CN101146838A - Coated fine particle and their manufacturing method, and conductive fine particle - Google Patents

Coated fine particle and their manufacturing method, and conductive fine particle Download PDF

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Publication number
CN101146838A
CN101146838A CNA2006800090393A CN200680009039A CN101146838A CN 101146838 A CN101146838 A CN 101146838A CN A2006800090393 A CNA2006800090393 A CN A2006800090393A CN 200680009039 A CN200680009039 A CN 200680009039A CN 101146838 A CN101146838 A CN 101146838A
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fine particle
mentioned
particle
coating
group
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CN101146838B (en
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山下毅
串野光雄
黑泽真实子
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Non-Insulated Conductors (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Chemically Coating (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The present invention provides a coated fine particle that is flexible and excellent in elasticity and has good adhesion to metals, a manufacturing method thereof, and conductive fine particle having the polymer coated fine particle as a core fine particle. 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 formed by ring-opening reaction and/or polycondensation reaction on the surface of the core fine particle.

Description

Fine particle of a kind of coating and preparation method thereof and conductive fine particle
Technical field
The present invention relates to fine particle of a kind of coating with good metal adhesion performance and preparation method thereof, also relate to a kind of fine grain conductive fine particle that uses coating.
Background technology
Polymer beads is widely used in indicating meter such as liquid-crystal display; The spacer such as the touch pad of cell gap (or plate crack); The electro-conductive adhesive that is used for fixing microelement; Conductive gap weighting material such as anisotropy conductiving glue stick.In these were used, polymer beads need have uniform particle shape and toughness and excellent elasticity.From then on viewpoint is set out, and the organic and inorganic composite materials of organic materials and common use organic constituent and inorganic component is used as the material of polymer beads.
For example, Japan has examined patent publication No. H7-17723 and discloses a kind of organic resin particle of being made up of aminoresin (for example, urea-formaldehyde resin, melamine resin and guanidine amine type resin).Because these aminoresin fine particles have many functional groups on the fine particle surface, thereby they have good metal adhesion performance, form metal carbonyl coat easily.Therefore, they are widely used in substrate material particle.
On the other hand, the open 2003-183337 of Japan's special permission discloses a kind of organic and inorganic compounding fine particle with organic polymer skeleton structure and polysiloxane skeleton structure.According to this technology,, can access fine particle with required character by control fines fraction type of material and content.
Summary of the invention
Yet because above-mentioned aminoresin fine particle has meticulous crosslinking structure, this particle is difficult to compressive set; For example, as the conductive fine particle between the electrode time, they can not increase the contact area with electrode surface, and are difficult to reduce contact resistance.In addition, also have such problem, promptly when the compressive set volume enlarged with the increase contact area, particle damaged when particle strain becomes big, and the result causes the connection reliability variation.On the other hand, also there is such problem, promptly because above-mentioned organic and inorganic compounding fine particle has toughness, but the fine grain metal adhesion of above-mentioned aminoresin is poor, and metal carbonyl coat organic at this and that inorganic compounding fine particle surface makes can not adapt to this fine grain distortion and peel off.In addition, the open 2001-126532 of Japan's special permission discloses a kind of technology to address the above problem, and this technology has been improved the adhesivity between pole plate and the silicone resin fine particle.Yet in the etching process that carries out before electroplating process does not finish as yet fully, silicone resin exists fusion and accumulative problem, thereby has further improved space.
Carried out the present invention at above-mentioned situation, the object of the present invention is to provide fine particle of a kind of coating with excellent in toughness and metal adhesion performance and preparation method thereof, and a kind of fine grain conductive fine particle that contains as the coating of fine particle nuclear is provided.
The fine grain key point that the present invention that can address the above problem coats is that the fine particle of this coating comprises the fine particle nuclear that contains organic materials or organic and inorganic composite materials; With the polymer covering layer that is positioned at described fine particle nuclear surface, wherein, described polymer covering layer is formed at the surface of fine particle nuclear by ring-opening reaction and/or polycondensation.
The inventor has carried out further research in order to obtain this fine particle that has good toughness and elasticity and have good metal adhesion performance; Based on obtaining above-mentioned performance with the gratifying thought that addresses the above problem by differing materials with in conjunction with these materials respectively, the inventor has repeated this experimentation and error.Certainly, only by can not fully demonstrating above-mentioned performance in conjunction with these materials.Key point of the present invention is, the preparation said composition is to make it have the metal adhesion performance by made this fine particle have toughness and elasticity and form polymer covering layer by ring-opening reaction and/or polycondensation by the fine particle nuclear of forming this fine grain centre portions with coatedparticles nuclear.That is to say, because the homogeneous polymer coating layer is positioned on the described fine particle nuclear, the fine particle that makes the coating that may obtain having toughness and elasticity and good metal adhesion performance.
The fine grain preparation method that a kind of the present invention coats, this method is used to prepare the fine particle of the coating with the polymer covering layer that is positioned at described granular core surface, this granular core contains organic materials or organic and inorganic composite materials, wherein, in being dispersed with the aqueous medium of described granular core and in the presence of tensio-active agent, form described polymer covering layer by ring-opening reaction and/or polycondensation.
Description of drawings
The fine grain cross sectional representation that Fig. 1 coats for the present invention;
Fig. 2 is the cross sectional representation of conductive fine particle of the present invention;
Fig. 3 is for before polymer covering layer forms, the electron microscope of fine particle nuclear (SEM: scanning electronic microscope) photo (synthetic embodiment 3);
Fig. 4 is for after polymer covering layer forms, electron microscope (SEM) photo of fine particle nuclear (preparation embodiment 1).
Description of reference numerals:
1: fine particle nuclear
2: polymer covering layer
3: conductive layer
Embodiment
Fine grain being characterised in that the present invention coats has the polymer covering layer that is formed at the fine particle nuclear surface of containing organic materials or organic and inorganic composite materials by ring-opening reaction and/or polycondensation.
As mentioned above, key point of the present invention is that described fine particle nuclear not only needs to have physicals (for example, toughness and elasticity), and the polymer covering layer that also needs evenly to be formed at described fine particle nuclear surface has good metal adhesion performance.Therefore, at first above-mentioned polymer covering layer is described.
Comprise the fine particle that polymer covering layer in the present invention coats the present invention and have good metal adhesion performance, can be in the aqueous medium that is dispersed with above-mentioned fine particle nuclear and (for example at tensio-active agent, the compound shown in the general formula 1 hereinafter) under the existence, use the starting compound of above-mentioned polymer covering layer, be formed at described fine particle nuclear surface by ring-opening reaction and/or polycondensation.
Compound (A) and compound (B) (will be described hereinafter) can be called the raw material of above-mentioned polymer covering layer.Above-claimed cpd (A) preferably contains a kind of mixture, and this mixture contains the compound that is selected from the group of being made up of urea, thiocarbamide, trimeric cyanamide, benzo guanamine, acetylguanamine and cyclohexyl guanamines (hereinafter becoming " aminocompound ") by at least a; With formaldehyde or by at least a compound and the resulting initial condenses of formaldehyde reaction that is selected from these aminocompounds.In addition, can synthesize and have higher wetting ability fast in order to make described polymer covering layer, compound (A) preferably uses initial condenses.
Here, the compound that above-mentioned aminocompound and formaldehyde reaction obtain is so-called aminoresin (Precondensed UreaFormaldehyde Resin, melamine resin and a guanidine amine type resin), and initial condenses is meant the precursor of aminoresin.That is, polymer covering layer comprises the aminoresin structure by using above-claimed cpd (A) to form in fact.
In addition, when using (i) at least a urea and thiocarbamide (hereinafter referred to as " urea type compound ") and formaldehyde, above-mentioned initial condenses is the initial condensation compound as the Precondensed UreaFormaldehyde Resin component; When using (ii) trimeric cyanamide and formaldehyde, above-mentioned initial condenses is a melamine resin; (iii) at least a when being selected from compound in the group of being made up of benzo guanamine, acetylguanamine and cyclohexyl guanamines (hereinafter becoming " trimeric cyanamide series compound ") and formaldehyde when using, above-mentioned initial condenses is the initial condensation compound as guanamines type resin Composition.In addition, when using (iv) the compound that obtains by two or more urea type compound, trimeric cyanamide and guanamines type compound and formaldehyde reaction, above-mentioned initial condenses is the compound as the component of two or more hybrid resin in Precondensed UreaFormaldehyde Resin, melamine resin and the guanidine amine type resin.Can use any one initial condenses, perhaps use two or more initial condenses simultaneously as above-mentioned initial condenses.
When above-mentioned initial condenses was synthetic, suitable aminocompound was preferably cocondensate and the trimeric cyanamide and the guanamines type compound cocondensate of urea type compound, trimeric cyanamide, urea type compound and trimeric cyanamide; The cocondensate of urea type compound, trimeric cyanamide and urea type compound and trimeric cyanamide more preferably; The cocondensate of trimeric cyanamide and urea type compound and trimeric cyanamide more preferably.
In addition, can use above-mentioned aminocompound other aminocompound in addition simultaneously.For example, other aminocompound can be octyl group trimeric cyanamide, americium amine (amerine), americyl amine (ameride), ethylidene-urea, propylidene urea and acetylene urea.When using other aminocompound, above-mentioned aminocompound and other aminocompound will common raw material ammonia based compounds (maybe can be included in the polymer covering layer) as above-mentioned condenses.
Formaldehyde with above-mentioned aminocompound reaction is had no particular limits, can be in reaction system, producing any compound of formaldehyde.In addition, in the reaction that obtains above-mentioned initial condenses, because water, can add trioxymethylene or Paraformaldehyde 96 in the entry, so that can produce formaldehyde in water therefore except formalin (formalin) usually as solvent.
Obtain the concrete reactive mode of above-mentioned initial condenses, be preferably following method: the method that aminocompound is added to (formalin) reaction in the formalin; Above-mentioned aminocompound is added to the method for reacting in the aqueous solution that is added with trioxymethylene or Paraformaldehyde 96; With other method.In the aforesaid method, preferred first method is because the bath and the formalin that do not need to prepare formalin obtain easily.In addition, above-mentioned reaction can be used as aminocompound and the formaldehyde mode in the admixture reaction; For example, except aminocompound being added to the mode in the formalin, this mode can also be for being added to formalin the mode in the aminocompound.Under the preferable case, using known whipping device to carry out carrying out above-mentioned reaction under the condition of stirring.
In the reaction that obtains above-mentioned initial condenses, the mol ratio of described aminocompound and formaldehyde (aminocompound (mole)/formaldehyde (mole)) is preferably 1/0.5 to 1/10, and more preferably 1/1 to 1/8, more preferably 1/1 to 1/6.When the blending ratio (mol ratio) of aminocompound and formaldehyde when exceeding above-mentioned scope, in the reaction system with residual a large amount of unreacted compound.
In addition, under the situation that makes water as solvent, the add-on of aminocompound and formaldehyde in the water promptly adds the concentration of fashionable aminocompound and formaldehyde, should be higher; Unless reaction does not hinder.
The water of above-mentioned initial condenses mixes degree (condensation speed extent index) and is preferably 100% or higher; More preferably 200% or higher; Be preferably 5000% or lower; More preferably 3000% or lower.When the described water degree of mixing is higher than above-mentioned scope, mean that described initial condenses has higher hydrophilicity, in this case, it is longer to form the needed time of polymer covering layer.On the other hand, when the described water degree of mixing is lower than above-mentioned scope,, and may be difficult to obtain the character (elasticity, physical strength, plating performance or the like) of polymer covering layer with the reaction that is difficult to during the controlling polymers coating layer forms.In addition, the described water degree of mixing is meant the percent polymerization degree of the initial condenses that the reaction by aminocompound and formaldehyde obtains, for adding water to initial condenses (5g adding, 15 ℃) situation under produce the quality of the required water of white opacity and multiply by 100 value with the mass ratio of initial condenses (that is, [water (g)/initial condenses (g)]).
Water mixes degree=[water (g)/initial condenses (g)] * 100
Though other method except water mixes the degree method also can be as the control method of the percent polymerization degree of above-mentioned initial condenses, for example, GPC (gel permeation chromatography), LC (liquid chromatography) or the like; But preferably adopt water to mix the degree method, because this method is simple to operate and repeating effect good.
The reaction of described initial condenses is preferably carried out under 65-75 ℃ of condition.This is because in this temperature range, the state of control reaction progress that can be instant, and mix the degree method by above-mentioned water and can determine required reaction end (object point) accurately, during reaction can more easily finish this reaction in addition by cooling off reaction solution etc.The not special restriction of described reaction times, under the progress of determining reaction, controlling reaction time that can be suitable.
