CN101490138A - Microparticle, process for producing microparticle, resin composition loaded with the microparticle and optical film - Google Patents

Microparticle, process for producing microparticle, resin composition loaded with the microparticle and optical film Download PDF

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Publication number
CN101490138A
CN101490138A CNA2007800275144A CN200780027514A CN101490138A CN 101490138 A CN101490138 A CN 101490138A CN A2007800275144 A CNA2007800275144 A CN A2007800275144A CN 200780027514 A CN200780027514 A CN 200780027514A CN 101490138 A CN101490138 A CN 101490138A
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particle
particulate
mentioned
classification
quality
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CN101490138B (en
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清水健次
富永美和子
高崎进治
保吕信一
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B5/00—Washing granular, powdered or lumpy materials; Wet separating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00654—Controlling the process by measures relating to the particulate material
    • B01J2208/00672—Particle size selection

Abstract

The invention provides microparticles having the content of coarse particles exceeding the average particle diameter reduced to a low level; a process for producing such microparticles; and a resin composition containing the microparticles. The microparticles are characterized in that the content of coarse particles with a diameter of twice or more the average particle diameter is 1000 particles/0.5g or less. The process for producing the microparticles comprises the steps of wet classification of a microparticle dispersion liquid of 0.5 to 50 mass% solid content and 0.5 to 20 mass B-viscosity; drying and pulverization of the microparticles after the wet classification to thereby obtain powdery microparticles of 0.05 to 2 mass% water content; and dry classification of the powdery microparticles.

Description

The preparation method of particulate, particulate, the resin combination that contains this particulate and optical thin film
Technical field
The present invention relates to particulate that a kind of particle diameter controlled to heavens and the resin combination that has used this particulate.
Background technology
In the past, attempted being used in the resin of various uses or the resin combination and contained particulate, with the rerum natura that improves this resin or resin combination or operability etc.Be used for liquid-crystal display (LCD), plasma display (PDP), electroluminescent display (ELD), transmissive viewing screen (Tou Over type ス Network リ-Application) and the optical resin material of the optical applications of touch panel etc. carried out this trial similarly, for example, in giving the optical resin film (sheet, plate) of light diffusing, the anti-dazzle property of antireflection, the optical resin composition that contains the particulate of being made up of organism material or inorganic material can be used as raw material and uses.
; in recent years; in above-mentioned image display device field; big pictureization and the high more and more advanced trend that becomes more meticulous; requirement to relative peripheral technology has also improved, and also carries out raising, the mechanical characteristics of particulate self and various researchs such as raising of optical property with the affinity of other material (resin or other additive) repeatedly for particulate.In addition, for these particulates that can be used as the optical resin film or be used for the distance piece (spacer) of liquid crystal display device, except that the characteristic of above-mentioned requirements, expect that also the content of narrow diameter distribution, coarse particle is few.This is because if size distribution is wide, then under the situation of the distance piece that is used as liquid crystal display device, just be difficult to keep the uniform film thickness of liquid crystal stable, and coarse particle can make film surface produce scar or as seen this particulate can directly make the demonstration grade of image display device reduce.
For example, in the patent documentation 1 that discloses the particulate that can be used in optical applications, mainly put down in writing preparation method, can obtain particulate with the purposes relevant particle size of wishing with the extremely precipitous state of size-grade distribution according to this particulate.In addition, in patent documentation 2-4, the viewpoint of the reason of the shortcoming that the demonstration grade that has proposed to become from coarse particle display unit is low, become optical thin film has reduced and has had the preparation method's (patent documentation 2) of particulate of content of particle who surpasses the particle diameter of prescribed level with respect to median size; And before using particulate, the particulate of emulsion or dispersion liquid state is carried out the method (patent documentation 3 and 4) of filtration treatment to remove coarse particle.
Patent documentation 1: the spy opens 2004-307644 communique etc.
Patent documentation 2: the spy opens 2002-166228 communique, patent claims etc.
Patent documentation 3: the spy opens 2005-309399 communique, patent claims etc.
Patent documentation 4: the spy opens 2004-191956 communique, patent claims etc.
Summary of the invention
Yet, as described in patent documentation 1, synthesis phase at particulate, in fact highly it is very difficult controlling size distribution, in addition, as pointed among the patent documentation 2-4, promptly allow to size distribution is controlled in the suitable scope, under the situation that the coarse particle that exceeds median size greatly exists, can produce the reduction that shows grade or in optical thin film, produce defective.Therefore,,, the trend of further raising is arranged from improving the viewpoint of visuognosis degree and productivity for the requirement of the amount that reduces coarse particle, even have the technology of above-mentioned patent documentation 2-4, the particulate of this requirement that also is difficult to attain full and complete satisfaction.
The present invention is conceived to above-mentioned situation, the resin combination that its purpose is to provide the content of the coarse particle that exceeds suitable particle diameter to be reduced to the preparation method of low-level particulate and this particulate and to contain this particulate.
The particulate of the present invention that has solved the problems referred to above is the particulate with following main points, in this particulate, the coarse particle with particle diameter more than 2 times of median size be 1000/below the 0.5g.
Above-mentioned particulate is preferably the organism mineral complex that contains organic polymer skeleton and polysiloxane skeleton.
The preparation method of particulate of the present invention is characterised in that this method comprises: with solid component concentration is that 0.5-50 quality %, Type B viscosity are the operation of the particle dispersion liquid wet classification of 0.5-20mPas; With particulate drying, the pulverizing behind the wet classification, making moisture content is the operation of the powder particulate of 0.05-2 quality %; With described powder particulate dry type fractionated operation.Like this, by handling raw material (particle dispersion liquid, powder), can reduce particle diameter more efficiently and exceed coarse particle and the fine particle that is fit to scope with specific rerum natura with the method for combination wet classification and dry classification.
This is being coated with the application composition is coated on the base material and is also containing composition in the optical thin film that obtains (light diffusion film, anti-dazzle film etc. have the film of concaveconvex shape on the surface).
Particulate of the present invention is that the content that particle diameter exceeds the coarse particle of proper range is reduced to low-level particulate.And,, when reducing the content of coarse particle that particle diameter exceeds proper range, also can reduce the content of fine particle according to method provided by the invention.Therefore, by the moulding product that the resin combination that contains particle of the present invention obtains, be difficult to produce the defective of bringing by coarse particle.Simultaneously, owing to also reduced the content of fine particle, also be difficult to the transparency of infringement resin self.Particulate of the present invention is particularly suitable for the optical resin composition, and the light diffusion film, the anti-dazzle film that are obtained by this resin combination, and the light diffusing sheet that contains particulate of the present invention demonstrates good optical characteristics.
Embodiment
Particulate of the present invention is characterised in that, in this particulate, the coarse particle with particle diameter more than 2 times of median size be 1000/below the 0.5g.
