CN101142239A - Spherical polymer fine particles and process for production thereof - Google Patents

Abstract

Spherical polymer fine particles which exhibit, when the compression/elastic deformation characteristic of one particle at X% deflection of particle diameter, K<SUB>x,</SUB> is defined by the formula [1]: K<SUB>X</SUB>=(3/v2)(S<SUB>X</SUB> <SUP>-3/2</su.

Description

Spherical polymer fine particles and preparation method thereof

Technical field

The present invention relates to spherical polymer fine particles and preparation method thereof.

Background technology

Recently, at the using polymer fine particle, and at electro-conductive material, comprise the dividing plate of liquid-crystal display in electrician and field of electronic materials, electroconductive binder is used in the microdevice assembling, obtains practical application in anisotropic electroconductive binder and the conduction connecting structure.

Require to have good connection resistance and connection reliability because be used for the conductive fine particle of these electro-conductive materials, although that yes is important so control is as the particle diameter of the polymer fine particles of matrix, and the character such as deformation-recovery rate after control example such as pellet hardness, elastic properties, the compression displacement also are important.

Hitherto known matrix polymer particle comprises following.

For example, patent documentation 1 (JP-A 62-185749) and patent documentation 2 (JP-A 1-225776) disclose conductive micro-balloons, and wherein polyphenylene sulfide particle or phenolic acid resin particle are used as the core microballoon.

Wherein such replys rate variance with pellets of synthetic resins as the compression set of the conductive micro-balloons of core microballoon.Therefore, when these conductive micro-balloons were used to carry out interelectrode connection, the removing of compressive load that acts on two electrodes caused forming slight void at the interface between conductive micro-balloons and electrode surface, and the result connects bad.

The soft low density cross-linked material that patent documentation 3 (JP-B 5-19241) discloses by will mainly being formed by vinylbenzene forms core particle, thereby obtains conductive fine particle with electro-conductive material painting core particulate surface then.

Yet the response rate that contains like this after the conductive fine particle compression set of soft nuclear only has 10% or lower, in addition and also this as time passes restoring force reduce.Therefore,, connect resistance as time passes and increase, cause connection reliability poor even when the conductive fine particle with soft nuclear is used for interelectrode connection.

Patent documentation 4 (JP-B 7-95165) and patent documentation 5 (JP-A 2000-309715) disclose conductive fine particle, the core particle that compressive modulus of elasticity when it uses particle diameter 10% displacement and compression set response rate control to preset value.Patent documentation 6 (JP-A 2003-313304) discloses the conductive fine particle by polymer manufacture, wherein use Vinylstyrene-ethyl vinyl benzol mixture as a monomeric part, and its particle diameter in displacement 10% time compressive modulus of elasticity, compression set response rate and breaking strain control to preset value.

But because all these conductive fine particles all demonstrate breaking point when compression displacement surpasses 50% basically, it is difficult increasing the deformation-recovery rate when suffering from the high compression displacement.And during plating is handled (forming conductive coating in this process), core particle is subjected to the chemical etching of acid or alkaline media easily, and consequently plated metal peels off with disruptive trend increases.

From above obviously finding out, have good high compression deformation-recovery rate and can demonstrate the surface area contacted conductive fine particle that between conductive particle and electrode surface, increases also not by known to the people.

Patent documentation 1:JP-A 62-185749

Patent documentation 2:JP-A 1-225776

Patent documentation 3:JP-B 5-19241

Patent documentation 4:JP-B 7-95165

Patent documentation 5:JP-A 2000-309715

Patent documentation 6:JP-A 2003-313304

Summary of the invention

Therefore, the object of the invention provides has suitable stiffness and elastic spherical polymer fine particles, it can eliminate the disadvantageous effect bad owing to contacting, that swipe and break and cause that produces when too hard polymer fine particles uses, and observed because the disadvantageous effect that the reduction of compression set response rate produces in too soft polymer fine particles uses.Another order of the present invention provides the method for the such spherical polymer fine particles of preparation.

Result as broad research, the inventor has been found that the spherical polymer fine particles of having given the elasticity that suitable hardness becomes reconciled and therefore not had the problems referred to above, wherein supposes at the displacement of the particle diameter elasticity of compression deformation characteristic K at the individual particle at X% place _xDefine with following formula:

K _x＝(3/)·(S _x ^-3/2)·(R ^-1/2)·F _x (1)，

F wherein _xBe the desired load of particulate X% displacement (N), S _xBe that R is particle radius (mm) in the compression set (mm) of particulate displacement at the X% place, when 20 ℃ are measured in the displacement of particle diameter at 60% elasticity of compression deformation characteristic K ₆₀Be 1,000 to 12,000N/mm ², be at least 20% in the displacement of particle diameter 60% o'clock particle diameter response rate 20 ℃ of mensuration.The inventor also finds by with the method for solution polymerization control particle, can be easily and obtain these particles effectively.

Therefore, the invention provides following content.

(1) spherical polymer fine particles is characterized in that,

Suppose at the displacement of particle diameter elasticity of compression deformation characteristic K at the individual particle of X% _xDefine with following formula:

K _x＝(3/)·(S _x ^-3/2)·(R ^-1/2)·F _x (1)，

F wherein _xBe the load (N) of particulate X% displacement request, S _xBe that R is particle radius (mm) in the compression set (mm) of particulate displacement at X%, 20 ℃ of mensuration in the displacement of particle diameter at 60% elasticity of compression deformation characteristic K ₆₀Be 1,000 to 12,000N/mm ², be at least 20% in the displacement of particle diameter 60% o'clock particle diameter response rate 20 ℃ of mensuration.

(2) spherical polymer fine particles of (1) is characterized in that within many 60% scopes of being moved to of particle diameter the flex point that does not exist breakpoint or compression deformation rate sharply to increase.

(3) spherical polymer fine particles of (1) or (2) is characterized in that when the compressive load for individual particle was 9.8mN (1gf), this particulate compression displacement was at least 40%.

(4) (1) to (3) any one spherical polymer fine particles is characterized in that the K in the formula (1) ₂₀And K ₃₀K satisfies condition ₂₀〉=K ₃₀

(5) (1) to (4) any one spherical polymer fine particles is characterized in that average particulate diameter between 0.1 to 100 μ m, and the coefficient of variation Cv of particle diameter is 20% to the maximum.

(6) (1) to (5) any one spherical polymer fine particles, it is characterized in that using at least, the monomer with two or more unsaturated double-bonds of 35wt% obtains described spherical fine particle.

(7) spherical polymer fine particles of (6) is characterized in that the monomer with two or more unsaturated double-bonds comprises at least a monomer that is selected from Vinylstyrene and multifunctional (methyl) acrylate monomer.

(8) spherical polymer fine particles of (7) is characterized in that multifunctional (methyl) acrylate monomer comprises at least a monomer that is selected from two (methyl) acrylate monomer.

(9) spherical polymer fine particles of (8) is characterized in that described two (methyl) acrylate monomer is C _6-18Alkanediol two (methyl) acrylate.

(10) prepare the method for spherical polymer fine particles, it is characterized in that in solvent, implementing the solution polymerization of starting monomer, described starting monomer comprises 35wt% or more contains the monomer with two or more unsaturated double-bonds that is selected from multifunctional (methyl) acrylate monomer, and described dissolution with solvents starting monomer is not lysigenous particle still.

(11) method for preparing spherical polymer fine particles of (10) is characterized in that the monomer with at least two unsaturated double-bonds comprises the monomer that two or more are different.

(12) method for preparing spherical polymer fine particles of (10) or (11) is characterized in that multifunctional (methyl) acrylate monomer comprises at least a monomer that is selected from two (methyl) acrylate monomer.

(13) (10) to (12) any one method for preparing spherical polymer fine particles is characterized in that except the monomer with at least two unsaturated double-bonds, contains the polymerisable monomer of the copolymerization with it of 5-60wt%.

Spherical polymer fine particles of the present invention has elasticity of compression deformation characteristic K in 60% of the displacement of particle diameter ₆₀From 1,000 to 12,000N/mm ², be at least 20% (both are all 20 ℃ of mensuration) 60% o'clock particle diameter response rate in the displacement of particle diameter.Therefore, although polymer fine particles of the present invention has big compressive modulus of elasticity, even but 60% or also be soft during bigger compression displacement and have good compression set response rate, therefore be suitable as the core of electro-conductive material electricity and field of electronic materials, for example be used as the dividing plate and the conductive fine particle of liquid-crystal display.

Especially; the conductive fine particle that is obtained by spherical polymer fine particles of the present invention has good connection resistance and connection reliability; therefore, be suitable as electro-conductive material at the electroconductive binder, anisotropic-electroconductive adhesive and the conduction connecting structure that are used for microdevice assembling.

Description of drawings

Fig. 1 is the scanning electron photomicrograph from the spherical polymer fine particles of embodiment 1 acquisition.

The compressive load of the spherical polymer fine particles that Fig. 2 obtains for embodiment 1 for expression is for the figure of compression displacement experimental result.

The spherical polymer fine particles load that Fig. 3 obtains for embodiment 1 for expression/unloading experiment (60% compression displacement) result's figure.

The spherical polymer fine particles load that Fig. 4 obtains for embodiment 1 for expression/unloading experiment (65% compression displacement) result's figure.

The spherical polymer fine particles load that Fig. 5 obtains for embodiment 1 for expression/unloading experiment (70% compression displacement) result's figure.

