CN109791813A - Electroconductive resin particle and its purposes - Google Patents

Electroconductive resin particle and its purposes Download PDF

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Publication number
CN109791813A
CN109791813A CN201780060713.9A CN201780060713A CN109791813A CN 109791813 A CN109791813 A CN 109791813A CN 201780060713 A CN201780060713 A CN 201780060713A CN 109791813 A CN109791813 A CN 109791813A
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particle
resin particle
electroconductive resin
mentioned
monomer
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CN109791813B (en
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田中浩平
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Sekisui Kasei Co Ltd
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Sekisui Plastics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/288—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polypropylene-co-ethylene oxide in the alcohol moiety

Abstract

The present invention provides the electroconductive resin particle with good conductivity.Electroconductive resin particle includes nuclear particle, is formed by polyme；It with, shell, covers aforementioned nuclear particle and is formed by electroconductive polymer, the compressive strength when compressive deformation 10% of the electroconductive resin particle is 0.1~30MPa.

Description

Electroconductive resin particle and its purposes
Technical field
The present invention relates to electroconductive resin particles and its purposes.Further specifically, the present invention relates to so that electric conductivity The use for the purpose that resin particle is closely sealed each other and embodies electric conductivity can be suitble to the electroconductive resin particle used and its purposes on the way (conductive resin composition, coating agent, film and clearance material).
Background technique
It has been known that there is: by that conductive paste made of dispersed electro-conductive particle will be located between electrode in binder resin So as to improve the electronic circuit board of interelectrode connection reliability.So far, in such conductive particle using having The conductive particle formed by metals such as gold, silver, nickel.However, the shape of such conductive particle is uneven or and binder Resin is larger compared to specific gravity, therefore, settles in conductive paste, or be difficult to equably once be divided in conductive paste It dissipates, therefore, lacks reliability.
Therefore, disclose a kind of conductive particle powder, contain: nuclear particle is formed by organic system particle；It is conductive Layer, is formed in the surface of the nuclear particle；With, electric conductive polymer, oxide of the aforesaid conductive layer comprising being selected from metal, metal Or the one kind or two or more electroconductive stuffing (patent document 1) in alloy.
Existing technical literature
Patent document
Patent document 1: No. 5630596 bulletins of Japan Patent
Summary of the invention
Problems to be solved by the invention
However, above-mentioned conductive particle powder includes a kind in oxide or alloy selected from metal, metal due to having Or electroconductive stuffing of more than two kinds, hard conductive layer, therefore by electroconductive resin particles compress and make electroconductive resin particle When closely sealed each other, the mutual adaptation of electroconductive resin particle wants the conduction being electrically connected by electroconductive resin particle Component (such as electrode) is low with the adaptation of electroconductive resin particle, the mutual contact area of electroconductive resin particle, conductive structure The contact area of part and electroconductive resin particle is small, and therefore, resistance when compression is high, is unable to get good conductivity.
The present invention is made in view of above-mentioned previous project, it is intended that providing: with good conductivity Electroconductive resin particle and conductive resin composition, coating agent, film and the clearance material for using it.
The solution to the problem
Therefore, in order to solve the above problems, present inventor has performed further investigations, as a result, it has been found that: have by polymer shape At nuclear particle and the aforementioned nuclear particle of covering and the shell formed by electroconductive polymer electroconductive resin particle in, make to compress Compressive strength when deforming 10% is 0.1~30MPa, so as to obtain having the electroconductive resin of good conductivity Grain, so far completes the present invention.
That is, electroconductive resin particle of the invention is characterized in that in order to solve aforementioned problems, nuclear particle is included, It is formed by polyme；With, shell, covers aforementioned nuclear particle and formed by electroconductive polymer, the electroconductive resin particle Compressive strength when compressive deformation 10% is 0.1~30MPa.
Feature according to the present invention, nuclear particle and shell are formed by polyme, and compressive strength when compressive deformation 10% is 30MPa is hereinafter, therefore, electroconductive resin soft granules, and when compression substantially deforms.Therefore, simultaneously by electroconductive resin particles compress When keeping electroconductive resin particle closely sealed each other, the mutual adaptation of electroconductive resin particle is wanted to pass through electroconductive resin particle The adaptation of the conductive member (such as electrode) and electroconductive resin particle that are electrically connected improves, and electroconductive resin particle is each other Contact area, the contact area of conductive member and electroconductive resin particle become larger, therefore, resistance when compression can be reduced, Available good conductivity.
In order to solve aforementioned problems, conductive resin composition of the invention is characterized in that, includes: conduction of the invention Property resin particle and matrix resin.
The conductive resin composition of above-mentioned composition includes the electroconductive resin of the invention with good conductivity Therefore grain forms the conductive resin composition of above-mentioned composition, so as to obtain electric conductivity and excellent antistatic property at Type product.
In order to solve aforementioned problems, coating agent of the invention is characterized in that, includes electroconductive resin particle of the invention And binder resin.
The coating agent of above-mentioned composition includes the electroconductive resin particle of the invention with good conductivity, therefore, will The coating agent of above-mentioned composition is coated on substrate, so as to obtain to be suitable as electric conductivity product (such as conductive membrane) Or the product that antistatic article (such as antistatic film) uses.
In order to solve aforementioned problems, film of the invention is characterized in that, includes electroconductive resin particle of the invention.
The film of above-mentioned composition includes that the electroconductive resin particle of the invention with good conductivity therefore can be with It is suitable as conductive membrane or antistatic film uses.
In order to solve aforementioned problems, clearance material of the invention is characterized in that, includes electroconductive resin of the invention Grain.
The clearance material of above-mentioned composition includes the electroconductive resin particle of the invention with good conductivity, therefore, It is conductive, play anti-static function.
The effect of invention
The effect that the present invention plays is, can provide the electroconductive resin particle with good conductivity and use it Conductive resin composition, coating agent, film and clearance material.
Specific embodiment
Hereinafter, the present invention is described in detail.
(electroconductive resin particle)
Electroconductive resin particle of the invention includes nuclear particle, is formed by polyme；With, shell, the aforementioned core of covering It grain and being formed by electroconductive polymer, the compressive strength when compressive deformation 10% of the electroconductive resin particle is 0.1~ 30MPa。
The compressive strength when compressive deformation 10% of above-mentioned electroconductive resin particle is 0.1~30MPa, preferably 0.1~ 17MPa.The bad mechanical strength of electroconductive resin particle of the compressive strength less than 0.1MPa when compressive deformation 10%, when having use The worry that can be destroyed.Compressive strength when for compressive deformation 10% is 17MPa electroconductive resin particle below, will be conductive Property resin particle when compressing and keeping electroconductive resin particle closely sealed each other, the mutual adaptation of electroconductive resin particle, want it is logical It crosses conductive member (such as electrode) that electroconductive resin particle is electrically connected and the adaptation of electroconductive resin particle is further It improves, the contact area of the mutual contact area of electroconductive resin particle, conductive member and electroconductive resin particle further becomes Greatly, therefore, resistance when compression, available further excellent conductivity can be further decreased.It should be noted that this In application documents, " compressive strength when compressive deformation 10% " refers to the measuring method by illustrating in aftermentioned implementation item Compressive strength (hereinafter referred to as " 10% compressive strength ") when obtained compressive deformation 10%.
Above-mentioned electroconductive resin particle preferably has 1~200 μm of volume average particle size.Above-mentioned electroconductive resin particle tool There is 1 μm or more of volume average particle size, it is available good for being improved whens conductive paste etc. to the dispersibility of various solvents Good operability.Above-mentioned electroconductive resin particle has 200 μm of volume average particle sizes below, to make electroconductive resin particle When closely sealed each other, when making conductive member and closely sealed electroconductive resin particle, their mutual contacts become good, it is available more More conductive paths.It should be noted that " volume average particle size " refers in present specification, pass through aftermentioned implementation item Volume average particle size obtained from the measuring method of middle explanation.
The coefficient of variation preferably 10% or more of the partial size of the volume reference of above-mentioned electroconductive resin particle, is more preferably in In the range of 20%~50%.The coefficient of variation of the partial size of volume reference is the electric conductivity of 10% or more (especially 20% or more) Resin particle with the coefficient of variation of same composition, volume reference partial size be 15% electroconductive resin particle below compared with, Electroconductive resin particle comprising a large amount of nominal particle size (the obvious small partial size compared with volume average particle size), by electric conductivity tree Rouge particles compress and when keeping electroconductive resin particle closely sealed each other, the electroconductive resin particle of a large amount of nominal particle sizes enter except this it Filling rate raising between outer electroconductive resin particle.Therefore, the mutual adaptation of electroconductive resin particle, desired pass through are led The adaptation of conductive member (such as electrode) and electroconductive resin particle that electrical resin particle is electrically connected improves, electric conductivity The contact area of the mutual contact area of resin particle, conductive member and electroconductive resin particle becomes larger, and therefore, can reduce pressure Resistance when contracting, available further excellent conductivity.It should be noted that in present specification, it should be noted that In present specification, " coefficient of variation of the partial size of volume reference " refers to the measuring method by illustrating in aftermentioned implementation item Obtained from volume reference partial size the coefficient of variation.
The recovery rate preferably 15% of above-mentioned electroconductive resin particle is more than or lower than 30%, more preferable 15% or more and 25% Below, further preferably 15% or more and 20% or less.The recovery rate of above-mentioned electroconductive resin particle is 15% or more, to lead In the case that compression stress reduces after electrical resin particle is compressed, the shape of electroconductive resin particle is also restored, and can maintain The mutual adaptation of electroconductive resin particle.Therefore, good conductivity can be stably obtained.Above-mentioned electroconductive resin particle Recovery rate be lower than 30%, thus be easy keep by the shape after electroconductive resin particles compress, as a result can maintain good Adaptation.
The conductivity preferably 5.0 × 10 of electroconductive resin particle of the invention-3~5.0 × 10-1More preferable 9 (S/cm), × 10-3~1 × 10-1(S/cm), further preferred 1 × 10-2~5 × 10-2(S/cm).The conductivity of above-mentioned electroconductive resin particle More than the lower limit of above range, so as to realize the electroconductive resin particle with good conductivity.