In addition, as the raw material of above-mentioned polymer covering layer, can use epoxy compounds (compound) to substitute above-claimed cpd (A), or use with above-claimed cpd (A) is common with epoxide group as compound (B).Therefore, be also included within the scope of the invention by the ring-opening reaction of epoxy compounds and the polymer covering layer that contains Resins, epoxy of polycondensation formation.By containing Resins, epoxy, the fine particle of described coating can obtain the physical strength of better toughness and Geng Gao.
As the epoxy compounds of above-mentioned Resins, epoxy raw material, this compound preferably has two or more epoxide groups on individual molecule, and has water-soluble.For example, this epoxy compounds comprises sorbyl alcohol poly glycidyl ester, (gathering) glycerol poly glycidyl ester, tetramethylolmethane poly glycidyl ester, glycidyl three (2-hydroxyethyl) isocyanuric acid ester, TriMethylolPropane(TMP) poly glycidyl ester, neopentyl glycol 2-glycidyl ester, ethylene glycol bisthioglycolate glycidyl ester, polyoxyethylene glycol 2-glycidyl ester, propylene glycol 2-glycidyl ester, polypropylene glycol 2-glycidyl ester and hexanodioic acid 2-glycidyl ester.These compounds can use separately, also can two or more be used in combination.
The dissolution rate of above-mentioned epoxy compounds in water is preferably 50 quality % or higher; 60 quality % or higher more preferably; 70 quality % or higher more preferably; Be preferably 100 quality % especially.When described dissolution rate is in this scope, can access such good result, i.e. the formation of epoxy resin layer (polymer covering layer) is evenly and fast, the while is the thickness of gate ring epoxy layer easily.In addition, the dissolution rate of the Resins, epoxy of defined in water is meant the numerical value that obtains by following detection method among the present invention.Accurately take by weighing 25.0g sample compound (epoxy compounds), and be added to and add 225g water in the 300ml beaker simultaneously, by this mixture of magnetic stirrer, churning time is 1 hour, to dissolve this sample compound.Then, this solution was placed 1 hour.Take out subsequently and be deposited in the undissolved sample compound (oleaginous materials) of beaker bottom, and put it in the graduated cylinder of 10ml (or 5ml), graduated cylinder was placed 30 minutes.Then, the fluid volume that reads this sample compound (containing material) first decimal place to the radix point.In institute's value substitution following formula, the dissolution rate (%) of calculation sample compound (epoxy compounds) in water.
Dissolution rate in water (%)=100-(A/21) * 100
(wherein, A is meant the fluid volume (ml) of this sample compound that reads)
The weight-average molecular weight of above-mentioned epoxy compounds is preferably 300 or bigger and 10000 or littler; More preferably about 300 or bigger and 5000 or littler.When weight-average molecular weight is in above-mentioned scope, can access such good result, promptly can control the thickness of described epoxy resin layer (polymer covering layer) easily.On the other hand, when described weight-average molecular weight during, be difficult to the elasticity that the formation by epoxy resin layer is improved, and be difficult to form uniform epoxy resin layer less than above-mentioned scope.When described weight-average molecular weight during greater than above-mentioned scope, during polymer covering layer formed, the viscosity of reacting fluid raise rapidly, and was difficult to stir.Stirring reaction fluid by force in this case can make the fine particle of coating be damaged or broken.
When above-mentioned epoxy resin layer forms, except epoxy compounds, can also add linking agent.Can improve the intensity of epoxy resin layer by the use linking agent, thereby further improve the fine grain intensity that coats, the result can effectively control the fine grain insulativity of coating and damage and the fragmentation in the cleaning process.To not special restriction on the opportunity that adds above-mentioned linking agent, can add simultaneously with epoxy compounds, also can add front or rear the adding at epoxy compounds, preferably add the back and add at epoxy compounds.
For example, above-mentioned linking agent includes, but are not limited to Thiocarb (comprising hydrate (hydrate)), diethylammonium diethyldithiocarbamate(DDDC) (comprising hydrate), dithio oxalic acid and dithiocarbonic acid.These compounds can use separately, and two or more that also can be in them is used in combination.In addition, though to the add-on of above-mentioned linking agent without limits,, under the preferable case, with respect to the epoxy compounds of 100 mass parts, add-on is the 1-100 mass parts; 5-80 mass parts more preferably.When the add-on of above-mentioned linking agent is less than above-mentioned scope, be difficult to the thickness of the described epoxy resin layer of control etc.When add-on during greater than above-mentioned scope, with the overreact of epoxide group on the epoxy compounds, the result can not form the epoxy resin layer with higher toughness and good metal adhesion performance.
When above-mentioned polymer covering layer forms, with coexist as that tensio-active agent in the reaction system comprises the compound shown in the following general formula (1) and the description of the fine particle nuclear that will be explained hereinafter in the exemplary emulsifying agent that provides, for example, anion surfactant, cats product, nonionogenic tenside, amphoterics and polymeric surface active agent.
R 1-(CH 2-CH 2-O-) n-X m-R 2 (1)
When keeping the dispersion state of fine particle nuclear in reaction system, above-mentioned tensio-active agent is used for being formed uniformly polymer covering layer on the surface of fine particle nuclear, and the tensio-active agent shown in the above-mentioned general formula (1) becomes the composition of described polymer covering layer.Promptly, comprise that polymer covering layer in the present invention forms by utilizing intermolecular forces, for example, hydrophobic interaction, tensio-active agent and above-claimed cpd (A) between described fine particle nuclear and the tensio-active agent and/or the hydrophobic interaction between the compound (B).When forming polymer covering layer under the non-existent condition of above-mentioned tensio-active agent, the ring-opening reaction of above-claimed cpd (A) and/or compound (B) and polycondensation are not only carried out on the surface of described fine particle nuclear, but carry out all having everywhere of described fine particle nuclear, the result, except the coating fine particle that the present invention includes, also produce the polymeric constituent that does not have fine particle nuclear and derive from compound (A) and compound (B).Therefore, when polymer covering layer forms, preferably use tensio-active agent.In addition, form the viewpoint of homogeneous polymer coating layer from fine particle nuclear surface, in above-mentioned tensio-active agent, preferably use the tensio-active agent shown in the above-mentioned general formula (1).
In the above-mentioned general formula (1), R 1Expression comprises the hydrophobic grouping of aliphatic alkyl or organic alkyl, for example, and aliphatic alkyl such as phenyl, hexyl, heptyl, octyl group, decyl, octadecyl, stearyl-and docosyl; Aryl such as phenyl, phenmethyl, tolyl, xylyl, xenyl and naphthyl.The carbonatoms of described hydrophobic grouping is preferably 5 or more and 25 or still less (more preferably 18 or still less).When carbonatoms too hour because the wetting ability of ethylene oxide chain will cause the dispersion of fine particle nuclear insufficient.On the other hand, when carbonatoms was too big, hydrophobicity was too high, and tensio-active agent is difficult to dissolving in water (reaction solvent).
In above-mentioned general formula (1): [(CH 2-CH 2-O-) n] being polymer chain with polyether structure (polyoxyethylene structure), the quantity n of above-mentioned polyether structure is preferably 3 or bigger, and more preferably 5 or bigger, be preferably 85 or littler, more preferably 60 or littler, more preferably 50 or littler.When polyether structure is very few (though depend on above-mentioned hydrophobic grouping balance), above-claimed cpd is difficult to disperse in aqueous medium.On the other hand, when polyether structure was too much, the dissolution rate in the aqueous medium was too high, the result, and this compound is difficult to polymer covering layer.In addition, if n is in above-mentioned scope, when polymer covering layer forms, part surface promoting agent and above-claimed cpd (A) that is used for this polymer covering layer and compound (B) reaction, make the fine particle of coating can have appropriate elasticity, as a result, improved the fine grain physical strength of described coating.
In above-mentioned general formula (1), X represents to derive from the group that can react with at least a group that is selected from the group of being made up of amino, imido grpup and carboxyl and is formed at this reacted group (bonding reaction).In addition, in general formula (1), m represents 0 or 1.Here, above-mentioned amino, imido grpup close carboxyl and are meant the amino that can be present in the polymkeric substance with polyamine structure and imido grpup, the R that will be described below 2Maybe can be present in the carboxyl in the polymkeric substance with poly carboxylic acid structure.
For example, the group shown in the above-mentioned X is by deriving from R 2Functional group and following general formula (3) in the group that produces of the radical reaction shown in the X, especially, can be exemplary provide following groups: [the CH that derives from group shown in the following general formula (b) 2-CH 2-S-], derive from isocyanate groups [NH-CO-], must be from [the CO-NH-CH of oxazoline group 2-CH 2For a short time derive from aldehyde groups [CH (OH)-], derive from carboxylic group [CO-], derive from [NH-] of amino group and derive from [=the N-] of imido grpup group.
In general formula (1), R 2The weight-average molecular weight that expression has polyamine structure or poly carboxylic acid structure is the polymeric groups of 300-100000 (300-50000 more preferably).When described weight-average molecular weight was too small, polymkeric substance was difficult to be precipitated as insolubles, need could form polymer covering layer for a long time, and the insufficient strength of polymer covering layer.When weight-average molecular weight was excessive, the viscosity of whole reaction system sharply raise, and was difficult to stir.
To the not special restriction of the polymeric groups with above-mentioned polyamine groups, but comprise have the polyamine structure that contains primary amine groups group and/or secondary amine group polymeric groups, for example, have at least a being selected from by polymine, polyamine, polyetheramine, polyvinylamine, modified poly ethylene amine, poly-alkylamine, polymeric amide, polyamine Epicholorohydrin (polyamine epichlorohydrin), poly-diakyl amido alkyl vinyl ether, poly-diakyl amido alkyl (methyl) acrylate, polypropylene amine, the polymeric groups of the structure in the group that polymine grafted daiamid (polyamideamine) and protonated daiamid are formed.
To the not special restriction of the polymeric groups with above-mentioned poly carboxylic acid structure, but comprise polymeric groups with water soluble polycarboxylic acid structure, this polymeric groups obtains by the polycondensation that contains 30 moles of % or more unsaturated carboxylic acid monomer composition, and this unsaturated carboxylic acid comprises vinylformic acid, methacrylic acid, Alpha-hydroxy vinylformic acid, butenoic acid, phthalic acid, toxilic acid, FUMARIC ACID TECH GRADE, methylene-succinic acid, citraconic acid, aconitic acid and vinyl acetate between to for plastic.
Preparation method to the tensio-active agent shown in the above-mentioned general formula (1) has no particular limits, for example, preferably adopt following method, promptly, compound shown in following general formula (2) or (3) is dropwise added in the aqueous solution of polyamine or poly carboxylic acid, and under stirring condition, react.
R 1-(CH 2-CH 2-O-) n-1-X 1 (2)
Wherein, X 1Be the group shown in the following structural formula (a):
R 1-(CH 2-CH 2-O-) n-X 2 (3)
Wherein, X 2Be any group that is selected from the group of forming by group, isocyanate groups, oxazoline group, aldehyde groups, carboxylic group, amino group and imido grpup group shown in the following structural formula (b),
Figure A20068000903900142
Be X 2For can with at least a group that is selected from the radical reaction (bonding reaction) in the group of forming by amino group, imido grpup group and carboxylic group.
State in the use under the situation of the tensio-active agent shown in the above-mentioned general formula of compound (1) shown in the general formula (2), there is not the group shown in the X in above-mentioned general formula (that is, m=0) in (1).On the other hand, state in the use under the situation of the tensio-active agent shown in the above-mentioned general formula of compound (1) shown in the general formula (3), there is the group shown in the X in above-mentioned general formula (that is, m=1) in (1).
Though the temperature of reaction for preparing during the above-mentioned tensio-active agent has no particular limits, under the situation of using polyamine, temperature of reaction is preferably 10-90 ℃, more preferably 10-80 ℃; Under the situation of using poly carboxylic acid, temperature of reaction is preferably 20-100 ℃, more preferably 20-90 ℃.Though the reaction times is had no particular limits, under the preferable case, is 0.5-5 hour, more preferably 1-5 hour.
Among the present invention, in the scope that does not upset effect of the present invention, other compound also can use with tensio-active agent shown in the above-mentioned general formula (1) or the emulsifying agent of hereinafter being mentioned.In addition, can imagine, carry out easily that above-mentioned other compound also is water miscible material for the formation that makes polymer covering layer is reflected in the aqueous medium.Other compound of available of the present invention comprises tensio-active agent and the following emulsifying agent that will describe, natural polymer dispersion agent such as gelatin and gum arabic, synthetic polymer dispersion agent such as styrene-maleic acid copolymer and their salt of polyvinylpyrrolidone, polyvinyl alcohol, all kinds except the tensio-active agent shown in the above-mentioned general formula (1).
