as to get the flexibility and elasticity of the fine particle from the core fine particle constituting the center parts of the fine particle and to get the adhesion to metals from polymer coated layer coating the core particle and further this polymer coated layer is formed by ring-opening and/or polycondensation reaction. That is, because uniform polymer coated layer exist on the core fine particle, it became possible to obtain the coated fine particle that have, of course, flexibility and elasticity and are excellent in adhesion to metals.
  • a method of manufacturing a coated fine particle of the present invention is manufacturing a coated fine particle having a polymer coated layer on a surface of the core particle containing an organic material or an organic and inorganic composite material, wherein said polymer coated layer is formed by a ring-opening reaction and/or polycondensation reaction in a water-based medium in which said core particle is dispersed, and in the presence of a surfactant .
  • Fig. 1 is a schematic cro s s -sect ional diagram of a coated fine particle of the present invention.
  • Fig. 2 is a schematic cros s - s ect ional diagram of a conductive fine particle of the present invention .
  • Fig. 3 is an electron microscopic (SEM: scanning electron microscope) picture showing a core fine particle before the formation of a polymer coated layer (Synthesis example (3) ) .
  • Fig. 4 is an electron microscopic (SEM) picture showing a core fine particle after the formation of a polymer coated layer (Manufacturing example 1) . (Explanation of Numerals)
  • the coated fine particle of the present invention is characterized in that it has polymer coated layer formed by ring-opening reaction and/or polycondensation reaction on the surface of the core fine particle comprising an organic material or an organic and inorganic composite material.
  • the points of the present invention are that not only physical properties to be reguired for the core fine particle (for example, flexibility and elasticity) are provided, but polymer coated layer, which is excellent in adhesion to metals, are uniformly formed on the surfaces of the core fine particle. Accordingly, first, the above-mentioned polymer coated layer will be described.
  • the polymer coated layer included in the present invention give good adhesion to metals to the coated fine particle of the present invention and are formed on the surface of the core fine particle through the ring-opening reaction and/or polycondensation reaction of a compound, which is a raw material of the above-mentioned polymer coated layer, in a water-based medium in which the above-mentioned core particles are dispersed, and in the presence of a surfactant (for example a compound shown by the general formula (1) as described later) .
  • a surfactant for example a compound shown by the general formula (1) as described later
  • compounds (A) and compounds (B) (will be described later) can be cited.
  • the above-mentioned compounds (A) are preferable to be those containing a m.ixture of at least one kind selected from th.e group consisting of urea, thio urea, melamine, benz oguanamine , acetoguanamine , and cyclohexylguanamine .(hereinafter referred to as the "amino compounds”) and of formaldehyde, or an initial condensation compound obtained by reacting at least one kind selected from these amino compounds with formaldehyde. Further, it is preferable to use an initial condensation compound as a compound (A) in terms of high affinity for water and the rapid formation of a polymer coated layer.
  • an amino resin urea type resins, melamine type resins, and guanamine type resins
  • an initial condensation compound is a compound that is a precursor of an amino resin. That is, a polymer coated layer that essentially contains an amino resin structure is formed by the use of the above-mentioned compound (A) .
  • the above-mentioned initial condensation compound is, in case of using (i) at least one kind of urea and thio urea (hereinafter referred to as the "urea type compounds") and formaldehyde, an initial condensation compound that can be a constituent in a urea resin, in case of using (ii) melamine and formaldehyde, an melamine resin, and in case of using (iii) at least one kind selected from the group consisting of benzoguanamine , acetoguanamine, and cyclohexylguanamine (hereinafter, compounds of guanamine series) and formaldehyde, an initial condensation compound that can be a constituent in guanamine resins.
  • urea type compounds an initial condensation compound that can be a constituent in a urea resin
  • melamine and formaldehyde an initial condensation compound that can be a constituent in a urea resin
  • formaldehyde an initial condensation compound that can be a constituent in gu
  • the above-mentioned initial condensation compound is a compound that can be a constituent in a resin in which two kinds or more among urea type resins, melamine resin and guanamine type resins are mixed. Any one kind of these initial condensation compounds may be used, or two or more kinds may be used together as the above-mentioned initial condensation compound.
  • urea type compounds, melamine, co-condensates of a urea type compounds and melamine, and co-condensates of melamine and a guanamine type compounds are preferable, urea type compounds, melamine, and co-condensation compounds of a urea type compounds and melamine are more preferable, and melamine, and co-condensates of a urea type compounds and melamine are further preferable.
  • other amino compounds other than the above-mentioned amino compounds may be used together.
  • amino compounds for example, capryguanamine , amerine, ameride, ethyleneurea , propyleneurea , and acethyleneurea can be cited.
  • the above-mentioned amino compound and other amino compound shall be collectively treated as an amino compound that may be a raw material for the above-mentioned condensation compound (or may be contained in a polymer coated layer) .
  • Formaldehyde to be reacted with the above-mentioned amino compounds is especially not limited as long as any compound that yields formaldehyde within the reaction system. Moreover, in the reaction from which the above-mentioned initial condensation compounds are obtained, since water is generally used as a solvent, in addition to aqueous formaldehyde solution (formalin), trioxane or paraformaldehyde may be added into water so as to be able to generate formaldehyde in water.
  • the following methods can be preferably cited: a method that an amino compound is added in aqueous formaldehyde solution (formalin) and reacted, a method that the above-mentioned amino compound is added in the aqueous solution in which trioxane or paraformaldehyde has been added and reacted, and others.
  • the former method is preferable because no bath for preparing aqueous formaldehyde solution is needed and formalin is available easily.
  • the above-mentioned reaction is acceptable to be a mode in which an amino compound and formaldehyde react in the mixed state, for example, the mode may be a mode in which aqueous formaldehyde solution is added into an amino compound other than a mode in which an amino compound is added into aqueous formaldehyde solution.
  • the above-mentioned reaction is preferably carried out under stirring with a well known stirring device.
  • mole ratio of an amino compound and formaldehyde is preferable to be 1 / 0.5 to 1 / 10, more preferable to be 1 / 1 to 1 / 8, and further preferable to be 1 / 1 to 1 / 6.
  • mole ratio of an amino compound and formaldehyde (mole ratio) is out of the above-mentioned range, either of the compounds remains in large amounts as it is unreacted in the reaction system.
  • the amount an amino compound and formaldehyde added to water that is, the concentration of the amino compound and formaldehyde at the time of feeding is desirable to be higher unless no obstacle is observed in the reaction.
  • the above-mentioned initial condensation compound is preferable to be 100% or more in water mixing degree (an index of the degree of polycondens at ion rate) and more preferable to be 200% or more, and preferable to be 5000% or less and more preferable to be 3000% or less.
  • water mixing degree is over the above-mentioned range, it means that the initial condensation compound has high hydrophilic property, and in such a case, the formation of a polymer coated layer is apt to need a long time.
  • the water mixing degree indicates the degree of the polymerization rate of the initial condensation compound obtained by the reaction of an amino compound with formaldehyde, and is a value obtained by multiplying the ratio of the mass of water needed to generate white turbidity in case of addition of water in the initial condensation compound (5 g, 15°C) and the mass of the initial condensation compound (that is, [water (g) / initial condensation compound (g)]) by 100.
  • the degree of the polycondens at ion rate of the above-mentioned initial condensation compound can be controlled methods other than that of water mixing degree, for example, GPC (Gel Permeation Chromatography) , LC (Liquid Chromatography) and the like, the method of water mixing degree is preferably adopted because it can be easily carried out and its repeatability is also good.
  • GPC Gel Permeation Chromatography
  • LC Liquid Chromatography
  • the reaction of the initial condensation compound is preferably carried out within the range of 65 to 75°C. It is because in such temperature range, the state of progress of the reaction can be grasped with time and instantly and the desired end of the reaction (the aimed point) can be exactly ascertained by the above-mentioned water mixing degree, and further the reaction can be easily stopped by cooling the reaction liquid and the like at the time.
  • the reaction time is not especially limited, and may be decided properly while confirming the progress situation of the reaction.
  • an epoxy compound (a compound having an epoxy group) can be used as compound (B) .
  • the polymer coated layer containing an epoxy resin formed by ring-opening and polycondensati on of an epoxy compound is also included in the present invention. Through containing an epoxy resin, the coated fine particle that is more flexible and have higher mechanical strength can be obtained.
  • epoxy compounds that are raw materials of the above-mentioned epoxy resins, compounds having two or more epoxy groups in one molecule and showing water solubility are preferable.
  • Such epoxy compounds include, for example-, sorbitol polyglycidyl ester, ( poly ) glycerol polyglycidyl ester, pent ae rythrit ol polyglycidyl ester, glycidyl t ri s ( 2 -hydroxyethyl ) i socyanurate , t rimethylolpropane polyglycidyl ester, neopent ylglycol diglycidyl ester, ethylene glycol diglycidyl ester, polyethylene glycol diglycidyl ester, propylene glycol diglycidyl ester, polypropylene glycol diglycidyl ester, and diglycidyl adipate. These compounds may be used independently, and may be used in combination of two or more
  • the dissolution ratio of the above-mentioned epoxy compound in water is preferable to be 50 % by mass or more, more preferable to be 60 % by mass or more, further preferable to be 70 % by mass or more, and especially preferable to be 100 % by mass.