As mentioned above, in can be used in the particulate of optical field, when containing particle diameter and exceed the coarse particle of proper range, have film surface easily produce scar or this particulate easily by visuognosis may.According to the inventor's research, confirmed that especially that above-mentioned phenomenon can become is remarkable when there be (increase) in the particulate of the particle diameter more than 2 times of the median size with employed particulate.Therefore, the coarse particle that preferably has the particle diameter more than 2 times of median size among the present invention be 500/below the 0.5g, more preferably 200/below the 0.5g, more preferably 100/below the 0.5g, most preferably be 50/below the 0.5g.
Moreover the coarse grain subnumber that the amount of coarse particle has the particle diameter more than 2.5 times of median size in above-mentioned scope is 50/a particulate below the 0.5g, and when being used for optical applications, the defective of being brought by the coarse particle more difficult labour that becomes is given birth to, and is therefore preferred.More preferably above-mentioned coarse grain subnumber is the following particulate of 30/0.5g, and further preferred above-mentioned coarse grain subnumber is the following particulate of 10/0.5g.
In addition, the particulate that reduced of the particulate of the present invention fine particle number that is preferably the particle diameter below 1/2 with median size.If contain this small particulate in a large number, then when this particulate is used for optical applications (for example be arranged on the picture display face of various image display devices the anti-dazzle property of light dispersion film, antireflection film etc.), the possibility that has the transparency or brightness to reduce.Therefore, the fine particle with particle diameter below 1/2 of median size is preferably below the 10 volume %, more preferably below the 7 volume %.
And there is no particular limitation for the median size of particulate of the present invention, but be preferably 0.1-50 μ m, more preferably 1-30 μ m, more preferably 2-20 μ m.The situation of median size in above-mentioned scope for example, when being used for optical applications, can obtain bringing into play the favourable effect of good light diffusing and face luminous (brightness) etc.When median size is too small, have reduction to as the dispersiveness of the resin of medium may, when excessive, the possibility that can not get sufficient light diffusion effect is arranged.In addition, the content of particle size distribution, median size and described fine particle uses the accurate particle size distribution device utilized Coulter principle (ベ for example Star" the マ Le チ サ イ ザ-II " of Network マ Application コ-Le — She System) measuring, is that benchmark calculates with the volume.
There is no particular limitation for the shape of particulate of the present invention, for example, can list spherical, needle-like, sheet, flakey, disintegrated, shape (shape partially), dumbbell shaped (ま ゆ shape) and granule candy shape (こ ん ペ い sugar shape) etc. partially.Preferred especially: when being used for the situation of optical applications (be used for optical resin composition etc. situation) is spherical or closely spherical, and the ratio of long particle diameter and short particle diameter is in the scope of 1.0-1.2, and the coefficient of variation of particle diameter is below 10%.
The particulate of the invention described above carries out the particulate that dry classification obtains for the powder particulate to moisture content, true specific gravity, Bulk Specific Gravity and particle diameter with regulation.
The moisture content that offers the powder particle in the above-mentioned dry classification is 0.05-2 quality %.Under the too much situation of water content, during classification, this moisture plays the tackiness agent effect to be made between particle and condenses, on the other hand, at present very few in water content, make between particle by static and to condense, therefore, the trend that all has effectiveness of classification step-down, coarse particle to increase in either event.If moisture content in above-mentioned scope, then because particle is difficult to cohesion, can successfully be carried out progressive operation.In addition, preferred true specific gravity is that 1-1.25g/ml, Bulk Specific Gravity are that 0.1-1g/ml, median size are 1-50 μ m.Under the too small situation of the true specific gravity of powder particulate, owing to be difficult to produce the difference of the centrifugal force that the size by particle diameter causes and the resistance that causes by wind-force poor, cause that effectiveness of classification can step-down sometimes.Under the excessive situation of true specific gravity, not preferred owing to needing very big equipment and power.In addition, not preferred owing to need very big equipment and power under the excessive situation of Bulk Specific Gravity, on the other hand, under too small situation, owing to be difficult to produce poor that size by particle diameter produces, effectiveness of classification can step-down sometimes.Under the too small situation of particle diameter, the cohesion between powder is very strong, and can not get good dispersion state and effectiveness of classification sometimes can reduce; Under excessive situation and since become need be very big equipment and power and not preferred.
By wet classification, it is below 200,000 that the content that offers the coarse particle more than 2 times of the powder particle of dry classification and the median size in the dispersion soln that obtains by wet classification is preferably every 0.5g.More preferably 100,000/below the 0.5g, more preferably 50,000/below the 0.5g.When the coarse grain subnumber of contained specific size is in above-mentioned scope in the dispersion soln that offers the powder particle of dry classification and obtain by wet classification, because preferred by carrying out dry classification to obtain the poor particulate of coarse particle with high yield and/or high classification processing speed easily.
Therefore, preferred moisture content, true specific gravity, Bulk Specific Gravity and particle diameter are in above-mentioned scope, more preferably: the moisture content of powder particulate is preferably 0.1-0.5 quality %, and true specific gravity is preferably 1-1.5g/ml, Bulk Specific Gravity is preferably 0.3-0.8g/ml, and median size is preferably 2-20 μ m.
Moreover above-mentioned " water content " is the value of measuring by Ka Er-Fei Xiu moisture content tester (for example flat natural pond Industry Co., Ltd system, moisture determination device).Above-mentioned " loose density " is to join the value that the amount of the powder in the container is represented with the quality of per unit volume when joining powder in certain volumetrical container under certain state, and the value of above-mentioned loose density is the numerical value of measuring with powder tester (powder tester) (ホ ソ カ ワ ミ Network ロ Application system)." true specific gravity " of powder particulate is the value that the relation of the quality of the powder particulate of filling in value and the container that the powder particulate is filled in certain volumetrical container and then with liquid the space of test portion is replaced fully, deducted from the volume of container behind the volume of the liquid that needs this moment calculates, and is to measure the value that machine (for example セ of Co., Ltd. イ シ Application enterprise system) mensuration obtains by true specific gravity.The value of above-mentioned particle diameter is by described accurate particle size distribution device (ベ for example StarWhat " the マ Le チ サ イ ザ-II " of Network マ Application コ-Le -society's system) mensuration obtained is the value of benchmark with the volume.
In the dry classification of above-mentioned powder particulate, the preferred airflow classification device that has utilized wind-force that uses.Airflow classification device is to utilize air-flow that particulate (powder body layer) is carried out isolating device (that is, the balance decision of inertia that has according to particle and the suffered resistance that comes from air-flow fly out distance carry out classification) according to granularity (particle diameter of powder body, quality).Usually, only using in the sorting equipment of sieve or strainer, because the rerum natura of the particle that reclaims depends on the filtration efficiency of the mesh or the strainer of employed sieve, in order to have to desirable rerum natura, for example particle diameter is included in the particle of specific scope, need carry out the multiple fractionation operation.Relative therewith, if use air splitter means, can remove coarse particle and fine particle simultaneously.