Next, description is comprised in the present invention fine particle nuclear.Fine particle nuclear as the fine grain body material that comprises coating in the present invention all has great influence to fine grain toughness, elasticity and the mechanical property that coats.To the not special restriction of the material of fine particle nuclear, can use any organic materials, organic and inorganic composite materials or inorganic materials.Described organic materials comprises linear polymer such as polystyrene, polymethylmethacrylate, polyethylene, polypropylene, polyethylene terephthalate, polybutyleneterephthalate, polysulfones, polycarbonate and polymeric amide; By the network polymer that obtains with other polymerisable monomeric homopolymerization or polyreaction, described polymerisable monomer is a divinylbenzene, hexatriene, divinyl ether, divinylsulfone, diallyl methyl alcohol, the alkylidene group diacrylate, oligomeric or poly alkylidene group glycol diacrylate, oligomeric or poly alkylidene group ethylene glycol dimethacrylate, the alkylidene group triacrylate, the alkylidene group tetraacrylate, the alkylidene group trimethacrylate, alkylidene group tetramethyl-acrylate, the alkylidene group bisacrylamide, the polyhutadiene oligopolymer that alkylidene group DMAA and two ends propenyl are modified; The aminoresin that polycondensation by aminocompound (for example, benzo guanamine, trimeric cyanamide, urea etc.) and formaldehyde obtains; By the homopolymerization of divinylbenzene or the divinylbenzene crosslink resin particle that obtains with other vinyl monomer copolyreaction.Described organic and inorganic composite materials comprises organic substance and the inorganic compound particles that obtains by the polysiloxane reaction; the raw material of this reaction be have the silicon compound of hydrolysable silyl group group and have polymerizable groups (for example, vinyl, (methyl) acryl etc.) but polycondensation monomer or the like.Inorganic materials comprises, for example, and glass, silicon and aluminum oxide.In addition, consider from the angle of the character that can relatively optionally design this fine particle nuclear, preferred use by organic materials or organic and inorganic composite materials is formed those.
As above-mentioned organic and inorganic compounding fine particle, preferred especially the use has the polysiloxane skeleton that is formed on tridimensional network and the polymer fine particles of organic polymer skeleton.The preparation method's of this polymer fine particles a example as shown below.
Above-mentioned organic and inorganic compounding fine particle is a polymer fine particles, this polymer fine particles contains as the polysiloxane skeleton of mineral parts with as organic substance organic polymer skeleton partly, and has the organosilicon atom, in this organosilicon atom, at least one carbon atom on the organic polymer skeleton and the Siliciumatom on the polysiloxane skeleton form the direct chemical bond of intramolecularly (chemical bond type).
Above-mentioned polysiloxane preferably have can with organic polymer skeleton bonded unsaturated group, for example, preferably have vinyl.This polysiloxane with vinyl is the compound with polysiloxane skeleton structure, and this compound prepares by the starting compound that hydrolysis and condensation contain the silicon compound with vinyl.For example, the hydrolyzable silicon compound that is present in the water-containing solvent by hydrolysis and condensation prepares this compound.In addition, to not special restriction on the opportunity of introducing vinyl groups, for example, can adopt any following pattern: use to have the pattern of the silicon compound of vinyl as hydrolyzable silicon compound; And the hydrolyzable silicon compound that does not have vinyl by hydrolysis and condensation, behind generation kind of the particle (polysiloxane that does not have vinyl), this kind particle (polysiloxane that does not have vinyl) and hydrolyzable silicon compound with vinyl are hydrolyzed and condensation, in polysiloxane, to introduce vinyl.In the later case, during the hydrolysis and condensation of described kind of particle and soluble silicon compound, carry out polycondensation fast with polymerizable components simultaneously with vinyl.
Though above-mentioned soluble silicon compound is had no particular limits, for example, can use silane compound shown in the following general formula (4) and their derivative.
R 3 1SiX 4-1 (4)
(wherein, R3 can have substituting group, represent at least a group that is selected from the group of being made up of alkyl, aryl, aralkyl and unsaturated fatty acids base, X represents at least a group that is selected from the group of being made up of hydroxyl, alkoxyl group and acyloxy, and 1 is the integer of 0-3.)
As the silane compound shown in the above-mentioned general formula (4), for example, can be exemplary provide following compound.When 1=O, can be silicane of four functional groups, for example tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan and four butoxy silanes; When 1=1, can be trifunctional silane, methyltrimethoxy silane for example, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, the hexyl triethoxyl silane, the decyl Trimethoxy silane, phenyltrimethoxysila,e, the phenmethyl Trimethoxy silane, the naphthyl Trimethoxy silane, methyl triacetoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-glycidoxypropyltrime,hoxysilane, vinyltrimethoxy silane, 3-(methyl) acryloxy propyl trimethoxy silicane and 3,3,3-three fluoro propyl trimethoxy silicanes; When 1=2, can be bifunctional silane, for example, dimethylsilane, dimethyldiethoxysilane, diacetoxy dimethylsilane and dimethoxy Diphenylsilanediol; When 1=3, can be monofunctional silanes, for example, trimethyl silane, trimethylethoxysilane and trimethyl silanol.
Above-mentioned silicon compound can a kind of independent use, also can two or more be used in combination.In addition, when the silicon compound of 1=3 and derivative thereof are as raw material in only using above-mentioned general formula (4), can't obtain composite particles.
For example, above-mentioned hydrolyzable silicon compound with vinyl comprises that those have the compound of the polymerizable reactive group shown in for example following general formula (5), (6) and (7).
CH 2＝C(-R 4)-COOR 5- (5)
Wherein, R 4Be hydrogen atom or methyl, R 5For having substituent and carbonatoms is the divalent organic group of 1-20.
CH 2＝C(-R 6)- (6)
Wherein, R 6Be hydrogen atom or methyl.
CH 2＝C(-R 7)-R 8- (7)
Wherein, R 7Be hydrogen atom or methyl, R 8For having substituent and carbonatoms is the divalent organic group of 1-20.
For example, the polymerisable reactive group shown in the above-mentioned general formula (5) comprises acryloxy and methacryloxy; For example, the silicon compound with this organic group shown in the above-mentioned general formula (4) comprises γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, γ-acryloxy propyl trimethoxy silicane, γ-acryloxy propyl-triethoxysilicane, γ-methacryloxypropyl triacetoxysilane, γ-methacryloxy ethoxycarbonyl propyl Trimethoxy silane (or, be also referred to as γ-trimethoxy-silylpropyl-Beta-methyl acryloyl-oxy benzyl ethyl ether), 11-methacryloxy 11 methylene tri methoxy silane, γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl methyldiethoxysilane and γ-acryloxy propyl group methyl dimethoxysilane.
For example, the polymerisable reactive group shown in the above-mentioned general formula (6) comprises vinyl and pseudoallyl; For example, the silicon compound that has this organic group shown in the above-mentioned general formula (4) comprises vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, 4-vinyl tetramethylene Trimethoxy silane, 8-vinyl eight methylene tri methoxy silane, 3-trimethoxy-silylpropyl Vinyl Ether, vinyl methyl dimethoxysilane, vinyl methyldiethoxysilane and vinyl methyl diacetoxy silane.These compounds can a kind of independent use, also can two or more be used in combination.
For example, polymerisable shown in the above-mentioned general formula (7) answers group to comprise 1-thiazolinyl or vinyl phenyl and isoolefine base or isoolefine base phenyl; For example, the silicon compound with this organic group shown in the above-mentioned general formula (4) comprises 1-hexenyl Trimethoxy silane, 1-hexenyl triethoxyl silane, 1-octenyl Trimethoxy silane, 1-decene base Trimethoxy silane, γ-trimethoxy-silylpropyl Vinyl Ether, ω-trimethoxysilyl undecanoic acid vinyl acetate, to trimethoxysilyl vinylbenzene, to triethoxysilyl vinylbenzene, to trimethoxysilyl-alpha-methyl styrene, to triethoxysilyl-alpha-methyl styrene, N-β-(N-vinyl benzene methyl aminoethyl-γ-aminopropyl) Trimethoxy silane hydrochloride, 1-hexenyl methyl dimethoxysilane and 1-hexenyl methyldiethoxysilane.These compounds can a kind of independent use, also can two or more be used in combination.
Above-mentioned polysiloxane can be by in aqueous solvent, and the compound that comprises in the above-mentioned group of silicon compounds of hydrolysis and condensation obtains.For hydrolysis and condensation, can adopt various primary treatments, batch treatment and processed continuously method or the like.In addition, when being hydrolyzed, can use various catalyzer with condensation, for example, ammonia, urea, thanomin, tetramethyl-ammonium oxyhydroxide, alkali metal hydroxide and alkaline earth metal hydroxides.In addition, in solvent, except water and catalyzer, also can there be organic solvent.
Though above-mentioned organic solvent is had no particular limits, the following organic solvent of preferred use, for example, alcohol, for example, methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, ethylene glycol, propylene glycol and 1,4-butyleneglycol; Ketone, for example, acetone and methyl ethyl ketone; Ester, for example, ethyl acetate; (ring) alkane, for example, octane-iso and cyclohexane; Ether, for example ， diox and diethyl ether; Aromatic hydrocarbons, for example, benzene and toluene.These solvents can a kind of independent use, also can two or more be used in combination.
Be hydrolyzed and condensation reaction under the 0-70 ℃ of temperature by adding above-mentioned silicon compound and organic solvent etc. and stir in water-containing solvent, being preferably at 0-100 ℃, the reaction times is 30-100 hour.In addition, in this stage, under the preferable case, with the reaction mixture total amount is benchmark, and the concentration of described water is 10-99.99 quality %, and described catalyst concentration is 0.01-10 quality %, the concentration of described organic solvent is 0-90 quality %, and the concentration of above-mentioned silicon compound is 0.1-30 quality %.In addition, under the preferable case, the time that adds above-mentioned silicon compound is 0.001-500 hour, and temperature of reaction is 0-100 ℃.In addition, the particle that uses the hydrolysis before carried out and condensation reaction to obtain as kind of particulate situation under, be benchmark with the total amount of reaction mixture, described kind of particulate concentration is preferably 0.1-30 quality %.
In addition, at first the particle that hydrolysis and condensation reaction are obtained is added in the synthetic system as planting particle, then above-mentioned silicon compound is joined in this system, and above-mentioned kind of particle grown up.Therefore, obtain polysiloxane particle.In this method, under the condition that is fit to, above-mentioned silicon compound is hydrolyzed and condensation in aqueous solvent, and solids precipitation forms slurry.Owing to use the above-mentioned silicon compound with vinyl to obtain particle as basal component, therefore, described sedimentary particle forms the polysiloxane particle with vinyl group.Here, though do not limit to the condition that is fit to is special, under the preferable case, contain (preferred concentration is 0.1-20 quality %) in kind of the particulate slurry by what the hydrolysis formerly carried out and condensation reaction obtained, total amount with respect to this reaction mixture, the concentration of above-mentioned hydrolyzable silicon compound is 20 quality % or still less, the concentration of water is 50 quality % or more, and described catalyst concentration is 10 quality % or still less.
Shape to above-mentioned polysiloxane particle has no particular limits, and can have any shape, and comprises sphere, aciculiform, plate shape, sheet shape, powder shape, bag shape (cylindrical), cocoon shape and bits shape.
Though the median size to above-mentioned polysiloxane particle has no particular limits, under the preferable case, median size is 0.1-700 μ m, and more preferably 0.5-70 μ m most preferably is 1-50 μ m.When the median size of above-mentioned polysiloxane particle is in above-mentioned scope, can demonstrate such beneficial effect, that is, that the absorption of the polymerizable components that is described hereinafter is more effective.On the other hand, when the average particle diameter of above-mentioned polysiloxane particle is too small, that the absorption of the polymerizable components that is described hereinafter is abundant inadequately; When the average particle diameter of above-mentioned polysiloxane particle was excessive, polymer fine particles precipitated in increase of particulate quality and the reactor, and adheres to each other mutually easily between the particle.
The above-mentioned polysiloxane particle that obtains is meant and can adsorbs polymerizable components of hereinafter describing and the particle that can keep this component in constituting particulate silane skeleton.That is to say that this is because the condensation level of above-mentioned polysiloxane particle is suitable for adsorbing polymerizable components described below.
Below, will describe can with above-mentioned polysiloxane particle polymeric polymerizable components.Above-mentioned polymerizable components is had no particular limits, but consider Combination with above-mentioned polysiloxane particle, preferably use the vinyl monomer of free redical polymerization and on individual molecule, have the bifunctional oligopolymer of two (methyl) acryls.