  • the dissolution ratio is within the range, such excellent effects can be obtained as the formation of epoxy resin layer (polymer coated layer) progresses uniformly and rapidly and the thickness of the epoxy resin layer can be easily controlled.
  • the dissolution ratio of an epoxy resin in water that is prescribed in the present invention • means values obtained by the following measurement method.
  • the weight average molecular weight of the above-mentioned epoxy compound is preferable to be 300 or more and 10,000 or less, and more preferable to be 300 or more and .5,000 or less.
  • the weight average molecular weight is within the above-mentioned range, such excellent effects can be obtained as the thickness of the epoxy resin layer (the polymer coated layer) can be easily controlled.
  • the weight average molecular weight is less than the above-mentioned range, it is difficult to obtain the improvement of flexibility by the formation of epoxy resin layer and the formation of uniform epoxy resin layer may be difficult.
  • the viscosity of the reaction fluid rises rapidly at the time of the formation of polymer coated layer and stirring may be difficult. At this time, the reaction fluid is stirred by force, coated fine particle may be damaged or broken .
  • a crosslinking agent may be added. Strength of the epoxy resin layer, consequently strength of the coated fine particle can be further increased by using a crosslinking agent, and as a result, isolation of coated fine particles and their damage and broken in the cleaning process can be effectively controlled.
  • the timing of the addition of the above-mentioned crosslinking agent is not especially limited, it may be added together with an epoxy compound and may be added before or afte.r the addition of an epoxy compound, it is preferably added after the addition of an epoxy compound.
  • crosslinking agents are not especially limited but include, for example, sodium diethyldithiocarbamate (including hydrates), diethylammonium diethyldithiocarbamate (including hydrates) , dithiooxalic acid, and dithio carbonic acid These compounds may be used independently, and two or more kinds of them may be used together.
  • the amount of the above-mentioned crosslinking agent added is not limited, it is preferable to be 1 to 100 mass parts to 100 mass parts of an epoxy compound and more preferable to be 5 to 80 mass parts.
  • surfactants to be made coexist within the reaction system include compounds shown by the following formula (1) and emulsifying agents to be exemplified in the description of the core fine particles to be described later, for example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and high-molecular surfactants.
  • the above-mentioned surfactants are used to form polymer coated layer uniformly on the surfaces of the core fine particles while keeping the dispersion state of the core fine particles in the reaction system, and surfactants shown by the above-mentioned formula (1) becomes constituents of the polymer coated layer. That is, the polymer coated layer included in the present invention is formed by utilizing intermolecular force such as hydrophobic interaction acting between the core fine particles and a surfactant, and between a surfactant and the above-mentioned compound (A) and/or compound (B) .
  • the opening reaction and polycondensat ion reaction of the above-mentioned compound (A) and/or compound (B) progress not only on the surfaces of core fine particles but everywhere and, as a result, polymer components having no core fine particle and derived from compound (A) and compound (B) are produced in addition to the coated fine particles included in the present invention. Consequently, it is preferable to use a surfactant, when the polymer coated layer is formed. Further, from a viewpoint of forming uniform polymer coated layer on the surface of the core fine particle, among the above-mentioned surfactants, surfactants shown by the above-mentioned formula (1) are preferably used.
  • R 1 indicates hydrophobic groups including aliphatic or organic hydrocarbon groups, for example, aliphatic hydrocarbon groups such as a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, an octadecyl group, a stearyl group, and a behenyl group, and aromatic hydrocarbon groups such as a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, and a naphthyl group can be cited.
  • aliphatic hydrocarbon groups such as a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, an octadecyl group, a stearyl group, and a behenyl group
  • aromatic hydrocarbon groups such as
  • the carbon number of the hydrophobic groups is preferable to be 5 or more and 25 or less (more preferably 18 or less) .
  • the carbon number is preferable to be 5 or more and 25 or less (more preferably 18 or less) .
  • the carbon number is too small, the dispersion of core fine particles is apt to be insufficient because of hydrophil icity derived from ethylene oxide chains.
  • the carbon number is too large, hydrophobicity is too high and the surfactant becomes difficult to be dissolved in water (a reaction solvent) .
  • [- ( CH 2 -CH 2 -O- ) n ] is a polymer chain having a polyether structure (polyethylene oxide structure), and the number n of the above-mentioned polyether structures is preferable to be 3 or more, more preferable to be 5 or more, preferable to be 85 or less, more preferable to be 60 or less, and further preferable to be 50 or less.
  • polyether structures are too few (though depending on the balance with the above-mentioned hydrophobic group), the above-mentioned compound might be difficult to be dissolved in water-based mediums.
  • n is within the above-mentioned range, when polymer coated layer are formed, part of the surfactant reacts with the above-mentioned compound (A) and compound (B) to be taken in the polymer coated layer, which can give moderate flexibility to the coated fine particle and consequently, contributes to improve mechanical strength of the coated fine particle.
  • X indicates a group being derived from groups that can react (bonding reaction) with at least one kind selected from the group consisting of an amino group, an imino group, and a carboxyl group and being formed after the reaction (bonding reaction) .
  • m indicates 0 or 1.
  • the above-mentioned amino group, imino group, and carboxyl group mean an amino group and an imino group that can exist in a polymer having a polyamine structure, R 2 , which will be described later, or a carboxyl group that can exist in a polymer having a polycarboxyl ic acid structure.
  • R 2 indicates a polymer group having a polyamine structure or a polycarboxyIic acid structure of 300 to 100,000 (more preferable 300 to 50, 000) in weight average molecular weight.
  • the weight average molecular weight is too small, the polymer is difficult to be precipitated as an insoluble matter, a long time may be reguired to form the polymer coated layer, and further the strength of the polymer coated layer may become insufficient. While the weight average molecular weight is too large, the viscosity of the whole reaction system rises rapidly and stirring may be difficult.
  • Polymer groups having the above-mentioned polyamine group are not limited, but include polymer groups having polyamine structure containing a primary amino group and/or a secondary amino group, for example, polymer groups having at least one kind of structure selected from the group consisting of polyethyleneimine , polyamine, polyetheramine , polyvinylamine , modified polyvinylamine , polyalkylamine , polyamide, polyamine epi chlorohydrin , polydial kylamino alkylvinyl ether, polydialkylamino al kyl (meth ) aerylate , polyallylamine , polyethyleneimine graft polyamideamine , and protonated polyamideamine .
  • Polymer groups having the above-mentioned polycarboxylic acid structure are not limited, but include polymer groups having the structure of water soluble polycarboxylic acid obtained by the polymerization of a monomer component containing 30 mole% or more of unsaturated carboxylic acid including acrylic acid, methacrylic acid, ⁇ -hydroxy acrylic acid, crotonic acid, phthalic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid, and vinyl acetate.
  • the preparation methods of surfactants shown by the above-mentioned general formula (1) are not especially limited, for example, it is preferable to adopt such a method that a compound shown by the following general formula (2) or (3) is added dropwise in an agueous solution of polyamine or polycarboxylic acid and reacted under stirring.
  • X 2 indicates a group that can react (bonding reaction) with at least one kind of group selected from the group consisting of an amino group, an imino group, and a carboxyl group.
  • reaction temperatures at the time of preparing the above-mentioned surfactant are not especially limited, in case of using polyamine, the reaction temperature is preferable to be 10 to 90°C and more preferable to be 15 to 80 0 C, and in case of using polycarboxyl i c acid, the reaction temperature is preferable to be 20 to 100°C and more preferable to be 20 to 90°C.
  • the reaction time is not limited, it is preferable to be 0.5 to 5 hours and more preferable to be 1 to 5 hours.
  • other compounds may be used together with a surfactant shown by the above-mentioned formula (1) or the after-mentioned emulsifying agents in the range where the effect of the present invention is not disturbe.
  • the above-mentioned other compounds are also water soluble as a matter of convenience that the forming reaction of polymer coated layer is carried out in water-based medium.
  • Usable other compounds in the present invention include polyvinyl pyrrolidone, polyvinyl alcohols, all kinds of surfactants other than those shown by the above-mentioned formula (1) and the after-mentioned emulsifying agents, natural polymer dispersants such as gelatin and gum arabic, and synthetic polymer dispersants such as s tyrene-maleic acid copolymer and i t s s a l t s .
  • Core fine particle that is base material of the coated fine particle included in the present invention have a great influence on flexibility, elasticity, and mechanical properties of the coated fine particle.
  • Material of core fine particle is not especially limited, and any of organic materials, organic and inorganic composite materials, or inorganic materials can be adopted.