Embodiment

Hereinafter the present invention is more at large described.

Spherical polymer fine particles of the present invention is supposed at the elasticity of compression deformation characteristic K of particle diameter displacement at per 1 particle of X% _xDefine with following formula:

K _x＝(3/)·(S _x ^-3/2)·(R ^-1/2)·F _x (1)，

F wherein _xBe the load (N) of particulate X% displacement request, S _xBe that R is particle radius (mm) in the compression set (mm) of particulate displacement at X%, 20 ℃ of mensuration in the displacement of particle diameter at 60% elasticity of compression deformation characteristic K ₆₀Be 1,000 to 12,000N/mm ², be at least 20% in the displacement of particle diameter 60% o'clock response rate 20 ℃ of mensuration.

Herein, " displacement is at 60% elasticity of compression deformation characteristic K when particle diameter ₆₀" (also being shown " 60%K value " hereinafter) be meant and using the minute-pressure experiment instrument (MCT-W201, SHimadzu company make) that contracts; smooth, the smooth end surface that is had the diamond penetrator of 50 μ m diameters when the fine particle that obtains is 0.225g/s when compressing at compressive hardness, measures the back values that obtain according to following formula such as load, compression displacement:

K ₆₀＝(3/)·(S ₆₀ ^-3/2)·(R ^-1/2)·F ₆₀

Wherein, F ₆₀It is the load (N) of particulate 60% displacement request

S ₆₀Be in 60% compression set (mm) in the particulate displacement

R is particle radius (mm).

K _xValue has been expressed fine grain hardness at large and quantitatively.By as the present invention, using the 60%K value, can be quantitatively and express displacement clearly in 60% fine grain suitable hardness.

Spherical polymer fine particles of the present invention, less than 2,000N/mm ²60%K value (K ₆₀) under, granule strength may reduce, yet, surpassing 15,000N/mm ², particle may lack enough flexible.

Therefore, 60%K value (K ₆₀) preferably 2,600 and 9,000N/mm ²Between, more preferably 3,200 and 8,000N/mm ²Between, most preferably 4,000 and 7,500N/mm ²Between.

In the displacement of particle diameter percentage response rate (also being known as " 60% compression set response rate " hereinafter),, be at least 20%, between preferred 20 and 80%, more preferably between 25 and 65% when when measuring for 20 ℃ at 60% o'clock.

Percentage response rate after compression displacement was less than 20% o'clock, and the spherical polymer fine particles of acquisition has low elasticity.For example, when the conductive fine particle of being made up of such polymer fine particles is used for connecting between electrode, the possibility that exists connection reliability to reduce.The upper limit of percentage response rate is preferably 100% response rate, although be limited to 90% or lower on actual.

Herein, " 60% compression set response rate " is meant to work as and uses above-mentioned compression experiment instrument that fine particle is compressed to 60% of particle diameter, when reducing load then, by measuring the value of the relation acquisition between load value and the compression displacement.By the initial point load value being set at 0.02gf (0.196mN), the compression speed in load and when unloading being set at 0.145gf/s (1.421mN/s), terminal point when measuring unloading, measure this value, express up to the displacement (L1) of inversion point and from inversion point to load with per-cent (%) and to return the ratio L2/L1 of displacement between the initial value point (L2), obtain described value.

Can expect that particle may produce bigger compression displacement.Even in this case for can keep elasticity, the compression displacement response rate of spherical polymer fine particles of the present invention to following degree is favourable: the displacement of particle diameter is in 65% response rate at least 20%, preferred 20-70%, more preferably 25-55%.In addition, the displacement of particle diameter is in 70% response rate at least 15%, preferred 20-60%, more preferably 21-45%.

In these cases, for 65%K value (K ₆₅) and 70%K value (K ₇₀) drop on and above-mentioned 60%K value (K ₆₀) identical scope is favourable.

Because spherical polymer fine particles of the present invention has at least 20% compression deflection characteristics at least 60% the time in the displacement of particle diameter; for example when using anisotropic-electroconductive adhesive material (anisotropic conductive film; anisotropic conducting film) will be applied to by the conductive fine particle that these polymer fine particles obtain between electrode conduction in conjunction with the time, can prevent electrode or base plate deformation or damage.And, when keeping the electrode hole, can increase conductive surface area, so connection reliability strengthens.

In addition, preferred spherical polymer fine particles of the present invention within many 60% scopes of being moved to of particle diameter, preferred displacement at the most 65%, the flex point that does not exist breakpoint or compression deformation rate sharply to increase.

That is to say that preferred spherical polymer fine particles of the present invention is not to destroy the back to reply or surpass answer after the flex point displacement from the answer of elastic displacement, but the answer that in the elastic limit scope, produces (elastic recovery).

Especially, when each particulate compressive load was 1gf (9.8mN), the particulate compression displacement was preferably at least 40%.By make particle in this mode is soft and elastic (hereinafter being referred to as the quality of " soft elasticity "), and the connection reliability of above-mentioned conductive fine particle further strengthens.Compression displacement preferably at least 45%, more preferably at least 50%, most preferably at least 54%.

Can expect described particle is applied to even the purposes of bigger compressive load.Under these circumstances, in order to keep soft elasticity, in the compression displacement of 1.5gf (14.7mN) preferably at least 45%.Compression displacement more preferably at least 50%, even more preferably at least 55%, most preferably at least 60%.

For the purposes that requires bigger hardness, the principal character of spherical polymer fine particles of the present invention is not only them soft elasticity, and they can keep resisting fully each particle 1.8gf (17.6mN) or bigger compressive load and not have the hardness of the flex point that breakpoint or compression deformation rate sharply increase, in some cases, can keep to resist 2.0gf (19.6mN) or bigger fully, even 2.2.gf (21.6mN) or bigger, sometimes even up to the hardness of 2.4gf (23.5mN) or bigger compressive load.The size of particle diameter is depended in the variation of the upper limit basically, although from the fine grain application point of the present invention, the enough actual purpose of the upper limit of 5.0gf (49mN) need.

And, in order to obtain soft elasticity, and therefore further strengthen the connection reliability of above-mentioned conductive fine particle, in above-mentioned formula (1), the displacement of preferred particulates diameter is at 20% elasticity of compression deformation characteristic K ₂₀The displacement of (also being known as " 20%K value " hereinafter) and particle diameter is at 30% elasticity of compression deformation characteristic K ₃₀K satisfies condition (also being known as " 30%K value " hereinafter) ₂₀〉=K ₃₀

The average particulate diameter of spherical polymer fine particles of the present invention is from 0.1 to 100 μ m preferably, more preferably from 0.2 to 30 μ m, even more preferably from 0.3 to 20 μ m.During less than 0.1 μ m, fine particle has the tendency of cohesion at average particulate diameter.On the other hand, having the particle that average particulate diameter surpasses 100 μ m seldom uses.

The coefficient of variation of particle diameter (Cv value) preferably is no more than 20%.Surpass at 20% o'clock in the Cv value, the performance of spherical polymer fine particles in application may reduce (for example, may reduce, and quantitative property may reduce in examination of living tissue (biopsy) equipment) on connection reliability when making conductive fine particle.The Cv value of particle diameter preferably is no more than 12%, more preferably no more than 8%, is most preferably not exceeding 5%.

In enforcement of the present invention, " Cv value " is meant the coefficient of variation of determining by following equation.

Cv value (%)=[(particle diameter standard deviation)/(average particulate diameter)] * 100

The average particulate diameter of as above mentioning is the mean value that obtains by the following method: use the scanning electronic microscope (S-4800 that Hitachi company limited makes; Hereinafter be called " SEM ") particle (n=300) is taken a picture can measuring under the magnification (from 300 to 200,000 times), on the two dimensional image that obtains, measure particle diameter.The Cv value of as above mentioning (%) is the standard deviation of the particle diameter of calculating thus.

The material of preparation spherical polymer fine particles of the present invention is not subjected to any specific restriction as long as it is macromolecular compound (resin) composition that obtains by the polymerisable monomer polymerization.Exemplary example comprises styrene resin, acrylic resin, methacrylic resin, polyvinyl resin, acrylic resin, silicone resin, vibrin, urethane resin, polyamide resin, Resins, epoxy, polyvinylbutyral resin, Gum Rosin, terpene resin, resol, melamine resin, guanamine resin,  azoles quinoline resin, carbodiimide resin and the cured resin that aforementioned any polymkeric substance is obtained through crosslinking reaction.These materials can use separately or be used in combination as two or more.

The method for preparing spherical polymer fine particles of the present invention is not subjected to any specific restriction, as long as the spherical polymer fine particles that this method can obtain to have above-mentioned character.But but preferable methods is to finish the method for the solution polymerization of starting monomer in solvent, and described starting monomer comprises the monomer that 35wt% at least has two or more unsaturated double-bonds, described solvent solubilized starting monomer not lysigenous particle.

Solution polymerization can exemplify emulsion or the suspension polymerization of (1) carrying out in the aqueous solution; (2) dispersion polymerization of in the organic solvent of non-water or water and non-aqueous organic solvent mixture, in the presence of dispersion agent, carrying out; (3) method that the method for above-mentioned (1) or (2) is combined with the crystal seed polymerization.Preferred using dispersion polymerization, is easy because handle in the operation subsequently of washing etc., and granular size is controlled easily.Can also suitably use, for example in document (Journal of Polymer Science.Part A:Polymer Chemistry (U.S.), 31,3257 (1993)), describe based on diffuse-aggregate precipitation polymerization process.