The vinyl monomer of described free redical polymerization is preferably the monomer that contains at least one alkene unsaturated group in the molecule, and this monomer is by fully suitably selecting to make described polymer beads can demonstrate required physical properties.Can introduce following concrete monomer: have the monomer of oh group, for example, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate and 2-hydroxyl butyl (methyl) acrylate; The monomer such as methoxy poly (ethylene glycol) (methyl) acrylate that contain the polyoxyethylene glycol component; Alkyl (methyl) acrylate such as butyl (methyl) acrylate, methyl (methyl) acrylate, ethyl (methyl) acrylate, isopentyl acrylate, dodecyl (methyl) acrylate, phenmethyl (methyl) acrylate and tetrahydrofurfuryl alcohol methacrylic ester; Fluorine-containing (methyl) acrylate such as trifluoroethyl (methyl) acrylate, tetrafluoro propyl group (methyl) acrylate, five fluoropropyls (methyl) acrylate and octafluoro amyl group (methyl) acrylate; Aromatic ethenyl compound such as vinylbenzene, alpha-methyl styrene, Vinyl toluene, alpha-chloro vinylbenzene, adjacent chlorostyrene, a chloro vinylbenzene, to chlorostyrene with to ethyl styrene; Glycidyl (methyl) acrylate; (methyl) vinylformic acid; (methyl) acrylamide; (methyl) vinyl cyanide.
The bifunctional oligopolymer that has two (methyl) acryl group in individual molecule, relatively and the total amount of water and bifunctional oligopolymer, the solubleness in water under 25 ℃ of conditions is preferably 10 quality % or still less, and weight-average molecular weight is 300 or bigger.Such component is adsorbed in the above-mentioned polysiloxane particle easily, and helps improving the performance (for example, toughness and elasticity etc.) of polymer fine particles.
Above-mentioned bifunctional oligopolymer is had no particular limits,, for example, comprise polyoxyethylene glycol two (methyl) acrylate as long as have above-mentioned character; Polypropylene glycol two (methyl) acrylate such as propylene glycol two (methyl) acrylate; Three polypropylene glycol two (methyl) acrylate; Polytetramethylene glycol two (methyl) acrylate; Neopentyl glycol two (methyl) acrylate; 1,3 butylene glycol two (methyl) acrylate; 2,2-two [4-(methacryloxy polyethoxye) phenyl] propane two (methyl) acrylate is as 2,2-two [4-(methacryloxy oxyethyl group) phenyl] propane two (methyl) acrylate; Dihydroxyphenyl propane two (methyl) acrylate of EO modification is as 2,2-hydrogenation two [4-(acryloxy polyethoxye) phenyl] propane two (methyl) acrylate (2,2-hydrogenated bis[4-(acryloxypolyethoxy) phenyl] propane di (meth) acrylate); Two (methyl) acrylate of tricarbimide EO modification (isocyanuric acid EOmodified di (meth) acrylates).
For example, bifunctional oligopolymer with said structure comprises Shin-Nakamura Chemical Co., Ltd. the NK ester series of Sheng Chaning is as " 9PG ", " APG-200 ", " APG-400 ", " APG-700 ", " BPE-100 ", " BPE-200 " and " BPE-500 "; Nippon Kayaku Co., the product that Ltd. produces is as " KAYARAD HX-220 " and " KAYARAD HX-620 "; With Kyoeisha ChemicalCo., the product that Ltd. produces, as, " Lightacrylate PTMGA-250 ".Except these products, also can preferably use Nippon Kayaku Co., " the KAYARAD MANDA " and " KAYARAD R-167 " that Ltd. produces.
These polymerizable components can use separately, also can two or more be used in combination.Under above-mentioned polymerizable components is adsorbed to situation in the polysiloxane particle, by during emulsification and disperseing above-mentioned polymerizable components to form emulsion, but preferably use hydrophobicity rapid polymerization vinyl monomer with stable emulsion.
In addition, except above-mentioned polymerizable components, can also use crosslinkable monomers.In this case, control the mechanical properties of the polymer fine particles that obtains easily.To the not special restriction of above-mentioned crosslinkable monomers, for example, comprise Vinylstyrene, 1, trimethylolpropane tris (methyl) acrylate of 6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythritol three (methyl) acrylate, tetra methylol propane four (methyl) acrylate, dipentaerythritol acrylate, diallyl phthalate, oxyethane modification and their isomer; And cyanacrylate and its derivative.These compounds can use separately, also can two or more be used in combination.
In above-mentioned polymerizable components, can contain above-mentioned hydrolyzable silicon compound.Can use and have hydrolyzable silicon compound vinyl groups and that do not have vinyl groups.Yet, when using the polysiloxane particle do not have vinyl groups, be necessary in polymerizable components, to add hydrolyzable silicon compound as kind of particle.
Though the blending ratio to above-mentioned polymerizable components has no particular limits, and can suitably regulate according to the character of expection, for example, in the above-mentioned polymerizable components of 100 quality % (promptly, above-mentioned bifunctional oligopolymer and the monomeric total amount of above-mentioned polymerizable vinyl), the blending ratio of above-mentioned bifunctional oligopolymer is preferably 20 quality % or higher; 30 quality % or higher more preferably; 40 quality % more preferably.When the amount of the described bifunctional oligopolymer that contains is in above-mentioned scope, can easier control the compressive set recovery rate (compressive deformationrecovery factor) of the polymer fine particles that obtains.In addition, all polymerizable components can be above-mentioned bifunctional oligopolymer.
In addition, the component that derives from the bifunctional oligopolymer in the polymer fine particles is preferably 10 quality % or more, 20 quality % or more more preferably, 30 quality % or more more preferably, be preferably 99 quality % or still less, 95 quality % or still less more preferably, more preferably 90 quality % or still less.
As the preparation method of above-mentioned polysiloxane particle, can adopt various following methods:
[A] has the method for above-mentioned hydrolyzable silicon compound preparation kind of the particle (polysiloxane with vinyl groups) of vinyl groups by hydrolysis and condensation.
[B] do not have hydrolyzable silicon compound preparation kind of the particle (1) (polysiloxane that does not have vinyl groups) of vinyl groups by hydrolysis and condensation, then, this kind particle (1) and hydrolyzable silicon compound with vinyl groups obtain kind of a particle (2) (polysiloxane with vinyl groups) by hydrolysis and condensation.
[C] do not have hydrolyzable silicon compound preparation kind of the particle (1) (polysiloxane that does not have vinyl groups) of vinyl groups by hydrolysis and condensation, the polymerizable components that will have the hydrolyzable silicon compound of vinyl groups and hereinafter describe is adsorbed in this kind particle (1), during this period, the polysiloxane in the above-mentioned kind of particle (1) obtains kind of a particle (2) (polysiloxane with vinyl groups) with the hydrolyzable silicon compound with vinyl groups by hydrolysis and condensation.
Above-mentioned polymer fine particles can obtain by adsorption process and polymerization process, in described adsorption process, above-mentionedly be in that emulsified and polymerizable components dispersion state is added into and is adsorbed in the above-mentioned polysiloxane particle with vinyl groups in the water, perhaps in described adsorption process, contain above-mentioned polymerizable components and requisite polymerizable components basically and be in that emulsified and dispersive state is added into and is adsorbed in the above-mentioned polysiloxane particle with vinyl groups in the water with polymerisable monomer of vinyl groups and hydrolysable silyl group group; In described polymerization process, make the above-mentioned polymerizable components that in above-mentioned adsorption process, is adsorbed onto in the above-mentioned polysiloxane particle carry out radical polymerization.
To the not special restriction of above-mentioned adsorption process, as long as exist when having above-mentioned polysiloxane particle under the state of above-mentioned polymerizable components, this process can get final product.In addition, though in adsorption process, above-mentioned polymerizable components is adsorbed in the above-mentioned polysiloxane particle structure, described adsorption process is preferably carried out after setting various conditions, so that adsorption process is carried out fast, described condition comprises blending ratio, blended treatment process and the device of the concentration of various above-mentioned polysiloxane particles and polymerizable components, above-mentioned poly-silica particle and polymerizable components. blended temperature and time and mixed treatment process and means.
In the above-mentioned absorption process, the add-on of described polymerizable components is preferably as the 0.01-100 of the silicon compound quality of polysiloxane particle raw material doubly, more preferably 0.5-30 doubly, more preferably 1-15 is doubly.When described add-on during less than above-mentioned scope, the amount that is adsorbed in the polymerizable components of polysiloxane particle will be seldom, and be difficult to obtain having the polymer fine particles of above-mentioned mechanical property; When described add-on is higher than above-mentioned scope, the polymerizable components that adds is adsorbed in fully and will becomes very difficult in the described polysiloxane particle, because the still residual polymerizable components that absorption is arranged not at ensuing polymerization stage, is easy to take place coacervation between particle.
In order to mix described polymerizable components and polysiloxane particle, above-mentioned polymerizable components can be added in the solvent that is dispersed with polysiloxane particle, or polysiloxane particle is added in the solvent that contains above-mentioned polymerizable components.Among them, preferably polymerizable components is joined in the solvent that is dispersed with polysiloxane particle in advance.Further under the preferable case, from the polysiloxane particle dispersion liquid that synthetic polysiloxane particle obtains, do not take out polysiloxane particle, but described polymerizable components is joined in the dispersion liquid, because this process and uncomplicated and have a good productive rate.
In above-mentioned adsorption process, joining day of polymerizable components is had no particular limits, described polymerizable components can disposablely add, and can divide several times to add, and also can add with any speed.In addition, when adding polymerizable components, only add polymerizable components, also can add the solution of polymerizable components.Yet, preferably polymerizable components is joined to be in advance and uses in emulsifying agent emulsification and the dispersive polysiloxane particle, because can be adsorbed in the polysiloxane particle effectively.
To the not special restriction of mentioned emulsifier, for example, comprise the polymerisable surfactant that has one or more polymerisable unsaturated C-Cs in anion surfactant, cats product, nonionogenic tenside, amphoterics, polymeric surface active agent and the molecule.Among them, preferred anionic tensio-active agent and nonionogenic tenside because they can stablize polysiloxane particle, the polymerizable components that adsorbed by polysiloxane particle and the dispersion state of polymer fine particles.These emulsifying agents can a kind of independent use, also can two or more be used in combination.
To the not special restriction of above-mentioned anion surfactant, specifically comprise alkali metal alkyl sulfate such as sodium lauryl sulphate and dodecyl sulphate potassium; Alkylsurfuric acid ammonium such as ammonium lauryl sulfate; An alkali metal salt such as dodecyl polyoxyethylene glycol ether sodium sulfate, Sodium Thiocyanate 99 and sulfonation paraffin; The ammonium salt of alkylsulfonate such as sulfonation paraffin; Soap such as sodium laurate, trolamine oleate and trolamine sylvate; The alkali metal sulfates of alkylaryl sulphonate such as Sodium dodecylbenzene sulfonate and alkaline phenol hydroxy ethylene; High sulfonated alkyl naphathalene, naphthalenesulfonate formalin condenses, dialkyl sulfosuccinates, laureth sulfate and polyxyethylated aryl-sulfate.
To the not special restriction of above-mentioned cats product, for example, can comprise amine salt, quaternary ammonium salt, oxygen ethene add-on type hydrochloric acid ammonium (oxyethylene addition type ammoniumhydrochlorides).Exemplary, specifically comprise trimethylammonium alkyl hydrochloric acid ammonium, dimethyl dialkyl hydrochloric acid ammonium, monoalkyl amine acetate and alkyl methyl two polyoxyethylene groups hydrochloric acid ammoniums etc.The alkyl group that these cats products comprised is preferably saturated aliphatic alkyl group and the undersaturated aliphatic alkyl group that carbonatoms is 4-26; for example, octyl group, dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl, oil base and stearyl-etc.
To the not special restriction of above-mentioned nonionogenic tenside, specifically comprise glycerine monofatty ester such as polyxyethylated ester, polyxyethylated aryl ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and glycerol mono-laurate; The condensation product of polyoxyethylene oxypropylene multipolymer and oxyethane and fatty acid amine, acid amides or acid.
Above-mentioned amphoterics comprises amino acid type amphoteric surface active agent and betaine type amphoteric surfac-tant.For example, alkyl two (aminoethyl) glycine, alkyl polyamine ethyl glycine hydrochloride, 2-alkyl-N-propyloic-N-hydroxyethyl imidazole quinoline trimethyl-glycine, N-tetradecyl-N, the N-betaine type amphoteric surfac-tant (for example, Dai-ichi Kogyo Seiyaku Co., Ltd. produces " Amogen K ") or the like.