(nuclear particle)
Above-mentioned nuclear particle can be the condensation polymer of polyurethane, organic silicon-type polymer etc., preferably by ethylene base system list The polymer of body is formed.As long as above-mentioned vinyl monomer is at least one ethylenically unsaturated group (vinyl of broad sense) Compound, can be monofunctional vinyl's base system monomer with 1 ethylenically unsaturated group, or have 2 The polyfunctional vinyl system monomer of the above ethylenically unsaturated group.
As above-mentioned monofunctional vinyl's base system monomer, for example, simple function (methyl) acrylate that back segment is described in detail Monomer；The styrenic monomers such as styrene, p-methylstyrene, α-methylstyrene；The vinyl esters such as vinyl acetate system is single Body etc..Among them, simple function (methyl) acrylate monomer is preferably as monofunctional vinyl's base system monomer.It needs to illustrate It is that in present specification, " (methyl) acrylic acid " refers to acrylic acid and/or methacrylic acid, and " (methyl) acrylate " refers to Acrylate and/or methacrylate.
It as above-mentioned polyfunctional vinyl system monomer, can enumerate: the following general formula (I)
CH2=C (R1)-COO-(CH2CH2O)n-CO-C(R1)=CH2···(I)
(in formula, R1For hydrogen or methyl, the integer that n is 1~4.) shown in monomer, monomer shown in logical formula (II), it is following Logical formula (II)
CH2=C (R2)-COO-(CH2CH2O)m-CO-C(R2)=CH2···(II)
(in formula, R2For hydrogen or methyl, the integer that m is 5~15.) shown in monomer, 1,3-BDO two (methyl) propylene Acid esters, 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate, glycerol two (methyl) acrylic acid Ester, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, O-phthalic acid diethylene glycol two (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate, caprolactone modification hydroxy new pentane acid ester are new Diacrylate, polyester acrylate, urethane acrylate oligomer (being described in detail in back segment) etc. have 2 The multifunctional (methyl) acrylate system monomer of a above ethylenically unsaturated group；Divinylbenzene, divinyl naphthalene, they Aromatic diethylenes base system monomer such as derivative etc..Among them, monomer, above-mentioned general formula shown in preferably above-mentioned logical formula (I) (II) monomer and urethane acrylate shown in.These vinyl monomers can use individually or combine 2 kinds It is used above.
Above-mentioned nuclear particle preferably comprises: comprising single shown in simple function (methyl) acrylate monomer and the following general formula (I) The polymer of the monomer mixture (vinyl monomer) of body,
CH2=C (R1)-COO-(CH2CH2O)n-CO-C(R1)=CH2···(I)
(in formula, R1For hydrogen or methyl, the integer that n is 1~4.).The polymer is the polymer with cross-linked structure, because This, can assign nuclear particle restorative.Therefore, above-mentioned nuclear particle is contained in by the polymer, may be implemented to have good Recovery rate electroconductive resin particle.
As above-mentioned simple function (methyl) acrylate monomer, it is not particularly limited, can be used for example: acrylic acid first The acrylic acid such as ester, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA Ester；Methyl methacrylate, ethyl methacrylate, Isobutyl methacrylate, cyclohexyl methacrylate, methacrylic acid Benzyl ester, isobornyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2- methoxy acrylate, metering system Acid glycidyl ester, tetrahydrofurfuryl methacrylate, diethyl aminoethyl methacrylate, trifluoroethyl methacrylate, 17 fluorine last of the ten Heavenly stems ester of methacrylic acid, n-BMA, Tert-butyl Methacrylate, 2-Ethylhexyl Methacrylate etc. Methacrylate, (methyl) acrylate (being described in detail in back segment) with epoxy alkyl etc.,.These simple functions (methyl) acrylate monomer can use individually or combine two or more use.
In above-mentioned simple function (methyl) acrylate monomer, the alkyl acrylate that the carbon number of optimizing alkyl is 1~12, more The alkyl acrylate that the carbon number of optimizing alkyl is 1~8.By using such alkyl acrylate, on reducing 10% compressive strength of nuclear particle is stated, therefore, the upper limit easy to accomplish with aforementioned range 10% compressive strength below is led Electrical resin particle.
In addition, the content of simple function (methyl) acrylate monomer in above-mentioned monomer mixture is mixed relative to above-mentioned monomer Close 100 parts by weight of object, preferably 70~99 parts by weight.By the content above range for making simple function (methyl) acrylate monomer It is interior, thus the electroconductive resin particle of the recovery rate easy to accomplish with aforementioned range.
As monomer shown in above-mentioned logical formula (I), for example, ethylene glycol two (methyl) acrylate, diethylene glycol Two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate etc..These general formulas (I) in monomer shown in, particularly preferred ethylene glycol two (methyl) acrylate, use (methyl) acrylate of ethylene glycol two as When monomer shown in logical formula (I), the solvent resistance of electroconductive resin particle can be more effectively improved relative to additive amount.
The content of monomer shown in logical formula (I) in above-mentioned monomer mixture is relative to above-mentioned 100 weight of monomer mixture Part, preferably 1~30 parts by weight.In content above range by making monomer shown in logical formula (I), so that easy to accomplish have The electroconductive resin particle of the recovery rate of aforementioned range.
The polymer of above-mentioned monomer mixture contained in above-mentioned nuclear particle is preferably in above-mentioned simple function (methyl) acrylic acid On the basis of monomer shown in ester monomer and above-mentioned logical formula (I), the monomer of monomer shown in the following general formula (II) is further included The polymer of mixture,
CH2=C (R2)-COO-(CH2CH2O)m-CO-C(R2)=CH2···(II)
(in formula, R2For hydrogen or methyl, the integer that m is 5~15.).Thus, it is possible to polymerize to contained in above-mentioned nuclear particle Therefore soft cross-linked structure is imported in object can reduce by 10% compressive strength of electroconductive resin particle, furthermore it is possible to mention The recovery rate of highly conductive resin particle.Therefore, the upper limit easy to accomplish with aforementioned range 10% compressive strength below Electroconductive resin particle, in addition, the electroconductive resin particle of the recovery rate more than lower limit easy to accomplish with aforementioned range.
As monomer shown in above-mentioned logical formula (II), for example, five ethylene glycol two (methyl) acrylate, six second Glycol two (methyl) acrylate, seven ethylene glycol two (methyl) acrylate, eight ethylene glycol two (methyl) acrylate, nine second two Alcohol two (methyl) acrylate, ten ethylene glycol two (methyl) acrylate, ten tetraethylene glycol two (methyl) acrylate, 15 second Glycol two (methyl) acrylate etc..In monomer shown in these logical formula (II)s, nine ethylene glycol are in using the m in logical formula (II) Monomer between two (methyl) acrylate (m=9) and ten tetraethylene glycol two (methyl) acrylate (m=14), that is, general formula (II) m in be in 9~14 in the range of monomer when, the conduction of 10% compressive strength easy to accomplish with range above-mentioned Property resin particle, in addition, the electroconductive resin particle of the recovery rate easy to accomplish with aforementioned range.
The content of monomer shown in logical formula (II) in above-mentioned monomer mixture is relative to above-mentioned 100 weight of monomer mixture Part, preferably 1~20 parts by weight, more preferable 10~20 parts by weight.By the above-mentioned model of content for making monomer shown in logical formula (II) In enclosing, thus the electroconductive resin particle of 10% compressive strength easy to accomplish with range above-mentioned, in addition, tool easy to accomplish There is the electroconductive resin particle of the recovery rate of aforementioned range.
It should be noted that may include the other monomers in addition to above-mentioned monomer in above-mentioned monomer mixture.For example, In above-mentioned monomer mixture, it may include other monofunctional vinyl's base systems that can be copolymerized with simple function (methyl) acrylate monomer Monomer.As other monofunctional vinyl's base system monomers that can be copolymerized with simple function (methyl) acrylate monomer, such as can lift Aforementioned styrenic monomers, aforementioned vinyl esters system monomer etc. out.These other monofunctional vinyl's base system monomers can individually make With, or combine two or more and use.
In addition, in above-mentioned monomer mixture, may include in addition to shown in above-mentioned logical formula (I) and logical formula (II) other are more Functional ethylene's base system monomer.As other polyfunctional vinyl system monomers, for example, aforementioned multifunctional (methyl) propylene Acid esters system monomer, aforementioned fragrance race divinyl base system monomer etc..
In addition, above-mentioned vinyl monomer is preferably contain as part of it and has the hydrophilic radicals such as carboxyl, hydroxyl Monomer, more preferably comprising with epoxy alkyl (methyl) acrylate.Vinyl monomer is originated from nuclear particle as a result, Other compositions part hydrophobicity it is high in the case where, hydrophily can also be assigned to nuclear particle surface.As a result, passing through water Property medium in be dispersed with monomer in the dispersion liquid of nuclear particle oxidation polymerization form shell in the case where, nuclear particle can be made with one Secondary particle is readily dispersed in aqueous medium, easily can cover each nuclear particle with shell.There is alkylene oxide as such (methyl) acrylate of base, for example, the following general formula compound represented.
In above-mentioned general formula, R3Indicate H or CH3, R4And R5Difference, and indicate to be selected from C2H4、C3H6、C4H8、C5H10In alkylene Base, p are that 0~50, q is 0~50 (wherein, 0) p and q does not become simultaneously, R6Indicate H or CH3。
It should be noted that in the case that p is greater than 50 and in the case that q is greater than 50, polymerization is steady in the monomer of above-mentioned general formula Qualitative reduction, generates composite particles sometimes.The range of preferred p and q is 0~30, and the range of preferred p and q are 0~15.
As (methyl) acrylate with epoxy alkyl, commercially available product can use.As commercially available product, such as can lift Brenmar (registered trademark) series of Japan Oil Co out.It is suitable in further Brenmar (registered trademark) series It is that Brenmar (registered trademark) 50PEP-300 (is R3For CH3、R4For C2H5、R5For C3H6, p and q be averaged p=3.5 and q=2.5 Mixture, R6It (is R for H), Brenmar (registered trademark) 70PEP-350B3For CH3、R4For C2H5、R5For C3H6, p and q it is average For the mixture of p=3.5 and q=2.5, R6It (is R for H), Brenmar (registered trademark) PP-10003For CH3、R4For C2H5、R5 For C3H6, p 0, q average out to 4~6 mixture, R6It (is R for H), Brenmar (registered trademark) PME-4003For CH3、R4For C2H5、R5For C3H6, p average out to 9 mixture, q 0, R6For CH3) etc..