In enforcement of the present invention, if the monomer content that contains at least two unsaturated double-bonds in the starting monomer less than 35wt%, the percentage response rate of the spherical polymer fine particles that obtains after the high compression distortion may reduce.For example, in the time will being used for connecting between electrode by the conductive fine particle that polymer fine particles of the present invention obtains, As time goes on connecting resistance may increase, and causes connection reliability bad.Be further to increase elastic recovery rate, preferably comprise monomer ratio in the starting monomer preferably from 40 to 95wt% with at least two unsaturated link(age)s, more preferably from 45 to 90wt%, most preferably from 55 to 85wt%.

Monomer with at least two unsaturated double-bonds is not done any specific restriction.Operable such monomer suitably is selected from known polyfunctional vinyl monomer and multifunctional (methyl) acrylate derivative.

Exemplary example comprises Vinylstyrene; Divinyl biphenyl; The divinyl naphthalene; (gathering) aklylene glycol two (methyl) acrylate for example (gathers) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate and (gathering) tetramethylene glycol two (methyl) acrylate; Alkanediol two (methyl) acrylate, for example 1,6-hexylene glycol two (methyl) acrylate, 1,8-ethohexadiol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-decanediol two (methyl) acrylate, 1,12-dodecanediol two (methyl) acrylate, the 3-methyl isophthalic acid, 5-pentanediol two (methyl) acrylate, 2,4-diethyl-1,5-pentanediol two (methyl) acrylate, butyl ethyl propylene glycol two (methyl) acrylate, the 3-methyl isophthalic acid, 7-ethohexadiol two (methyl) acrylate and 2-methyl isophthalic acid, 8-ethohexadiol two (methyl) acrylate; Dimethyltrimethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetra methylol propane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, cyclohexanedimethanol two (methyl) acrylate of ethoxylation, dihydroxyphenyl propane two (methyl) acrylate of ethoxylation, tristane dimethanol two (methyl) acrylate, dihydroxyphenyl propane two (methyl) acrylate of propenoxylated ethoxylation, 1,1,1-three (hydroxymethyl ethane) two (methyl) acrylate, 1,1,1-three (hydroxymethyl ethane) three (methyl) acrylate, 1,1,1-three (hydroxymethyl propane) triacrylate, diallyl phthalate and isomer thereof and cyanacrylate and derivative thereof.These can use separately or two or more being used in combination.

The example of name of product comprise the NK ester that Shin-Nakamura chemistry company limited produces (A-TMPT-6P0, A-TMPT-3E0, A-TMM-3LMN, A-GLY series, A-9300, AD-TMP, AD-TMP-4CL, ATM-4E, A-DPH).These monomers can use separately or two or more are used in combination.

In above-mentioned monomer, the preferred monomer that uses comprises at least a monomer that is selected from Vinylstyrene and multifunctional (methyl) acrylate.Can easily increase in high compression distortion back response rate by the spherical polymer fine particles that uses these monomers to obtain.

Be the response rate that the spherical polymer fine particles that further has increased access to is out of shape from high compression, the preferred monomer that comprises two (methyl) acrylate monomer that uses more preferably uses to comprise C _6-18The monomer of alkane diol two (methyl) acrylate most preferably uses to comprise C _8-12The monomer of alkane diol two (methyl) acrylate.

For keeping elasticity of compression characteristic K _xAnd the balance between the response rate after the high compression distortion, it is suitable using the multipolymer of Vinylstyrene and multifunctional (methyl) acrylate monomer.

Except that monomer, can also and use the polymerisable monomer of copolymerization with it with two or more unsaturated double-bonds.

The ratio that can be included in the polymerisable monomer in the starting monomer is the arbitrary proportion of 0-65wt%.But, preferably measure for adapting to above-mentioned monomer with two or more unsaturated double-bonds, the amount of the polymerisable monomer that comprises is preferably from 5 to 60wt%, more preferably from 10 to 55wt%, in addition more preferably from 15 to 45wt%.

The illustrative example of polymerisable monomer comprises (i) distyryl compound, for example vinylbenzene, o-methyl styrene, a vinyl toluene, p-methylstyrene, alpha-methyl styrene, adjacent ethyl styrene, an ethyl styrene, to ethyl styrene, 2, the 4-dimethyl styrene, align butylstyrene, to t-butyl styrene, to positive hexyl phenenyl ethene, to n-octyl vinylbenzene, align nonyl benzene ethene, align decyl vinylbenzene, align dodecyl vinylbenzene, to methoxy styrene, to styryl phenyl, to chloro-styrene and 3, the 4-dichlorostyrene; (ii) (methyl) acrylate, for example methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, Ethyl acrylate, the 2-ethylhexyl acrylate, the vinylformic acid n-octyl, the dodecyl acrylate, the bay alkyl acrylate, the octadecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-Lv Bingxisuanjiazhi, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, propyl methacrylate, N-Hexyl methacrylate, 2-ethylhexyl methacrylic ester, n octyl methacrylate, the dodecyl methyl acrylate, methacrylic acid bay alkyl ester and methacrylic acid stearyl; (iii) vinyl ester, for example vinyl-acetic ester, propionate, vinyl benzoate and vinyl butyrate; (iv) N-vinyl compound, for example N-vinyl pyrrole, N-vinylcarbazole, N-vinyl indoles and N-vinyl pyrrolidone; (v) vinyl fluoride, vinylidene, tetrafluoroethylene, R 1216 and have (methyl) acrylate of fluoroalkyl group, for example trifluoroethyl acrylate and tetrafluoro propyl group acrylate; (vi) conjugated diolefine, for example divinyl and isoprene.These compounds can be used alone or two or more are used in combination.

In these compounds, preferably use styrenic, (methyl) esters of acrylic acid and vinyl ester as polymerisable monomer.By using these, can easily obtain to have the spherical polymer particles of above-mentioned character.

Except that above-mentioned polymerisable monomer, can also use unsaturated monomer with hydrophilic functional groups or active hydrogen group.Hydrophilic functional groups or active hydrogen group can exemplify amino group, carboxylic group, oh group, thiol group group, carbonyl group, ether group, cyano group, amide group, sulfonic acid group, phosphate group, quaternary ammonium (salt) group and alkylene oxide group.This unsaturated monomer can only have a kind of of aforementioned functional groups, or has two or more dissimilar functional groups of aforementioned functional groups.

Example with unsaturated monomer of such hydrophilic functional groups or active hydrogen group comprises following material.In the explanation hereinafter, " C " represents carbon atom.

(1) has the monomer of amino group

Example comprises the alkyl derivative that has amino group of acrylic or methacrylic acid, for example amino-ethyl acrylate, N-propyl group amino-ethyl acrylate, N-ethylamino propyl group (methyl) acrylate, N-phenyl amino ethyl (methyl) acrylate and N-cyclohexyl amino-ethyl (methyl) acrylate; Allyl amine and allyl amine derivative, for example N-methacrylic amine; The styrene derivatives that has amino group, for example p-aminophenyl ethene; And pyrrolotriazine derivatives, 2-vinyl-4 for example, 6-diamino-S-triazine.In these compounds, preferably has the compound of primary amino and secondary amino group.These compounds can use separately or two or more are used in combination.

(2) have the monomer of carboxylic group

The monomeric example that has carboxylic group comprises unsaturated carboxylic acid, for example vinylformic acid, methacrylic acid, Ba Dousuan, styracin, methylene-succinic acid, toxilic acid and fumaric acid; List (the C of methylene-succinic acid _1-8Alkyl) ester, for example methylene-succinic acid mono; List (the C of toxilic acid _1-8Alkyl) ester, for example butyl maleate; The aromatic carboxylic acid that has vinyl groups, for example vinyl benzoic acid; Salt with above-mentioned acid.These compounds can be used alone or two or more are used in combination.

(3) have the monomer of oh group

The example that has oh group comprises hydroxyl (methyl) Acrylic Acid Monomer, for example 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate and 4-hydroxybutyl (methyl) acrylate; (gathering) aklylene glycol (methyl) Acrylic Acid Monomer for example (gathers) glycol monomethyl (methyl) acrylate and (gathering) propylene glycol list (methyl) acrylate; Hydroxyalkyl vinyl ether monomers, for example hydroxyethyl vinyl ether and hydroxybutyl vinyl ether; With the allyl monomer that has oh group, for example allyl alcohol and 2-hydroxyethyl allyl ethers.These compounds can be used alone or two or more are used in combination.

(4) have the monomer of mercaptan (sulfydryl) group

Example comprises 2-mercaptoethyl (methyl) acrylate, 2-sulfydryl-1-carboxy ethyl (methyl) acrylate, N-(2-mercaptoethyl) acrylamide, N-(2-sulfydryl-1-carboxy ethyl) acrylamide, N-(2-mercaptoethyl) Methacrylamide, N-(4-sulfydryl phenyl) acrylamide, N-(7-sulfydryl naphthyl) acrylamide and single (2-mercaptoethyl acid amides) maleic acid ester.

(5) have the monomer of carbonyl group

Example comprises vinyl ketone, for example ethenyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone.

The compound of each the above-mentioned type can be used alone or two or more are used in combination.

(6) have the monomer of ether group

Example comprises the monomer of vinyl ether type, for example vinyl methyl ether, EVE and vinyl isobutyl ether etc.

(7) have the monomer of cyano group

Example comprises vinyl cyanide, methacrylonitrile, hexene nitrile, allyl acetonitrile and to cyano-styrene etc.