Above-mentioned polymeric surface active agent specifically comprises polyvinyl alcohol, poly-(methyl) sodium acrylate, poly-(methyl) potassium acrylate, poly-(methyl) ammonium acrylate, poly-hydroxyethyl (methyl) acrylate, the multipolymer that gathers unitary two or more polymerisable monomer of formation of hydroxypropyl (methyl) acrylate, polyvinylpyrrolidone, these monomers and other monomeric these polymkeric substance arbitrarily or multipolymer, crown ether phase transfer catalysts or the like.
To the not special restriction of above-mentioned polymerisable surfactant, for example, comprise the sulfuric ester (sulfate ester of polyoxyethylene (meth) acrylate) of polymerizable negative ion surfactant such as propenyl-2-ethylhexyl benzene sodium sulfo-succinate, polyoxyethylene (methyl) acrylate, polyxyethylated propylene ether ammonium sulfate and polyoxyethylene (methyl) vinylformic acid phosphoric acid ester; With polymerizable nonionogenic tenside such as polyxyethylated phenylate (methyl) acrylate and Voranol EP 2001 (methyl) acrylate.
Consumption to mentioned emulsifier has no particular limits, and under the particular case, with respect to the total amount of above-mentioned polymerizable components, the consumption of emulsifying agent is preferably 0.01-10 quality %, more preferably 0.05-8 quality %, more preferably 1-5 quality %.When the consumption of mentioned emulsifier is lower than 0.01 quality %, can not obtains the emulsification of stable polymerizable components and disperse product; When the consumption of mentioned emulsifier was higher than 10 quality %, side reactions such as letex polymerization may take place simultaneously.About above-mentioned emulsifying effect and dissemination, generally speaking, preferably use uniform mixer or ultrasonic homogenizer in water, to obtain the emulsion of above-mentioned polymerizable components with emulsifying agent.
When using emulsifying agent emulsification and disperseing polymerizable components, preferably use the 0.3-10 water or the water-miscible organic solvent doubly of polymerizable components quality.Above-mentioned water-miscible organic solvent comprises that alcohol is as methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, ethylene glycol, propylene glycol and 1,4-butyleneglycol; Ketone such as acetone and methyl ethyl ketone; And ester such as ethyl acetate.
Under the preferable case, above-mentioned adsorption process is that 0-60 ℃, time are to carry out under 5-720 minute and the agitation condition in temperature.Kind according to the polymerizable components of polysiloxane particle and use is suitably set this condition.These conditions can a kind of independent use, also can two or more be used in combination.
In the above-mentioned adsorption process, in order to judge whether above-mentioned polymerizable components adsorbs, after can be before described polymerizable components adds finishing with described absorption phase by this particle of microscopic examination, and by confirming because the growth of the particle size that absorption polymerizable components etc. cause, and judge at an easy rate.
After described adsorption process is finished, preferably in the polysiloxane particle dispersion liquid, add entry, so that with respect to the total amount of dispersion liquid and water, will adsorb concentration dilution to the 40 quality % of polysiloxane particle of polymerizable components or lower.Described concentration is preferably 30 quality % or lower, more preferably 20 quality % or lower.When the granule density of above-mentioned dispersion liquid is too high, in ensuing polymerization process, will be difficult to controlled temperature owing to being accompanied by the heat that polyreaction produces.In this stage, can add above-mentioned tensio-active agent extraly to improve the particulate dispersion stabilization.
In polymerization process, the method for carrying out radical polymerization is had no particular limits, for example, comprise the method for using radical polymerization initiator; The method of ultraviolet ray or radiation exposure; Method with heating.Above-mentioned radical polymerization initiator is had no particular limits, for example, preferably include persulphate such as Potassium Persulphate; Peroxide type initiator such as hydrogen peroxide, peracetic acid, benzoyl peroxide, lauroyl peroxide, adjacent chlorobenzoyl peroxide, O-methoxy benzoyl peroxide, 3,5,5-trimethylammonium peroxidation hexanoyl, t-butyl peroxy-2-ethylhexanoate, ditertiary butyl peroxide, benzoyl peroxide, 1,1-two (t-butyl peroxy)-3,3,5-trimethylammonium cyclohexane and t-butyl hydroperoxide; Azo-type compound such as Diisopropyl azodicarboxylate, the two cyclohexanenitriles of azo, azo two (2, the 4-methyl pentane nitrile), 2 ＇-azobis isobutyronitrile, 2, two (2-amidine propane) dihydrochlorides, 4 of 2 ＇-azo, 4 ＇-azo two (4-cyanopentanoic acid), 2,2 ＇-azo two (2-methylbutyronitrile), 2,2 ＇-azobis isobutyronitrile and 2,2 ＇-azo two (2, the 4-methyl pentane nitrile).These radical polymerization initiators can use separately, also can two or more be used in combination.
With respect to the total amount of above-mentioned polymerizable components, the consumption of above-mentioned radical polymerization initiator is preferably 0.001-20 quality %, more preferably 0.01-10 quality %, more preferably 0.1-5 quality %.When the consumption of above-mentioned radical polymerization initiator was less than 0.001 quality %, the extent of polymerization of described polymerizable components can't form raising.The method that above-mentioned radical polymerization initiator is joined in the above-mentioned solvent is had no particular limits, can adopt any present known technology, (a kind of mode is that radical polymerization initiator is carried out emulsification and dispersion with polymerizable components for example to add the method for whole consumptions in the starting stage (before reaction beginning), another kind of mode is after polymerizable components is adsorbed, and adds radical polymerization initiator); Add part initiator, the method for successive or the remaining initiator of desultory adding then in the starting stage; The technology that perhaps adopts these methods to combine.
When carrying out above-mentioned Raolical polymerizable, temperature of reaction is preferably 40-100 ℃, more preferably 50-80 ℃.Spend when low when reaction temperature,, will be difficult to obtain having the polymer fine particles of described mechanical properties because the polyreaction degree has composition to improve.On the other hand, when temperature of reaction is too high, during polyreaction, condense easily between the described aggregated particles.In addition, when carrying out above-mentioned Raolical polymerizable, though according to the type of employed polymerization starter can be suitable the adjustment reaction times, generally speaking, the reaction times is 5-600 minute, more preferably 10-300 minute.When the described reaction times was too short, the polyreaction degree can not fully improve; And when the reaction times is long, condense mutually easily between the polymer beads.
Below description is included in the fine grain preparation method of the coating in the present invention.The included preparation method of the present invention is meant on fine particle nuclear surface to have the fine grain preparation method of the coating of aggregate packet coating, described fine particle nuclear contains organic materials or organic and inorganic composite materials, the method is characterized in that, described polymer covering layer is in the presence of tensio-active agent, forms by ring-opening reaction in the aqueous medium that is dispersed with described fine particle nuclear and/or polycondensation.
By adopting this preparation method, around fine particle nuclear, can form the homogeneous polymer coating layer.In addition, when the compound shown in the above-mentioned general formula (1) during, wherein derive from the polymer covering layer that contains tensio-active agent in the insoluble reaction product of above-claimed cpd (A) and/or compound (B) and form on fine particle nuclear surface as tensio-active agent.That is, preparation method of the present invention is for by utilizing between fine particle nuclear and the tensio-active agent even the molecule between tensio-active agent and above-claimed cpd (A) and/or the compound (B) asks that power such as hydrophobic interaction form coating layer.That is, the tensio-active agent that adds in the aqueous medium condenses upon the surface of described fine particle nuclear, and the result can control the phase mutual coagulation of described fine particle nuclear, examines the state that is distributed in the aqueous medium to form described fine particle.Subsequently, add above-claimed cpd (A) (initial condensation compound) and/or compound (B) (epoxy compounds) at this, these compounds around this tensio-active agent be fine particle nuclear carry out ring-opening reaction and/or polycondensation in this case.As a result, form the homogeneous polymer coating layer on the surface of fine particle nuclear.
In addition, though by producing polymer covering layer (when's using the tensio-active agent shown in the above-mentioned general formula (1)) above-mentioned ring-opening reaction and/or polycondensation, between compound (A) or epoxy compounds and tensio-active agent, form chemical bond, but between fine particle nuclear and polymer covering layer, only there is intermolecular forces, for example hydrophobic interaction and hydrogen bond; Even and between fine particle nuclear and polymer covering layer, do not form chemical bond by above-mentioned reaction process yet.
Being formed in the aqueous medium of the polymer covering layer that the present invention is included carried out.Except only making water as the reaction solvent, above-mentioned aqueous medium also comprises the mixed solvent of water and organic solvent.The preferred hydrophilic organic solvent that uses for example, comprises alcohol, for example, and methyl alcohol, ethanol, Virahol, propyl carbinol and vinylcarbinol; Glycol, for example, ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol (hexylene glycol), pentanediol, hexylene glycol (hexanediol), heptanediol and dipropylene glycol; Ketone, for example, acetone, methyl ethyl ketone and methyl propyl ketone; Ester, for example, methyl-formiate, ethyl formate, methyl acetate and methyl acetoacetate; Ether, for example, Diethylene Glycol monomethyl ether, Diethylene Glycol monoethyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.These solvents can use separately, also can two or more be used in combination.In addition, be insoluble under the situation of water, preferably use above-mentioned mixed solvent at above-mentioned initial condensation compound.In this case, with respect to the total amount of organic solvent and water, the combined amount of organic solvent is preferably 50 quality % or still less, more preferably 40 quality % or still less.
In addition, can use organic solvent (other solvent) except above-mentioned hydrophilic organic solvent.Exemplary, can be specially diox, hexane, pentamethylene, pentane, iso-pentane, octane, benzene,toluene,xylene, ethylbenzene, sherwood oil, terpene, castor-oil plant, soya-bean oil, paraffin and kerosene or the like.Using under the situation of these other organic solvents, in containing the mixed solvent of above-mentioned hydrophilic organic solvent, its consumption is preferably 30 quality % or still less, 25 quality % or still less more preferably, more preferably 20 quality % or still less.
The concentration of the nuclear of fine particle described in the aqueous medium is preferably 1 quality % or bigger, more preferably 2 quality % or bigger; Be preferably 60 quality % or littler, more preferably 50 quality % or littler.When the amount of described fine particle nuclear is too much, in the coating process, coacervation will take place in described fine particle nuclear; When the amount of described fine particle nuclear was very few, the polymerizable components that is derived from composition (A) and composition (B) that does not have fine particle nuclear may precipitate in medium.
With respect to fine particle nuclear, the add-on of above-mentioned tensio-active agent is preferably 1 quality % or more, more preferably 3 quality % or more, more preferably 5 quality % or more; Be preferably 50 quality % or still less, 30 quality % or still less more preferably, more preferably 25 quality % or still less.When the combined amount of described tensio-active agent was very few, described fine grain dispersion state can not be kept stable fully, may condense between the fine particle nuclear.On the other hand, when combined amount was too much, the viscosity of whole reaction system raise rapidly, was difficult to stir.In addition,, when the combined amount of tensio-active agent is in above-mentioned scope, can make polymer covering layer have suitable elasticity, thereby and can improve the physical strength of polymer covering layer from the viewpoint of the fine grain physicals that obtains coating.
Among the preparation method of the present invention, the dispersing method of fine particle nuclear in aqueous medium had no particular limits, can adopt present known dispersing method.For example, with aqueous medium with contain fine particle nuclear and surfactant mixtures is carried out violent mechanical stirring, and use ultra-sonic dispersion device, decollator, uniform mixer (Tokushu Kikai Kogyo Co., Ltd. produces), homogenizer (production of Nippon Seiki company limited) etc. to disperse.
In addition, above-mentioned tensio-active agent can be dissolved in the aqueous medium before fine particle nuclear is scattered in aqueous medium, or can or be dissolved in the aqueous medium afterwards in the dispersive while.Time to adding has no particular limits.
Afterwards, initial condensation compound is added in the aqueous medium that is dispersed with fine particle nuclear.Though the add-on to above-mentioned initial condensation compound has no particular limits, but above-mentioned tensio-active agent with respect to 1 mass parts, its add-on is preferably 0.1 mass parts or more, more preferably 0.2 mass parts or more, more preferably 0.3 mass parts or more; Be preferably 10 mass parts or still less, 5 mass parts or still less more preferably, more preferably 3 mass parts or still less.Can easily control the thickness of described polymer covering layer by the add-on of regulating initial condensation compound.When the add-on of above-mentioned initial condensation compound was very few, very difficult formation had the polymer covering layer of adequate thickness.When the add-on of above-mentioned initial condensation compound is too much, the component of described polymer overmold layer composition is formed will produce very big deviation.As a result, cause the intensity of described polymer covering layer to reduce, and cause the metal adhesion variation.