Total amount of the dosage of above-mentioned (methyl) acrylate with epoxy alkyl relative to vinyl monomer, preferably 40 Weight % or less, more preferable 1~15 weight %, further preferred 2~10 weight %, particularly preferred 3~7 weight %.By making The dosage of above-mentioned (methyl) acrylate with epoxy alkyl is the lower limit of above range or more, to make nuclear particle with primary Particle, which is scattered in aqueous medium, to be become easier to.The dosage of above-mentioned (methyl) acrylate with epoxy alkyl is relative to poly- When the total amount of conjunction sex ethylene base system monomer is more than 40 weight %, polymerization stability is reduced, and composite particles have time-varying more.
In addition, above-mentioned vinyl monomer is it is also preferred that with monofunctional vinyls' base system such as (methyl) acrylate monomer Monomer together, include the urethane acrylate oligomer as polyfunctional vinyl system monomer.Thus, it is possible to reduce 10% compressive strength of nuclear particle is stated, therefore, the upper limit easy to accomplish with range above-mentioned 10% compressive strength below Electroconductive resin particle.When above-mentioned urethane acrylate oligomer individually solidifies, 0~30 DEG C of vitrifying is preferably shown Transition temperature (Tg) (measures) according to viscoplasticity.In the case that Tg is lower than 0 DEG C, adhesiveness is generated in nuclear particle sometimes.Tg For in 30 DEG C of situations below, available restorative high electroconductive resin particle.Above-mentioned urethane acrylate is low Tg shown in when polymers individually solidifies is 0~28 DEG C more preferable, 0~25 DEG C further preferred.
Above-mentioned urethane acrylate oligomer shows the pencil hardness of H~HB when preferably individually solidifying.Use this In the case where the urethane acrylate oligomer of sample, the available electroconductive resin with higher recovery rate Grain.
As the commercially available product of above-mentioned urethane acrylate oligomer, for example, the first industrial pharmaceutical strain formula " New frontier (registered trademark) RST-402 " and " New of New frontier (registered trademark) RST series of commercial firm The urethane acrylate of New frontier (registered trademark) series such as frontier (registered trademark) RST-201 " is low Polymers, UF serial " UF-A01P " of Kyoeisha Chemical Co., Ltd. etc..
(manufacturing method of nuclear particle)
It, can be by making ethylene base system list in the case that nuclear particle of the invention is formed by the polymer of vinyl monomer Body polymerization obtains.As polymerization, emulsion polymerization, dispersin polymerization, suspension polymerisation, seeding polymerization etc. can be used and be used for To the well known method of resin particle.
(utilizing the manufacturing method of the nuclear particle of suspension polymerisation)
Above-mentioned suspension polymerisation is the method in an aqueous medium polymerizeing vinyl monomer.As above-mentioned aqueous medium, The mixture of water and water and water-miscible organic solvent (such as the lower alcohol below of carbon number 5) can be enumerated.
Above-mentioned suspension polymerisation can according to need to be carried out in the presence of polymerization initiator.As polymerization initiator, such as Benzoyl peroxide, lauroyl peroxide, caprylyl peroxide, adjacent chlorobenzoyl peroxide, methyl ethyl ketone peroxide, mistake can be enumerated Aoxidize the oil soluble peroxides such as two diisopropyl carbonates, cumene hydroperoxide, tert-butyl hydroperoxide；2,2 '-azos are double The oil-solubles azo-compounds such as isobutyronitrile, 2,2 '-azos bis- (2,4- methyl pentane nitriles).These polymerization initiators can be single respectively It solely uses, or combines two or more use.It should be noted that the dosage of polymerization initiator is relative to 100 weight of vinyl monomer It is sufficient that part, which is measured, as 0.1~1 parts by weight or so.
It is carried out in the presence of dispersing agent and/or surfactant in addition, above-mentioned suspension polymerisation can according to need.As Dispersing agent, for example, the hardly possible water-soluble inorganic salt such as calcium phosphate and magnesium pyrophosphate；Polyvinyl alcohol, methylcellulose and poly- Water soluble polymers such as vinylpyrrolidone etc..
In addition, as surfactant, for example, enuatrol, NaLS, neopelex, The anionic surfactants such as alkylnaphthalene sulfonate, alkyl phosphate salt；Polyoxyethylene alkane ether, polyoxyethylene benzene Ether, polyoxyethylene aliphatic ester, fatty acid esters of sorbitan, polyoxysorbitan fatty acid esters, polyoxyethylene alkane The nonionic surfactants such as base amine, fatty acid glyceride；Amphoteric surfactantes such as lauryl dimethyl amine oxide etc..
Above-mentioned dispersing agent and surfactant can use individually or combine two or more and use.Wherein, from dispersion Set out in terms of stability, preferably by the dispersing agent of the difficult water-soluble phosphate such as calcium phosphate, magnesium pyrophosphate, with alkyl sulfate, The anionic surfactants such as alkylbenzene sulfonate combine and use.
For the dosage of above-mentioned dispersing agent relative to 100 parts by weight of vinyl monomer, preferably 0.5~10 parts by weight, surface is living The dosage of property agent is relative to 100 parts by weight of aqueous medium, preferably 0.01~0.2 parts by weight.
It can include the oily phase of above-mentioned vinyl monomer by preparation, simultaneously side makes to prepare for above-mentioned suspension polymerisation Oil be mutually scattered in the water phase comprising aqueous medium side for the heated aqueous for being dispersed with the oil phase to cause suspension polymerisation.It needs It is noted that using in the case where polymerization initiator, the mixed polymerization initiator in above-mentioned vinyl monomer and prepare oil Phase.In addition, in the case where using dispersing agent and/or surfactant, mixed dispersant and/or surface-active in an aqueous medium Agent and prepare water phase.It should be noted that the volume average particle size of nuclear particle can be by adjusting the mixing ratio of oily phase and water phase Rate, dispersing agent, the dosage of surfactant and stirring condition, dispersion condition and be suitable for control.
As making oil mutually be scattered in the method in water phase, for example, following various methods: directly adding in water phase Oiling phase makes the oil mutually be scattered in the method in water phase in droplets using the mixing power of spiral paddle etc.；In water phase Oily phase is directly added, using the homogenizer for the dispersion machine using high shear force being made of rotor and stator, disperses the oil mutually Method in water phase；Oily phase is directly added in water phase, is scattered in the oil mutually in water phase using ultrasonic dispersing machine etc. Method etc..Wherein, if utilizing the high pressures such as microjet, Nanomizer (registered trademark) by directly adding oily phase in water phase Type dispersion machine, the collision using the mutual collision of the drop of mixture or mixture to machine wall, makes oil phase in droplets The method being scattered in water phase；By MPG (micropore glass) perforated membrane, divide oily method etc. of the mutually indentation into water phase It dissipates, then the partial size of nuclear particle can be made more uniformly to arrange, therefore it is preferred that.
In addition, preferably 40~90 DEG C or so of polymerization temperature.Moreover, as the time for keeping the polymerization temperature, preferably 0.1~ 10 hours or so.It should be noted that polymerization reaction can as nitrogen atmosphere, to the reactant in polymerization reaction system (oily phase) is to carry out under inactive non-active gas atmosphere.In addition, the boiling point of vinyl monomer be polymerization temperature nearby or In polymerization temperature situation below, it is preferable to use the pressure resistance polymerization such as autoclave in such a way that vinyl monomer is not volatilized Equipment carries out suspension polymerisation under closed lower or pressurization.
Then, after polymerization reaction, the decomposition such as dispersing agent acid are removed according to expectation, is filtered, water cleaning, takes off Water, drying, crushing, classification etc., so as to obtain target nuclear particle.
(utilizing the manufacturing method of the nuclear particle of seeding polymerization)
In manufacturing method using the nuclear particle of seeded polymerization, firstly, by vinyl monomer and aqueous medium structure At water-based emulsion in addition kind of a particle.As aqueous medium, can enumerate water, water and water-soluble solvent (such as carbon number 5 with Under lower alcohol) blending agent.
In aqueous medium, surfactant is preferably comprised.As surfactant, Anionic surfactants can be used Agent, cationic surfactant, nonionic surfactant and amphoteric ion surfactant,.
As above-mentioned anionic surfactant, for example, the fatty acid soaps, the moon such as enuatrol, castor oil potash soap The alkylbenzene sulfonates such as alkyl sulfates salt, the neopelexes such as osmanthus base sodium sulphate, Texapon Special, alkylnaphthalene sulphur The dialkyl sulfosuccinates, alkenyl succinate (two such as hydrochlorate, alkyl sulfonate, two (2- ethylhexyl) sodium sulfosuccinates Sylvite), alkyl phosphate salt, naphthalene sulfonic acid-formaldehyde condensation product, polyoxyethylene phenylate sulfuric acid, polyoxyethylenelauryl The polyoxyethylenes alkane such as ether sodium sulfate ether sulfate, polyoxyethylene sulfuric acid etc..
As above-mentioned cationic surfactant, for example, the alkane such as lauryl amine acetic acid esters, stearylamine acetic acid esters Quaternary ammonium salts such as base amine salt, lauryl trimethyl ammonium chloride etc..
As above-mentioned amphoteric ion surfactant, lauryl dimethyl amine oxide, phosphate system or Asia can be enumerated Phosphate system surfactant.Above-mentioned surfactant can be used alone or in combination of two or more kinds.Above-mentioned surfactant In, dispersion stabilization when polymerization, preferred anionic surfactant.
Water-based emulsion can be made by well known method.For example, vinyl monomer is added in an aqueous medium, Make its dispersion using the fine mulser such as homogenizer, ultrasonic processor, Nanomizer, so as to obtain water-based emulsion. Vinyl monomer can according to need comprising polymerization initiator.Polymerization initiator can be pre-mixed in vinyl monomer Afterwards, it is scattered in aqueous medium, or the substance for being dispersed with the two respectively in an aqueous medium can also be mixed.Gained When the partial size of the drop of vinyl monomer in water-based emulsion is less than kind particle, vinyl monomer can be planted effectively Particle absorbs, therefore it is preferred that.