  • Organic materials include linear polymers such as polystyrene, polymethyl methacrylate , polyethylene, polypropylene, polyethylene terephthalate , polybutylene terephthalate , polysulfone, polycarbonate, and polyamide; network polymers obtained by the homopolymerization or polymerization with other polymeri zable monomers of divinylben zene , hexatriene, divinyl ether, divinyl sulfone, diallyl carbinol, alkylene diacrylate, oligo- or polyalkylene glycol diacrylate, oligo- or polyalkylene glycol dimethacrylate , alkylene triacrylate, alkylene tetracrylate , alkylene trimethacrylate , alkylene tetramethacrylate , alkylene bisacrylamide , alkylene bi smethacrylamide , and both terminal acryl-modi fied polybutadiene oligomer; amino resin
  • Organic and inorganic composite materials include organic matter and inorganic composite particles that can be obtained by the reaction of polysiloxane that the raw material is a silicon compound having a hydrolyzable silyl group and a polymeri z able monomer having a polymeri zable group (for example, a vinyl group, a (meth ) acryloyl group and the like) and the like.
  • Inorganic materials include, for example, glass, silica, and alumina. Further, from the viewpoint of being possible to relatively freely design properties of core fine particle, those consisting of organic materials or organic and inorganic composite materials are preferable.
  • polymer fine particle in which a polysiloxane skeleton and an organic polymer skeleton formed three-dimensional network structure are especially preferable.
  • One example of the production method of such polymer fine particle is shown in the following.
  • the above-mentioned organic and inorganic composite fine particle is polymer fine particle that contain a polysiloxane skeleton as a mineral part and an organic polymer skeleton as an organic matter part and have an organo s il icon atom in which at least one carbon atom in the organic polymer skeleton forms a direct chemical bond with a silicon atom in the polysiloxane skeleton (a chemical bonding type) within the molecule.
  • the above-mentioned polysiloxane is preferable to have an unsaturated group that can be bonded with an organic polymer skeleton, for example, preferable to have a vinyl group.
  • This polysiloxane having a vinyl group is a compound having a polysiloxane skeleton structure that is produced by hydrolyzing and condensing a raw material of compounds containing a silicon compound having a vinyl group.
  • the timing of introducing a vinyl group is not especially limited, for example, any of the following modes can be adopted: a mode of using a silicon compound having a vinyl group as a hydrolysable silicon compound, and a mode in which after seed particles ( polys iloxane having no vinyl group) are produced by hydrolyzing and condensing a hydrolyzable silicon compound having no vinyl group, this seed particles ( polys iloxane having no vinyl group) and a hydrolyzable silicon compound having a vinyl group are hydrolyzed and condensed to introduce a vinyl group into polysiloxane .
  • hydrolysable silicon compounds are not especially limited, for example, silane compounds shown by the following general formula (4) and their derivatives can be used.
  • R 3 may have a substituent and indicates at least one kind of group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, and unsaturated aliphatic groups
  • X indicates at least one kind of group selected from the group consi sting -of the hydroxyl group, an alkoxy group, and an acyloxy group
  • 1 indicates an integer of 0 to 3.
  • silane compounds shown by the above-mentioned general formula (4) for example, the following compounds can be exemplified.
  • tetrafunctional silanes such as tetramethoxys ilane , tetraethoxys ilane , tetrai sopropoxysilane , and tetrabutoxysilane;
  • trifunctional silanes such as methyltrimethoxysilane , methyltriethoxys ilane , ethyItrimethoxys ilane , ethyltriethoxys ilane, hexyltriethoxys ilane, decyltrimethoxys ilane, phenyltrimethoxys ilane, benzyltrimethoxysilane, naphthyltrimethoxysilane, methyltriacetoxysilane , ⁇ - (3, 4 -epoxycyclohexy
  • hydrolyzable silicon compounds having a vinyl group include, for example, those having a polymeri z able reactive group shown by, for example, the following general formulas (5) , (6) and (7) .
  • CH 2 C(-R 4 )-COOR 5 - (5) wherein, R 4 indicates the hydrogen atom or the methyl group, and R5 indicates a divalent organic group that may have a substituent and has the carbon number of 1 to 20.
  • CH 2 C(-R 6 )- (6) wherein, R6 indicates the hydrogen atom or the methyl group .
  • R 7 indicates the hydrogen atom or the methyl group
  • R 8 indicates a divalent organic group that may have a substituent and has the carbon number of 1 to 20.
  • Polymeri zable reactive groups shown by the above-mentioned general formula (5) include, for example, acryloxy groups and methacryl oxy groups, and silicon compounds that have such organic group and shown by the above-mentioned general formula (4) include, for example, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltriethoxysilane, ⁇ -methacryloxypropyltriacetoxysilane, ⁇ -methacryloxyethoxypropyltrimethoxys ilane (or, also called ⁇ -trimethoxys ily Ipropyl- ⁇ -methacryloxyethyl ether) , ll-methacryloxyundecamethylenetrimethoxys ilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxyprop
  • Polymeri zable reactive groups shown by the above-mentioned general formula (6) include, for example, vinyl group and isopropenyl group, and silicon compounds that have such organic group and shown by the above-mentioned general formula (4) include, for example, vinylt rimethoxys ilane , vinyltriethoxysilane , vinyIt riacetoxys ilane , 4 -vinyltetramethylenetrimethoxys ilane, 8 -vinyloctamethylenetrimethoxysilane, 3 -1rimethoxys ilylpropy1 vinyl ether, vinylmethyldimethoxysilane, vinylmethyldiethoxys ilane , and vinyImethyldiacetoxys ilane . These compounds may be used only in one kind, and may be used in two or more kinds together.
  • Polymeri zable reactive groups shown by the above-mentioned general formula (7) include, for example, 1-alkenyl groups or vinyl phenyl group, and isoalkenyl group or isopropynyl phenyl group, and silicon compounds that have such organic group and shown by the above-mentioned general formula (4) include, for example, 1-hexenyltrimethoxys ilane ,
  • 1-hexenylmethyldimethoxys ilane and 1-hexenylmethyldiethoxysilane . These compounds may be used only in one kind independently, and may be used in two or more kinds together.
  • the above-mentioned polys i loxane s are obtained through the hydrolysis and condensation of compounds included in the above-mentioned silicon compound group in a solvent containing water.
  • a solvent containing water any method of batch processing, division processing, continuous processing and the like can be adopted.
  • any of catalysts such as ammonia, urea, ethanolamine , tet ramethylammonium hydroxide, alkali metal hydroxides, and alkaline-earth metal hydroxides can be used.
  • an organic solvent may exist other than water and a catalyst.
  • organic solvents are not especially limited, for example, the following solvents are preferably cited: alcohols such as methanol, ethanol, isopropanol, n-butanol, is.obutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, and 1 , 4 -but anediol ; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; ( cycl o ) paraffins such as isooctane and cyclohexane; ethers such as dioxane and diethyl ether; aromatic hydrocarbons such as benzene and toluene. These solvents may be used only in one kind, and may be used in two or more kinds together.
  • alcohols such as methanol, ethanol, isopropanol, n-butanol, is.obutano
  • Hydrolysis and condensation reactions are carried out by adding the above-mentioned silicon compounds and organic solvents and the like in a solvent containing water and stirring for 30 minutes to 100 hours at the temperature range of 0 to 100°C, preferably at 0 to 7O 0 C.
  • the water concentration is 10 to 99.99 % by mass
  • the catalyst concentration is 0.01 to 10 % by mass
  • the organic solvent concentration is 0 to 90 % by mass
  • the concentration of the above-mentioned silicon compound is 0.1 to 30 % by mass to the total amount of the reaction mixture.
  • the time of adding the above-mentioned silicon compounds is 0.001 to 500 hours and the reaction temperature is 0 to 100°C.
  • the concentration of the seed particles is preferably set to be 0.1 to 30 % by mass to the total amount of the reaction mixture.
  • particles obtained by the hydrolysis and the condensation reaction have been previously put in the synthesis system as the seed particles, and then the above-mentioned silicon compounds are added in the system to make the above-mentioned seed particles grow. Polysiloxane particles can thus be obtained. In this way, the above-mentioned silicon compounds are hydrolyzed and condensed under the suitable conditions in a solvent where water is contained and particles precipitate to form slurry.
  • the precipitated particles become polysiloxane particles having vinyl groups because the particles are obtained by using the above-mentioned silicon compound having a vinyl group as the essential component.
  • the suitable conditions are not especially limited, for example, it is preferable that the slurry containing the seed particles that were obtained by previously carrying out hydrolysis and condensation reaction (preferably 0.1 to 20 % by mass in concentration) has the concentration of the above-mentioned hydrolysable silicon compound of 20 % by mass or less to the total amount of the reaction mixture, the water concentration of 50 % by mass or more, and the catalyst concentration of 10 % by mass or less.
  • the shapes of the above-mentioned polysiloxane particles may be arbitrary shapes including a globular shape, a needle shape, a plate shape, a scale shape, a pulverized shape, a straw bag (cilinder) shape, a cocoon shape, and a confetti shape, and not especially limited.