To the not special restriction of the method that in aqueous medium, adds above-mentioned initial condensation compound.Can disposablely add, also can add (add continuously and/or intermittently add) in succession.
Among the preparation method of the present invention, the temperature during the formation polymer covering layer (being dispersed with the temperature that fine particle nuclear and adding have the aqueous medium of water-soluble cpds) is preferably 25-85 ℃, and more preferably 30-70 ℃, more preferably 35-60 ℃.
In addition, the pH of reaction solution is preferably 2-13 during the formation polymer covering layer, more preferably 3-12, more preferably 4-11.When the pH of reaction solution was in above-mentioned scope, described fine particle nuclear was difficult for condensing, and easier controls reaction speed.Reaction times is preferably 10-480 minute, and more preferably 30-360 minute, more preferably 60-300 minute.
After aging time can be arranged on above-mentioned polymer covering layer and forms.To the not special restriction of the temperature of aging time, but under the preferable case, for example, temperature can be 200 ℃ or lower.To the not special restriction of digestion time, be preferably 1-5 hour, more preferably 1-3 hour.The pH of solution is preferably 2-13 between aging time.In addition, can also under pressure state, wear out.In this case, to the not special restriction of described pressure, but under the preferable case, for example can be 1-20 normal atmosphere.
In addition, when described polymer covering layer contained Resins, epoxy, though the add-on of described Resins, epoxy is had no particular limits, with respect to the fine particle nuclear of 1 mass parts, preferred amount was 0.5 mass parts or more; With 10 mass parts or still less.By the add-on of regulating ring epoxy resins, the thickness of gate ring epoxy layer (polymer covering layer) more easily.In addition, cross when low, be difficult to play the effect that improves the metal adhesion performance by forming epoxy resin layer when add-on.Even 10 mass parts are not special yet to be hindered though add-on surpasses, can not further improve the metal adhesion performance according to increasing add-on, very uneconomical.Therefore, be limited to 5 mass parts on more preferably, more preferably 3 mass parts.
When adopting compound (A), form during the above-mentioned epoxy resin layer temperature preferably with form above-mentioned polymer covering layer during temperature identical.
Among the preparation method of the present invention, if desired, after forming above-mentioned polymer covering layer and behind the aging time, obtain being dispersed with in the aqueous medium the fine grain adjustment liquid of coating.
Among the preparation method of the present invention, if desired, in above-mentioned adjustment liquid, can also add tensio-active agent and above-claimed cpd (A) and/or compound (B), and carry out ring-opening reaction and/or polycondensation.This will cause the surface of the polymer covering layer that formerly forms to form similar polymerization thing coating layer.As a result, can access the fine particle of coating with stratified polymer covering layer.For example, wherein preparation has the coated polymer of a plurality of polymer covering layers can improve by the resulting physical properties of single polymer layer coating layer.In addition, change the skin of polymer covering layer and the composition of internal layer and form, can demonstrate different physical propertiess.Be specially, except having the initial character of polymer covering layer, further can also introduce other physical properties that comprises physical strength and hydrophilic nmature easily.
After polymer covering layer formed, if desired, the fine particle of described coating can be an insulating.For example, behind the fine particle that regulate to coat, only need the fine particle of described coating is separated by suction filtration or natural filtration and aqueous medium etc.
In addition, in order to obtain the fine particle of the narrower coating of size distribution, can after separating described coating fine particle, carry out classification to it.About classification, preferably adopt hygrometric state staging (wet classification).Described wet classification is meant in being dispersed with the fine grain adjustment liquid of coating the fine particle that coats is carried out the fractionated method.Because classification is carried out, therefore become wet classification in above-mentioned adjustment liquid.Described wet classification is meant that above-mentioned adjustment liquid carries out stage treatment after diluting or dilute by various aqueous mediums, and with the fine grain method of the coating in the classification adjustment liquid, the fine particle of the coating after the classification has required particle diameter or size distribution like this.For example, described wet classification can carry out classification by using method such as sieve method (sievemethod) (filter method), centrifugal, the spontaneous precipitator method or device.About the fine particle of coating, use sieve method more effective with relatively large particle diameter.
In addition, in order to remove impurity improving quality product, under the preferable case, the fine particle of the coating that obtains is washed.
Hereinafter, will the fine grain feature and the various physicals of coating of the present invention be described.
The fine particle that the present invention coats all is aggregated the particle that the thing coating layer covers except comprising fine particle nuclear surface, also comprises the particle that the surface of fine particle nuclear exposes the fine fraction that coats.Yet when the expose portion of fine particle nuclear is too much, metal adhesion will reduce and be difficult in the fine particle surface and form uniform conductive layer (hereinafter being described).When as conductive fine particle, this defective will cause the lower problem of the relatively poor or successional reliability of continuity.Therefore, the coverage that described fine particle nuclear is gone up polymer covering layer is preferably 40% or more, and more preferably 50% or more, more preferably 55% or more.Certainly, most preferably be 100%.
Fine particle about the present invention's coating, the form that is derived from the component of above-mentioned tensio-active agent has no particular limits, and can be the form of being made up of the unit molecule of tensio-active agent, also can be the form of two or more molecule aggregations, for example, dimer and tripolymer.Among them, described polymer covering layer can only comprise a kind of, also can comprise two or more.
Though the components contents ratio that is derived from above-mentioned tensio-active agent is had no particular limits, with respect to the total amount of polymer covering layer, be preferably 5 quality % or more, more preferably 10 quality % or more, more preferably 15 quality % or more; Be preferably 80 quality % or still less, 75 quality % or still less more preferably, more preferably 70 quality % or still less.When content ratio is crossed when low, elasticity is crossed low and will be reduced the physical strength of polymer covering layer.When content ratio is too high, metal adhesion will reduce.
Similarly, for the form of the composition that is derived from initial condensation compound (compd A), can be component, the various aminoresin (urea type resin, melamine resin and guanidine amine type resin) of the polymer covering layer in the fine particle of the present invention's coating.In these resins, described polymer covering layer can only contain a kind of resin, also can contain two or more resin.
Be derived from the components contents ratio of compound (A) and/or compound (B),, be preferably 20 quality % or more with respect to the total amount of polymer covering layer, more preferably 25% or more, 30 quality % or more more preferably; Be preferably 95 quality % or still less, 90 quality % or still less more preferably, more preferably 85 quality % or still less.When described content ratio is lower than above-mentioned scope, can not obtain sufficient metal adhesion performance; When being higher than above-mentioned scope, the elasticity of described polymer covering layer is relatively poor, and physical strength is lower.
The fine grain polymer covering layer that the present invention coats can also contain other component except containing the said components that does not influence in the effective scope of the present invention.For example, described other component can be the component that is derived from above-mentioned other compound that can use with above-mentioned tensio-active agent.Be specifically as follows, be derived from polyvinyl alcohol component, be derived from the various tensio-active agents except above-mentioned tensio-active agent component, be derived from natural polymer dispersion agent such as gelatin and gum arabic component, be derived from component of the synthetic macromolecule dispersion agent that comprises styrene-maleic acid copolymer and salt thereof or the like.
Fine grain shape to coating of the present invention has no particular limits, and for example, can comprise sphere, aciculiform, plate shape, sheet shape, powder shape, bag shape (cylindrical), cocoon shape and bits shape.
When the fine grain vary in diameter 10% of described coating, have the fine particle that the present invention of said components coats and preferably have 50N/mm 2Or bigger compressive modulus of elasticity (10%K value), have 5% or bigger compressive set recovery rate.Described compressive modulus of elasticity is preferably 1000N/mm 2Or bigger, 2450N/mm more preferably 2Or it is bigger; Described compressive set recovery rate is preferably 10% or bigger, and more preferably 15% or bigger.Here, above-mentioned compressive modulus of elasticity (10%K value) is the fine grain elasticity indexes of described coating, and the compressive set recovery rate is the fine grain stretch index of described coating.Though to the not special restriction of the upper limit, compressive modulus of elasticity is preferably 20000N/mm 2Or littler, 15000N/mm more preferably 2Or littler, 10000N/mm more preferably 2Or it is littler.When compressive modulus of elasticity is too small,, as the gap propping material between the various base materials time, be difficult to keep uniform gap because the fine grain toughness of described coating is strong excessively.On the other hand, when compressive modulus of elasticity is excessive,, as the gap propping material time, will damage the surface of base material because the fine particle that coats is too hard.
Above-mentioned compressive set recovery rate is the fine grain stretch index of described coating.Described compressive set recovery rate is by after applying constant load and load on the fine particle of described coating and removing, before applying by load and after applying, and the variation of the fine particle particle diameter of coating and obtaining.The fine grain compressive set recovery rate of coating of the present invention is preferably 5% or bigger, and more preferably 10% or bigger, more preferably 15% or bigger.The upper limit to described compressive set recovery rate has no particular limits, and can not surpass 100% certainly; That is, the fine grain particle diameter of described coating does not preferably change before applying load He after the load.
In addition, in the fine particle that the present invention coats, with respect to the fine grain diameter that coats, when load was 1g, displacement was preferably 5% or bigger.Above-mentioned displacement when load is 1g is meant the fine grain deformation difficulty or ease index that the present invention coats, the deformation difficulty or ease index when particularly hanging down load.Above-mentioned displacement when load is 1g is preferably 5% or bigger, and more preferably 10% or bigger, more preferably 20% or bigger; Be preferably 85% or littler, more preferably 80% is littler, more preferably 75% or littler.The same with the compressive set recovery rate, the above-mentioned displacement when load is 1g is in above-mentioned scope the time, as the gap propping material between the various base materials time, is difficult to keep the homogeneity in gap.
Though the fine grain median size that the present invention is coated has no particular limits, and is preferably 1.0 μ m or bigger, more preferably 2.0 μ m or bigger; Be preferably 100 μ m or littler, more preferably 70 μ m or littler and 50 μ m or littler more preferably.When the fine grain particle diameter that coats was too small, described particle can be for only forming the polymer fine particles that does not comprise granular core by initial condenses; When described particle diameter is excessive, be difficult to keep the fine particle physical properties desired that coats as normal.
Though the narrow degree of the fine grain size distribution that the present invention is coated has no particular limits, the variation coefficient of described particle diameter (Cv value) is preferably 10% or littler, more preferably 5% or littler, more preferably 4% or littler.When the described variation coefficient (Cv value) was in above-mentioned scope, when making gap between the various base materials keep even as the gap propping material, the fine particle of described coating was keeping the gap to demonstrate useful effect on evenly.On the other hand, when the described variation coefficient (Cv value) exceeded in the above-mentioned scope, as the gap propping material time, described particle can not fully keep the homogeneity in gap.
In addition, the fine grain particle diameter of above-mentioned character (elasticity and compressive modulus of elasticity) and the present invention coating and the variation coefficient (that is the narrow degree of size distribution) thereof depend primarily on the character (particle dia and size distribution) of fine particle nuclear.Therefore, by the preparation condition of suitable adjustment fine particle nuclear, can access the fine particle of coating with required character.
Though the thickness to polymer overmold of the present invention has no particular limits, be preferably 0.001 μ m or thicker, more preferably 0.005 μ m or thicker, more preferably 0.008 μ m or thicker; Be preferably 10 μ m or thinner.Cross when thin when the thickness of polymer overmold, not only coating layer has the danger of metal adhesion reduction, and the fine grain intensity that coats is lower.On the other hand, when the thickness of polymer overmold is blocked up,, therefore will cause toughness and elasticity not enough because the nuclear of fine particle described in the fine particle that coats proportion diminishes.
The various details conductive fine particle.
Conductive fine particle of the present invention forms conductive layer by the fine particle surface that coats in the invention described above and prepares.Above-mentioned conductive layer only forms on the fine particle that coats to small part.
Though the metal that constitutes above-mentioned conductive layer is had no particular limits, for example, described metal comprises nickel, gold and silver, copper, indium and their alloy.In above-mentioned metal, owing to have higher electroconductibility, preferred nickel, gold and indium.Though the thickness to above-mentioned conductive layer has no particular limits, as long as have enough electroconductibility, described thickness is preferably 0.01 μ m or thicker, and more the candidate is 0.02 μ m or thicker; Be preferably 5.0 μ m or thinner, 2.0 μ m or thinner more preferably.Cross when thin when the thickness of described conductive layer, conductivity is not enough.On the other hand, when the thickness of described conductive layer was blocked up, because conductive layer is different with the thermal expansivity of polymer covering layer, described conductive layer can peel off.Described conductive layer can be individual layer, also can be for more than two-layer or two-layer.Under the situation more than two-layer or two-layer, different metals can laminatedly use.