There is no particular limitation for the classifying mechanism of said flow sorting equipment.Therefore, can be for only utilizing the mechanism of air-flow; Possessing has the rotary blade of giving the air-flow propulsive force, the guide vane that is used for guides wind, utilizes them to act on the mechanism of the air-flow of generation compoundly; Also has the mechanism that the stage division of these and other (sieve or sieve aperture) combines.
As concrete airflow classification device, can list DXF type (Japanese ニ ユ-マ チ StarNetwork industry society system) etc. high precision airflow classification device; Turbine classifier (-ボ Network ラ シ Off アイ ア, day clear エ Application ジ ニ ア リ Application グ society system), high-level efficiency Precision Air Classifier (Network ラ Starシ-Le, セ イ シ Application society system), -ボ プ レ StarThe wheeled airflow classification device of the pivoting leaf with classifying turbine of Network ス (registered trademark, ホ ソ カ ワ ミ Network ロ Application society system) etc.; Elbow nozzle (エ Le ボ-ジ The エ Starト, day iron
Figure A200780027514D0008084359QIETU
Industry society system) etc. utilization the airflow classification device of wall attachment effect (elbow nozzle type grading machine (エ Le ボ-ジ The エ Starト type Fen Grade Machine)); The high powder shifter (of dry screen Qian Shi Sieve Ha イ ボ Le —, East ocean Ha イ テ StarNetwork society system), gas blower phase shifter (Qian Shi Sieve Block ロ ワ-シ Off -, ユ-グ ロ Starプ society system) etc. utilization the airflow classification device of sieve aperture of net.Wherein, because high precision airflow classification device, the wheeled airflow classification device of pivoting leaf and utilized the airflow classification device of attached wall effect to remove coarse particle effectively and preferred.
Above-mentioned high precision air splitter means is meant does not have moving parts (mobilizable parts), by producing the high speed gyration airflow to discrete areas and stepped zone leaked-in air, to supplying to when particle in the device gives centrifugal force, by attracting gas blower (attraction Block ロ ワ-) that air is discharged from stepped zone, become giving resistance, particle is classified into the device of meal and micro mist by the balance of this centrifugal force and resistance to the centrifugal force of particle.The wheeled airflow classification device of pivoting leaf is meant, have cylinder (classifying turbine) that rotates freely and the suction hole that sucks air by the device outside to device inside, high speed rotating by above-mentioned impeller produces eddy current in device, give centrifugal force by eddy current to the particle that supplies in the device, on the other hand, suck air, make it to become the resistance of centrifugal force from suction hole, by the balance of this centrifugal force and resistance, particle is classified into the device of meal and micro mist.Utilize the airflow classification device of wall attachment effect to be meant when jet flow only is arranged on the one side wall surface, utilize device along the so-called wall attachment effect of this wall mobile; This device is provided with in position arbitrarily: with the injector portion of air-flow (reinforced air (feed air)) ejection particle in device, guiding jet flow (containing particle) in the grading room attached wall sheet (coanda block) and according to classification rib (the branch Grade エ of proterties (meal, fine powder (target compound), micro mist etc.) spacer particle Starジ).Jet flow (containing particle) by the ejection of above-mentioned injector portion flows along attached wall sheet.This moment by acting on particle mass force (mass force that acts in fine particle and coarse particle has difference, and it is farther that coarse particle can fly) and the balance of fluid resistance, coarse particle and fine particle are by classification.
Even in said flow formula sorting equipment, also preferably utilized the airflow classification device (elbow nozzle (elbow jet) type grading machine) of wall attachment effect.When using this elbow nozzle type grading machine, in order to improve effectiveness of classification, the air that preferably will feed in raw material is brought up to the maximum value of recommending air pressure.In addition, usually, reinforced air turns round under 0.1-10kgf, from improving the viewpoint of effectiveness of classification, is recommended as 1-5kgf.Usually, if reinforced air improves too much, then the flying distance of coarse particle can be elongated, and bumping the coarse particle that is reflected back on the wall in front, to sneak into the possibility of fine powder very high.Yet the particulate that the present invention relates to is the particulate that obtains after the wet classification operation, through dry classification as described later, because coarse particle is removed in above-mentioned wet classification operation to a certain extent, therefore the coarse particle that does not reflect back is blended into the situation in the fine powder.Therefore, by improving reinforced air effectiveness of classification is improved.
In addition, owing to use elongated ribs (slim edge) also can improve effectiveness of classification as the classification rib, therefore preferred.As mentioned above, because the classification rib is the parts that come spacer particle to use for according to proterties, therefore has an end (particle approaching side) and approach, arrive the other end shape of the wedge shape of thickening gradually.In addition, its basal cross section (in the wedge shape thicker an end) is rectangle slightly, and certain width is arranged.And the width that usually width of classification rib is designed to the stream that flows through with the jet flow that contains particle approximately equates.At this, to compare with usually used standard rib, above-mentioned elongated ribs forms distance between the inclined-plane of wedge shape short (particularly partly be about at basal cross section standard rib half).Usually, when handling the particle of strong band electricity, in order to prevent that piling up particle at the tip of rib can reduce effectiveness of classification and use elongated ribs.By the reason of using elongated ribs that effectiveness of classification is improved, except the purpose (inhibition) of above-mentioned elongated ribs, also be difficult for taking place the turbulent flow of air-flow because the effectiveness of classification that the accumulation of particle causes reduces.
It is after 0.5-50 quality %, Type B viscosity are the particle dispersion liquid wet classification of 0.5-20mPas that the above-mentioned powder particulate that offers dry classification is preferably solid component concentration, the particulate dry, that pulverizing obtains.The solid component concentration of particle dispersion liquid is preferably 0.5-20 quality %, and Type B viscosity is preferably 0.5-10mPas.
Under the high situation of situation that the solid component concentration of the microparticulate solution in supplying to the wet classification device is high or viscosity, there is classification to need the long period, the load of sieve is increased, makes the sieve aperture expansion of sieve become possibility big, that effectiveness of classification reduces.In addition, solid component concentration was than 0.5 quality % hour, and classification also becomes needs the long period.
In addition, the particle that supplies to wet classification is preferably more than the poor particle of coarse particle of 2 times particle diameter of median size.Particularly, being preferably every 0.5g greater than the content of the coarse particle of 2 times particle diameter of median size is below 1,000,000.More preferably 500,000/below the 0.5g, more preferably 200,000/below the 0.5g.
The particle dispersion liquid that above-mentioned particle dispersion liquid can be the microparticulate that will prepare in advance in the dispersion medium (water, organic solvent etc.), contain at particulate under the situation of organic polymer described later or organism mineral complex material, also can directly use the reaction solution after the polyreaction.In addition, also can directly use the particle dispersion liquid that obtains in the wet type operation.