Kind of particle can be added directly to water-based emulsion, can also be to be dispersed with the shape of kind of particle in aqueous dispersion medium State addition.After kind particle is to water-based emulsion addition, vinyl monomer is made to be absorbed in kind of a particle.The absorption, which will usually pass through, to plant Water-based emulsion after particle addition is stirred 1~12 hour under room temperature (about 20 DEG C) and is carried out.In addition, by by aqueous emulsifying Liquid is heated up to 30~50 DEG C or so, so as to promote to absorb.
Kind particle is swollen by absorbing vinyl monomer.For vinyl monomer and kind particle blending ratio, Relative to 1 parts by weight of kind of particle, the vinyl monomer preferably range of 5~150 parts by weight, more preferable 10~120 parts by weight Range.When vinyl monomer becomes smaller relative to the blending ratio of kind of particle, the increase for polymerizeing caused partial size becomes smaller, thus Productivity reduces sometimes.When vinyl monomer becomes larger relative to the blending ratio of kind of particle, vinyl monomer completely not by Kind particle absorbs, suspension polymerisation alone in an aqueous medium, and generates abnormal grain sometimes.It should be noted that the knot absorbed Beam determines and with the amplification of the observation confirmation partial size of optical microscopy.
In water-based emulsion, addition polymerization initiator can according to need.As polymerization initiator, for example, mistake Benzoyl Oxide, lauroyl peroxide, adjacent chlorobenzoyl peroxide, O-methoxy benzoyl peroxide, 3,5,5- trimethyl oneself The organic peroxides such as acyl peroxide, tert-butyl hydroperoxide -2 ethyl hexanoic acid ester, di-tert-butyl peroxide, 2,2 '-are occasionally Azo compounds such as nitrogen double isobutyronitrile, 1,1 '-azo bis cyclohexane formonitrile HCNs, 2,2 '-azos bis- (2,4- methyl pentane nitriles) etc.. Polymerization initiator is used preferably with respect to 100 parts by weight of vinyl monomer with the range of 0.1~3 parts by weight.
Then, by polymerizeing the vinyl monomer for being absorbed in kind of particle, so as to obtain nuclear particle.Polymerization Temperature is suitable for selection according to vinyl monomer, the type of polymerization initiator.The range that preferably 25~110 DEG C of polymerization temperature, More preferable 50~100 DEG C of range.Polymerization reaction preferably carries out as follows: fully absorbing monomer, polymerization initiator by kind of a particle Afterwards, it is heated up and is carried out.After polymerization, nuclear particle is centrifuged as needed and removes aqueous medium, uses water After solvent cleaning, it is dried, separates.
In above-mentioned polymerization process, in order to improve the dispersion stabilization of nuclear particle, macromolecular dispersion stabilizer can be added.Make For macromolecular dispersion stabilizer, polyvinyl alcohol, polycarboxylic acids, cellulose family (hydroxy ethyl cellulose, carboxyl first can be used for example Base cellulose etc.), polyvinylpyrrolidone etc..Alternatively, it is also possible to by these macromolecular dispersion stabilizers and sodium tripolyphosphate etc. Inorganic system's water-soluble high-molecular compound is applied in combination.Among them, preferably polyvinyl alcohol, polyvinylpyrrolidone are as high score Sub- dispersion stabilizer.The additive amount of macromolecular dispersion stabilizer is relative to 100 parts by weight of vinyl monomer, preferably 1~10 weight Measure part.
In addition, the generation in order to inhibit the emulsified particles in water system, can be used nitrites, sulfites, hydrogen The water-soluble polymerization inhibitors such as quinones, Vitamin C acids, water-soluble (vitamin) B class, citric acid, Polyphenols.
(shell)
Above-mentioned shell is formed by electroconductive polymer.Above-mentioned electroconductive polymer can be polyphenylamine series of polymers, gather different sulphur Indenes based polymer etc., from shell and the available electroconductive resin particle with desired electric conductivity more evenly easy to form Aspect set out, at least 1 be preferably selected from the group being made of nitrogenous heteroaromatic compound and sulfur-bearing heteroaromatic compound The polymer of kind monomer.
As above-mentioned nitrogenous heteroaromatic compound, can enumerate pyrroles, indoles, imidazoles, pyridine, pyrimidine, pyrazine and it Alkyl substituents (such as substituent as obtained from the alkyl of the carbon numbers such as methyl, ethyl, propyl, butyl 1~4), halogen The derivative of substituent (such as substituent as obtained from the halogen groups such as fluorine-based, chloro, bromo), nitrile substituent etc.From It sets out in terms of shell and the available electroconductive resin particle with desired electric conductivity more evenly easy to form, preferably The polymer of the derivative of pyrroles and pyrroles is as nitrogenous heteroaromatic compound.As the derivative of pyrroles, 3 can be enumerated, 4- dimethyl pyrrole.
As above-mentioned sulfur-containing aromatic compound, from the available electroconductive resin particle with desired electric conductivity Aspect is set out, and preferably the derivative of thiophene and thiophene is as nitrogen-containing aromatic compound.As the derivative of thiophene, can enumerate 3,4- ethyldioxythiophene, 3 methyl thiophene, 3- octyl thiophene etc..These monomers can be used alone and form homopolymer, Or two or more can also be applied in combination and forms copolymer.
The thickness of above-mentioned the shell preferably range of 30~300nm, the range of more preferable 50~200nm.The thickness of above-mentioned shell is such as Fruit is then available sufficient electric conductivity in above range.The amplitude of the thickness of above-mentioned shell preferably 50% or less, more preferably 40% or less.
(forming method of shell)
The electroconductive polymer for constituting the shell is selected from by nitrogenous heteroaromatic compound and sulfur-bearing heteroaromatic compound In the case where the polymer of at least one kind of monomer (hreinafter referred to as " monomer ") in the group of composition, above-mentioned electroconductive resin particle It can be manufactured and covering the method for polymer of above-mentioned monomer on above-mentioned nuclear particle.It is covered as on above-mentioned nuclear particle Preferably following method: the method for the polymer of above-mentioned monomer is scattered in above-mentioned nuclear particle in the aqueous medium comprising oxidant It is formed dispersion liquid (emulsion or suspension), monomer is added in the dispersion liquid and stirred, by oxidation polymerization in above-mentioned core The surface of particle covers the polymer of above-mentioned monomer.
The additive amount of above-mentioned monomer can be set according to desired electric conductivity, relative to 100 parts by weight of nuclear particle, It is preferred that the range of 1~30 parts by weight, more preferable 3~20 parts by weight.Make the additive amount of above-mentioned monomer relative to 100 weight of nuclear particle When part is 1 parts by weight or more, the entire surface of nuclear particle is equably covered by the polymer of above-mentioned monomer, available desired Electric conductivity.On the other hand, by making the additive amount of monomer relative to 100 parts by weight of nuclear particle, 30 parts by weight hereinafter, to institute The monomer of addition is polymerized alone, and can prevent from forming the substance in addition to target electroconductive resin particle.
(1) oxidant
As above-mentioned oxidant, inorganic acid as hydrochloric acid, sulfuric acid, chlorosulfonic acid, alkyl benzene sulphonate, alkylnaphthalene can be enumerated Metal halide as organic acid as sulfonic acid, iron chloride, aluminium chloride, the acid of halogen as potassium hyperchlorate, potassium peroxydisulfate, Peroxide as ammonium persulfate, sodium peroxydisulfate, hydrogen peroxide etc..They can be used alone or mix and use.As Oxidant, the preferably alkali metal salt of inorganic peroxy acid.As the alkali metal salt of inorganic peroxy acid, specifically, can enumerate Potassium sulfate, sodium peroxydisulfate etc..
The dosage of above-mentioned oxidant is relative to monomer total amount, preferably 0.5~2.0 molar equivalent.By the use for making oxidant Amount is 0.5 molar equivalent or more relative to monomer total amount, so that the entire surface of nuclear particle can be by the polymer comprising monomer Shell equably cover, available desired electric conductivity.On the other hand, by making the dosage of oxidant relative to monomer total amount For 2.0 molar equivalents hereinafter, being polymerized alone to added monomer, can prevent from being formed except target electroconductive resin particle with Outer substance.
Be added to the aqueous medium of above-mentioned oxidant as long as can make monomer dissolve or dispersion as long as be not particularly limited, can be with Enumerate water；Or, the alcohols such as water and methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol；Ether, isopropyl ether, butyl ether, first The ethers such as base cellosolve, tetrahydrofuran；The blending agent of the ketones such as acetone, methyl ethyl ketone, metacetone.
(2) aqueous medium
The aqueous medium for being added to above-mentioned oxidant preferably has 3 or more pH.PH if it is 3 or more, nuclear particle Entire surface can equably be covered by the shell of the polymer comprising monomer, available desired electric conductivity.In order to steadily PH, is more preferably adjusted to 3~10 range by covering.
(3) surfactant
Surfactant can be added in above-mentioned aqueous medium.As surfactant, anionic surface can be used Activating agent, cationic surfactant, amphoteric ion surfactant, nonionic surfactant,.
As above-mentioned anionic surfactant, for example, the fatty acid soaps, the moon such as enuatrol, castor oil potash soap The alkylbenzene sulfonates, alkyl sulfonic acid such as alkyl sulfates salt, the neopelexes such as osmanthus base sodium sulphate, Texapon Special Salt, alkyl sulfonate, dialkyl sulfosuccinates, alkyl phosphate salt, naphthalene sulfonic acid-formaldehyde condensation product, gathers alkylnaphthalene sulfonate Oxygen ethylidene alkylbenzene ether sulfuric ester salt, polyoxyethylene sulfuric acid etc..
As above-mentioned nonionic surfactant, for example, polyoxyethylene alkane ether, polyoxyethylene Phenylate, polyoxyethylene aliphatic ester, fatty acid esters of sorbitan, polyoxysorbitan fatty acid esters, polyoxyethylene Alkylamine, fatty acid glyceride, oxyethylene-oxypropylene block polymer etc..
As above-mentioned cationic surfactant, for example, the alkane such as lauryl amine acetic acid esters, stearylamine acetic acid esters Quaternary ammonium salts such as base amine salt, lauryl trimethyl ammonium chloride etc..
As above-mentioned zwitterionic surfactant, lauryl dimethyl amine oxide, phosphate system or phosphorous can be enumerated Acid esters system surfactant etc..Above-mentioned surfactant can be used alone or in combination of two or more kinds.Surfactant adds Dosage is relative to 100 parts by weight of aqueous medium, the preferably range of 0.0001~1 parts by weight.