The method that the fine particle surface that coats in the present invention is formed conductive layer has no particular limits, and can adopt various present known method.For example, electroless plating (electroless plating) method, cladding process, PVD method (vacuum deposition method, sputtering method, ion plating method etc.) etc.In the aforesaid method,, preferably adopt electroless plating method owing to form conductive layer easily.
Generally, above-mentioned electroless plating method comprises etching process, reactivation process and electroless plating process.Here, though above-mentioned etching process is in order to improve the adhesivity of chemical plating, form the process of concave surface and convex surface on the fine particle surface that coats, because the fine particle that the present invention coats comprises the polymer covering layer with good metal adsorption performance, therefore, etching process is not essential, can dispense.In addition, when carrying out etching process, this process only need be used as the alkaline aqueous solution of aqueous sodium hydroxide solution or the acidic aqueous solution of example hydrochloric acid, sulfuric acid and chromium trioxide, as etching solution.In addition, carry out ensuing reactivation process and electroless plating process according to present known method.
Because conductive fine particle of the present invention is meant fine particle with the above-mentioned coating of the present invention particle as substrate particles, therefore described conductive particle must have hardness and compressive set recovery rate, make between the counter electrode substrate to keep the constant gap and be electrically connected, and be difficult for counter electrode and produce physical hazard.Therefore, it is constant that the gap between the counter electrode substrate is easier to keep, and can avoid following problems: because the coming off of the conductive layer that causes of extruding; The not short circuit between the electrode that should be electrically connected; Loose contact between the electrode that should be electrically connected; And other problem.
This conductive fine particle that the present invention obtains has the identical mechanical properties (hardness, breaking tenacity) of fine particle that coats with the invention described above.Therefore, described conductive particle can be particularly useful as the contact material of electrical equipment, for example, and the panel of liquid-crystal display, LSI and printed circuit board.
Embodiment
Hereinafter, will be described in detail the present invention by embodiment.Yet following examples are not meant to limit the present invention, do not deviate from above-mentioned purport and below under the situation of the purport that will describe, various changes and enforcement thereof include within the technology of the present invention scope.Described measuring method is as described below.
[measurement of polymer overmold layer thickness]
Use Coulter multicizerII (manufacturing of Bechmann Coulter company) to measure the particle dia that forms the coating layer front and back.Difference by will forming the particle diameter before and after the coating layer is divided by 2 thickness that calculate coating layers.
The fine grain particle diameter and the particle diameter variation coefficient of described coating are as shown in table 1.
Figure A20068000903900381
[evaluation of polymer covering layer appearance]
Use scanning electronic microscope (SEM, Hitachi, the S3500N that Ltd. makes) observation polymer covering layer forms the state of the particle surface after preceding and the formation; And three steps of branch according to following standard are estimated the gained result.
(judgement criteria)
1, the polymer covering layer on fine particle nuclear surface is very thin; Or polymer covering layer does not form and described fine particle independently exists.
2, the granular core surface coverage has the homogeneous polymer coating layer, and described fine particle independently exists.
3, the granular core surface coverage has a large amount of resins, and described particle is together adhering to each other by resin.
[adhesion property of coating]
The fine particle that the 10g that obtains by following preparation embodiment is coated carries out the electroless plating processing.By the coating state of the particle surface after the electron microscope observation processing, and according to following criterion evaluation gained result.
(judgement criteria)
" O " (good): particle surface is coated with the nickel coating layer uniformly.
" X " (poor): particle surface does not form the nickel coating layer.
[variation coefficient of median size and median size]
About the median size of polysiloxane particle and polymer fine particles, detect 30000 particle grain size by Coulter multicizer I (manufacturing of Beckmann Coulter company), and obtain median size.
Calculate the variation coefficient of particle diameter according to following formula.
Figure A20068000903900382
Here, σ is meant the standard deviation of particle diameter, Be meant median size.[10% compressive modulus of elasticity (10%K value: hardness)]
By use diameter be 50 μ m circular dull and stereotyped pressure head (material: diamond) with constant loaded speed (2.275mN/ second) under room temperature (25 ℃) by Shimazu minute-pressure test machine (MCTW-500, Shimazu company the makes) (material: the SKS flat board) carry out applying load in the heart in the sample particle of scattering on sample table that contracts; Particle deformation up to compression displacement be particle diameter 10% the time, the amount of sensing lead and displacement (mm).To calculate 10% compressive modulus of elasticity value in the compressive load, particle compression displacement and the particle diameter substitution formula that record:
E = 3 × F × 10 - 3 2 1 / 2 × S 3 / 2 × R 1 / 2
(wherein, E: compressive modulus of elasticity (N/mm 2), F: compressive load (N), S: compression displacement (mm), R: particle radius).Carry out this operation on 3 different particles, mean value is 10% compression compressive modulus of elasticity.
[compressive set recovery rate (recovery rate)]
Use the minute-pressure test machine (MCTW-500, Shimazu company makes) that contracts to make the sample particle pressurized after the inversion load of 9.8mN, when load reduced, the value that the relation by sensing lead value and compression displacement obtains was the compressive set recovery rate.The terminal point of removing load is set to the point of beginning load value of 0.098mN, and the compression speed when applying load and removing load is set to 1.486mN/ second, measures then.Be recovery rate [%] to the displacement (L1) of being inverted point with from being inverted point to the value shown in the ratio (L1/L2) of the displacement (L2) of the point of starting point load value.
[displacement when load is 1g (compressibility)]
(25 ℃) are by the minute-pressure test machine (MCTW-500 that contracts under the room temperature, Shimazu company makes) at (material: the SKS flat board) carry out applying load on the sample particle of scattering on the sample table, by using diameter is the circular dull and stereotyped pressure head (material: diamond) contract by the Shimazu minute-pressure with constant loaded speed (2.275 mN/ second) (25 ℃) under room temperature that (material: the SKS flat board) the sample particle center of carrying out scattering applies load to test machine (MCTW-500, Shimazu company makes) on sample table of 50 μ m.When POL applied 0.098 mN (1g load), the numerical value (L3/D) [%] shown in the ratio of particulate displacement (L3) and particle diameter (D) was displacement.
Synthetic embodiment 1: initially condensation compound is synthetic; Synthesizing of compound (A)
In the separable flask of 50ml, adding 3g urea, 7g trimeric cyanamide, 20g concentration are that formalin and the 1.5g concentration of 37 quality % is the ammoniacal liquor of 25 quality %, and this mixture is 70 ℃ of following heated and stirred.Kept this temperature 15 minutes, cool off this mixture then to room temperature, obtain homogeneous phase solution (with respect to the total amount of the homogeneous phase solution of compound (A), solid content concentration: 55 quality %) as the compound (A) of the initial condensation compound of trimeric cyanamide, urea and formaldehyde.
Synthetic embodiment 2: synthetic (compound (B)) of tensio-active agent
In the separable flask of 300ml, add 14.5g polymine (" EpomineSP006 ", weight-average molecular weight=600, Nippon Shokubai Co., Ltd. manufacturing) and 43.5g water at first.Then, in 10 minutes, drip the epoxy compounds that 97.2g concentration is the previous preparation of 25 quality % (lauryl alcohol polyethylene glycol oxide (n=22) glycidyl ester, the solubleness in water: 100%) also stir.
During dripping, fluid temperature remains on 25 ℃ or lower.After dripping end, about 30 minutes of this mixture of continuously stirring is heated to 70 ℃ then.Keep this temperature after 2 hours, cool off this mixture to normal temperature, obtain having dispersing property compound (B) (with respect to the total amount of mixture, solid content concentration: 25 quality %).
Synthetic embodiment 3: fine particle is examined the synthetic of (organic and inorganic compounding fine particle)
In having four neck flasks of condenser, thermometer and dropping funnel, adding contains 250g water and 10g concentration is the mixed solution of the ammoniacal liquor of 25 quality %; And drip the mixed solution contain 30g γ-methacryloxypropyl trimethoxy silane and 125g methyl alcohol, and stir by dropping funnel.γ-methacryloxypropyl trimethoxy silane thereby hydrolysis and condensation obtain polysiloxane particle (inorganic particle).After reaction was carried out 1 hour, the water that adds 250g by dropping funnel diluted the polysiloxane particle dispersion liquid.Begin continuously stirring 2 hours from reaction, obtain polysiloxane particle dispersion liquid (median size: 1.83 μ m; The variation coefficient: 3.17%).
With 0.7g anionic emulsifier (LA-10, Dai-ichi Kogyo Seiyaku Co., Ltd. manufacturing), 70g water, 100gNK ester APG-400 (Shin-Nakamura Chemical Co., Ltd.), 20g 1,6-hexanediol dimethacrylate and 0.5g 2,2-azo two (2, the 4-methyl pentane nitrile) (" V-65 ", WakoPure Chemical Industries, Ltd. make) in the flask that is different from above-mentioned four neck flasks, mix, mixed solution carries out emulsification and dispersion by homogenizer, and the time is 5 minutes, obtains the monomer emulsion.
Above-mentioned organic and inorganic compound particles dispersion liquid stirred after 30 minutes, in 15 seconds, above-mentioned monomer emulsion joined in the dispersion liquid, and with mixture restir 30 minutes.During this period, by the microscopic examination polysiloxane particle, and the increase by particle diameter confirms that inorganic particle has been adsorbed with monomer.Add the monomer emulsion after 1 hour, in the dispersion liquid that is adsorbed with monomeric organic and inorganic compound particles, adding the water of 1000g.Under nitrogen atmosphere, reacting by heating liquid to 75 ℃, and kept this temperature 30 minutes.As a result, Raolical polymerizable taking place in reaction solution, produces fine particle nucleus emulsion (median size: 3.8 μ m, the variation coefficient: 2.9%).
After the fine particle nucleus emulsion that obtains being filtered and washing, under 100 ℃ of conditions of vacuum dry 4 hours, obtain fine particle nuclear with ethanol.The character of the fine particle nuclear that obtains is as shown in table 1.
Synthetic embodiment 4: granules of polystyrene synthetic
In having four neck flasks of condenser, thermometer and dropping funnel, 2g polyvinylpyrrolidone (weight-average molecular weight (Mw) is 30000) and the two methyl valeronitriles of 1g azo are dissolved in the 150g Virahol.In nitrogen atmosphere, stir in this solution, in solution, add 15g vinylbenzene.Then, heat this solution to 60 ℃, polyreaction was carried out 24 hours, obtained granules of polystyrene dispersion liquid (median size: 5.1 μ m, the variation coefficient: 7.3%).
From the dispersion liquid that obtains, separate granules of polystyrene, and wash, classification and drying, obtain granules of polystyrene (median size: 5.1 μ m, the variation coefficient: 4.8%).The character of the granules of polystyrene that obtains is as shown in table 1.
Table 1
Synthetic embodiment Particle diameter (μ m) The variation coefficient (%) 10%K value (N/mm 2) Recovery rate (%) Rate of compression (%)
3 3.8 2.9 6754 36 59
4 5.1 4.8 4410 3 68
Preparation embodiment 1
In the 300ml beaker, add 10g and examine by the fine particle that synthetic embodiment 3 obtains, and use spatula to stir by compound (B) solution and the 20g that synthetic embodiment 2 obtains, in mixture, add 50g water then.Then, this mixture is carried out supersound process, disperse fine particle nuclear (dispersion liquid Cl).
In the flat separable flask of the 300ml with agitator, in the process that stirs (revolution is 200rpm), add the solution of above-mentioned dispersion liquid Cl and 6g compound (A), then with mixture heating up to 40 ℃.Keep this temperature after 2 hours (this moment, the pH of reaction solution is 10), in solution, add 150ml water cooling mixture to room temperature, the fine particle D1 that obtains coating.The evaluation result of the fine particle D1 appearance of the thickness of polymer covering layer and coating is as shown in table 2.In addition, electron microscope (SEM) photo of the fine particle D1 of used coating of fine particle nuclear and this moment respectively as shown in Figure 3 and Figure 4.
Use Ni to handle, estimate the adhesivity of coating then by the fine particle D1 of electroless plating method to the coating that obtains.The result is as shown in table 2.