The compound of each the above-mentioned type can be used alone or two or more are used in combination.

(8) have the monomer of amide group

Example comprises (methyl) acrylamide, α-ethyl (methyl) acrylamide, N-methyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, two acetone (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, the N-dimethyl-to the vinylbenzene sulphonamide, N, N-dimethyl aminoethyl (methyl) acrylamide, N, N-diethylamino ethyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide and N, N-diethylamino propyl group (methyl) acrylamide.These compounds can be used alone or two or more are used in combination.

(9) have the monomer of sulfonic acid group

Example comprises alkene sulfonic acid for example ethylidene sulfonic acid, vinyl sulfonic acid and (methyl) allyl sulphonic acid; Aromatic sulphonic acid, for example styrene sulfonic acid and alpha-methyl styrene sulfonic acid; C _1-10Alkyl (methyl) allyl group sulfosuccinate; Sulfo group-C _2-6Alkyl (methyl) acrylate, for example sulfo group propyl group (methyl) acrylate; With the unsaturated ester that has sulfonic acid group; for example methyl ethylene sulphonate, 2-hydroxyl-3-(methyl) acryloxy propyl sulfonic acid ester, 2-(methyl) acryl amino-2; 2-dimethyl ethane sulfonic acid, 3-(methyl) acryl oxygen base ethane sulfonic acid, 3-(methyl) acryl oxygen base-2-hydroxypropanesulfonic acid, 2-(methyl) acrylamido-2-methyl propane sulfonic acid and 3-(methyl) acrylamido-2-hydroxypropanesulfonic acid, and salt.

(10) have the monomer of phosphate group

Example comprises (methyl) vinylformic acid hydroxyalkyl phosphate monoester, and 2-hydroxyethyl (methyl) acryl phosphoric acid ester and phenyl-2-acryl oxygen base ethyl phosphonic acid ester for example has the unsaturated ester of phosphate group, for example vinyl phosphoric acid, and salt.

The compound of each the above-mentioned type can be used alone or two or more being used in combination.

(11) have the monomer of quaternary ammonium (salt) group

Example comprises by quaternizing agent C for example _1-12Alkyl chloride, dialkyl group sulfuric acid, dialkyl carbonate or the quaternised tertiary amine of benzyl chloride.

Exemplary example comprises the quaternary ammonium salt of alkyl (methyl) acrylate type, for example chlorination 2-(methyl) acryl oxygen base ethyl trimethyl ammonium, bromination 2-(methyl) acryl oxygen base ethyl trimethyl ammonium, chlorination (methyl) acryl oxygen base ethyl triethyl ammonium, chlorination (methyl) acryl oxygen base ethyl dimethyl benzyl ammonium, chlorination (methyl) acryl oxygen base ethyl-methyl morpholino ammonium; The quaternary ammonium salt of alkyl (methyl) acrylamide type, for example chlorination (methyl) acryl amino-ethyl trimethyl ammonium, bromination (methyl) acryl amino-ethyl trimethyl ammonium, chlorination (methyl) acryl amino-ethyl triethyl ammonium and chlorination (methyl) acryl amino-ethyl dimethyl benzyl ammonium; With dimethyl diallyl methylsulfuric acid ammonium, chlorination trimethyl-ethylene base phenyl ammonium, the tetrabutyl (methyl) ammonium acrylate, trimethyl benzyl (methyl) ammonium acrylate and 2-(methacryloyl oxygen base) ethyl-trimethyl dimethyl ammonium phosphate.These compounds can be used alone or two or more are used in combination.

(12) have the monomer of alkylene oxide group

Example comprises (gathering) aklylene glycol (methyl) Acrylic Acid Monomer, for example (gathers) glycol monomethyl (methyl) acrylate and (gathering) propylene glycol list (methyl) acrylate; And alkoxyl group (gathering) aklylene glycol (methyl) Acrylic Acid Monomer, for example methoxyl group (gathering) glycol monomethyl (methyl) acrylate and methoxyl group (gathering) propylene glycol list (methyl) acrylate.These compounds can be used alone or two or more are used in combination.

In the above-mentioned unsaturated monomer that has hydrophilic functional groups or an active hydrogen group, monomer with the functional group that is selected from oh group, carboxylic group, amino group, amide group and alkylene oxide group is preferred, and the monomer with the functional group that is selected from oh group, carboxylic group and ethylene oxide group is preferred.By using these functional groups, repulsive interaction enhancing in solution has increased dispersion stabilization between the particle that obtains, and makes that further strengthening monodispersity becomes possibility.Make conversely thus because the situation of the granular size accuracy variation that viscosity and cohesion cause reduces, also make to obtain being endowed the dispersed and good powder dispersiveness of excellent heat resistance, chemical-resistant, reactivity and solution and the spheric polymer fine particles of mechanical property becomes possibility.

And, be fit to become water soluble compounds for the unsaturated monomer that contains hydrophilic functional groups or active hydrogen group.By using water-soluble monomer, the monodispersity of as above mentioning can further improve, and the polymer fine particles that obtains can single dispersion in water or water medium easily.

The polymerization starter that uses is not subjected to any specific restriction, can suitably be selected from known radical polymerization initiator.Exemplary example comprises benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, persulphate, for example Sodium Persulfate and ammonium persulphate, and azo-compound, for example Diisopropyl azodicarboxylate, azo nitrile dimethyl and 2,2'-Azobis(2,4-dimethylvaleronitrile).These compounds can be used alone or two or more are used in combination.The such radical polymerization initiator that in per 100 weight part starting monomers, comprises from 0.1 to 50 weight part in general.

Be used for synthetic solvent (medium) and be not subjected to any specific restriction, can be dissolving raw material monomer but any solvent of not lysigenous particulate.Preferably from common solvent, select to be fit to the solvent of raw material and the use of other composition.

Operable solvent comprises water and alcohol, for example methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, primary isoamyl alcohol, tertiary amyl alcohol, 1-hexanol, 2-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2-ethyl butanol, 1-enanthol, 2-enanthol, 3-enanthol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, benzylalcohol and hexalin; Ether alcohol, for example methylcyclohexane, ethyl cellosolve, ispropyl cellosolve, ethylene glycol butyl ether, diethylene glycol monoethyl ether and Diethylene Glycol single-butyl ether; Ketone, for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and pimelinketone; Ester, for example ethyl acetate, butylacetate, ethyl propionate, (alkyl) cellosolve acetic ester, TC acetic ester and Diethylene Glycol single-butyl ether acetic ester; Fat or aromatic hydrocarbon, for example pentane, 2-methylbutane, normal hexane, hexanaphthene, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, octane-iso, 2,2,3-trimethylpentane, decane, nonane, pentamethylene, methylcyclopentane, methylcyclohexane, ethylcyclohexane, to menthane, connection hexanaphthene (dicyclohexyl), benzene,toluene,xylene and ethylbenzene; Halohydrocarbon, for example tetracol phenixin, trieline, chlorobenzene and tetrabromoethane; Ether, for example ether, dimethyl ether, three  alkane and tetrahydrofuran (THF)s; Acetal, for example methylal and diethyl acetal; Lipid acid, for example formic acid, acetate and propionic acid; With the organic compound of sulfur-bearing or nitrogen, for example nitro propylene, oil of mirbane, dimethyl amine, monoethanolamine, pyridine, dimethyl formamide, dimethyl sulfoxide (DMSO), acetonitrile and N-N-methyl-2-2-pyrrolidone N-.These compounds can be used alone or two or more are used in combination.

In these solvents, from granular size control and dispersed viewpoint, the preferred solvent of at least 105 ℃ of water-soluble and boiling points by adding appropriate amount, for example TC acetic ester, TC, Diethylene Glycol single-butyl ether, dimethyl formamide or N-N-methyl-2-2-pyrrolidone N-and the mixed solvent that obtains.More preferably pass through the solvent mixture of the solvent acquisition of at least 140 ℃ of adding boiling points.

The amount of the starting monomer that in reaction soln, comprises preferably account for the reaction soln total amount 1 to 50wt% between, more preferably between 2 to 30wt%, even more preferably between 3 to 20wt%, most preferably between 6 to 15wt%.

Starting monomer content surpasses 50wt%, is difficult to the spherical polymer fine particles that has above-mentioned character in the acquisition of monodisperse status high yield.On the other hand, content is less than 1wt%, and reaction needed reaches fully for a long time, sees it is unpractical from industrial point.

Temperature of reaction during polymerization changes according to the type of solvent of using, therefore can not be strictly clear and definite, but typical temperature is from about 10 to about 200 ℃, preferably from 30 to 130 ℃, and more preferably from 40 to 90 ℃.

Reaction times is not subjected to any specific restriction, as long as long to goal response is finished basically, the reaction times is subjected to the strong influence of the factors such as diameter of the viscosity of used monomeric type and amount, solution and concentration, target particles.40 to 90 ℃ of temperature ranges, the reaction times can be from about 1 to about 72 hours, preferably from about 2 to about 24 hours.

The particle that obtains can contain core/shell structure because of seeding polymerization, perhaps can be prepared as the composite particles of for example having introduced other reactive functional, can adopt suitable form according to the purposes form.

In addition, in preparing the method for spherical polymer fine particles of the present invention, preferably carry out polyreaction in the presence of organic compound, described organic compound does not react with starting monomer under polymerizing condition and contains at least 5 carbon atoms.