In addition, macromolecular dispersion stabilizer can be added in addition to surfactant in above-mentioned aqueous medium.As high score Sub- dispersion stabilizer, for example, polyacrylic acid, its copolymer and their corrective and polymethylacrylic acid, it is total Corrective, polyvinylpyrrolidone, the hydroxy propyl cellulose (HPC) etc. of polymers and they.Macromolecular dispersion stabilizer can To be used with above-mentioned surfactant package.
(4) oxidation polymerization
In manufacturing method using the electroconductive resin particle of above-mentioned oxidation polymerization, by making above-mentioned nuclear particle be scattered in packet Dispersion liquid is formed in aqueous medium containing oxidant, adds monomer in the dispersion liquid, is stirred and is carried out oxidation polymerization, from And obtain the electroconductive resin particle that nuclear particle is covered by the polymer of above-mentioned monomer.The temperature of oxidation polymerization preferably -20~40 DEG C range, the time of oxidation polymerization preferably 0.5~10 hour range.
It should be noted that the emulsion for being dispersed with electroconductive resin particle is centrifuged as needed and goes to remove water Property medium, after being cleaned with water and solvent, dry, separation.
In above explanation, as making polymer be covered on the method on nuclear particle, to including nuclear particle and oxidant Aqueous medium in mixed with monomer and the method that polymerize monomer oxidation is illustrated, but polymer is made to be covered on nuclear particle On method be not limited to this method.It such as can also be with the following method: using the method for dry type, polymer being made to be covered on core Method on particle.It as the method for above-mentioned dry type, such as can use: using the method for ball mill, using V-Mixer Method, the method using flow at high speed drying machine, the method using mixing grinding machine, mechanical welding (Mechano Fusion) method Deng.
(purposes of electroconductive resin particle)
Electroconductive resin particle of the invention can be suitble to so that electroconductive resin particle is closely sealed each other and embodies conductive The purpose of property with using on the way.Electroconductive resin particle of the invention can be used as being electrically connected in electronic circuit board etc. The conductive paste (substance of conductive particle is dispersed in binder resin) that connects, when being coated and drying for electronics electricity The electric conductivity ink that can form conductive film of electrical connection in base board etc. is (in a solvent in the solution dissolved with binder resin Dispersed the substance of conductive particle), the conductive elastomer layer of conductive roll that utilizes in transfer roll etc. (disperses in elastomer The substance of conductive particle), conductive particle uses used in antiblocking agent etc..
(conductive resin composition)
Conductive resin composition of the invention includes electroconductive resin particle and matrix resin of the invention.Of the invention Conductive resin composition can be manufactured and mixing electroconductive resin particle of the invention in matrix resin.
It as aforementioned matrix resin, can be used: polycarbonate, polyethylene terephthalate, poly terephthalic acid Butanediol ester, polyamide 6, polyamide 66, polyamide 12, ABS resin (acrylonitrile-butadiene-styrene), AS tree Rouge (acrylonitrile styrene copolymer resins), polypropylene, polyacetals, polyamidoimide, polyether sulfone, polyimides, gathers polyethylene Phenylate, polyphenylene sulfide, polystyrene, thermoplastic polyurethane elastomer, thermoplastic polyester elastomer, polyamide thermoplastic elasticity Body, polyvinyl chloride, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer (ETFE resin), tetrafluoroethene perfluoroalkyl vinyl ether One kind or two or more mixture in the thermoplastic resins such as copolymer (PFA resin), polyether-ketone.Make as aforementioned matrix resin The type of thermoplastic resin can be according to characteristic (mechanical strength, wearability, resistance toization of the conductive resin composition of target Learn drug, heat resistance, mouldability when forming conductive resin composition and being manufactured product etc.) and it is suitable for selection.
Said conductive resin particle is relative to aforementioned 100 parts by weight of matrix resin, preferably 1~200 parts by weight of addition.
In said conductive resin combination, can the function according to required by target molded product and be suitable for add other function It can property filler.As aforementioned functional filler, can enumerate the reinforcing fibers such as glass fibre, carbon fiber, fire retardant, delustering agent, Heat stabilizer, light stabilizer, colorant, lubricant etc..
Conductive resin composition of the invention can by by aforementioned matrix resin, electroconductive resin particle and other Be suitable for that the functional filler for including is mixed (mixing), by it is hot-forming be required shape, so as to be formed into Type product.Or, conductive resin composition of the invention can by by aforementioned matrix resin, electroconductive resin particle and other Be suitable for the functional filler for including with heated condition it is suitable for being mixed (mixing), after being shaped to pellet, using the pellet, passes through Extrusion molding, injection moulding etc. form molded product.Thus, it is possible to obtain the molded product of electric conductivity and excellent antistatic property.
(coating agent)
Coating agent of the invention includes electroconductive resin particle and binder resin of the invention.
As above-mentioned binder resin, as long as according to the transparency, dispersibility of electroconductive resin particle, light resistance, resistance to Characteristic required by moist and heat resistance etc. and be that user is just not particularly limited in this field.As above-mentioned binder tree Rouge, for example, (methyl) acrylic resin；(methyl) acrylic-urethane system resin；Carbamate system Resin；Polyvinyl chloride resin；Polyvinylidene chloride resin；Melamine series resin；Phenylethylene resin series；Alkyd system tree Rouge；Phenolic aldehyde system resin；Epoxy system resin；Polyester based resin；The organic silicon-type resins such as alkyl polysiloxane system resin；(methyl) third Olefin(e) acid-organic silicon-type resin, organosilicon -ol acid system resin, organosilicon-carbamate system resin, organosilicon-polyester resin etc. Modified organic silicone resin；Fluorine resins such as polyvinylidene fluoride, fluoroolefin vinylic-ether polymer etc..
From the viewpoint of the durability for improving coating agent, above-mentioned binder resin can preferably be formed by cross-linking reaction and be handed over It is coupled the curable resin of structure.Above-mentioned curable resin can solidify under various conditions of cure.Above-mentioned curable resin according to Cured type and can be divided into the ionization radial lines curable resins such as uv curing resin, electronic beam curing resin, Thermosetting resin, warm wind curable resin etc..
As above-mentioned thermosetting resin, the heat cure formed by the pure and mild isocyanate prepolymer of acrylic acid multielement can be enumerated Type carbamate resins, phenolic resin, urea melmac, epoxy resin, unsaturated polyester resin, organic siliconresin Deng.
As above-mentioned ionization radial line curable resin, it is such that polyalcohol multifunctional (methyl) acrylate etc. can be enumerated Multifunctional (methyl) acrylate resin；It is closed by diisocyanate, polyalcohol and (methyl) acrylate with hydroxyl etc. Polyfunctional carbamate acrylate as etc..It is preferably more as above-mentioned ionization radial line curable resin Function (methyl) acrylate, the polyalcohol in more preferable 1 molecule with 3 or more (methyl) acryloyl groups are multifunctional (methyl) acrylate.As multifunctional (methyl) acrylic acid of polyalcohol in 1 molecule with 3 or more (methyl) acryloyl groups Ester, specifically, trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylic acid can be enumerated Ester, 1,2,4- hexamethylene four (methyl) acrylate, five glycerol tri-acrylates, pentaerythrite four (methyl) acrylate, season Penta tetrol three (methyl) acrylate, dipentaerythritol triacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol triacrylate, tripentaerythritol 6 third Olefin(e) acid ester etc..Above-mentioned ionization radial line curable resin can use two kinds of combination of the above.
As above-mentioned ionization radial line curable resin, in addition to this it is possible to use: the function with acrylic ester Polyether resin, the polyester resin, epoxy resin, alkyd resin, spiral shell acetal resin, polybutadiene, polymercaptan polyenoid tree of group Rouge etc..
In the case where using uv curing resin in above-mentioned ionization radial line curable resin, ultra-violet solidified Photoepolymerizationinitiater initiater is added in resin and forms binder resin.Arbitrary substance can be used in above-mentioned Photoepolymerizationinitiater initiater, preferably makes With the substance being consistent with used uv curing resin.
As above-mentioned Photoepolymerizationinitiater initiater, acetophenones, benzoin class, benzophenone, phosphinoxides, contracting can be enumerated Ketone, Alpha-hydroxy alkylbenzene ketone, alpha-aminoalkyl benzophenone, Anthraquinones, thioxanthene ketone class, azo-compound, peroxide (note Be loaded in Japanese Unexamined Patent Publication 2001-139663 bulletin etc.), 2,3- dialkyl group dione compounds class, disulfides, fluorine amine compounds Class, aromatic matte class, salt, borate, active halogen compound, α-acyl group oxime ester etc..
As above-mentioned acetophenones, for example, acetophenone, 2,2- diethoxy acetophenone, to dimethyl benzene second Ketone, 1- hydroxyl 3,5-dimethylphenyl ketone, 1- hydroxycyclohexylphenylketone, 2- methyl -4- methyl thio -2- raorpholino propiophenone, 2- Benzyl -2- dimethylamino -1- (4- morpholino phenyl)-butanone etc..As above-mentioned benzoin class, for example, benzene is even Relation by marriage, benzoin benzoic ether, benzoin benzene sulfonate, benzoin tosylate, benzoin methylether, benzoin ethyl ether, benzene are even Relation by marriage isopropyl ether etc..As above-mentioned benzophenone, for example, benzophenone, 2,4- dichloro benzophenone, 4,4- dichloro Benzophenone, p-dichlorobenzene ketone etc..As above-mentioned phosphinoxides, for example, 2,4,6- trimethylbenzoyl diphenyl Phosphine oxide etc..As above-mentioned ketal class, for example, the benzyls first such as 2,2- dimethoxy -1,2- diphenylethane -1- ketone Base ketal class.As above-mentioned Alpha-hydroxy alkylbenzene ketone, for example, 1- hydroxycyclohexylphenylketone.As above-mentioned α-ammonia Base alkylbenzene ketone, for example, 2- methyl-1-[4- (methyl thio) phenyl]-2- (4- morpholinyl)-1- acetone.
As commercially available optical free radical polymerization initiator, the trade name of BASF Japan Co., Ltd. can be enumerated " Irgacure (registered trademark) 651 " (2,2- dimethoxy -1,2- diphenylethane -1- ketone), BASF Japan Co., Ltd. The trade name " Irgacure (registered trademark) 184 " of system, the " Irgacure (registration of the trade name of BASF Japan Co., Ltd. Trade mark) 907 " (2- methyl-1-[4- (methyl thio) phenyl]-2- (4- morpholinyl)-1- acetone) etc. are used as preference.