In addition, plate Ni by the following method.The fine particle D1 that 10 grams are coated is scattered in the aqueous sodium hydroxide solution that 200g concentration is 1 quality %, and stirs etching 2 hours under 60 ℃ of conditions.After filtration and the drying, at room temperature, the fine particle D1 that coats is immersed in the tin protochloride aqueous solution that concentration is 1g/l, strengthened 5 minutes.When stirring, the fine particle of the coating after strengthening is joined in the catalytic solution by the hydrochloric acid of the palladium chloride aqueous solution of 0.1ml/1/1 and 0.1ml/1/1, and then stirred 5 minutes, make the fine particles palladium ion of coating.Then, the fine particle of coating through filtration, washing, and at room temperature, further be immersed in the sodium hypophosphite solution of 1g/l reduction 5 minutes.Like this, the fine particle surface that obtains coating is loaded with the substrate material particle of palladium.Subsequently, this substrate material particle is added and be scattered in (20g/l) in the glycine solution, under agitation condition, be heated to 65 ℃ and make slurries.Under agitation, with 5ml/ minute speed, the nickel chemical plating fluid that will contain nickel sulfate solution, aqueous sodium hypochlorite solution and aqueous sodium hydroxide solution joined in the above-mentioned slurries.After all the nickel chemical plating fluid added, keeping fluid temperature was 65 ℃, and lasting the stirring stops bubbling up to hydrogen.After hydrogen blistering stops, fine particle is filtered and washs, and in Vacuumdrier, carry out drying (100 ℃), obtain the conductive fine particle that nickel coats.
Preparation embodiment 2
In the flat separable flask of the 300ml with agitator, (revolution is 200rpm) adds the solution of dispersion liquid Cl and 6g compound (A) in the time of stirring, then with mixture heating up to 40 ℃.Keep this temperature after 3 hours, add 150ml water, mixture is cooled to room temperature, the fine particle D2 that obtains coating.Then, use Ni by preparation method identical among the embodiment 1 and handle the fine particle D2 that plating coats with above-mentioned.The evaluation result of the character of the fine particle D2 of the coating that obtains (thickness of polymer covering layer, condition of surface and plating adhesion) is as shown in table 2.
Preparation embodiment 3
In the 300ml beaker, add compound (B) that 5g obtains by synthetic embodiment 2 and 20g by synthesizing the organic and inorganic compound particles that embodiment 3 obtains, and use the spatula mixing; Then, in mixture, add 50g water.Then mixture is carried out supersound process, disperse fine particle nuclear (dispersion liquid C2).
In the flat separable flask of the 300ml with agitator, (revolution is 200rpm) adds the solution of above-mentioned dispersion liquid C2 and 6g compound (A) in the process that stirs, then with mixture heating up to 40 ℃.Keep this temperature after 3 hours, in mixture, add 150ml water with cooling mixture to room temperature, the fine particle D3 that obtains coating.Then, use Ni by preparing the fine particle D3 that method plating identical among the embodiment 1 coats with above-mentioned.The character of the fine particle D3 that the trimeric cyanamide that obtains coats is as shown in table 2.
Preparation embodiment 4
In the flat separable flask of the 300ml with agitator, (revolution is 200rpm) adds the solution of above-mentioned dispersion liquid Cl and 6g compound (A) in the process that stirs, then with mixture heating up to 50 ℃.Keep this temperature after 1 hour, in mixture, add 150ml water with cooling mixture to room temperature, the fine particle D4 that obtains coating.Then, use Ni by preparing the fine particle D4 that method plating identical among the embodiment 1 coats with above-mentioned.The character of the fine particle D4 of the coating that obtains is as shown in table 2.
Preparation embodiment 5
In the 300ml beaker, add the solution of the compound (B) that 10g obtains by synthetic embodiment 2 and the granules of polystyrene that 20g is obtained by synthetic embodiment 4, and use the spatula mixing; In mixture, add 50g water then.Then mixture is carried out supersound process, disperse fine particle (dispersion liquid C3).
In the flat separable flask of the 300ml with agitator, (revolution is 200rpm) adds the solution of above-mentioned dispersion liquid C3 and 6g compound (A) in the process that stirs, then with mixture heating up to 50 ℃.Keep this temperature after 1 hour, in mixture, add 150ml water with cooling mixture to room temperature, the fine particle D5 that obtains coating.Then, use Ni by preparing the fine particle D5 that method plating identical among the embodiment 1 coats with above-mentioned.The character of the fine particle D5 of the coating that obtains is as shown in table 2.
Preparation embodiment 6: the formation of conductive layer
Use Ni by non-etching chemistry plating method, the fine particle D3 for preparing the coating that embodiment 3 obtains is carried out plating; Then, on fine particle, form nickel-gold plate, obtain conductive fine particle by replacement(metathesis)reaction with gold.
Described gold plate forms by the following method.(the composition solution that contains the Au of the potassium cyanide of disodium citrate, 3.0g/l of vinyl ethylenediamine tetraacetic acid (EDTA) four sodium, the 10g/l of 10g/l and 2.1g/l in chemical plating fluid, regulating pH with sodium hydroxide is 6), bath temperature remains under 60 ℃ the condition, add the nickel plating fine particle and under stirring condition, carry out plating with Au.Behind the plating, the fine particle of plating Au filters, washs, and carries out drying (100 ℃) in vacuum drier, obtains having the conductive fine particle of the gold-plated coating of nickel.
When using the adhesion property of SEM (scanning electronic microscope) and the observable conductive fine particle coating of XMA (X-ray microanalyzer), determine that the fine particle surface that coats is covered by nickel, further gold plate is formed on the nickel coating.
Preparation embodiment 7
In the 300ml beaker, add the organic and inorganic compound particles that compound (B) that 10g obtains by synthetic embodiment 2 and 20g are obtained by synthetic embodiment 3, and leak with spatula and to spare; Then, in mixture, add 30g water and 20g methyl alcohol.Then mixture is carried out supersound process, organic and inorganic compound particles are disperseed (dispersion liquid C4).
In the flat separable flask of the 300ml with agitator, (revolution is 200rpm) adds above-mentioned dispersion liquid C4 in the process that stirs, then with mixture heating up to 70 ℃, then, the glycerol polyglycidyl ether (Denacol EX-145, Nagase Chemtex company makes) that adds 3g.Keep this temperature after 1 hour, adding 150ml water to room temperature, obtains the fine particle that epoxy coats with cooling mixture in solution.To the particle that obtains wash, classification and drying, obtain the fine particle D6 that epoxy coats.Then, use Ni by preparation method identical among the embodiment 1 and handle the fine particle D6 that coats with above-mentioned.Adopt and the above-mentioned fine particle D6 for preparing the identical method plating coating of embodiment 1 with nickel.The fine particle D6 character of the coating that obtains is as shown in table 2.
Preparation embodiment 8
Use the fine particle nuclear that synthetic embodiment 3 obtains (organic with inorganic compound particles) and chemical Ni-plating layer by carrying out replacement(metathesis)reaction, obtain forming the conductive fine particle of nickel-gold plate with the above-mentioned embodiment of preparation 6 identical method and gold.The evaluation result of the plating adhesion of the conductive fine particle that obtains is as shown in table 2.
Preparation embodiment 9
Use granules of polystyrene that synthetic embodiment 4 obtains and chemical Ni-plating layer by carrying out replacement(metathesis)reaction, obtain forming the conductive fine particle of nickel-gold plate with the above-mentioned embodiment of preparation 6 identical method and gold.The evaluation result of the plating adhesion of the conductive fine particle that obtains is as shown in table 2.
Preparation embodiment 10
In the 300ml beaker that adds 50g water, add the fine particle nuclear that 20g is obtained by synthetic embodiment 3; Mixture is carried out supersound process, to disperse fine particle nuclear (dispersion liquid C5).
In the flat separable flask of the 300ml with agitator, (revolution is 200rpm) adds above-mentioned dispersion liquid C5 in the process that stirs, and then, adds 6g compound (A) solution, mixed solution is heated to 40 ℃ then.As a result, from react initial carry out 30 minutes to reaction after, obtain coherent substance and throw out.By the described throw out of observation by light microscope, confirm that described fine particle nuclear adheres to each other with squamous precipitation (scaly deposit).In addition, owing to can't from described throw out, separate individual particle, therefore, need not to adhere to the evaluation of coating.
Preparation embodiment 11
In the 300ml beaker, add fine particle nuclear (organic and inorganic compound particles) and 0.5g Sodium dodecylbenzene sulfonate that 20g is obtained by synthetic embodiment 3, and use the spatula mixing; Then, in mixture, add 30g water.Then mixture is carried out supersound process, disperse fine particle nuclear (dispersion liquid C6).
In the flat separable flask of the 300ml with agitator, (revolution is 200rpm) adds above-mentioned dispersion liquid C6 in the process that stirs, then with mixture heating up to 90 ℃, the solution and the 5g concentration that add the compound (A) that 6g obtains by synthetic embodiment 1 then are the Witco 1298 Soft Acid aqueous solution of 10 quality %.Then, keep this temperature after 8 hours, adding 150ml water to room temperature, obtains the fine particle of polymer overmold with cooling mixture in solution.Because the coated pellet that obtains has adhesivity, therefore, after washing and drying, described particle is pulverized, carry out classification and concise subsequently.As a result, obtain the particle D7 of polymer overmold.
Use Ni by preparing the fine particle D7 that method plating identical among the embodiment 1 coats with above-mentioned.The character of the fine particle D7 of the coating that obtains is as shown in table 2.
Table 2
The fine particle that coats Coating thickness (μ m) The variation coefficient of coating layer (%) SEM The plating adhesion energy
Preparation embodiment 1 D1 0.01 2.98 2 ○
Preparation embodiment 2 D2 0.03 3.23 3 ○
Preparation embodiment 3 D3 0.03 3.17 2 ○
Preparation embodiment 4 D4 0.04 2.82 3 ○
Preparation embodiment 5 D5 0.06 4.70 3 ○
Preparation embodiment 6 D3 0.03 2.97 2 O
Preparation embodiment 7 D6 0.02 3.21 2 ○
Preparation embodiment 8 Organic and inorganic compound particles ×
Preparation embodiment 9 Granules of polystyrene ×
Preparation embodiment 11 D7 0.06 3.19 3 ○
As can be seen from Table 2, the fine particle of the present invention with coating of polymer covering layer demonstrates good plating adhesion energy.In contrast to this, the fine grain plating adhesion that does not have polymer covering layer that obtains among the preparation embodiment 8 and 9 can be relatively poor.
Industrial usability
According to the present invention, can access the fine grain performance of easy control such as toughness and elasticity and have the fine grained of the coating of good metal adhesion performance. In addition, have fine grained as the above-mentioned coating of base material owing to be included in conductive fine particle in the present invention, therefore, described conductive fine particle has the fine grained of above-mentioned coating as matrix material, therefore has equally good metal adhesion performance; And for example, this conductive fine particle is as anisotropic conductive material the time, and conductive layer is difficult for peeling off.

Claims (7)

1. the fine particle of a coating, this fine particle comprises the polymer covering layer on fine particle nuclear and fine particle nuclear surface, this fine particle nuclear contains organic materials or organic and inorganic composite materials, and this polymer covering layer is formed on the surface of fine particle nuclear by ring-opening reaction and/or polycondensation.
2. the fine particle of coating according to claim 1, wherein, described fine grain median size is 1.0-100 μ m, and the variation coefficient Cv value of described particle diameter is 10% or littler.
3. the fine particle of coating according to claim 1 and 2, wherein, described polymer covering layer contains polymkeric substance, and this polymkeric substance has at least a organic group that is selected from the group of being made up of amino, imido grpup, carboxyl, hydroxyl, epoxy group(ing), sulfonic group, aldehyde radical and phosphate.
4. the fine grain preparation method of a coating, this particle has the polymer covering layer that is positioned at the fine particle nuclear surface of containing organic materials or organic and inorganic composite materials, wherein, described polymer covering layer is in the presence of surface-active, form by ring-opening reaction in the aqueous medium that is dispersed with described fine particle nuclear and/or polycondensation.
5. according to the fine grain preparation method of the described coating of claim 4, wherein, described tensio-active agent has the structure shown in the following general formula,
R 1-(CH 2-CH 2-O-) n-X m-R 2
Wherein, R 1The expression carbonatoms is aliphatics or the aromatic series hydrophobic group of 5-25; R 2The expression weight-average molecular weight is 300-10,000 the polymer chain with polyamine structure or poly carboxylic acid structure; N represents the integer of 3-85; X express possibility with at least a group that is selected from the radical reaction in the group of forming by amino, imido grpup and carboxyl in group derive obtain and be formed at this reacted group; M represents 1 or 0.
6. according to the fine grain preparation method of claim 4 or 5 described coatings, wherein, described polymer covering layer has the structure that obtains by at least a polycondensation that is selected from compound in the group of being made up of urea, thiocarbamide, trimeric cyanamide, benzo guanamine, acetylguanamine and cyclohexyl guanamines and formaldehyde.
7. conductive fine particle, this fine particle comprise according to the fine particle of any described coating among the claim 1-3 and are positioned at the conductive layer on the fine particle surface of described coating.
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