By in reactive system, containing such organic compound, can improve the dispersiveness of spherical polymer fine particles, so that make particle diameter control more evenly.

Organic compound with at least 5 carbon atoms is not subjected to any specific restriction, as long as be solid or liquid at normal temperatures, can mix (comprising dispersion) or dissolving in the solvent that uses, and the formation of spherical polymer fine particles is not had adverse influence.But the organic compound that uses fusing point to be no more than 80 ℃ is favourable, preferably is no more than 60 ℃, even more preferably no more than 40 ℃, also more preferably no more than 30 ℃.As long as can reach the object of the invention, have fusing point and be no more than about 80 ℃ low-melting relatively organic compound and can be used as solvent (medium).

Although at least 5 of carbonatomss are enough, but consider the needs that organic compound exists under polymerizing condition, and also consider the others for example volatility and the boiling point of organic compound, preferably at least 6 of carbon numbers, more preferably at least 8, most preferably at least 10.

The amount of the above-mentioned organic compound that adds is from about 0.1 to about 50wt% based on polymer solvent, preferably from about 1 to about 25wt%, more preferably from about 2 to about 10wt%.Herein, add-on surpasses 50wt%, and organic compound may cause the rising of entire reaction soltion viscosity, makes to have to be difficult to control the situation of granular size to required uniformity coefficient.On the other hand, less than 0.1wt%, the monodispersed effect of particle has and can not fully show.

For increasing particle list dispersion effect, preferably use at least a compound that is selected from hydrocarbon compound and silicone compounds as above-mentioned organic compound.

Herein, the exemplary example of hydrocarbon compound comprises the compound with hydrocarbyl group, for example acyclic aliphatic hydrocarbon (for example, stable hydrocarbon, unsaturated hydrocarbons), alicyclic hydrocarbon, aromatic hydrocarbon, higher alcohols, higher fatty acid, fat, oil, wax, animal and plant grease, with other oil, for example mineral oil and petroleum product; And derivative.

In these hydrocarbon compounds, preferred acyclic aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon and oils.

In hydrocarbon compound of the present invention, one or more hydrogen atoms can be replaced by halogen atom or some other functional groups.The illustrative example of described functional group comprises oh group and hydroxy derivatives group, for example its ester group, carbonate group and ether group; Carboxylic group and carboxy derivatives group, for example its ester group, amide group and carbamate groups; With amino group and its derivatives group, for example amide group, carbamate groups and urea groups.

In can realizing scope of the present invention, these hydrocarbon compounds can comprise the atom except carbon atom, nitrogen, oxygen, hydrogen and halogen.Hydrocarbon compound can use separately or two or more are used in combination.

The exemplary example of hydrocarbon compound comprises following.

(1) hydro carbons

Whiteruss, pentane, hexane, heptane, octane, decane, undecane, dodecane, the tetradecane, n-Hexadecane, octadecane, eicosane, the 1-amylene, the 1-hexene, 3-methyl-1-butene, the 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, the 1-octene, 1-decene, the 1-dodecylene, tetradecene, cetene, the 1-vaccenic acid, the 1-eicosylene, cyclopentenes, tetrahydrobenzene, suberene, cyclooctene, pentamethylene, hexanaphthene, suberane, cyclooctane, 1, the 4-hexadiene, 4-ethylidene-2-norbornylene, Dicyclopentadiene (DCPD), the 5-vinyl norbornene, 6,7-dimethyl-4-ethylidene-1, the 6-octadiene, 6,7-dimethyl-4-ethylidene-1, the 6-nonadiene, 7-methyl-6-propyl group-4-ethylidene-1, the 6-octadiene, 8-methyl-4-ethylidene-1, the 7-nonadiene, 7,8-dimethyl-4-ethylidene-1, the 7-nonadiene, 7,8-dimethyl-4-ethylidene-1, the 7-nonadiene, 9-methyl-4-ethylidene-1,8-decadiene and 8,9-dimethyl-4-ethylidene-1,8-decadiene etc.

(2) alcohols

Amylalcohol, enanthol, octanol, decyl alcohol, dodecanol, cetyl alcohol, Stearyl alcohol, eicosanol, V-1326, Tetracosyl alcohol, n-Hexacosanol, policosanol, lanolin alcohol, myricyl alcohol, the benzo anthrol, hexadecenol, gadoleyl alcohol, two lanolin alcohols, pineneglycol, Hinokitiol, butynediol, nonanediol, isophthalic alcohol, the Lay base glycerol, terephthalyl alcohol, hexylene glycol, decanediol, dodecanediol, tetradecane glycol, the n-Hexadecane glycol, the docosane glycol, the tetracosane glycol, Terpineol 350, phenyl glycerine, the eicosane glycol, ethohexadiol, the phenyl propylene glycol, dihydroxyphenyl propane, p-α-cumyl phenol, phenylethyl alcohol, hydrocinnamyl alcohol etc.

(3) organic acid

Valeric acid, caproic acid, sad, capric acid, dodecylic acid, hexadecanoic acid, octadecanoic acid, mountain Yu acid, the Yu acid of 2-acetylnaphthalene ketone mountain, 12-oxystearic acid, dihydroxystearic acid etc.

(4) ketone

Benzyl methyl ketone, benzyl acetone, pimelinketone benzoyl acetone, diacetyl benzene, benzophenone, 23 carbon-2-ketone, 27 carbon-2-ketone, 37 carbon-2-ketone, hentriaconta-carbon-2-ketone, 37 carbon-2-ketone, stearone, laurone, two methyl-phenoxides etc.

(5) amides

Oleylamide; laurylamide; stearylamide; ricinoleic acid amide; palmitic amide; the tetrahydrochysene furoamide; the sinapinic acid acid amides; myristic amide; 12-hydroxyl stearylamide; N-stearyl sinapinic acid acid amides; N-oleoyl stearylamide; N; N '-ethylenebis laurylamide; N; N '-ethylenebisstearamide; N; N '-ethylenebisoleoamide; N; N '-methylene-bis stearylamide; N; N '-ethylenebis mountain Yu acid acid amides; N; N '-xylylene bis-stearamides; N; N '-butylidene bis-stearamides; N; N '-dioleoyl adipamide; N; N '-two-octadecyl adipamide; N; N '-dioleoyl sebacoyl amine; N; N '-two-octadecyl sebacoyl amine; N; N '-two-octadecyl terephthaloyl amine; N, N '-two-octadecyl isophthaloyl amine; phenacetin; toluamide; ethanamide etc.

(6) sulfonamides

Para toluene sulfonamide, ethylbenzene sulphonamide, butylbenzene sulphonamide etc.

(7) cholesterol fatty acid ester class

Cholesterol ester stearic acid, cholesterol cetylate, cholesterol myristinate, cholesterol behenate, cholesterol laurate, cholesterol melissate etc.

(8) sugar fatty acid ester class

Sucrose stearate, Surfhope SE Cosme C 1616, sucrose behenate, Surfhope SE Cosme C 1216, sucrose melissate, lactose stearate, lactose cetylate, lactose myristinate, lactose behenate, lactose laurate, lactose melissate etc.

(9) ester class

The amyl group acetic ester, the benzylacetic acid ester, the styroyl acetic ester, the phenoxy group ethylhexoate, the phenylacetic acid ethyl ester, the benzyl propionic ester, the ethylamino benzonitrile acid esters, the butylbenzoic acid ester, butyl laurate, isopropyl myristic acid ester, triethyl phosphate, the Tributyl phosphate ester, diethyl phthalate, dibutyl phthalate, diethyl malonic ester, the dipropyl malonic ester, diethyl malonic ester, the diethyl succinate, the dibutyl succinate, the diethyl glutarate ester, the diethyl adipic acid ester, the dipropyl adipic acid ester, the dibutyl adipic acid ester, two (2-methoxy ethyl) adipic acid ester, the diethyl sebate, the diethyl maleic acid ester, the dibutyl maleic acid ester, the dioctyl maleic acid ester, the diethyl fumarate, the dioctyl fumarate, 3-hexenyl styracin etc.

(10) ethers

Butyl phenylate, benzyl ethyl ether, hexyl ether etc.

(11) wax class

Beeswax, carnauba wax, rice wax, Japan tallow, jojoba wax, spermaceti, Kan Taili wax, lanolin, montanin wax, ceresine, silk gum, paraffin, polyvinyl paraffin wax derivative, microcrystalline wax, soft wax etc.

(12) oils

Mineral oil by the refining petroleum preparation; Industrial lubricant, for example engine oil, shafting oil, machinery oil, cylinder stock oil and gear oil; (chemical ingredients is a hydro carbons for example to the ucon oil for preparing by chemosynthesis, comprises polyolefine, for example polybutene; With alkyl-aromatic compounds alkylbenzene for example); Vegetables oil, for example Oleum Cocois, plam oil, sweet oil, sunflower oil, Viscotrol C, soybean oil, oleum lini, Canola oil, tung oil and Oleum Gossypii semen; And animal grease, for example whale oil and tallow.

The preferred organopolysiloxane of silicone compounds of the present invention.

Organopolysiloxane is commonly referred to as silicone, is to have on skeleton by siloxane bond (O-Si-) as the polymkeric substance of the repeating unit of main chain.Usually substituting group is selected from the group of being made up of hydrogen atom and straight or branched alkyl, and described alkyl is the saturated or undersaturated hydrocarbon of from 1 to 50 carbon atom, comprises alkyl group, phenyl group and aromatic alkyl group.Substituting group can be for identical or different.