The dosage of above-mentioned Photoepolymerizationinitiater initiater is relative to 100 weight % of binder resin, usually 0.5~20 weight % In range, in the range of preferably 1~5 weight %.
As above-mentioned binder resin, in addition to above-mentioned curable resin, thermoplastic resin can also be used.As above-mentioned It is fine can to enumerate acetylcellulose, NC Nitroncellulose, acetyl group butyl cellulose, ethyl cellulose, methyl for thermoplastic resin Tie up the cellulose derivatives such as element；The homopolymer and copolymer of vinyl acetate, the homopolymer of vinyl chloride and copolymer, inclined two chloroethene The vinyl resins such as the homopolymer and copolymer of alkene；The acetal resins such as polyvinylformal, polyvinyl butyral；Propylene (methyl) acrylic resin such as the homopolymer and copolymer of acid esters, the homopolymer of methacrylate and copolymer；Polyphenyl second Olefine resin；Polyamide；Linear polyester resin；Polycarbonate resin etc..
Above-mentioned coating agent can further include water and/or organic solvent.Above-mentioned coating agent is coated on base film In the case of, above-mentioned organic solvent in through coating agent containing its coating agent to the coating transfiguration easily of base film as long as do not have It is particularly limited to.As above-mentioned organic solvent, the aromatic systems solvent such as toluene, dimethylbenzene can be used for example；Methanol, ethyl alcohol, just The alcohol series solvents such as propyl alcohol, isopropanol, n-butanol, isobutanol, propylene glycol monomethyl ether；The ester series solvents such as ethyl acetate, butyl acetate； The ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclohexanone；2-methyl cellosolve, cellosolvo, 2- The glycol ethers such as butyl cellosolve, glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether；2- first Oxygroup ethylhexoate, acetic acid 2- ethoxyethyl acetate (cellosolve acetate), 2- butoxy ethyl acetate, propylene glycol The diol alcohol esters such as methyl ether acetate；The chlorine series solvent such as chloroform, methylene chloride, chloroform, methylene chloride；Tetrahydrofuran, second The ether series solvents such as ether, 1,4- dioxane, 1,3- dioxolanes；N-Methyl pyrrolidone, dimethylformamide, dimethyl Acid amides series solvents such as sulfoxide, dimethyl acetamide etc..These organic solvents can be used a kind can also by two or more mix and It uses.
(film)
Film of the invention includes electroconductive resin particle of the invention.Film of the invention will include for example, electric conductivity The coating agent of resin particle and binder resin is constituted made of being coated on base film.The film of this composition can be suitable for It is used for conductive membrane or antistatic film.
Above-mentioned base film is preferably transparent.As transparent base film, for example: by poly terephthalic acid Polyester based polymers, diacetyl cellulose, three such as glycol ester (hereinafter, brief note makees " PET "), polyethylene naphthalate The acrylic compounds such as the cellulose-based polymer such as acetylcellulose (TAC), polycarbonate based polymer, polymethyl methacrylate The film that the polymer such as polymer are formed.In addition, can also be enumerated as transparent base film: by polystyrene, propylene The styrenics such as nitrile styrol copolymer, polyethylene, polypropylene, with cyclic annular and/or norbornene structure poly- The amides such as the olefin polymers such as alkene, ethylene propylene copolymer, vinyl chloride-based polymer, nylon, aromatic polyamide system The film that the polymer such as polymer are formed.Further, as transparent base film, it can also enumerate: be polymerize by imide series Object, sulfone based polymer, polyether sulfone based polymer, polyether-ether-ketone based polymer, polyphenylene thioether based polymer, ethenol system polymerization Object, vinylidene chloride based polymer, polyvinyl butyral based polymer, aromatic ester based polymer, polyformaldehyde based polymer, epoxy Polymer, film for being formed of the polymer such as blend of above-mentioned polymer etc..Film as above-mentioned base material is particularly suitable for using double The few film of refractive index.In addition, the film for being further provided with adhesive layer on the film formed by these polymer can also be with Film uses as above-mentioned base material.Above-mentioned adhesive layer can be by (methyl) acrylic resin, copolyester system resin, poly- ammonia The resins such as ester system resin, styrene-maleic acid grafted polyester resin, acrylic acid-grafted polyester resin are formed.It should be noted that In this specification, " (methyl) acrylic acid " refers to, acrylic or methacrylic acid.
The thickness of above-mentioned base film can be suitable for determining, generally according to the side such as the workability such as intensity, operation, thin layer Face, in the range of being 10~500 μm, in the range of preferably 20~300 μm, it is 30~200 μm more preferable in the range of.
In addition, additive can be added in above-mentioned base film.As above-mentioned additive, for example, ultraviolet light Absorbent, infrared absorbent, antistatic agent, adjustable refractive index agent, reinforcing agent etc..
As the method for coating above-mentioned coating agent on base film, stick painting, scraper plate coating, spin coating, inverse formula can be enumerated It is coated well known to coating, die coating, spraying, roller coating, rotogravure application, micro- rotogravure application, lip coating, air knife coating, infusion process etc. Method.
In the case that binder resin contained in above-mentioned coating agent is ionization radial line curable resin, in above-mentioned coating After agent coating, makes solvent seasoning as needed, further irradiate active energy beam, so as to so that ionization radial line curability Resin solidification.
As above-mentioned active energy beam, can be used for example: xenon lamp, low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, The ultraviolet light that metal halide lamp, carbon arc lamp, tungsten lamp etc. are issued from light source；Usually from the Cockroft- of 20~2000KeV Walton type, VandeGraaff type, resonance variable-pressure, insulating core conversion hysteria, linear type, Dinamitron type, high-frequency type etc. Electron beam, alpha ray, β ray, the gamma-rays etc. that electron-beam accelerator takes out.
It is being formed by the coating (and solidification) of above-mentioned coating agent, electroconductive resin particle is dispersed in binder resin The thickness of layer (antiglare layer) be not particularly limited, can be suitable for determining according to the partial size of electroconductive resin particle, preferably 1~ In the range of 10 μm, it is 3~7 μm more preferable in the range of.
It should be noted that film of the invention is not limited to above-mentioned composition, can will with include electroconductive resin particle Molding resin composition same with the coating agent of binder resin is shaped to thin film shape.The film of this composition can be suitble to It is used as conductive membrane or antistatic film.
(clearance material)
Clearance material of the invention includes electroconductive resin particle of the invention.Clearance material of the invention can be used as liquid Spacer, sealing spacer used for liquid crystal display element, EL (electroluminescent) display element interval in crystal display element face Object, touch panel spacer, between capable of equably keeping the gap holding material in gap between the various substrates such as ceramics, plastics etc. Stand-off distance is used from holding with spacer.Clearance material of the invention includes the electric conductivity tree of the invention with good conductivity Rouge particle, it is therefore, conductive, play anti-static function.
In the case that clearance material of the invention has uniform coverage effect, the volume base of said conductive resin particle The coefficient of variation preferably 20% or less of quasi- partial size, more preferably less than 10%.
Embodiment
Hereinafter, the present invention will be described according to examples and comparative examples, but the present invention is not limited thereto.Firstly, to Under embodiment and comparative example in the volume average particle size of electroconductive resin particle, volume reference partial size the coefficient of variation, The measuring method of 10% compressive strength and conductivity is illustrated.
(measuring method of the coefficient of variation of the partial size of the volume average particle size and volume reference of electroconductive resin particle)
The measurement of the coefficient of variation (CV value) of the partial size of the volume average particle size and volume reference of electroconductive resin particle is such as It is carried out below by way of Kurt method.
The volume average particle size of electroconductive resin particle utilizes Kurt MultisizerTM3 (Beckman Kurt strains Formula commercial firm measurement device) measurement.Measurement uses the Multisizer according to the distribution of Beckman Kurt Co., Ltd.TM3 use Family handbook correction aperture and implement.
It should be noted that aperture used in measurement is suitable for choosing according to the size for the electroconductive resin particle to be measured It selects.Current (aperture electric current) and Gain (gain) is suitable for setting according to the size of selected aperture.For example, selection tool In the case where the aperture for having 50 μm of size, Current (aperture electric current) is set as -800, Gain (gain) and is set as 4.
As measurement sample, the dispersion liquid obtained as follows is used: using Touch Mixer (Yamato Scientific Inc. system, " TOUCHMIXER MT-31 ") and ultrasonic cleaner (Velvoklya Corporation system, " ULTRASONIC CLEANER VS-150 "), so that electroconductive resin particle 0.1g is scattered in 0.1 weight % non-ionic surface In aqueous surfactant solutions 10ml, dispersion liquid is formed.In measurement, it is slowly stirred in advance in beaker with not entering the degree of bubble, Terminate to measure at the time of measuring electroconductive resin particle 100,000.The volume average particle size of electroconductive resin particle is 100,000 Arithmetic average in the size distribution of the volume reference of particle.
The coefficient of variation of the partial size of the volume reference of electroconductive resin particle is calculated by mathematical expression below.
The coefficient of variation of the partial size of the volume reference of electroconductive resin particle
=(the standard deviation of the size distribution of the volume reference of electroconductive resin particle
The volume average particle size of ÷ electroconductive resin particle) × 100
(measuring method of 10% compressive strength of electroconductive resin particle)
10% compressive strength (S10 intensity) of resin particle is tested using the slight compression of Shimadzu Scisakusho Ltd Machine " MCTM-200 ", is measured under following determination conditions.
Specifically, the dispersion liquid that resin particle is dispersed in ethyl alcohol is coated on the steel sample table through mirror finish, And it is dry, prepare measurement sample.Then, aobvious with the optics of MCTM-200 in the environment of 20 DEG C of room temperature, relative humidity 65% Micro mirror selects an independent fine resin particle, and (at least there is no other resin particles in the range of 100 μm of diameter State), the diameter for the resin particle selected is measured under the particle size determination cursor of MCTM-200.At this point, resin particle is from base In resin particle of the volume average particle size selection that the measuring method of aforementioned Kurt method confirms in the range of ± 0.5 μm. Resin particle outside its range is not used in the measurement of compressive strength.Then, make test with pressure head with following load speeds fall to The vertex for the resin particle selected, to slowly apply load up to maximum load 9.81mN, by said determination to resin particle Load at the time of be displaced 10% of the diameter of resin particle find out compressive strength according to the following formula.Each resin particle is carried out 6 measurements, remove maximum value, the data of minimum value, using the average value of 4 data as 10% compressive strength (S10 intensity).