  • the average particle diameter of the above-mentioned polysiloxane particles is not especially limited, it is preferable to be 0.1 to 700 ⁇ m, more preferable to be 0.5 to 70 ⁇ m, and most preferable to be 1 to 50 ⁇ m .
  • the average particle diameter of the above-mentioned polysiloxane particles is within the above-mentioned range, such advantageous effects can be exhibited that the absorption of polymeri zable components as described later progresses efficiently.
  • Polysiloxane particles obtained as described above are such particles that they can easily absorb polymer i zable components to be described later and hold the components in the siloxane skeleton constituting the particles. It can be said that this is because the above-mentioned polysiloxane particles are in the degree of condensation suitable for absorbing polymeri zable components to be described later.
  • the above-mentioned polymeri zable components are not especially limited, but considering miscibility with the above-mentioned polysiloxane particles, it is preferable to use radical polymeri zable vinyl monomers and bifunctional oligomers having two (meth ) acryloy1 groups in one molecule.
  • Radical polymeri zable vinyl monomers are preferably monomers containing at least one ethyleninc unsaturated group within the molecule, and are sufficient to be properly selected so that the polymer particles can exhibit the desired physical properties.
  • the following monomers can be cited: monomers having the hydroxyl group such as 2 -hydroxyethy1 (meth ) acrylate , 2 -hydroxypropy1 (meth ) acrylate , and 2 -hydroxybutyl (meth ) acrylat e ; monomers containing a polyethylene glycol component such as methoxypolyethylene glycol (meth ) acrylat e ; alkyl (meth ) acryl ates such as butyl (meth) acrylate, methyl (meth ) acrylates , ethyl (meth ) acrylat e , isoamyl acrylate, lauryl
  • (meth ) acrylat e benzyl (meth ) acrylate , and t et rahydro furfury1 methacrylate ; fluorine-containing (meth ) acrylat es such as t rifluoroethy1 (meth) acrylate, t etrafluoropropy1 (meth ) acrylate , pentafluoropropyl (meth) acrylate, and octafluoroamyl (meth) acrylat e ; aromatic vinyl compounds such as styrene, ⁇ -methyl styrene, vinyltoluene , ⁇ -chlorostyrene , o-chloros t yrene , m-chlorostyrene , p-chloros tyrene , and p-ethyl styrene; glycidyl (meth ) )
  • (meth ) acryloyl groups in one molecule is preferably such one that the solubility in water at 25°C is 10 % by mass or less to the total amount of water and the bifunctional oligomer and the weight average molecular weight is 300 or more.
  • Such a component is easily absorbed into the above-mentioned polysiloxane particle and greatly contributes to improving the properties of the polymer fine particle (for example, flexibility, elasticity and the like) .
  • the above-mentioned bifunctional oligomers are not especially limited as long as they meet the above-mentioned properties and include, for example, polyethylene glycol di (meth ) aerylate ; polypropylene glycol di (meth ) acrylate s such as propylene glycol di (meth ) aerylate ; tripolypropylene glycol di (meth ) acryIate ; polytetramethylene glycol di (meth ) aerylate ; neopentyl glycol di (meth ) acrylate ; 1, 3-butylene glycol di (meth) acrylate;
  • Bifunctional oligomers having the above-mentioned structures include, for example, NK ester series manufactured by Shin-Nakamura Chemical Co., Ltd.
  • polymeri zable components may be used independently, and may be used in two or more kinds together.
  • hydrophobic radical polymeri zable vinyl monomers are preferably used to make the emulsion stable.
  • a crosslinking monomer may be used.
  • the above-mentioned crosslinking monomers are not especially limited, and include, for example, divinylbenzene , 1 , 6-hexanediol di (meth ) aerylate , neopentyl glycol di (meth ) acrylat e , trimethylolpropane tri (meth) acrylate, tetramethylolmethane.
  • the above-mentioned hydrolyzable silicon compound may be contained.
  • a hydrolyzable silicon compound both of those having a vinyl group and those having no vinyl group can be used.
  • polysiloxane particles having no vinyl group are used as the seed particles, it is necessary to add a hydrolyzable silicon compound in the polymeri zable component .
  • the blending ratio of the above-mentioned polymeri zable components is not especially limited and can be suitably set according to the desired properties, for example, the blending amount of the above-mentioned bifunctional oligomer is preferable to be 20 % by mass or more in 100 % by mass of the above-mentioned polymeri zable components
  • the amount of the bifunctional oligomer is included within the above-mentioned range, it is easy to control the compressive deformation recovery factor of the obtained polymer fine particles.
  • all of the polymeri z able components may be ones of the above-mentioned bifunctional oligomers.
  • the components derived from bifunctional oligomers in the polymer fine particle to be obtained are preferable to be 10 % by mass or more, more preferable to be 20 % by mass or more, and further preferable to be 30 % by mass or more, and preferable to be 99 % by mass or less, more preferable to be 95 % by mass or less, and further preferable to be 90 % by mass or less.
  • any of the following methods can be adopted:
  • [A] A method of producing the seed particles (polysiloxane having vinyl groups) by hydrolyzing and • condensing the above-mentioned hydrolyzable silicon compound having a vinyl group.
  • [B] A method in which the seed particles (1) ( polys i1oxane having no vinyl group) are produced by hydrolyzing and condensing a hydrolyzable silicon compound having no vinyl group, after that, this seed particles (1) and a hydrolyzable silicon compound having a vinyl group are hydrolyzed and condensed to produce the seed particles (2) ( polys iloxane having vinyl groups ) .
  • [C] A method in which the seed particles (1) ( polys iloxane having no vinyl group) are produced by hydrolyzing and condensing a hydrolyzable silicon compound having no vinyl group, a hydrolyzable silicon compound having a vinyl group and a polymeri zable component described later are made to absorbed into this seed particles (1), at this time, the polysiloxane in the above-mentioned seed particles (1) and the hydrolyzable silicon compound having a vinyl group are hydrolyzed and condensed to produce the seed particles (2) (polysiloxane having vinyl groups ) .
  • the above-mentioned polymer fine particle can be obtained through the absorption process where the above-mentioned polymerizable component in the state of being emulsified and dispersed in water is added and absorbed in the above-mentioned polysiloxane particles having vinyl groups, or the absorption process where the polymer i zable components essentially containing the above-mentioned polymeri zable component and a polymeri zable monomer indispensably having a vinyl group and a hydrolyzable silyl group in the state of being emulsified and dispersed in water are added and absorbed in the above-mentioned polysiloxane particles having no vinyl group, and through the polymerization process where the radical polymerization of the above-mentioned polymeri z able components absorbed into the above-mentioned polysiloxane particles at the above-mentioned absorption process are performed .
  • the above-mentioned absorption process is not especially limited as long as the process progresses in the state that the above-mentioned polymeri z able components exist in the presence of the above-mentioned polysiloxane particles.
  • the above-mentioned polymeri zable component is absorbed into the structure of the above-mentioned polysiloxane particle in the absorption process
  • the absorption is preferably carried out after setting various kinds of conditions including the concentration of each of the above-mentioned polysiloxane particles and polymeri zable components, the mixing ratio of the above-mentioned polysiloxane particles and polymeri zable component, the treating method and means of the mixing, the temperature and time when mixing them, and the treating method and means after the mixing so that the absorption process progresses rapidly .
  • the mass of the polymeri zable component added in the above-mentioned absorption process is preferable to be 0.01 to 100 times the mass of silicon compound used as a raw material of polysiloxane particle, more preferable to be 0.5 to 30 times, and further preferable to be 1 to 15 times.
  • the mass added When the mass added is less than the above-mentioned range, the amount of the polymeri zable component absorbed into the polysiloxane particle becomes small and it may be difficult to obtain the polymer fine particle having the above-mentioned mechanical properties, and when the mass added is over the above-mentioned range, the complete absorption into the polysiloxane particle of the polymeri zable component added is apt to become difficult, and because unabsorbed polymeri zable components remain, it may become easy to generate the cohesion between the particles in the following polymerization stage.
  • the above-mentioned polymeri z able component may be added in the solvent in which polysiloxane particles are dispersed, or polysiloxane particles may be added in the solvent containing the above-mentioned polymeri zable component.
  • the polymeri z able component is added in the dispersion liquid, because the process does not become complex and is excellent in productivity.
  • the timing of adding the polymer i zable component is not especially limited, the polymeri zable component may be added in a lump, may be added dividing in several times, and may be fed at any speed. Moreover, at the time of adding the polymeri zable component, only the ⁇ polymeri zable component may be added, and the solution of the polymeri zable component may be added. However, it is preferable to add the polymeri zable component in the polysiloxane particles in advance in the state of being emulsified and dispersed with an emulsifying agent because the absorption into the polysiloxane particles is performed efficiently.