The illustrative example of general polysiloxane comprises polydimethylsiloxane, PSI, poly-diphenyl siloxane and composition thereof.

The weight-average molecular weight of these organopolysiloxanes is not subjected to any specific restriction, but the organopolysiloxane with molecular weight of from about 100 to about 500,000 is suitable.Especially the organopolysiloxane of preferred liquid.

Those organopolysiloxanes (or silicone) at normal temperatures, have about 0.65 to about 1,000,000mm ²S ^-1(cSt) kinematic viscosity of scope, so liquid is known as silicone oil.

In enforcement of the present invention, the such silicone oil of preferred use in these organopolysiloxanes.Preferably have 1 to 10,000mm at 25 ℃ ²S ^-1The silicone oil of the kinematic viscosity (cSt) has 10 to 5,000mm at 25 ℃ ²S ^-1The silicone oil of the kinematic viscosity (cSt) is preferred.

If the kinematic viscosity of organopolysiloxane drops on outside the above-mentioned scope, be difficult to control granular size.Particle may precipitate, and sedimentary particle may condense, and the possibility of result can not get monodisperse particles.

The exemplary that can be advantageously used for the commercial organopolysiloxane (silicone oil) of organic compound of the present invention comprises dimethyl silicone oil, for example KF-96, KF-69, KF-965 and KF-968 (all can obtain from Shin-Etsu chemical company limited), SH200 (Dow Corning Toray organosilicon company limited) and L-45 (Nippon Unicar company limited); Methyl phenyl silicone oil, for example KF-50, KF-54 and KF-56 (Shin-Etsu chemical company limited) and SH510, SH550 and SH710 (Dow Corning Toray organosilicon company limited); With methyl hydrogen silicone oil, for example KF-99 (Shin-Etsu chemical company limited) and SH1107 (Dow Corning Toray organosilicon company limited).

In enforcement of the present invention; can use the silicone oil into property, wherein the side chain of organopolysiloxane or end group are by polyethers for example, vinyl toluene base, alkyl, high-grade aliphatic ester, alkoxyl group, fluorine-based, amino, epoxy group(ing), carboxyl, methanol-based, methacryloyl, sulfydryl or phenolic groups modification.

The illustrative example of the organopolysiloxane of commercially available modification (modified silicon oil) comprises KF-100, KF-102, KF-103, KF-105, KF-351, KF-352, KF-353, KF-354, KF-355, KF-393, KF-410, KF-412, KF-413, KF-414, KF-615, KF-618, KF-851, KF-857, KF-858, KF-859, KF-860, KF-861, KF-862, KF-864, KF-865, KF-867, KF-868, KF-869, KF-880, KF-905, KF-910, KF-945, KF-6001, KF-6002, KF-6003, KF-3935, KF-8001, KF-8002, KF-8003, KF-8004, KF-8005, X-22-160, X-22-161, X-22-162, X-22-163, X-22-165, X-22-167, X-22-169, X-22-170, X-22-173, X-22-174, X-22-176, X-22-715, X-22-800, X-22-801, X-22-819, X-22-820, X-22-821, X-22-822, X-22-904, X-22-980, X-22-3367, X-22-3701, X-22-3710, X-22-3939, X-22-4015, X-22-5002, X-22-6008, FL-100 (from Shin-Etsu chemical company limited), SF8410, SF8411, SF8413, SF8416, SF8417, SF8418, SF8419, SF8421, SF8427, SF8428, SH203, SH230, SH3746, SH3749, SH3771, SH8400, SH8700 and FS1265 (Dow Corning Toray silicone).

For increasing single dispersion efficiency, the preferred above-mentioned organic compound that contains 5 or more a plurality of carbon atoms is a hydrophobic compound.

When enforcement the present invention prepares the method for spherical polymer fine particles, according to polymerization process, can within based on 0.01 and 50wt% scope of starting monomer, comprise other composition for example (polymer) dispersion agent, stablizer and emulsifying agent (tensio-active agent) with appropriate vol.

Dispersion agent and stablizer can exemplify various types of hydrophobic or hydrophilic dispersion agents and stablizer, comprise polystyrene derivative, for example polycarboxylated styrene, polystyrolsulfon acid, vinylphenol-(methyl) acrylate copolymer, vinylbenzene-(methyl) acrylate copolymer and styrene-ethylene base phenol-(methyl) acrylate copolymer; Poly-(methyl) acrylic acid derivative, for example poly-(methyl) vinylformic acid, poly-(methyl) acrylamide, polyacrylonitrile, poly-ethyl (methyl) acrylate and poly-butyl (methyl) acrylate; Poly-(vinyl alkyl ethers) derivative, for example poly-(methylvinylether), poly-(ethyl vinyl ether), poly-(butyl vinyl ether) and poly-(IVE); Mierocrystalline cellulose and derivatived cellulose, for example methylcellulose gum, cellulose ethanoate, cellulose nitrate, Walocel MT 20.000PV, Natvosol, hydroxypropylcellulose and carboxymethyl cellulose; Polyvinyl acetate derivative, for example polyvinyl alcohol, polyvinyl butyral acetal, polyvinyl formal and polyvinyl acetate; Polymer with nitrogen derivative, for example polyvinyl pyridine, polyvinylpyrrolidone, polymine and poly--2-methyl-2- azoles quinoline; With the polyvinylhalide derivative, for example polyvinyl chloride and polyvinylidene dichloride.These can be used alone or two or more are used in combination.

Emulsifying agent (tensio-active agent) can exemplify anionic emulsifier, comprises alkyl sulfuric ester salt, for example sodium lauryl sulphate, alkylbenzene sulfonate, Sodium dodecylbenzene sulfonate for example, sulfonated alkyl naphathalene, soap, alkylphosphonic and alkyl sulfo succinate; Cationic emulsifier is alkylamine, quaternary ammonium salt, alkyl betaine and amine oxide for example; And nonionic emulsifying agent, for example Voranol EP 2001, Voranol EP 2001, polyxyethylated allyl ethers, polyoxyethylene alkyl phenyl ether, sorbitan-fatty acid ester, glycerol fatty acid ester and polyoxyethylene fatty acid ester.These can be used alone or two or more are used in combination.

Spherical polymer fine particles of the present invention is suitable as the dividing plate of used for liquid crystal display element.That especially preferably particle is made under these circumstances, has given the spherical dividing plate of the resin layer with adhesive properties to its upper layer.

By giving binder layer by this way, can prevent that dividing plate from moving in the substrate hole.As a result, the damage that controlling diaphragm scratches can be prevented from for example to be orientated, the accuracy of hole between the quality of display image and the substrate can be improved.

Usually the binding property dividing plate can exemplify the dividing plate of when heating fusing and adhesion and because reactive functional groups etc. is incorporated into core or fine particle surface, because of the dividing plate of chemical reaction formation bonding adhesion.Spherical polymer fine particles of the present invention can be used in various types of dividing plates.

The resin that can form bonding coat is not subjected to any specific restriction, comprises styrene resin, acrylic resin, methacrylic resin, polyvinyl resin, acrylic resin, silicone resin, vibrin, urethane resin, polyamide resin, Resins, epoxy, polyvinyl butyral resin, rosin, terpine resin, resol, melamine resin, guanamine resin,  azoles quinoline resin and carbodiimide resin.These can be used alone or two or more are used in combination.

The adhesive separator that especially preferably has binder layer, described binder layer and spherical polymer fine particles surface chemistry bonding of the present invention.

Can not be subjected to any specific restriction with the functional group that the functional group on spherical fine particle surface forms in the resinous principle of binder layer; But any bonded functional group that can form the chemistry bonding between two kinds of functional groups all can select.

The exemplary example of described functional group comprises vinyl, '-aziridino,  azoles quinoline base, epoxy group(ing), sulphur epoxy group(ing), amide group, isocyanate group, carbodiimide, acetoacetyl, carboxyl, carbonyl, hydroxyl, amino, aldehyde, sulfydryl and sulfo group.

Spherical polymer fine particles of the present invention can be used as conductive fine particle.Under these circumstances, as core particle, form conducting film by electro-conductive material by spherical polymer fine particles of the present invention, thereby formed conductive fine particle on its surface.

The metallic substance that can be used for forming conducting film is not subjected to any specific restriction.The example of metallic substance comprises copper, nickel, cobalt, palladium, gold, platinum, rhodium, silver, zinc, iron, lead, tin, aluminium, indium, chromium, antimony, bismuth, germanium, cadmium and silicon like this.

Usually conductive layer has from about 0.01 thickness to about 10.0 μ m, preferably from 0.05 to 5 μ m, more preferably from 0.1 to 2 μ m.During less than 0.01 μ m, be difficult to obtain required electroconductibility at conductive layer thickness.On the other hand, thickness surpasses 10 μ m, and when conductive fine particle is placed between the electrode pair and pressure when being applied on two electrodes, flexible being not easy of conductive fine particle occurs effectively, and conductive fine particle may show the tendency of cohesion.

There is not specific restriction for the method that forms conductive layer.Example comprises electroless method, with metal fine powder separately to the method for particle coating, with metal-powder and tackiness agent being mixed the mashed prod that obtains method to the particle coating, and the physical vapor intermediate processing, for example vacuum plating, ion plating and ion sputtering.The homogeneity viewpoint of and conducting film thickness dispersed from the particulate that obtains, preferred electroless method.