The calculating formula > of < compressive strength
Compressive strength (MPa)=2.8 × load (N)/{ π × (partial size (mm))2}
The determination condition > of < compressive strength
Test temperature: room temperature (20 DEG C) relative humidity 65%
Pressurize pressure head on top: 50 μm of diameter of plane pressure head (material: diamond)
Lower part pressure plate: SKS plate
Test type: compression test (MODE1)
Test load: 9.81mN
Load speed: 0.732mN/ seconds
It is displaced full scale；20(μm)
(measuring method of the conductivity of electroconductive resin particle)
With " powder resistance measures system MCP-PD51 type " (Mitsubishi Chemical Analytech Co., Ltd. System), for being filled in the electroconductive resin particle of probe, with oil pressure pump every 4kN from 0kN gradually apply load up to 20kN, the electroconductive resin particle of the state for being applied with each load (0,4kN, 8kN, 12kN, 16kN and 20kN) carry out electricity The measurement of conductance.Highest numerical value is as the conductance of the electroconductive resin particle in conductivity obtained from surveying under each load Rate.For electroconductive resin particle, measured by karr Fischer moisture to measure containing amount of moisture in advance, it is thus identified that contain water Component is 1.0 weight % or less.As resistrivity meter used in " powder resistance measures system MCP-PD51 type ", low electricity is used Resistance rate meter " Loresta (registered trademark)-GX MCP-T700 " (Mitsubishi Chemical Analytech Co., Ltd. System).
(embodiment 1)
[manufacture of nuclear particle]
(preparation of water phase)
In beaker, 200 parts by weight of deionized water as aqueous medium, 10 weight of magnesium pyrophosphate as dispersing agent are put into Part and 0.04 parts by weight of NaLS as anionic surfactant are measured, water phase is prepared.
(preparation of oily phase)
In other beakers of the beaker used in the preparation for being different from water phase, investment is used as simple function (methyl) acrylic acid 60 parts by weight of n-butyl acrylate of ester monomer, 15 parts by weight of methyl acrylate, 10 parts by weight of 2-EHA and poly- (ethylene glycol and 1,2-propylene glycol) monomethacrylates (" Brenmar (registered trademark) 50PEP-300 " of Japan Oil Co) 5 Parts by weight, as monomer shown in above-mentioned logical formula (I) ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd. " the Light Ester EG " made) 10 parts by weight and bis- (the 2,4- dimethyl-pentens of 2,2 '-azos as polymerization initiator Nitrile) 0.15 parts by weight of 0.2 parts by weight and benzoyl peroxide, it is sufficiently stirred, prepares the mixture as oily phase.
(polymerization reaction)
The oily phase prepared is added in the water phase prepared in advance, it is (PRIMIX Co. Ltd. system, desk-top using homogenizer Type, product name " 2.5 type of homogenizer MARKII "), with mixing speed 5000rpm stirring 10 minutes, oil is made mutually to be scattered in water phase In, obtain dispersion liquid.The dispersion liquid is put into, in the polymer reactor for having blender, heating device and thermometer with 60 DEG C Stirring 6 hours, to carry out suspension polymerization.Then, the suspension (reaction solution) in polymer reactor is made to be cooled to 30 DEG C Afterwards, hydrochloric acid is added, decomposes magnesium pyrophosphate.Then, suspension is filtered.The residue of filtering is carried out clearly using ion exchange water It washes, be dehydrated, obtain the aqueous filter cake body of the nuclear particle formed by the polymer of target vinyl monomer.
[manufacture of electroconductive resin particle]
[polymerization reaction]
In beaker, aqueous 25 parts by weight of filter cake body of the nuclear particle made are scattered in 50 parts by weight of deionized water, obtain To nuclear particle dispersion liquid.Then, so that 20 parts by weight of potassium peroxydisulfate as oxidant is dissolved in 300 parts by weight of deionized water, make Standby persulfate aqueous solution.In above-mentioned persulfate aqueous solution, the nuclear particle dispersion liquid prepared in advance is mixed, stirs 30 points Clock.In obtained mixed liquor, 5 parts by weight of pyrroles as nitrogen-containing aromatic compound are added, is stirred 5 hours, is made with 25 DEG C Pyrroles polymerization, thus obtain target, using is formed as the polypyrrole as electroconductive polymer shell covering nuclear particle made of Electroconductive resin particle (nucleocapsid particles).Obtained electroconductive resin particle is as follows: volume average particle size is 14.8 μm, volume base It is 1.4MPa that the coefficient of variation of quasi- partial size, which is 45%, 10% compressive strength,.
[conductance measurement]
The conductivity of electroconductive resin particle obtained in above-mentioned operation is measured, result is 2.4 × 10-2S/cm。
(embodiment 2)
[manufacture of nuclear particle]
Using 79 parts by weight of n-butyl acrylate replace 60 parts by weight of n-butyl acrylate, 15 parts by weight of methyl acrylate, With 10 parts by weight of 2-EHA, using ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd. " the Light Ester EG " made) 1 parts by weight and the ten tetraethylene glycol diformazans as monomer shown in above-mentioned logical formula (II) Base acrylate (" the Light Ester 14EG " of Kyoeisha Chemical Co., Ltd.) 15 parts by weight replace second two The dosage of benzoyl peroxide is changed to 0.3 parts by weight by 10 parts by weight of alcohol dimethylacrylate, and oil will be made mutually to be scattered in water Stirring condition when in phase is changed in addition to this, obtain similarly to Example 1 " with mixing speed 3500rpm, 5 minutes " The aqueous filter cake body of target nuclear particle.
[manufacture of electroconductive resin particle]
The nuclear particle that embodiment 1 is replaced using the aqueous filter cake body of nuclear particle obtained in above-mentioned operation, will obtain core In addition to this quantitative change more 25 parts by weight of the deionized water used when grain dispersion liquid obtain target similarly to Example 1 and lead Electrical resin particle.Obtained electroconductive resin particle is as follows: volume average particle size is the change of 15.4 μm, the partial size of volume reference Different coefficient is that 39%, 10% compressive strength is 2.3MPa.
[conductance measurement]
The conductivity of electroconductive resin particle obtained in above-mentioned operation is measured, result is 2.8 × 10-2S/cm。
(embodiment 3)
[manufacture of nuclear particle]
The aqueous filter cake body of target nuclear particle is obtained similarly to Example 1.
[manufacture of electroconductive resin particle]
Pyrroles is replaced using 3,4- ethyldioxythiophene, mixing time when polymerizeing is changed to 24 hours, except this it Outside, obtain similarly to Example 1 target, using by as electroconductive polymer poly- (3,4- ethyldioxythiophene) formation Shell covering nuclear particle made of electroconductive resin particle.Obtained electroconductive resin particle is as follows: volume average particle size is 16.2 μm, the coefficient of variation of the partial size of volume reference be 46%, 10% compressive strength be 2.5MPa.
[conductance measurement]
The conductivity of electroconductive resin particle obtained in above-mentioned operation is measured, result is 1.8 × 10-2S/cm。
(embodiment 4)
[manufacture of nuclear particle]
(soap-free polymerization)
In beaker, mixed in 15 parts by weight of methyl methacrylate as simple function (methyl) acrylate monomer As 0.2 parts by weight of n octylmercaptan of molecular weight regulator, oily phase is made.
It is being different from above-mentioned beaker, 0.1 parts by weight of potassium peroxydisulfate as polymerization initiator is made to be dissolved in ion friendship 80 parts by weight of water are changed, persulfate aqueous solution is prepared, above-mentioned oily phase is mixed in the persulfate aqueous solution, carries out 12 with 55 DEG C Hour soap-free polymerization.The dispersion liquid comprising the kind particle formed by polymethyl methacrylate is obtained as a result,.Obtained kind particle Volume average particle size be 0.51 μm.
(seeding polymerization)
It then, will be as 70 weight of n-butyl acrylate of simple function (methyl) acrylate monomer in new beaker Part, 5 parts by weight of methyl acrylate, 5 parts by weight of 2-EHA and poly- (ethylene glycol and 1,2-propylene glycol) monomethacrylate Ester (" Brenmar (registered trademark) 50PEP-300 " of Japan Oil Co) 5 parts by weight, as shown in above-mentioned logical formula (I) 10 parts by weight of ethylene glycol dimethacrylate of monomer and 2,2 '-azos as polymerization initiator are bis- (2- methylbutyronitrile) The mixing of 0.01 parts by weight.In obtained mixture, make two (2- ethylhexyl) sulfo groups as anionic surfactant 0.08 parts by weight of sodium succinate are dissolved in 80 parts by weight of ion exchange water as aqueous medium and obtain aqueous solution, by what is obtained Aqueous solution mixing, using homogenizer (PRIMIX Co. Ltd. system, desktop type, product name " 2.5 type of homogenizer MARKII "), with Mixing speed 8000rpm handle within 10 minutes, to obtain emulsion.
40 parts by weight of dispersion liquid comprising kind of particle that side stirring is obtained above by soap-free polymerization, while being added to the emulsification In liquid.After stirring 3 hours, ion exchange of the investment dissolved with 0.03 parts by weight of polyvinyl alcohol as macromolecular dispersion stabilizer 240 parts by weight of water, while being polymerize, obtained polymer emulsion are dehydrated by filtering while being stirred 6 hours with 60 DEG C Afterwards, residue is cleaned using ion exchange water, thus the aqueous filter cake body for the nuclear particle being had sharp grain size distribution.Obtained core The volume average particle size of particle is 1.2 μm.
[manufacture of electroconductive resin particle]
The nuclear particle that embodiment 1 is replaced using the aqueous filter cake body of nuclear particle obtained in above-mentioned operation, will make nuclear particle Dispersion, obtains quantitative change more 25 parts by weight of the deionized water used when nuclear particle dispersion liquid, in addition to this, same with embodiment 1 Obtain to sample target electroconductive resin particle.Obtained electroconductive resin particle is as follows: volume average particle size is 1.3 μm, volume The coefficient of variation of the partial size of benchmark is that 9%, 10% compressive strength is 1.4MPa.