Operable device in the wet classification of above-mentioned particle dispersion liquid, there is no particular limitation, can list the filtration unit that has used strainer or sieve, utilized liquid cyclone device of centrifugal force, mass force etc.Can list filter core cylinder (cartridge filter) (for example ロ キ テ Network ノ society system, Japanese ボ-Le society system), utilize centrifugal force to carry out fractionated liquid cyclone (for example ラ サ industry society system, イ Application ダ ス ト リ ア society system) as concrete wet classification device.
The above-mentioned filter core cylinder of crossing also can a plurality ofly be used in combination, for example, the purpose that is reduced to the operational cost that caused by long lifetime also can be used in combination satisfying the post filter (final filter) of desired filtering accuracy and being used to prolong the strainer in post filter life-span.But the selected reference of post filter is preferably the type of 2 times particle can removing the above median size of 50 quality %.For example, since the filter core cylinder of crossing of the SLP type of ロ キ テ Network ノ society system have as the thickness of the filtering material of the feature of deep filter (depth filter) with as pleat strainer (プ リ-Star Off The イ Le-) the big filtration area of feature, therefore as post filter and preferred.As the selected reference of strainer, be preferably the type of the particle more than 3 times that can filter the above median size of 50 quality %.
The particle that aforesaid liquid swirler device is is medium with liquid, will be dispersed in this liquid passes through centrifugal force fractionated device.For example, situation with device of cylinder (or circular cone) parts, supply with particle dispersion liquid from the tangential direction of this device cylindrical portion, this particle dispersion liquid as rotating fluid cylindrical portion descend during, coarse particle is moved radially under action of centrifugal force, and the inwall of collision cylinder, make it drop to the device bottom along this inwall after, reclaim from the device bottom.On the other hand, therefore fine particle reclaims small particle from device top owing to being written near the rising rotating fluid that produces the central authorities and moving above device.
Particle behind the wet classification preferably carries out drying, pulverizing.As long as dry, condition when pulverizing can satisfy the rerum natura (moisture content is that 0.05-2 quality %, true specific gravity are that 1-1.25g/ml, Bulk Specific Gravity are that 0.1-1g/ml, particle diameter are 1-50 μ m) of above-mentioned powder particulate, there is no particular limitation.
Though particulate of the present invention obtains the powder particulate dry classification with rerum natura of regulation, but also can be as required and other stage division combination, especially be reduced to low-level viewpoint from the content that makes coarse particle and fine particle, preferably in the preparation of powder particulate, adopt above-mentioned wet classification operation.That is,, can list and to have the particle dispersion liquid wet classification of regulation rerum natura, after the particle drying behind the wet classification, the pulverizing, carry out the operation of dry classification again as preferred operation in order to obtain particulate of the present invention.By this operation, can obtain particulate of the present invention more expeditiously, the coarse particle that promptly has the particle diameter more than 2 times of median size is more than 1000/the following particulate of 0.5g.
Below, describe for the structure and the preparation method of the particulate that the present invention relates to.
There is no particular limitation for the form of the particulate that the present invention relates to, can be for containing any the particulate in organic polymer, inorganic material, the organism composite material of inorganic matter.Can list the simple linear polymer of polystyrene, polymethylmethacrylate, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polysulfones, polycarbonate, polymeric amide etc. as above-mentioned organic polymer; Vinylstyrene, hexatriene, divinyl ether, divinyl sulfone, diallyl methyl alcohol, alkylene diacrylate (alkylenediacrylate), oligomeric (oligo) or poly-alkyl diol diacrylate (polyalkyleneglycoldiacrylate), oligomeric or poly-alkyl diol dimethacrylate, alkylene triacrylate (alkylenetriacrylate), the alkylene tetraacrylate, the alkylene trimethacrylate, alkylene tetramethyl-acrylate, the alkylene bisacrylamide, the two Methacrylamides of alkylene, two terminal propenyl modified polybutadiene oligopolymer etc. separately or the network polymer that obtains with other polymerizable monomer polymerization; The organic polymer that contains the aminoresin that the polycondensation by aminocompound (for example benzoguanamine, trimeric cyanamide or urea etc.) and formaldehyde obtains.
As the organism composite material of inorganic matter, can list: (A) the inorganics microparticulate of the metal oxide of silicon-dioxide, aluminum oxide, titanium dioxide etc., metal nitride, metallic sulfide, metallic carbide etc. and be contained in the particulate that forms in the organic resin; (B) silicon of the poly methyl silsesquioxane that obtains of the carrying out of the hydrolysis of the particulate that is composited on molecular level of metal oxygen alkane (metalloxane) chain (molecular chain that contains " metal-oxygen-metal " key) of (organic) polysiloxane, poly-titanoxane (polytitanoxane) etc. and organic molecule or the organoalkoxysilane by methyltrimethoxy silane etc., condensation reaction etc. is particulate; (C) be the organism composite material of inorganic matter that contains organic polymer skeleton and polysiloxane skeleton that the polysiloxane of raw material and the reactions such as polymerizable monomer with polymerizable group (for example vinyl, (methyl) acryl etc.) obtain by making with silicon compound with water-disintegrable silyl.
As inorganic material, for example, can list glass, silicon-dioxide, aluminum oxide etc.
Even in above-mentioned example, contain the particulate of organic polymer or organism composite material of inorganic matter, owing to can more freely carry out the design of the characteristic of particulate, or can easily obtain having the particle of precipitous size distribution and preferred.And, in containing the particulate of organic polymer, be preferably organic polymer that contains aminoresin and the organic polymer particle that obtains by seeding polymerization method (シ-De coincidence method) (with respect to the ratio of the cross-linkable monomer of the full dose of polymerizable monomer be more than the 20 quality %, more preferably more than the 30 quality %, the particle more than the 50 quality % more preferably), in the particulate that forms by the organism composite material of inorganic matter, be preferably (C) especially.In addition, these particles are cured in its building-up process or are crosslinked, and are difficult to by organic solvent dissolution, swelling.Therefore, be used to form light diffusion layer described later, antiglare layer be coated with the application resin combination time, even owing to use simultaneously with organic solvent etc., particle also is difficult to rotten or particle diameter is difficult to change, therefore, can be made coarse particle be reduced to the interior effect of above-mentioned scope fully, thus preferred.
These particles preferably offer the wet classification operation under the state of the particle suspension that obtains when each particle synthetic.That is, this is poor (for example, the cause that obtains easily of the suspension of 1,000,000 of less thaies/0.5g) of the coarse particle more than 2 times of median size.Be preferably the particulate that contains the organism composite material of inorganic matter that makes by the preferred manufacturing procedure that contains with following explanation, the organic polymer particulate that contains aminoresin especially.
In addition, above-mentioned particle is preferably the coefficient of variation (size-grade distribution that calculates with volume reference is a benchmark) of particle diameter at the particle below 20%.More preferably below 10%.The value of the coefficient of variation of particle diameter is more little, represents the uneven few more of particle diameter, is satisfying under the situation of above-mentioned scope, and is because the amount of the coarse particle that is contained in the particulate after wet classification, dry classification operation is easy to reduction, therefore preferred.In addition, at this, the value of the coefficient of variation of particle diameter for calculating by following formula.