In the electroless treatment method, the electroless-plating particle can obtain in the following way, for example use known technology and equipment that spherical polymer particles is formed the water-based soup compound, add complexometric reagent and it is disperseed fully, add the metal electroless plating solution then and form metal deposit.

The complexometric reagent that adopts can suitably be selected from the various known compounds that the metal ion that uses had complexing action.Exemplary example comprises carboxylic acid (salt), for example citric acid, oxyacetic acid, tartrate, oxysuccinic acid, lactic acid, glyconic acid and its alkali metal salts or ammonium salt; Amino acid is glycine for example; Amine is quadrol and alkylamine for example; And ammonium salt, EDTA and tetra-sodium (salt) etc.

The preferred example of operable electroless plating solution comprises that those contain for example solution of copper, nickel, cobalt, palladium, gold, platinum and rhodium of one or more metals.Generally by with reductive agent for example the aqueous solution of sodium phosphite, hydrazine or sodium borohydride and pH regulator agent for example the aqueous solution of sodium hydroxide join and carry out the electroless plating reaction in the metal-salt.For example copper, nickel, silver and golden electroless plating solution can be commercially available to contain metal, can obtain cheaply.

Have specific 60%K value and specific compression set percentage response rate because spherical polymer fine particles of the present invention is as indicated above, when as electro-conductive material, particle of the present invention can scratch or is pierced through the substrate that is used for connecting between electrode, even the high compression distortion also can obtain point-device hole retentivity and stable connection reliability.And, because particle of the present invention contains considerable crosslinked composition, acidproof and alkali resistance improves, when using acid or alkali that particle is electroplated, can prevent that the spherical polymer fine particles as core particle is subjected to the chemical etching of bronsted lowry acids and bases bronsted lowry, can prevent thus because the peeling off or break of the plated metal that such chemical etching produces.

Because spherical polymer fine particles of the present invention has high compression deformation-recovery rate as indicated above, the such damage of orientation controlling diaphragm can prevent from for example to scratch, particulate during the may command high compression destroys, so particle of the present invention can use suitably as spacer for liquid crystal display element.

In addition, spherical polymer fine particles of the present invention is by having above-mentioned feature, not only can be used for electrician and field of electronic materials, and also can use in the scope widely of other application, comprise japanning and coating, light diffusing agent, makeup, medicine, examination of living tissue equipment, agricultural chemicals and material of construction.

The preparation method of spherical polymer particles of the present invention does not adopt the complicated seeding polymerization method of use kind particulate in the past.Use simply and easily method instead, although can obtain to have big elasticity of compression characteristic, both made 60% or big compression displacement under, also be softish and have good compression deformation-recovery rate.Therefore, principal character of the present invention is need not be by means of using kind of a particulate seeding polymerization can obtain having good soft elastic spherical polymer fine particles.

Embodiment

Hereinafter the present invention is illustrated in more detail by embodiment and comparative example.But, the invention is not restricted to the following example.

Embodiment 1

Compound shown in following is all once joined in the 500ml flask.With the dissolved oxygen of nitrogen replacement in mixture, subsequently material in the flask was heated about 6 hours in 82 ℃ of temperature oil baths, under nitrogen gas stream, stir simultaneously, obtain DVB/ methacrylic acid/NK-ester A-DOD (obtaining) copolymer pellet solution from Xin Zhong village chemical company limited with agitator.

DVB (96%. purity; DVB-960 is from chemical company limited of Nippon Steel

Obtain), contain 3% vinyl xylene, ethyl vinyl benzene 5.88g

Methacrylic 3.92g

NK-ester A-DOD (Xin Zhong village chemical company limited) (decamethylene-glycol two 9.8g

Acrylate)

Acetonitrile 196g

Diisopropyl azodicarboxylate (AIBN) 1.69g

N-dodecane 9.02g

TC acetic ester 9.8g

Then use known suction strainer equipment to use tetrahydrofuran (THF) (hereinafter referred to as " THF ") with particle solution repetitive scrubbing and about 3-5 time of filtration, vacuum-drying then obtains particle.The particle that obtains is detected down in scanning electronic microscope (SEM), measure particle diameter.The result is average particulate diameter spherical little with 3.8 μ m.The Cv value is 3.7%.Fig. 1 represents to obtain the particulate scanning electron photomicrograph.

Embodiment 2

The compound of representing is below all once joined in the 500ml flask.With the dissolved oxygen of nitrogen replacement in mixture, subsequently material in the flask was heated about 6 hours in 82 ℃ of temperature oil baths, under nitrogen gas stream, stir simultaneously, obtain DVB/ methacrylic acid/NK-ester A-DOD (obtaining) copolymer pellet solution from Xin Zhong village chemical company limited with agitator.

DVB(DVB-960) 5.88g

Methacrylic acid 3.92g

NK-ester A-DOD 9.8g

Acetonitrile 196g

Diisopropyl azodicarboxylate (AIBN) 1.69g

N-dodecane 9.02g

TC acetic ester 9.8g

Dimethyl formamide 1.96g

Then use known suction strainer equipment with THF with the particle solution repetitive scrubbing with filter about 3-5 time, vacuum-drying then obtains particle.The particle that obtains is detected and measures through SEM, show that they are the spheroidal particle with average particulate diameter of 5.2 μ m.The Cv value is 4.1%.

Embodiment 3

The compound of representing is below all once joined in the 500ml flask.With the dissolved oxygen of nitrogen replacement in mixture, subsequently material in the flask was heated about 6 hours in 80 ℃ of temperature oil baths, under nitrogen gas stream, stir simultaneously, obtain DVB/ methacrylic acid/NK-ester DOD-N (obtaining) copolymer pellet solution from Xin Zhong village chemical company limited with agitator.

DVB(DVB-960) 7.35g

Methacrylic acid 7.35g

NK-ester DOD-N (Xin Zhong village chemical company limited) (decamethylene-glycol two

Methacrylic ester) 9.8g

Acetonitrile 245g

Diisopropyl azodicarboxylate (AIBN) 2.1g

N-dodecane 11.2g

Virahol 12.25g

Then use known suction strainer equipment with THF with the particle solution repetitive scrubbing with filter about 3-5 time, vacuum-drying then obtains particle.The particle that obtains is detected and measures through SEM, show that they are the spheroidal particle with average particulate diameter of 4.2 μ m.The Cv value is 3.8%.

Embodiment 4

The compound of representing is below all once joined in the 500m1 flask.With the dissolved oxygen of nitrogen replacement in mixture, subsequently material in the flask was heated about 6 hours in 88 ℃ of temperature oil baths, under nitrogen gas stream, stir simultaneously, obtain DVB/ vinylformic acid/NK-ester A-IND (obtaining) copolymer pellet solution from Xin Zhong village chemical company limited with agitator.

DVB(DVB-960) 17.5g

Vinylformic acid 12.25g

NK-ester A-IND (Xin Zhong village chemical company limited) (2-methyl isophthalic acid, 8-

The ethohexadiol diacrylate, 85%; 1,9-nonanediol diacrylate,

15％) 5.25g

Acetonitrile 350g

Diisopropyl azodicarboxylate (AIBN) 4.75g

N-dodecane 12g

Then use known suction strainer equipment with THF with the particle solution repetitive scrubbing with filter about 3-5 time, vacuum-drying then obtains particle.The particle that obtains is detected down and measures in scanning electronic microscope (SEM), show that they are the spheroidal particle with average particulate diameter of 3.7 μ m.The Cv value is 3.5%.

Embodiment 5

Except using SH-550 (productions of Dow Corning Toray silicone company limited) replacement n-dodecane, obtain DVB/ methacrylic acid/1,10-decane omega-diol diacrylate copolymer pellet solution according to the method identical with embodiment 1.

Then use known suction strainer equipment with THF with this particle solution repetitive scrubbing with filter about 3-5 time, vacuum-drying then obtains particle.The particle that obtains is detected and measures through SEM, show that they are the spheroidal particle with average particulate diameter of 3.7 μ m.The Cv value is 4.1%.

Embodiment 6

Except adding 0.24g NK-ester AD-TMP (production of Xin Zhong village chemical company), obtain DVB/ methacrylic acid/decamethylene-glycol dimethacrylate/two trimethylolpropane tetra-acrylate copolymer pellet solution according to the method identical with embodiment 3.

Then use known suction strainer equipment with THF with the particle solution repetitive scrubbing with filter about 3-5 time, vacuum-drying then obtains particle.The particle that obtains is detected and measures through SEM, show that they are the spheroidal particle with average particulate diameter of 3.5 μ m.The Cv value is 4.3%.

Embodiment 7

Except using DVB (DVB-960) to replace the NK-ester DOD-N, obtain DVB/ Sipacril 2739OF particle solution according to the method identical with embodiment 3.

Then use known suction strainer equipment with THF with the particle solution repetitive scrubbing with filter about 3-5 time, vacuum-drying then obtains particle.The particle that obtains is detected and measures through SEM, show that they are the spheroidal particle with average particulate diameter of 3.5 μ m.The Cv value is 4.0%.

Comparative example 1

Following compounds is mixed with designated ratio, the mixture that obtains is all once joined in the 500ml flask.With the dissolved oxygen of nitrogen replacement in mixture, subsequently material in the flask was heated about 10 hours in 80 ℃ of temperature oil baths, under nitrogen gas stream, stir simultaneously with agitator, obtain styrene polymer beads solution.