  • the above-mentioned emulsifying agents are not especially limited and include, for example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, high-molecular surfactants, and polymeri zable surfactants having one or more polymeri z able unsaturated carbon-carbon bonds in the molecule.
  • anionic surfactants and nonionic surfactants are preferable because they can stabilize the dispersion states of polysiloxane particles, of polysiloxane particles absorbed polymeri zable components, and of polymer fine particles.
  • These emulsifying agents maybe used only in one kind, and may be used in two or more kinds together .
  • anionic surfactants are not especially limited and include, in concrete terms, alkali metal alkyl sulfates such as sodium dodecyl sulfate, and potassium dodecyl sulfate; ammonium alkyl sulfates such as ammonium dodecyl sulfate; alkali metal salts such as sodium dodecyl polyglycolether sulfate, sodium sulfocynoate , and sulfonated paraffin; alkylsulfonates such as ammonium salt of sulfonated paraffin; fatty acid salts such as sodium laurate, triethanolamine oleate, and triethano lamine abietate; alkylaryl sulfonates such as sodium dodecylbenz ene sulfonate , and alkali metal sulfate of alkaliphenol hydroxyethylene ; higher alkylnaphthalene sul
  • cationic surfactants are not especially limited and include, for example, amine salts, quaternary ammonium salts, and oxyethylene addition type ammonium hydrochlorides.
  • amine salts for example, quaternary ammonium salts, and oxyethylene addition type ammonium hydrochlorides.
  • trimethylal kylammonium hydrochlorides, dimethyldial kylammonium hydrochlorides, monoalkylamine acetates, alkylmethyl dipolyoxyethylene ammonium hydrochlorides, and the like can be exemplified.
  • Alkyl groups containing in these cationic surfactants are preferable to be saturated aliphatic hydrocarbon groups or unsaturated aliphatic hydrocarbon groups of 4 to 26 in carbon number, for example, the octyl group, the dodecyl group, the tetradecyl group, the hexadecyl group, the octadecyl group, the behenyl group, the oleyl group, the stearyl group, and the like can be cited.
  • nonionic surfactants are not especially limited and include, in concrete terms, fatty acid monoglycerides such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and glycerol monolaurat e ; polyoxyethylene oxypropylene copolymer, and condensation products of ethyleneoxide and a fatty acid amine, amide or acid.
  • fatty acid monoglycerides such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and glycerol monolaurat e ; polyoxyethylene oxypropylene copolymer, and condensation products of ethyleneoxide and a fatty acid amine, amide or acid.
  • amphoteric surfactants include amino acid type amphoteric surfactants and betaine type amphoteric surfactants.
  • the above-mentioned high-molecular surfactants- include, in concrete terms, polyvinyl alcohol, sodium poly (meth ) aerylate , potassium poly (meth ) acrylate , ammonium poly (meth ) acrylate , polyhydroxyethyl (meth ) aerylate , polyhydroxypropyl (meth) acrylate, polyvinyl pyrrolidone, copolymers of two kinds or more of polymeri zable monomers that are constitutional units of these polymers or copolymers of any of these monomers with other monomers, phase-transfer catalysts of crown ethers, and the like .
  • polymeri zable surfactants are not especially limited and include, for example, anionic polymeri zable surfactants such as propenyl-2 -ethylhexylbenzene sodium sul fosuccinate , sulfate ester of polyoxyethylene (meth ) acrylate , polyoxyethylene al kylpropenylether ammonium sulfate, and phosphate ester of polyoxyethylene (meth ) acrylate ; and nonionic polymeri zable surfactants such as polyoxyethylene alkylbenzeneether (meth) acrylate , and polyoxyethylene alkylether (meth ) acrylate .
  • anionic polymeri zable surfactants such as propenyl-2 -ethylhexylbenzene sodium sul fosuccinate , sulfate ester of polyoxyethylene (meth ) acrylate , polyoxyethylene al kylpropenylether ammonium
  • the amount of the above-mentioned emulsifying agent used is not especially limited, and in concrete terms, the amount is preferable to be 0.01 to 10 % by mass to the total mass of the above-mentioned polymeri zable component, more preferable to be 0.05 to 8% by mass, and further preferable to be 1 to 5% by mass.
  • the amount of the above-mentioned emulsifying agent used is less than 0.01 % by mass, the stable emulsified and dispersed product of the polymeri zable component may not be obtained, and when the amount is over 10 % by mass, emulsion polymerization and the like may be occurred at the same time as a side reaction.
  • the emulsion of the above-mentioned polymeri zable component with an emulsifying agent in water with the use of a homo mixer or an ultrasonic homogenizer.
  • water or a water-soluble organic solvent 0.3 to 10 times the mass of the polymeri z able component.
  • the above-mentioned water-soluble organic solvents include alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, and 1,4-butandiol; ketones such as acetone and methyl ethyl ketone; and esters such as ethyl acetate .
  • the above-mentioned absorption process is preferably carried out at the temperature range of 0 to 60°C for 5 to 720 minutes while stirring. It is sufficient to set these conditions suitably depending on polysiloxane particles and the kind of a polymeri zable component to be used. Only one of these conditions may be adopted, and two kinds or more of them may be adopted together.
  • the particles are observed with a microscope before the polymeri zable component is added and after the end of the absorption stage and the judgment can be made easily by confirming the particle size being grown by absorbing the polymeri zable component and the like.
  • the concentration of polysiloxane particles in which the polymeri zable component has been absorbed is diluted to 40 % by mass or less to the total amount of the dispersion liquid and water.
  • the concentration is more preferable to be 30 % by mass or less and further preferable to be 20 % by mass or less.
  • the particle concentration in the above-mentioned dispersion liquid is too high, in the following polymerization process, the temperature control may be difficult because of the heat generation accompanied by the polymerization reaction. And, at this time, the above-mentioned surfactant may additionally be added to improve the dispersion stability of the particles.
  • methods for performing the radical polymerization are not especially limited and include, for example, a method of using a radical polymerization initiator, a method of irradiating ultraviolet or radiation, and a method of heating.
  • the above-mentioned radical polymerization initiators are not especially limited and preferably include, for example, persulfates such as potassium persulfate; peroxide type initiators such as hydrogen peroxide, peracetic acid, benzoyl peroxide, lauroyl peroxide, orthochloro benzoyl peroxide, orthomethoxy benzoyl peroxide, 3, 5, 5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxide, benzoyl peroxide, 1, 1 -bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane, and t-butylhydroperoxide ; azo type
  • the amount of the above-mentioned radical polymerization initiator used is preferable to be 0.001 % by mass to 20 % by mass to the total amount of the above-mentioned polymeri zable component, more preferable to be 0.01 % by mass to 10 % by mass, and further preferable to be 0.1 % by mass to 5 % by mass.
  • the amount of the above-mentioned radical polymerization initiator used is less than 0.001 % by mass, the polymerization degree of the polymeri zable component may not be risen.
  • the method of feeding the above-mentioned radical polymerization initiator into the above-mentioned solvent is not especially limited and any of such heretofore known techniques can be adopted that a method of feeding the whole amount at the beginning (before starting the reaction) (a mode that a radical polymerization initiator is emulsified and dispersed together with the polymer i zable component, a mode that a radical polymerization initiator is fed after the polymeri z able component is absorbed) ; a method of feeding a part of the initiator at the beginning and adding the remaining with continuous feeding or with intermittent pulsing, or the technique of combining these methods.
  • the reaction temperature is preferable to be 40 to 100°C and more preferable to be 50 to 80°C.
  • the reaction temperature is too low, it is apt to become difficult to obtain the mechanical properties of the polymer fine particle because the degree of .polymerization does not rise sufficiently.
  • the reaction temperature is too high, the polymer particles are apt to easily cohere mutually during the polymerization reaction.
  • the reaction time can be suitably changed depending on the kind of the polymerization initiator to be used, generally, the reaction time is preferable to be 5 to 600 minutes and more preferable to be 10 to 300 minutes.
  • the reaction time is too short, the degree of polymerization may do not rise sufficiently, and when the reaction time is too long, the polymer particles are apt to easily cohere mutually .
  • the manufacturing method included in the present invention is a manufacturing method of the coated fine particle having polymer coated layer on the surface of the core fine particle comprising of an organic material or an organic and inorganic composite material, and the method is characterized in that the above-mentioned polymer coated layer is formed by ring-opening reaction and/or polycondensat ion reaction in a water-based medium in which the above-mentioned core particles are dispersed, and in the presence of a surfactant.
  • the manufacturing method of the present invention is to form polymer coated layer for coating the core fine particles by utilizing int ermolecular force such as hydrophobic interaction acting between the core fine particles and the surfactant, what is more, between the surfactant and the above-mentioned compound (A) and/or compound (B) .
  • the surfactant added in a water-base medium is cohered on the surfaces of the core fine particles and the mutual coherence of the core fine particles is, as a result, controlled to make the state of the core fine particles dispersing in the water-based _ medium .