[mathematical expression 1]
The coefficient of variation of particle diameter (%)=(σ/X) * 100
Wherein, σ represents the standard deviation of particle diameter, and X represents median size.
Among the present invention, the standard deviation of median size and particle diameter is to use described accurate particle size distribution device (ベ for example Star" the マ Le チ サ イ ザ-II " of Network マ Application コ-Le -society's system) measure, calculate with volume reference.
At this, to the particulate (aminoresin) that contains above-mentioned organic polymer, and, contain the organism composite material of inorganic matter particulate (above-mentioned (C)), with and structure and preparation method describe.
The preparation method of＜amino resin crosslinked particle 〉
At first, to describing as the preparation method who contains the aminoresin (amino resin crosslinked particle) of the particulate of above-mentioned organic polymer.
Can list first preparation method and second preparation method of following explanation as the preparation method of amino resin particle.According to this first and second preparation method, owing to can control particle diameter at the synthesis phase of particulate, thereby can how much suppress the generation of coarse particle.Therefore,, can more easily carry out the reduction that particle diameter exceeds the content of the particle that is fit to scope by being added to the operation that is used for obtaining the above-mentioned particulate that the present invention relates to by the amino resin crosslinked particle that this preparation method obtains, thus preferred.At first, first preparation method is described.
First preparation method
First preparation method of amino resin crosslinked particle (below, abbreviate " first preparation method " as) comprising: by making amino based compound and formaldehyde reaction to obtain the resinifying operation of aminoresin presoma; The aminoresin presoma that will in described resinifying operation, obtain in water-medium emulsification with the emulsification process of the emulsion that obtains the aminoresin presoma; And be cured reaction to adding the aminoresin presoma that catalyzer carries out after the emulsification in the emulsion that in described emulsification process, obtains, to obtain the curing process of amino resin crosslinked particle.
Above-mentioned resinifying operation is to make amino based compound and formaldehyde reaction to generate the operation as the aminoresin presoma of initial stage condensation reaction thing.Solvent when making amino based compound and formaldehyde reaction can make water.Concrete implementation method as this resinifying operation preferably can list: be to add the method that amino based compound reacts under the state of the aqueous solution (formalin) at formaldehyde; Or trioxane or Paraformaldehyde 96 added in the water, in water, regulate so that generate and add method that amino based compound reacts etc. in the aqueous solution of formaldehyde.Wherein, the former method does not need the regulating tank of formalin, and, obtain raw material easily, thus more preferred on the economy this point.In addition, when adopting any method, the resinifying operation is preferably carried out under the stirring by known whipping appts etc.
In the resinifying operation, can there is no particular limitation as the amino based compound of starting raw material, for example, can list benzoguanamine (2,4-diamino-6-phenyl s-triazine), hexanaphthene carbonyl guanamines (シ Network ロ ヘ キ サ Application カ Le ボ グ ア Na ミ Application), tetrahydrobenzene carbonyl guanamines (ジ Network ロ ヘ キ セ Application カ Le ボ グ ア Na ミ Application) and trimeric cyanamide etc.Wherein, the amino based compound that more preferably has triazine ring.Especially, because benzoguanamine has phenyl ring and two reactive groups, therefore when containing benzoguanamine as amino based compound, flexibility (hardness), stain resistance, thermotolerance, solvent resistance, the resistance to chemical reagents of the amino resin crosslinked particle that generates are good, thereby preferred especially benzoguanamine.Above-mentioned amino based compound may be used alone, used in two or more.
In the total amount of employed amino based compound, the shared ratio of above-mentioned amino based compound (benzoguanamine, hexanaphthene carbonyl guanamines, tetrahydrobenzene carbonyl guanamines and trimeric cyanamide), add up to and be preferably more than the 40 quality %, more preferably more than the 60 quality %, more preferably more than the 80 quality %, most preferably be 100 quality %.The content of above-mentioned amino based compound is when 40 quality % are above, and the amino resin crosslinked particle of generation becomes thermotolerance and the good particle of solvent resistance.
The amino based compound that reacts in the resinifying operation and the mol ratio of formaldehyde (amino based compound (mole)/formaldehyde (mole)) are preferably 1/3.5-1/1.5, more preferably 1/3.5-1/1.8, more preferably 1/3.2-1/2.During above-mentioned mol ratio less than 1/3.5, there is the unreacted reactant of formaldehyde to become many possibilities; Surpass at 1/1.5 o'clock, have the unreacted reactant of amino based compound to become many possibilities.
Moreover the aminocompound when resinifying operation reinforced and the concentration of formaldehyde only otherwise reaction is caused obstacle, are preferably than higher concentration.Particularly, be preferably and the viscosity adjustment of reaction solution in 95-98 ℃ temperature range that contains as the aminoresin presoma of resultant of reaction can be controlled at 2 * 10 -2-5.5 * 10 -2Concentration in the scope of Pas (20-55cP).More preferably can add reaction solution in the aqueous solution of emulsifying agent or the concentration that becomes in the scope of 30-60 quality % of the concentration of adding aqueous solution aminoresin presoma in the emulsion in reaction solution so that in emulsification process described later of emulsifying agent or emulsifying agent get final product.
Therefore, contain the viscosity of reaction solution in 95-98 ℃ temperature range of the aminoresin presoma that in the resinifying operation, obtains, be preferably 2 * 10 -2-5.5 * 10 -2Pas (20-55cP), more preferably 2.5 * 10 -2-5.5 * 10 -2Pas (25-55cP), more preferably 3.0 * 10 -2-5.5 * 10 -2Pas (30-55cP).As the measuring method of above-mentioned viscosity, be preferably use immediately (in real time) grasp carrying out state and can correctly differentiating the method for viscosity determinator of the terminal point of this reaction of reaction.As this viscosity determinator, can use oscillatory viscometer (MIVIITS ジ ヤパ Application society system, trade(brand)name: MIVI6001).This viscometer has the vibration section of frequent vibration, and by this vibration section is immersed in the reaction solution, the viscosity of this reaction solution increases and to the vibration section applying load, this load immediately is converted into viscosity and shows.
By amino based compound and formaldehyde in water (in water-medium) are reacted, can obtain so-called initial stage condenses---aminoresin presoma.In order immediately to grasp carrying out state, correctly identifying that the terminal point of this reaction, temperature of reaction are preferably in 95-98 ℃ the temperature range of reaction.Then, the viscosity at reaction solution becomes 2 * 10 -2-5.5 * 10 -2During time point in the scope of Pas, the reaction that stops amino based compound and formaldehyde by the operation with this reaction solution cooling etc. gets final product.Thus, can obtain containing the reaction solution of aminoresin presoma.In addition, there is no particular limitation the reaction times.