Vinylbenzene 86.0g

Methyl alcohol 138.0g

Ethanol 92.0g

Diisopropyl azodicarboxylate (AI BN) 6.5g

Polyvinylpyrrolidone (K-30) 35.0g

Then use known suction strainer equipment with methyl alcohol with the particle solution repetitive scrubbing with filter about 3-5 time, vacuum-drying then obtains proper sphere shape particle.The particle that obtains is detected and measures through SEM, show that they are the spheroidal particle with average particulate diameter of 3.5 μ m.The Cv value is 4.0%.When using the THF washing, the particle dissolving.

Comparative example 2

Following compounds is mixed in the 500ml flask with designated ratio.With 10,000rpm stirred 20 minutes, formed suspensoid thus at room temperature to use homogenizer (Ultra Turrax T18 Basic, IKA Works makes).

Vinylbenzene 8.16g

DVB(DVB-960) 3.5g

Water 153.39g

Diisopropyl azodicarboxylate (AIBN) 0.3g

Polyvinylpyrrolidone (K-30) 2.48g

Then suspension is transferred in the 500ml flask, heating is about 6 hours in 70 ℃ of temperature oil baths, stirs with agitator under nitrogen gas stream simultaneously, obtains vinylbenzene-DVB copolymer pellet solution thus.Classification subsequently, repetitive scrubbing and filtration, and vacuum-drying obtain spheroidal particle thus.The particle that obtains is detected and measures through SEM, show that they are the spheroidal particle with average particulate diameter of 3.4 μ m.The Cv value is 4.7%.

The above embodiment of the present invention and comparative example are summarised in the table 1 and sum up.

Table 1

	Particle diameter (μ m)	Standard deviation	Cv value (%)
				Embodiment 1	3.8	0.14	3.7
Embodiment 2	5.2	0.21	4.1
				Embodiment 3	4.2	0.16	3.8
Embodiment 4	3.7	0.13	3.5
				Embodiment 5	3.7	0.15	4.1
Embodiment 6	3.5	0.15	4.3
				Embodiment 7	3.5	0.14	4.0
Comparative example 1	3.5	0.14	4.0
				Comparative example 2	3.4	0.16	4.7

Evaluation test 1 (soft elasticity evaluation)

For the particle elastic property that in various embodiments of the present invention and comparative example, obtains (rate of compression, response rate, K value), use miniature compressing tester (MCT-W201, Tianjin, island company makes) (measuring temperature, 20 ℃) to estimate.

In addition, also measure each particulate compression displacement when each particle compressive load 1gf (9.8mN) and 1.5gf (14.7mN) (measuring temperature, 20 ℃), estimate.The result provides in to 6 at table 2.Fig. 2 to 5 is illustrated in and obtains particulate load-compression displacement and load/unloading test chart among the embodiment 1.

Table 2

	The evaluation of elastic property (compression displacement, 60%)
				Rate of compression (%)	Response rate (%)	60%K value (N/mm 2)
	Embodiment 1	61.0	34.9				5470
Embodiment 2				60.3	37.4	3763
	Embodiment 3	61.2	34.5				4664
Embodiment 4				60.5	32.5	5500
	Embodiment 5	60.7	33.3				5610
Embodiment 6				60.2	29.8	6430
	Embodiment 7	60.3	25.7				4430
Comparative example 1				60.1	9.7	820
	Comparative example 2	Cause breakpoint	--				--

Apply cause rate of compression to surpass 60% load after, measure response rate.

Table 3

	The evaluation of elastic property (compression displacement, 65%)
				Rate of compression (%)	Response rate (%)	65%K value (N/mm 2)
	Embodiment 1	65.5	25.2				7170
Embodiment 2				65.4	29.8	4378
	Embodiment 3	65.4	24.6				6052
Embodiment 4				65.3	24.1	7200
	Embodiment 5	65.2	24.6				7280
Embodiment 6				65.3	23.2	8230
	Embodiment 7	65.1	21.0				5320
Comparative example 1				65.4	7.6	910
	Comparative example 2	Cause breakpoint	--				--

Apply cause rate of compression to surpass 65% load after, measure response rate.

Table 4

	The evaluation of elastic property (compression displacement, 70%)
				Rate of compression (%)	Response rate (%)	70%K value (N/mm 2)
	Embodiment 1	70.0	23.0				7240
Embodiment 2				70.1	25.3	4539
	Embodiment 3	70.0	22.5				6319
Embodiment 4				70.2	21.4	7410
	Embodiment 5	70.0	21.5				7360
Embodiment 6				70.1	21.2	8390
	Embodiment 7	Cause breakpoint	--				--
Comparative example 1				70.1	6.3	1040
	Comparative example 2	Cause breakpoint	--				--

Apply cause rate of compression to surpass 70% load after, measure response rate.

Table 5

	Compression displacement at compressive load 1gf (9.8mN)
		Embodiment 1	55.2
Embodiment 2	51.1
		Embodiment 3	53.8
Embodiment 4	55.4
		Embodiment 5	55.6
Embodiment 6	55.8
		Embodiment 7	60.1
Comparative example 1	77.8
		Comparative example 2	23.6

Table 6

	Compression displacement at compressive load 1.5gf (14.7mN)
		Embodiment 1	62.3
Embodiment 2	58.1
		Embodiment 3	60.1
Embodiment 4	61.1
		Embodiment 5	62.2
Embodiment 6	62.6
		Embodiment 7	Cause breakpoint
Comparative example 1	78.1
		Comparative example 2	Cause breakpoint

Evaluation test 2 (soft elasticity)

Use miniature compressing tester (MCT-W201, Tianjin, island company make) (measuring temperature, 20 ℃), each particle that embodiment 1 to 7 and comparative example 2 are obtained is at the particle elasticity of compression deformation characteristic (K of compression displacement 20% and 30% ₂₀, K ₃₀) estimate.The results are shown in the table 7.

Table 7

	K 20 (N/mm 2)	K 30 (N/mm 2)	Estimate
				Embodiment
1	2075	1896	K 20＞K 30
				Embodiment 2	2411	2362	K 20＞K 30
Embodiment 3	2225	2113	K 20＞K 30
				Embodiment 4	2365	2289	K 20＞K 30
Embodiment 5	2488	2358	K 20＞K 30
				Embodiment 6	3027	2902	K 20＞K 30
Embodiment 7	3270	3045	K 20＞K 30
				Comparative example 2	8205	9023	K 20＜K 30

Claims (13)

1. spherical polymer fine particles is characterized in that, wherein supposes at the displacement of the particle diameter elasticity of compression deformation characteristic K at the individual particle of X% _xDefine with following formula:

K _x＝(3/)·(S _x ^-3/2)·(R ^-1/2)·F _x (1)，

F wherein _xBe the load (N) of particulate X% displacement request, S _xBe that R is particle radius (mm) in the compression set (mm) of particulate displacement at X%, 20 ℃ of mensuration in the displacement of particle diameter at 60% elasticity of compression deformation characteristic K ₆₀Be 1,000 to 12,000N/mm ², be at least 20% in the displacement of particle diameter 60% o'clock particle diameter response rate 20 ℃ of mensuration.

2. the spherical polymer fine particles of claim 1 is characterized in that within many 60% scopes of being moved to of particle diameter the flex point that does not exist breakpoint or compression deformation rate sharply to increase.

3. claim 1 or 2 spherical polymer fine particles is characterized in that when the compressive load for individual particle was 9.8mN (1gf), this particulate compression displacement was at least 40%.

4. any one spherical polymer fine particles of claim 1 to 3 is characterized in that the K in the formula (1) ₂₀And K ₃₀K satisfies condition ₂₀〉=K ₃₀

5. any one spherical polymer fine particles of claim 1 to 4 is characterized in that average particulate diameter between 0.1 to 100 μ m, and the coefficient of variation Cv of particle diameter is 20% to the maximum.

6. profit requires 1 to 5 any one spherical polymer fine particles, and it is characterized in that using at least, the monomer with two or more unsaturated double-bonds of 35wt% obtains described spherical fine particle.

7. the spherical polymer fine particles of claim 6 is characterized in that the monomer with two or more unsaturated double-bonds comprises at least a monomer that is selected from Vinylstyrene and multifunctional (methyl) acrylate monomer.

8. the spherical polymer fine particles of claim 7 is characterized in that multifunctional (methyl) acrylate monomer comprises at least a monomer that is selected from two (methyl) acrylate monomer.

9. the spherical polymer fine particles of claim 8 is characterized in that described two (methyl) acrylate monomer is C _6-18Alkanediol two (methyl) acrylate.

10. the method for preparing spherical polymer fine particles, it is characterized in that in solvent, implementing the solution polymerization of starting monomer, described starting monomer comprises 35wt% or more contains the monomer with two or more unsaturated double-bonds that is selected from multifunctional (methyl) acrylate monomer, and described dissolution with solvents starting monomer is not lysigenous particle still.

11. the method for preparing spherical polymer fine particles of claim 10 is characterized in that the monomer with at least two unsaturated double-bonds comprises the monomer that two or more are different.

12. the method for preparing spherical polymer fine particles of claim 10 or 11 is characterized in that multifunctional (methyl) acrylate monomer comprises at least a monomer that is selected from two (methyl) acrylate monomer.

13. the method for preparing spherical polymer fine particles that claim 10 to 12 is any is characterized in that except the monomer with at least two unsaturated double-bonds, contains the polymerisable monomer of the copolymerization with it of 5-60wt%.

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