[conductance measurement]
The conductivity of electroconductive resin particle obtained in above-mentioned operation is measured, result is 1.5 × 10-2S/cm。
(embodiment 5)
[manufacture of nuclear particle]
The dosage of NaLS is changed to 0.005 parts by weight, stirring when for being scattered in oil mutually in water phase, It is changed in addition to this, obtain mesh similarly to Example 1 without the use of homogenizer with mixing speed 200rpm progress 10 minutes Mark the aqueous filter cake body of nuclear particle.
[manufacture of electroconductive resin particle]
The nuclear particle of embodiment 1 is replaced using the aqueous filter cake body of nuclear particle obtained in above-mentioned operation, in addition to this, with Embodiment 1 gets similarly target electroconductive resin particle.Obtained electroconductive resin particle is as follows: volume average particle size is 198 μm, the coefficient of variation of the partial size of volume reference be 49%, 10% compressive strength be 1.7MPa.
[conductance measurement]
The conductivity of electroconductive resin particle obtained in above-mentioned operation is measured, result is 2.0 × 10-2S/cm。
(embodiment 6)
[manufacture of nuclear particle]
Using 45 parts by weight of n-butyl acrylate replace 60 parts by weight of n-butyl acrylate, 15 parts by weight of methyl acrylate, With 10 parts by weight of 2-EHA, urethane acrylate oligomer (product name " New frontier is used (registered trademark) RST-402 ", Di-ichi Kogyo Seiyaku Co., Ltd.'s system) 50 parts by weight replace ethylene glycol dimethacrylate 10 In addition to this parts by weight obtain the aqueous filter cake body of target nuclear particle similarly to Example 1.
[manufacture of electroconductive resin particle]
The nuclear particle that embodiment 1 is replaced using the aqueous filter cake body of nuclear particle obtained in above-mentioned operation, will make nuclear particle Dispersion obtains quantitative change more 25 parts by weight of the deionized water used when nuclear particle dispersion liquid, in addition to this, similarly to Example 1 Ground obtains target electroconductive resin particle.Obtained electroconductive resin particle is as follows: volume average particle size is 16.2 μm, volume base It is 1.2MPa that the coefficient of variation of quasi- partial size, which is 44%, 10% compressive strength,.
[conductance measurement]
The conductivity of electroconductive resin particle obtained in above-mentioned operation is measured, result is 2.6 × 10-2S/cm。
(embodiment 7)
[manufacture of nuclear particle]
The aqueous filter cake body of target nuclear particle is obtained similarly to Example 1.
[manufacture of electroconductive resin particle]
The nuclear particle that embodiment 3 is replaced using nuclear particle obtained in above-mentioned operation, will make nuclear particle disperse to obtain core In addition to this quantitative change more 50 parts by weight of the deionized water used when grain dispersion liquid obtain target similarly to Example 3 and lead Electrical resin particle.Obtained electroconductive resin particle is as follows: volume average particle size is the change of 16.5 μm, the partial size of volume reference Different coefficient is that 42%, 10% compressive strength is 1.2MPa.
[conductance measurement]
The conductivity of electroconductive resin particle obtained in above-mentioned operation is measured, result is 2.9 × 10-2S/cm。
(comparative example 1)
[manufacture of nuclear particle]
As simple function (methyl) acrylate monomer, the positive fourth of acrylic acid is replaced using 95 parts by weight of methyl methacrylate 60 parts by weight of ester, 15 parts by weight of methyl acrylate, 10 parts by weight of 2-EHA and poly- (ethylene glycol and 1,2-propylene glycol) list The dosage of ethylene glycol dimethacrylate is changed to 5 parts by weight by 5 parts by weight of methacrylate, in addition to this, with implementation Example 1 gets similarly nuclear particle.
[manufacture of electroconductive resin particle]
As the decentralized medium used when obtaining nuclear particle dispersion liquid, deionized water 50 is replaced using 25 parts by weight of isopropanol In addition to this parts by weight obtain electroconductive resin particle similarly to Example 1.The 10% of obtained electroconductive resin particle Compressive strength is 34.3MPa.
[conductance measurement]
The conductivity of electroconductive resin particle obtained in above-mentioned operation is measured, result is 2.2 × 10-3S/cm。
(comparative example 2)
Pyrroles is replaced using 3,4- ethyldioxythiophene, mixing time when polymerizeing is changed to 24 hours, except this it Outside, electroconductive resin particle is got similarly with comparative example 1.10% compressive strength of obtained electroconductive resin particle is 36.4MPa。
[conductance measurement]
The conductivity of electroconductive resin particle obtained in above-mentioned operation is measured, result is 2.2 × 10-3S/cm。
(comparative example 3)
[manufacture of nuclear particle]
In seeding polymerization, 70 parts by weight of n-butyl acrylate, acrylic acid are replaced using 70 parts by weight of methyl methacrylate 5 parts by weight of methyl esters, 5 parts by weight of 2-EHA and poly- (ethylene glycol and 1,2-propylene glycol) monomethacrylates (day oil strain " Brenmar (registered trademark) 50PEP-300 " of formula commercial firm) 5 parts by weight, ethylene glycol dimethacrylate is used into quantitative change In addition to this more 30 parts by weight obtain nuclear particle similarly to Example 4.The volume average particle size of obtained nuclear particle is 1.1μm。
[manufacture of electroconductive resin particle]
The nuclear particle of embodiment 4 is replaced using nuclear particle obtained in above-mentioned operation, in addition to this, similarly to Example 4 Ground obtains target electroconductive resin particle.Obtained electroconductive resin particle is as follows: volume average particle size is 1.2 μm, volume base It is 36.1MPa that the coefficient of variation of quasi- partial size, which is 9%, 10% compressive strength,.
[conductance measurement]
The conductivity of electroconductive resin particle obtained in above-mentioned operation is measured, result is 3.5 × 10-3S/cm。
By volume average particle size, the volume reference of electroconductive resin particle obtained in Examples 1 to 7 and comparative example 1~3 The coefficient of variation of partial size, 10% compressive strength and conductivity and nuclear particle manufacture used in monomer mixture composition The kind of monomer used in (composition in embodiment 4 and comparative example 3 for the monomer mixture of seeding polymerization) and the formation of shell Class is concluded shown in table 1 together.It should be noted that in table 1 n-butyl acrylate being abbreviated make " BA ", methyl acrylate respectively Brief note makees " MA ", 2-EHA brief note makees " 2EHA ", methyl methacrylate brief note makees " MMA ", poly- (ethylene glycol- Propylene glycol) monomethacrylates " Brenmar (registered trademark) 50PEP-300 ") brief note work " 50PEP-300 ", ethylene glycol two Methacrylate brief note makees " EGDMA ", ten tetraethylene glycol dimethylacrylates brief note makees " 14EG ", carbamate propylene Acid esters " New frontier (registered trademark) RST-402 " brief note makees " RST-402 ".
[table 1]
As it is above it is found that 10% compressive strength of the electroconductive resin particle of Examples 1 to 7 be 0.1~30MPa (1.2~ 2.5MPa), to be more than the electroconductive resin of the comparative example 1~3 of 30MPa (34.3~36.4MPa) with 10% compressive strength The conductivity (2.2~3.5 × 10 of grain-3S/cm it) compares, there is excellent conductivity (1.5~2.9 × 10-2S/cm)。
(embodiment 8)
Dissolved with the acrylic resin as binder resin in 50 parts by weight of toluene as organic solvent (Mitsubishi Chemical Corporation system, trade name " Dianal (registered trademark) BR-106 ") 10 parts by weight In binder solution, 10 parts by weight of electroconductive resin particle obtained in embodiment 1 are compounded, keep its evenly dispersed, preparation coating Agent.
Using 30 μm of applicator, which is coated on shape in the PET film as 100 μm of thickness of base film At film.2 hours are stood in 70 DEG C of high temperature slot, makes the dried coating film in PET film, to obtain conductive thin Film.
The present invention can be implemented in the case where not departing from its purport or main feature with various other ways.Therefore, on Embodiment example only simple in terms of all is stated, being not construed as limiting property is explained.Protection scope of the present invention is wanted by right It asks represented by book, not by any constraint of specification text.Further belong to deformation, the change of the equivalency range of claims In all protection scope of the present invention.
In addition, this application claims the priority based on the September 30th Patent 2016-194260 in Japanese publication in 2016. By mentioning wherein, so that entire contents are introduced in the application.

Claims (10)

1. a kind of electroconductive resin particle comprising:
Nuclear particle is formed by polyme；With,
Shell covers the nuclear particle and is formed by electroconductive polymer,
The compressive strength when compressive deformation 10% of the electroconductive resin particle is 0.1~30MPa.
2. electroconductive resin particle according to claim 1, which is characterized in that
The polymer contains: the monomer comprising monomer shown in simple function (methyl) acrylate monomer and the following general formula (I) The polymer of mixture,
CH2=C (R1)-COO-(CH2CH2O)n-CO-C(R1)=CH2…(I)
In formula, R1For hydrogen or methyl, the integer that n is 1~4.
3. electroconductive resin particle according to claim 2, which is characterized in that
The monomer mixture further includes monomer shown in the following general formula (II),
CH2=C (R2)-COO-(CH2CH2O)m-CO-C(R2)=CH2…(II)
In formula, R2For hydrogen or methyl, the integer that m is 5~15.
4. electroconductive resin particle described in any one of claim 1 to 3, which is characterized in that
The electroconductive polymer is in the group being made of nitrogenous heteroaromatic compound and sulfur-bearing heteroaromatic compound At least one kind of monomer polymer.
5. electroconductive resin particle according to any one of claims 1 to 4, which is characterized in that
With 1~200 μm of volume average particle size.
6. electroconductive resin particle according to any one of claims 1 to 5, which is characterized in that
The coefficient of variation of the partial size of volume reference is 10% or more.
7. a kind of conductive resin composition is, characterized by comprising: electric conductivity tree according to any one of claims 1 to 6 Rouge particle；With matrix resin.
8. a kind of coating agent is, characterized by comprising: electroconductive resin particle according to any one of claims 1 to 6；With, Binder resin.
9. a kind of film, which is characterized in that include electroconductive resin particle according to any one of claims 1 to 6.
10. a kind of clearance material, which is characterized in that include electroconductive resin particle according to any one of claims 1 to 6.
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