About the aminoresin presoma that obtains in the resinifying operation, the mol ratio (come from the structural unit (mole) of amino based compound/come from the structural unit (mole) of formaldehyde) that constitutes the structural unit that comes from amino based compound of this aminoresin presoma and come from the structural unit of formaldehyde is preferably 1/3.5-1/1.5, more preferably 1/3.5-1/1.8, more preferably 1/3.2-1/2.As long as above-mentioned mol ratio in above-mentioned scope, just can access the particle of narrow particle size distribution.
Usually, the aminoresin presoma, organic solvent for acetone Huo diox, methyl alcohol, ethanol, Virahol, butanols, ethyl acetate, butylacetate, methyl glycol, glycol monoethyl ether, butanone, toluene, dimethylbenzene etc. is soluble, and is insoluble to water base.
In first preparation method,, the particle diameter of the amino resin crosslinked particle that finally obtains is diminished by reducing the viscosity of the reaction solution in the resinifying operation of preparing the reaction solution that contains above-mentioned aminoresin presoma.Yet, in the viscosity less than 2 * 10 of reaction solution -2During Pas, or surpass 5.5 * 10 -2During Pas, the situation that is difficult to obtain roughly the same (narrow particle size distribution) amino resin crosslinked particle of final particle diameter is arranged.That is the viscosity less than 2 * 10 of reaction solution, -2During Pas (20cP), the emulsion that in emulsification process described later, the obtains deficient in stability that becomes.Therefore, when the aminoresin presoma is solidified, the possibility of condensing between rewarding amino resin crosslinked particle hypertrophyization, particle has the particle diameter that can not control amino resin crosslinked particle, the possibility that becomes the wide amino resin crosslinked particle of size-grade distribution.In addition, when the emulsion deficient in stability, in each preparation (in every batch), have the particle diameter (median size) of amino resin crosslinked particle to change, product produce uneven may.On the other hand, the viscosity of reaction solution surpasses 5.5 * 10 -2During Pas (55cP), have the load that employed homogenizer in emulsification process described later etc. is applied excessive, its shearing force is reduced, stirring reaction liquid (making its milkiness) may fully.Therefore, to the control of the particle diameter of the amino resin crosslinked particle that finally the obtains difficulty that becomes, the situation that becomes the wide amino resin crosslinked particle of size-grade distribution is arranged.Thereby, in the resinifying operation, preferably in advance reaction solution is adjusted to above-mentioned range of viscosities.
Emulsification process is the aminoresin presoma emulsification that will obtain by the resinifying operation operation with the emulsion of preparation aminoresin presoma.When the emulsification of aminoresin presoma, for example, preferred use can constitute the emulsifying agent of protective colloid, the preferred especially emulsifying agent that contains the water-soluble polymers that can constitute protective colloid that uses.
As mentioned emulsifier, for example, can use polyvinyl alcohol, carboxymethyl cellulose, sodium alginate, polyacrylic acid, water-soluble polyacrylate, polyvinylpyrrolidone etc.These emulsifying agents can be so that all be dissolved into the state of the aqueous solution in the water and use, and also wherein a part is used with the state of the aqueous solution, and surplus is used with its original state (for example powder shaped, particulate state, aqueous etc.).In the emulsifying agent illustrated above, consider the stability of emulsion, with the interaction of catalyzer etc., polyvinyl alcohol more preferably.Polyvinyl alcohol can be fully saponified thing, also can be partly-hydrolysed thing.In addition, there is no particular limitation for the polymerization degree of polyvinyl alcohol.
The usage quantity of emulsifying agent, the aminoresin presoma that obtains in above-mentioned resinifying operation with respect to 100 mass parts is preferably the 1-30 mass parts, more preferably the 1-5 mass parts.This usage quantity is outside above-mentioned scope the time, and emulsion has the possibility of the deficient in stability that becomes.In addition, many more with respect to the usage quantity of the emulsifying agent of aminoresin presoma, the particle diameter of the particle of generation has the tendency that diminishes.
In emulsification process, for example, add the reaction solution that obtains in the above-mentioned resinifying operation aqueous solution of emulsifying agent to, so that after the concentration of aminoresin presoma (being solid component concentration) becomes in the scope of 30-60 quality %, preferably in 50-100 ℃ temperature range, make its milkiness.More preferably 60-100 ℃, more preferably 70-95 ℃.There is no particular limitation for the concentration of the aqueous solution of emulsifying agent, so long as the concentration adjustment of aminoresin presoma can be got final product to the concentration in the above-mentioned scope.During the concentration less than 30 quality % of aminoresin presoma, the productivity of amino resin crosslinked particle has the possibility of reduction; When surpassing 60 quality %, the possibility that produces cohesion between amino resin crosslinked particle hypertrophyization that obtain, particle is arranged, the wide possibility of size-grade distribution change of the amino resin crosslinked particle that also have the control of the particle diameter of amino resin crosslinked particle to become difficult, to obtain.
In emulsification process, as alr mode, preferred use can be stirred the device (device with high shear force) of the aqueous solution of above-mentioned aminoresin presoma and emulsifying agent more forcefully.As concrete whipping appts, for example, can list so-called homogenizer, uniform mixing machine (ホ モ ミ キ サ-), TK uniform mixing machine (Te Shu Machine chemical industry (strain) system), high speed dispersion device (high speed デ イス パ-), dust crust Rameau Ilyushin Sa (エ バ ラ マ イ Le ザ-, (strain) Ren Yuan System does made), high-pressure homogenizer ((strain) イ ズ ミ Off-De マ シ Na リ system), static mixer ((strain) ノ リ ケ カ Application パ ニ-リ ミ テ StarDe system) etc.
In emulsification process, preferably promote resulting aminoresin presoma emulsification in the resinifying operation, till the particle diameter that forms regulation.And,, can suitably set the particle diameter of regulation as long as finally can obtain the amino resin crosslinked particle of desirable particle diameter.Particularly, kind by suitably considering container or agitating wing, stirring velocity, churning time, emulsifying temperature etc., preferably carry out emulsification and make that the median size of the aminoresin presoma after the emulsification is 0.1-20 μ m, more preferably 0.5-20 μ m, more preferably 1-5 μ m.Like this, make that by carrying out emulsification the aminoresin presoma is above-mentioned particle size range, the particle diameter that can control amino resin crosslinked particle is in desirable scope.
In first preparation method,, as required, can add inorganic particulate in advance behind the above-mentioned emulsification process in the resulting emulsion for the amino resin crosslinked particle that more positively prevents from finally to obtain condenses securely.As inorganic particulate, particularly, preferably can list for example silicon dioxide microparticle, zirconium white particulate, aluminium powder, alumina sol, ceric oxide sol (セ リ エ ゾ Le) etc., wherein, calm facile viewpoint is set out, more preferably silicon dioxide microparticle.The specific surface area of inorganic particulate is preferably 10-400m 2/ g, more preferably 20-350m 2/ g, more preferably 30-300m 2/ g.The particle diameter of inorganic particulate is more preferably below the 0.2 μ m, more preferably below the 0.1 μ m, more preferably below the 0.05 μ m.Specific surface area or particle diameter be as long as in above-mentioned scope, securely aspect the cohesion, just can bring into play better effect at the amino resin crosslinked particle that prevents from finally to obtain.