  • the above-mentioned compound (A) (an initial condensation compound) and/or compound (B) (an epoxy compound) are added here, and the ring-opening and/or polycondensat ion reaction progresses in such a situation that these compounds surround the surfactant, that is, the core fine particle.
  • uniform polymer coated layer is formed on the surface of the core fine particle.
  • the formation of the polymer coated layer included in the present invention is carried out in a water-based medium.
  • the above-mentioned water-based mediums include a mixed solvent of water and an organic solvent as well as the case of using only water as a reaction solvent.
  • Organic solvents are preferable to be hydrophilic and include, for example, alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and allyl alcohol; glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, pentanediol, hexanediol, heptanediol, and dipropylene glycol; ketones such as acetone, methyl ethyl ketone, and methyl propyl ketone; esters such as methyl formate, ethyl formate, methyl acetate, and methyl acetoacetate ; ethers such as diethylene glycol mono
  • the above-mentioned initial condensation compound is hard to dissolve in water
  • the blending amount of an organic solvent is preferable to be 50 % by mass or less to the total amount of the organic solvent and water, and more preferable to be 40 % by mass or less.
  • organic solvents other solvent
  • dioxane, hexane, cyclopentane , pentane, isopentane, octane, benzene, toluene, xylene, ethylbenzene , petroleum ether, terpene, ricinus, soy oil, paraffin, kerosene and the like can be exemplified.
  • the amount used is preferable to be 30 % by mass or less in the mixed solvent consisting of the above-mentioned water-a hydrophilic organic solvent, more preferable to be 25 % by mass or less, and further preferable to be 20 % by mass or less.
  • the concentration of the core fine particles in a water-based medium- is preferable to be 1 % by mass or more and more preferable to be 2 % by mass or more, and preferable to be 60 % by mass or less and more preferable to be 50 % bymass or less.
  • the amount of the core fine particles is too much, the coherence of the core fine particles may occur in the coating process, and when the amount is too little, the polymer component derived from compound (A) and compound (B) that having no core fine particle may precipitate in the medium.
  • the amount of the above-mentioned surfactant added is preferable to be 1 % by mass or more to the core fine particles, more preferable to be 3 % by mass or more and further preferable to be 5 % by mass or more, and preferable to be 50 % by mass or less, more preferable to be 30 % by mass or less and further preferable to be 25 % by mass or less.
  • the blending amount of the surfactant is too little, the dispersion state of the core fine particles may not be held sufficiently stable and the core fine particles may be cohered mutually .
  • the blending amount is too much, the viscosity of the whole reaction system rises rapidly and stirring may become difficult.
  • the method of dispersing the core fine particles in a water-based medium is not limited and heretofore known dispersion methods can be adopted.
  • a water-based medium and a mixture containing the core fine particles and a surfactant are strongly stirred mechanically and dispersed with a machine of an ultrasonic disperser, a disper, a homomixer (manufactured by Tokushu Kikai Kogyo Co., Ltd.), a homogenizer (manufactured by Nippon Seiki Co., Ltd.) or the like.
  • the above-mentioned surfactant may be dissolved in the water-based medium before the core fine particles are dispersed in the water-based medium, or may be dissolved at the same time or after of the dispersion.
  • the timing of the addition is not especially limited.
  • an initial condensation compound is added in the water-based medium in which the core fine particles have been dispersed.
  • the amount of the above-mentioned initial condensation compound added is not limited, the amount is preferable to be 0.1 parts by mass or more to 1 parts by mass of the above-mentioned surfactant, more preferable to be 0.2 parts by mass or more and further preferable to be 0.3 parts by mass or more, and preferable to be 10 parts by mass or less, more preferable to be 5 parts by mass or less and further preferable to be 3 parts by mass or less.
  • the thickness of the polymer coated layer can be easily controlled by adjusting the amount of the initial condensation compound added.
  • the polymer coated layer with sufficient thickness is hard to be formed.
  • the amount is too much, large deviation is produced in the component composition of the polymer coated layer. As a result, the strength of the polymer coated layer may be lowered and the adhesion with metals may be deteriorated.
  • the method for adding the above-mentioned initial condensation compound in a water-bas ed medium is not limited. Addition in one lot will be accepted and addition in succession (continuous addition and/or intermittent addition) will be also accepted.
  • temperature at the time of forming the polymer coated layer (temperature of the water-based medium in which the core fine particles have been dispersed and a water soluble compound has been added) is preferable to be 25 to 85°C, more preferable to be 30 to 70°C, and further preferable to be 35 to 60°C.
  • pH of the reaction liquid at the time of forming the polymer coated layer is preferable to be 2 to 13, more preferable to be 3 to 12, and further preferable to be 4 to 11.
  • the reaction time is preferable to be 10 to 480 minutes, more preferable to be 30 to 360 minutes, and further preferable to be 60 to 300 minutes.
  • An aging period may be set after forming the above-mentioned polymer coated layer. Temperature during the aging period is not especially limited, but is preferable to be, for example, 200°C or less.
  • the aging time is also not limited, and is preferable to be 1 to 5 hours and more preferable to be 1 to 3 hours.
  • the pH of the solution during the aging period- is preferable to be in the range of 2 to 13.
  • aging may be carried out under pressure. In this case, pressure is not especially limited, but is preferable to be, for example, in the range of atmospheric pressure to 20 atmosphere.
  • the amount of the epoxy compound added is not especially limited, the amount is preferable to be 0.5 parts by mass or more and 10 parts by mass or less to 1 parts by mass of the core fine particles. It becomes easy to control the thickness of the epoxy resin layer (polymer coated layer) to be formed by adjusting the amount of the epoxy compound added. In addition, when the amount added is too little, it may be difficult to obtain the effect of improving adhesion with metals by forming an epoxy resin layer.
  • Temperature at the time of forming the above-mentioned epoxy resin layer is preferable to be the same as that at the time of forming the above-mentioned polymer coated layer in cases where the compound (A) is adopted.
  • an adjusted liquid in which coated fine particles are dispersed in a water-based medium is obtained after forming the above-mentioned polymer coated layer and after aging to be carried out as occasion demands.
  • a surfactant and the above-mentioned compound (A) and/or compound (B) are further added in the above-mentioned adjusted liquid as occasion demands, and the ring-opening and/or polycondensation reaction may be carried out.
  • coated fine particles having a stratified polymer coated layer can be obtained.
  • a coated polymer in which plural polymer coated layers are prepared, for example, can improve physical properties that have been obtained by the single polymer coated layer.
  • changing the composition of the constituents in the outside layer and the inside layer in the polymer coated layer will reveal different physical properties.
  • the coated fine particles may be isolated as occasion demands. For example, after the coated fine particles are adjusted, the coated fine particles only have to be separated from the water-based medium and the like by suction filtration or spontaneous filtrat ion .
  • the coated fine particles after being isolated may be classified.
  • classification it is preferable to adopt a classification method in a wet state (wet classification) .
  • the wet classification is a method of classifying coated fine particles on an adjusted liquid in which the coated fine particles are dispersed. Because classification is carried out on the above-mentioned adjusted liquid, it is a wet classification.
  • The- wet classification is a method' that the above-mentioned adjusted liquid is subjected to classification treatment as it is or after diluting with any water-based medium to classify the coated fine particles in the adjusted liquid so that the classified coated fine particles become to have the desired particle size or particle size distribution.
  • the wet classification can be carried out with, for example, a method or device using a sieve method (a filter method), a centrifugal sedimentation method, a spontaneous sedimentation method or the like.
  • a sieve method a filter method
  • a centrifugal sedimentation method a centrifugal sedimentation method
  • a spontaneous sedimentation method a spontaneous sedimentation method or the like.
  • coated fine particles having relatively large particle diameter a sieve method can be used effectively.
  • coated fine particles are preferably washed.
  • the coated fine particle of the present invention include such particle as the surface of the core fine particle are exposed on the part of coated fine particle as well as such particle as the whole of the surface of the core fine particle is covered with polymer coated layer.
  • the adhesion with metals is lowered and forming a uniform conductor layer (described later) on the surface of the fine particle may become difficult.
  • Such defects cause bad continuity or lower the reliability of continuity when being used as conductive fine particle. Consequently, the coverage of the core fine particle with the polymer coated layer is preferable to be 40% or more, more preferable to be 50% or more, and further preferable to be 55% or more. Of course, the most preferable coverage is 100%.
  • the form of a constituent derived from the above-mentioned surfactant may be that consisting of one molecule of the surfactant, or may be those of two or more molecules gathered such as a dimer and a trimer, and the form is not limited. Among these, only one kind may be contained in the polymer coated layer, two or more kinds may be contained in the polymer coated layer.
  • the content ratio of a constituent derived from the above-mentioned surfactant is not limited, it is preferable to be 5 % by mass or more to the whole amount of the polymer coated layer, more preferable to be 10 % by mass or more and further preferable to be 15 % by mass or more, and preferable to be 80 % by mass or less, more preferable to be 75 % by mass or less and further preferable to be 70 % by mass.