Add the method for inorganic particulate in emulsion, there is no particular limitation, particularly, for example, can list the method that inorganic particulate is added with original state (granular), or the method that inorganic particulate is added with the state that is distributed to the dispersion liquid in the water.With respect to the addition of the inorganic particulate of emulsion, the aminoresin presoma in the emulsion of being contained in respect to 100 mass parts is preferably the 1-30 mass parts, more preferably 2-28 mass parts, more preferably 3-25 mass parts.During less than 1 mass parts, the possibility that has the amino resin crosslinked particle that can not prevent from fully finally to obtain to condense securely; When surpassing 30 mass parts, the possibility that produces the condensation product that has only inorganic particulate is arranged.In addition, the stirring means during as the interpolation inorganic particulate is considered from the aspect that inorganic particulate is firmly adhered on the amino resin particle, preferably uses described method with device of strong shearing force.
In curing process, by adding catalyzer (being specially curing catalysts) in the emulsion after in above-mentioned emulsification process, regulating so that the aminoresin presoma after the emulsification is cured reaction (make aminoresin presoma with milkiness state solidify), thereby generate amino resin crosslinked particle (being specially the suspension of amino resin crosslinked particle).
Be preferably acid catalyst as above-mentioned catalyzer (curing catalysts).Can use the mineral acid of hydrochloric acid, sulfuric acid, phosphoric acid etc. as acid catalyst; The sulfonic acid of the ammonium salt of these mineral acids, thionamic acid, Phenylsulfonic acid, tosic acid, Witco 1298 Soft Acid etc.; The organic acid of phthalic acid, phenylformic acid, acetate, propionic acid, Whitfield's ointment etc.In the above-mentioned illustrative acid catalyst, aspect curing speed, consider to be preferably mineral acid, further, from the aspect consideration to the corrodibility of installing, the security when using mineral acid etc., more preferably sulfuric acid.In addition,, when using sulfuric acid, compare when for example using Witco 1298 Soft Acid as above-mentioned catalyzer, the difficult variable color of the amino resin crosslinked particle that finally obtains, and also solvent resistance is strong, thus preferred.These acid catalysts can only use a kind of, also can two or more and usefulness.
The usage quantity of above-mentioned catalyzer, the aminoresin presoma in the emulsion that above-mentioned emulsification process obtains of passing through with respect to 100 mass parts is preferably the 0.1-5 mass parts, more preferably 0.3-4.5 mass parts, more preferably 0.5-4.0 mass parts.When the usage quantity of catalyzer surpasses 5 mass parts, have that the milkiness state is destroyed, produce the possibility of cohesion between particle; During less than 0.1 mass parts, responding needs the long period or solidifies inadequate possibility.In addition, similarly, the usage quantity of above-mentioned catalyzer, with respect to 1 mole as the amino based compound of starting compound, be preferably more than 0.002 mole, more preferably more than 0.005 mole, 0.01-0.1 mole more preferably.With respect to 1 mole amino based compound, during 0.002 mole of the usage quantity deficiency of catalyzer, respond need the long period or solidify inadequate may.
Curing reaction in curing process, preferably with reaction soln (emulsion) be preferably 15 ℃ (normal temperature) to 80 ℃, more preferably 20-70 ℃, more preferably under 30-60 ℃, keep after at least 1 hour, at normal pressure or add and depress, be preferably 60-150 ℃, more preferably 60-130 ℃, more preferably carry out under 60-100 ℃ the temperature of scope.During 60 ℃ of the temperature of reaction deficiencies of curing reaction, the solvent resistance of the amino resin crosslinked particle that curing can not carry out fully, obtain and the possibility that thermotolerance reduces are arranged.On the other hand, when temperature of reaction surpasses 150 ℃, need firm pressurized reactor, uneconomical.The terminal point of curing reaction gets final product by sampling or visual judgement.In addition, in the reaction times of curing reaction, do not limit especially.
Curing process preferably under agitation carries out, and as alr mode, uses known whipping appts to get final product.In curing process, preferably the median size of solidifying the amino resin crosslinked particle obtain by the aminoresin presoma that makes the milkiness state is 0.1-20 μ m, more preferably 0.5-20 μ m, more preferably 1-5 μ m.
In first preparation method, can comprise in the suspension of the emulsion of aminoresin presoma or amino resin crosslinked particle, adding dyestuff is dissolved in the water and the painted operation of the aqueous solution that obtains.
In first preparation method, also can comprise and carry out in the neutral and operation the suspension that contains the amino resin crosslinked particle that obtains by above-mentioned curing process.In and operation, preferably in above-mentioned curing process, when having used the acid catalyst of sulfuric acid as curing catalysts etc., carry out.By in carrying out and operation, can remove above-mentioned acid catalyst (being specially the neutralizing acid catalyzer), for example, and in heating process described later etc., the variable color of the amino resin crosslinked particle in the time of can suppressing to heat amino resin crosslinked particle (for example yellowing).
So-called in and " neutralization " in the operation be that to instigate the pH of the suspension that contains amino resin crosslinked particle be more than 5, more preferably making pH is 5-9.When the pH of this suspension less than 5, because the residue of acid catalyst, in heating process described later etc., the situation of amino resin crosslinked particle variable color is arranged.By above-mentioned neutralization with the pH that regulates this suspension in above-mentioned scope, can obtain hardness height, solvent resistance and excellent heat resistance and not have the amino resin crosslinked particle of variable color.As can in and the neutralizing agent that uses in the operation, for example, alkaline matter is fit to.As this alkaline matter, for example, can list yellow soda ash or sodium hydroxide, potassium hydroxide, ammonia, wherein consider from aspect simple to operate, preferably use sodium hydroxide, can compatibly use aqueous sodium hydroxide solution.These can only use a kind of, also can two or more and usefulness.
In first preparation method, also can comprise behind curing process or and select the separation circuit of this amino resin crosslinked particle in the suspension of the amino resin crosslinked particle that obtains after the operation.
As the method for from suspension, selecting amino resin crosslinked particle (separation method), can list filtering separation (Filter Do as easy method) method or use the method for the separating machine of whizzer etc., but there is no particular limitation, can use generally well-known any one separation method.
And, the amino resin crosslinked particle after selecting from suspension, also water etc. washs as required.