  • the content ratio is low, flexibility is lowered and the polymer coated layer may become low in mechanical strength.
  • the content ratio is too high, the adhesion with metals may be lowered.
  • a constituent derived from an initial condensation compound (a compound (A) ) that is the constituent of the polymer coated layer in the coated fine particle of the present invention
  • a wide variety of amino resins urea type resins, melamine resin, guanamine type resins
  • these resins only one kind may be contained in the polymer coated layer, and two or more kinds may be contained in the polymer coated layer.
  • the content ratio of a constituent derived from a compound (A) and/or a compound (B) is preferable to be 20 % by mass or more to the whole amount of the polymer coated layer, more preferable to be 25 % by mass or more and further preferable to be 30 % by mass or more, and preferable to be 95 % by mass or less, more preferable to be 90 % by mass or less and further preferable to be 85 % by mass or less.
  • the content ratio is less than the above-mentioned range, the adhesion with metals may not be sufficient, and when the content ratio is over the above-mentioned range, the polymer coated layer may become poor in flexibility and low in mechanical strength.
  • the polymer coated layer of the coated fine particle of the present invention may contain other component other than the above-mentioned component within the range where the effect of the present invention is not detracted.
  • other constituents for example, other constituents derived from the above-mentioned other compounds that can be used together with the above-mentioned surfactants can be cited.
  • constituents derived from polyvinyl alcohols, constituents derived from various surfactants other than the above-mentioned surfactants, components derived from natural high-molecular dispersants such as gelatin and gum arabic, components derived from synthetic high-molecular dispersants including styrene-maleic acid copolymer and its salts, and the like can be cited.
  • the shapes of the coated fine particle of the present invention are not especially limited and include, for example, a globular shape, a needle shape, a plate shape, a scale shape, a pulverized shape, a slanted shape, a cocoon shape, and a confetti shape.
  • the coated fine particles of the present invention that have the above-mentioned constitution is preferable to be 5O N / mm 2 or more in compressive elastic modulus (10% K value) and 5% or more in compressive deformation recovery factor when the diameter of the coated fine particle was transformed by 10%.
  • Compressive elastic modulus is preferable to be 1000 N / mm 2 or more and further preferable to be 2450 N / mm 2 or more, and compressive deformation recovery factor is preferable to be 10% or more and further preferable to be 15% or more.
  • the above-mentioned compressive elastic modulus (10% K value) is an index of flexibility of the coated fine particle and compressive deformation recovery factor is an index of elastic force of the coated fine particle, respectively.
  • the compressive elastic modulus is preferable to be 20000 N / mm 2 or less, more preferable to be 15000 N / mm 2 or less, and further preferable to be 10000 N / mm 2 or less.
  • the above-mentioned compressive deformation recovery factor is an index of elastic force of the coated fine particle. In cases where a constant load is applied on the coated fine particle and is removed, the compressive deformation recovery factor is obtained from the change in particle diameter of the coated fine particle before and after applying load.
  • the compression deformation recovery factor in the coated fine particle of the present invention is preferable to be 5% or more, more preferable to be 10% or more, and further preferable to be 15% or more.
  • the upper limit of the compression deformation recovery factor is not especially limited and, of course, it goes without saying that 100%, that is, the particle diameter of the coated fine particle preferably does not change before and after applying load.
  • the amount of displacement at the time of 1 g load is preferable to be 5% or more to the diameter of the coated fine particle.
  • the above-mentioned amount of displacement at the time of 1 g load is an index of easiness of deformation of the coated fine particle in the present invention, especially easiness of deformation at the time of applying low load.
  • the above-mentioned amount of displacement at the time of 1 g load is preferable to be 5% or more, more preferable to be 10% or more and further preferable to be 20% or more, and preferable to be 85% or less, more preferable to be 80% or less and further preferable to be 75% or less.
  • the average particle diameter of the coated fine particles of the present invention is not especially limited, it is preferable to be 1.0 ⁇ m or more, more preferable to be 2.0 ⁇ m or more, and preferable to be 100 ⁇ m or less, more preferable to be 70 ⁇ m or less and further preferable to be 50 ⁇ m or less.
  • the particle When the particle diameter of the coated fine particle is too small, the particle may be polymer fine particle consisting of only initial condensate involving no core particle, and when the particle diameter is -too large, it may be difficult to hold the physical properties required as normal coated fine particle.
  • the coefficient of variation (Cv value) of the particle diameter is preferable to be 10% or less, more preferable to be 5% or less, and further preferable to be 4% or less.
  • the coefficient of variation (Cv value) is within the above-mentioned range, in case of being used in the application as a gap holding material to make, gaps between various substrates uniform, the coated fine particle can exhibit the advantageous effect of keeping the gap interval uniformly.
  • the coefficient of variation (Cv value) is over the above-mentioned range, in case of being used as a gap holding material, the particle may not be sufficient to keep the uniformity of the gap interval. Further, the above-mentioned properties
  • the coated fine particle having the desired properties can be obtained by suitably adjusting manufacturing conditions of the core fine particle.
  • the thickness of the polymer coating of the present invention is not limited, it is preferable to be 0.001 ⁇ m or more, more preferable to be 0.005 ⁇ m or more and further preferable to be 0.008 ⁇ m or more, and preferable to be 10 ⁇ m or less.
  • the thickness of the polymer coating is too thin, not only the coating is in danger of lowering adhesion with metals, but also the strength of the coated fine particle may be lowered.
  • the thickness is too thick, because the rate of the core fine particle occupying in the coated fine particle becomes small, flexibility and elasticity may not be sufficient .
  • the conductive fine particle included in the present invention is made by forming conductor layer on the surface of the above-mentioned coated fine particle included in the present invention.
  • the above-mentioned conductor layer only has to be formed at least a part of the coated fine particle.
  • the metals include, for example, nickel, gold, silver, copper, indium, and their alloys. Among these metals, nickel, gold, and indium are preferable because of having high electric conductivity.
  • the thickness of the above-mentioned conductor layer is not especially limited as long as there is enough electric conductivity, the thickness is preferable to be 0.01 ⁇ m or more and more preferable to be 0.02 ⁇ m or more, and preferable to be 5.0 ⁇ m or less and more preferable to be 2.0 ⁇ m or less. When the thickness of the conductor layer is too thin, the electric conductivity may become insufficient.
  • the conductor layer when the thickness is too thick, the conductor layer may be apt to flake away because of the difference between coefficients of thermal expansion in the conductor layer and the polymer coated layer.
  • the conductor layer may be one layer or two layers or more. In case of two layers or more, different kinds of metals may be laminated.
  • the method for forming conductor layer on the surface of the coated fine particle of the present invention is not especially limited and heretofore known methods can be adopted.
  • the electroless plating (chemical plating) method, the coating method, the PVD (vacuum deposition, sputtering, ion plating, and the like) method, and the like can be cited.
  • the electroless plating method is preferable because a conductor layer can be formed easily.
  • the above-mentioned electroless plating method is comprised of an etching process, an activating process, and an electroless plating process.
  • the ab.ove-mentioned etching process is a process where concave and convexity are formed on the surface of the coated fine particle to improve the adhesion of the electroless plated layer
  • the coated fine particle included in the present invention is provided with polymer coated layer having good adhesion with metals
  • the etching process is not an essential process and can be omitted
  • the etching process when the etching process is carried out, it only has to use, for example, an alkali aqueous solution like caustic soda aqueous solution, or an aqueous solution of acids such as hydrochloric acid, sulfuric acid, and chromic anhydride as an etching solution.
  • activating process and electroless plating process only have to be carried out according to heretofore known methods.
  • the conductive fine particle of the present invention is those having the above-mentioned coated fine particle of the present invention as the base material particle, the conductive fine particle have necessary hardness and compressive deformation recovery factor to keep constantly the gap interval between one pair electrode base plates to be electrically connected and, in addition, is hard to give physical damage to the electrodes. Consequently, the gap interval between one pair electrode base plates is easily kept constantly, and the following troubles can be prevented: the exfoliation of a conductor layer owing to pres suri zat ion , a short-circuit between electrodes that should not be electrically connected, contact failure between electrodes that should be electrically connected, and others.
  • the conductive particle thus obtained of the present invention has the same mechanical properties (hardness, breaking strength) as the above-mentioned coated fine particle of the present invention. Consequently, the conductive particle is especially useful as an electric connection material in electronics such as a liquid crystal display panel, LSI, and a printed wiring board.
  • the surface state of particle before and after the formation of the polymer coated layer was observed with a scanning electron microscope (SEM, S3500N manufactured by Hitachi, Ltd., and the results were evaluated by three stages according to the following criteria .
  • the surfaces of the core particle is covered with a uniform polymer coated layer, the particle exists independently.
  • Electroless plating treatment was performed on 10 g of coated fine particles obtained by the following manufacturing examples.
  • the plated states of the surfaces of the particles after the treatment were observed with an electron microscope, and the results were evaluated according to the following criteria .
  • Average particle diameter, and the coefficient of variation of particle diameters As for the average particle diameters of polysiloxane particles and polymer fine particles, particle diameters of 30,000 pieces of particles were measured with Coulter multicizer (manufactured by Beckmann Coulter Inc.), and the average particle diameters were obtained.
  • ⁇ is standard deviation of particle diameter
  • X indicates average particle diameter
  • E Compressive elastic modulus (N / mm 2 ), F: Compressive load (N), S: Compressive displacement (mm) , and R: Radius of particle) .
  • This operation is performed on different 3 pieces of particles and the average value is referred to as 10% compressive elastic modulus.
  • a value obtained by measuring the relationship between the load value and the compression displacement is the compression deformation recovery factor.
  • the terminal point of load removing is set as the starting point load value of 0.098 mN and compression speed at load applying and load removing is set as 1.486 mN / second and then the measurement is carried out.
  • the value shown as the ratio of the displacement .(L 1) to the point of inversion and the displacement (L 2) from the point of inversion to the point of starting point load value (L 1 / L 2) is the recovery factor [%] .
  • Synthesis example (2) Synthesis of a surfactant ( compound ( b ) )
  • a surfactant compound ( b )
  • polyethylene imine polyethylene imine
  • Epomine SP006 polyethylene imine
  • the weight average molecular weight 600, manufactured by Nippon Shokubai Co., Ltd.
  • Liquid temperature was kept at 25°C or less during the dropping. After the end of dropping, the mixture was continuously stirred for about 30 minutes and then heated to 70°C. After being kept at the temperature for 2 hours, the mixture was cooled to ordinary temperature to give compound (b) having dispersibility (the concentration of solid content: 25 % by mass to the total amount of the mixture) .
  • Synthesis example (3) Synthesis of core fine particle (organic and inorganic composite fine particle)
  • the above-mentioned organic and inorganic composite particle dispersion liquid was stirred for 30 minutes, the above-mentioned monomer emulsion was added in the dispersion liquid in 15 seconds and the mixture was further stirred for 30 minutes. At this time, the polysiloxane particle was observed with a microscope, and it was confirmed that the inorganic particle had absorbed the monomer because the particle diameter was' increased.
  • 1000 parts of water was added in the dispersion liquid of the organic and inorganic composite particles in which the monomer had been absorbed.
  • the reaction, liquid was heated to 75°C under the nitrogen atmosphere and kept at the temperature for 30 minutes. As a result, the radical polymerization was performed in the reaction liquid to give a core fine particle emulsion (the average particle diameter: 3.8 ⁇ m, the coefficient of variation: 2.9%) .
  • Polystyrene particles were separated from the obtained dispersion liquid and washed, classified, and dried to give polystyrene particles (the average particle diameter is 5.1 ⁇ m and the coefficient of variation is 4.8%) .
  • the properties of the obtained polystyrene particles are shown in Table 1.
  • Manufacturing example 1 In a 300 ml beaker, 10 g of the solution of compound (b) obtained in Synthesis example (2) and 2Og of the core fine particles obtained in Synthesis example (3) were put and mixed with a spatula, and then 50 g of water was added in the mixture. After that, the mixture was subjected to ultrasonic and the core fine particles were dispersed (dispersion liquid Cl) .
  • the obtained coated fine particles Dl was plated with Ni by the electroless plating method, and the adhesion of plating was evaluated. The result is shown in addition in Table 2.
  • Ni plating was carried out as follows. Ten grams of the coated fine particles (Dl) was dispersed in 200 g of 1 mass % aqueous sodium hydroxide solution and etched by being stirred at 60°C for 2 hours. After being filtered and dried, the coated fine particles (Dl) were dipped into 1 g/1 aqueous solution of stannous chloride at room temperat . ure for 5 minutes and intensified. The coated fine particles after being intensified was added in a catalyzed liquid consisting of 0.1 ml/1 aqueous palladium chloride solution and 0.1 ml/1 hydrochloric acid while stirring and further stirred for 5 minutes to make the coated fine particles catch palladium ions.
  • the coated fine particles were filtered, washed, and further dipped into 1 g/1 -aqueous sodium hypophosphite solution at room temperature for 5 minutes and reduced.
  • base material particles that palladium was supported on the surfaces of coated fine particles were obtained.
  • the base material particles were added and dispersed in aqueous glycine solution (20 g/1) heated to 65°C under stirring to prepare slurry.
  • a nickel electroless plating liquid containing aqueous nickel sulfate solution, aqueous sodium hypochlorite solution, and aqueous sodium hydroxide solution was added at the rate of 5 ml/minute.
  • the liquid temperature was kept at 65°C and stirring was continued until hydrogen bubbling was stopped. After the stop of hydrogen bubbling, fine particles were filtered and washed, and dried in a vacuum dryer (at 100 0 C) to give conductive fine particles having nickel coating.
  • coated fine particles D2 were plated with Ni by the same method as that in the above-mentioned Manufacturing example 1.
  • the evaluation results on the properties (the thickness, the surface aspect and the adhesion of plating of the polymer coated layer) of the obtained coated fine particles D2 are shown in Table 2.
  • Manufacturing example 5 In a 300 ml beaker, 10 g of the solution of compound (b) obtained in Synthesis example (2) and 2Og of polystyrene particles obtained in Synthesis example (4) were put and mixed with a spatula, and then 50 g of water was added in the mixture. After that, the mixture was subjected to ultrasonic and the core fine particles were dispersed (dispersion liquid C3) .
  • the dispersion liquid C3 was put and 6 g of the solution of compound (a) was added while stirring (at the number of revolutions of 200 rpm) , and then the mixture was heated to 50°C. After being kept at the temperature for 1 hour, 150 ml of water was added in the mixture to cool it to room temperature and coated fine particles D5 was obtained. And, the coated fine particles D5 were plated with Ni by the same method as that in the above-mentioned Manufacturing example 1. The properties of the obtained coated fine particles D5 are shown in Table 2.
  • the coated fine particles D3 obtained in Manufacturing example 3 were plated with Ni by the electroless plating method without being etched, and then nickel-gold plating layer was formed on the fine particles by a substitution reaction with gold and conductive fine particles were obtained.
  • the gold plated layer was formed in the following manner.
  • an electroless plating liquid an aqueous solution that has a composition of 10 g/1 of ethylenediaminetetraacetic acid-4Na, 10 g/1 of citric acid-2Na, 3.0 g/1 of potassium cyanide, and further 2.1 g/1 of Au and pH is adjusted to be 6 with aqueous sodium hydroxide solution
  • liquid temperature was kept at 60°C
  • nickel plated fine particles were added and plated with Au while stirring.
  • Au plated fine particles were filtered, washed, and dried in a vacuum dryer (at 100 0 C) to give conductive fine particles having Au plated nickel c o a t i ng .
  • Synthesis example (3) electroless Ni plating and a substitution reaction with gold were performed by the same methods as those in the above-mentioned Manufacturing example 6 and conductive fine particles on which nickel-gold plated layer had been formed were obtained.
  • the evaluation result on the adhesion of plating of the obtained conductive fine particles is shown in Table 2.
  • the coated fine particles D7 were plated with Ni by the same method as that in the above-mentioned' Manufacturing example 1.
  • the properties of the obtained coated fine particles D7 are shown in Table 2. Table 2
  • the present invention it is possible to obtain coated fine particle that properties of the fine particle such as flexibility and elasticity can be controlled and adhesion to metals are also good. Moreover, since conductive fine particle included in the present invention have the above-mentioned coated fine particle as the base material, the conductive fine particle have also good adhesion to metals and, for example, in case of being used as such conductive fine particle as to be used in an anisotropic conductive material, the peeling of the conductive layer are hard to occur.

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Abstract

La présente invention prévoit une particule fine revêtue qui est souple, présente une excellente élasticité et une bonne adhérence sur les métaux ; l’invention décrit également un procédé pour la fabriquer, ainsi qu’une fine particule conductrice utilisant, en tant que particule formant noyau, la particule fine revêtue de polymère. La fine particule revêtue comprend une fine particule formant noyau, contenant un matériau organique ou un matériau composite organique et inorganique, et une couche de revêtement polymère sur une surface de la fine particule formant noyau, formée par une réaction d’ouverture de cycle et/ou de polycondensation sur la surface de la fine particule formant noyau.
PCT/JP2006/306597 2005-03-24 2006-03-23 Particule fine revetue, procede pour la fabriquer et particule fine conductrice WO2006101263A1 (fr)

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CN2006800090393A CN101146838B (zh) 2005-03-24 2006-03-23 一种包覆的细颗粒及其制备方法和导电细颗粒

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CN111813263B (zh) * 2020-07-10 2022-09-20 业成科技（成都）有限公司 热塑成形的修复粒子及方法

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JP4950662B2 (ja) 2012-06-13
KR20070121769A (ko) 2007-12-27
TW200641914A (en) 2006-12-01
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