In first preparation method, the preferred heating process that the amino resin crosslinked particle of selecting through separation circuit is heated under 130-190 ℃ temperature.By carrying out heating process, can remove attached to the moisture on the amino resin crosslinked particle and residual free (unreacted) formaldehyde, and can further promote the condensation (crosslinked) that amino resin crosslinked particle is interior.Above-mentioned Heating temperature has the condensation (crosslinked) that can not promote fully in the amino resin crosslinked particle, the hardness that can not improve amino resin crosslinked particle, solvent resistance and stable on heating possibility when lower than 130 ℃; When surpassing 190 ℃, the possibility of resulting amino resin crosslinked particle variable color is arranged.Even carried out above-mentioned in and under the situation of operation, the influence of Heating temperature outside the said temperature scope time also is same.From the viewpoint of all characteristics (hardness, solvent resistance, thermotolerance, discoloration-resistant) of improving resulting amino resin crosslinked particle, preferably in carrying out and the operation, the Heating temperature that also will make amino resin crosslinked particle is in above-mentioned scope.
Heating means in heating process, there is no particular limitation, uses generally well-known heating means to get final product.Heating process, for example, the stage that becomes (more preferably below the 2 quality %) below the 3 quality % at the water ratio of amino resin crosslinked particle finishes to get final product.In addition, heat-up time, there is no particular limitation.
Also the amino resin crosslinked particle that obtains in first preparation method can be separated from the water-medium when the described emulsification and dry, pulverize after, the crushed material that obtains is distributed to the suspension of making in the solvent supplies to wet type and dry classification operation.In addition, with the suspension behind the curing process (behind the curing process, comprise by in and the suspension that obtains of operation etc., supply to the suspension arbitrarily till the separation circuit) to supply to wet classification also be preferred mode in the method for the present invention.Preferably after the above-mentioned separation circuit or the heating process of carrying out as required, by with suspension drying, pulverizing behind the wet classification, obtaining moisture content is the powder particulate of 0.05-2 quality %, and it is supplied to the dry classification operation.
Below, second preparation method of amino resin crosslinked particle is described.
Second preparation method
Second preparation method of amino resin crosslinked particle (below, abbreviate " second preparation method " as) be meant and will in water-medium, mix by the aminoresin presoma that amino based compound and formaldehyde reaction are obtained with tensio-active agent, by in this mixed solution, adding catalyzer, make described aminoresin presoma in described water-medium particlized and separate out after, described amino resin crosslinked particle is separated and dry the method that the dry thing that obtains is pulverized from described water-medium.
Second preparation method is also the same with first preparation method, adopt the resinifying operation, in this resinifying operation, make amino based compound and formaldehyde reaction to generate the aminoresin presoma, but in second preparation method, from adopting mixed processes and adopting the aspect of solidifying the particlized operation, different with first preparation method, described mixed processes is that the aminoresin presoma that will obtain by the resinifying operation mixes with tensio-active agent in water-medium, described curing particlized operation is to add the particlized that catalyzer causes with the curing of carrying out by the aminoresin presoma and separate out in the mixed solution that contains this aminoresin presoma and tensio-active agent, thereby obtains amino resin crosslinked particle.
In second preparation method, begin to solidify by under aqueous solution state, making the aminoresin presoma, the preparation of the little amino resin crosslinked particle of particle diameter is become easily (for example, median size is 0.1-50 μ m).
In addition, as the amino based compound that uses in second preparation method, preferred suitably its kind of setting and group direct ratio are to satisfy water Combination described later.For example, more preferably must can generate the amino based compound of water miscible aminoresin presoma with the formalin reaction.
In addition, the aminoresin presoma that obtains in the resinifying operation is preferably water miscible.The tensio-active agent that uses in second preparation method uses in order to give wetting ability in the water-medium of aminoresin presoma, is not included in employed emulsifying agent among first preparation method in this tensio-active agent.
In the present invention, quality % (hereinafter referred to as the water mixedness) expression of above-mentioned wetting ability with respect to the initial stage condenses of the dripping quantity of the water when in as the aminoresin presoma of initial stage condenses, dripping water under 15 ℃ until the generation white opacity, its value is big more, and the expression wetting ability is high more.And in second preparation method, the water mixedness of the aminoresin presoma that is fit to is more than 100%.In the aminoresin presoma of water mixedness less than 100%, in containing the aqueous solution of tensio-active agent (water-based liquid), how it is disperseed, also can only form the bigger uneven suspension of particle diameter ratio, the spheroidal particle that finally obtains is difficult to become the particulate (size distribution is wide) with uniform particle diameter.
In mixed processes, in water-medium, stir grade by the aminoresin presoma that the resinifying operation is obtained and mix with tensio-active agent with the preparation mixed solution.
As above-mentioned tensio-active agent, for example, whole tensio-active agents such as aniorfic surfactant, cationic surfactant, nonionic surface active agent, amphoterics be can use, aniorfic surfactant or nonionic surface active agent or their mixtures are preferably especially.
As anion surfactant, can use as sodium lauryl sulphate, the alkali metal alkyl sulfate of dodecyl sulphate potassium etc., alkylsurfuric acid ammonium as ammonium lauryl sulfate etc., dodecyl polyoxyethylene glycol ether sodium sulfate, Sodium Thiocyanate 99 (Na ト リ ウ system ス Le ホ リ シ ノ エ-ト), an alkali metal salt as sulfonation paraffin (ス Le ホ Application パ ラ Off イ Application), the alkylsulfonate of the ammonium salt of sulfonation paraffin etc., as sodium laurate, triethanolamine oleate, the soap of sylvic acid trolamine etc. is as Sodium dodecylbenzene sulfonate, alkaline phenol hydroxyl ethene (ア Le カ リ Off エThe alkylaryl sulphonate of alkali metal sulfates ノ-Le ヒ De ロ キ シ エ チ レ Application) etc., high sulfonated alkyl naphathalene, naphthalene sulfonic acidformaldehyde condensation product, dialkyl sulfosuccinates, polyoxyethylene alkyl sulfuric ester salt, polyoxyethylene alkyl aryl sulfate salt etc.; As nonionic surface active agent, can use polyethylene oxide alkyl ethers, the polyoxyethylene alkyl aryl ether, sorbitan-fatty acid ester, the polyoxyethylene sorbitan-fatty acid ester, the glycerine monofatty ester of glyceryl monolaurate etc., polyoxyethylene propylene oxide copolymer, the condensation resultant of oxyethane and fatty amine, acid amides or acid etc.
The usage quantity of tensio-active agent, the aminoresin presoma that obtains in the above-mentioned resinifying operation with respect to 100 mass parts is preferably the scope of 0.01-10 mass parts.During less than 0.01 mass parts, sometimes can not obtain the steady suspension of amino resin crosslinked particle, in addition, when surpassing 10 mass parts, sometimes in above-mentioned suspension, unnecessary foaming phenomenon can be produced, adverse influence can be produced the rerum natura of the amino resin crosslinked particle that finally obtains.
In mixed processes, for example, preferably in the aqueous solution of tensio-active agent, add the reaction solution that obtains in the above-mentioned resinifying operation, the concentration (being the concentration of solids component) of aminoresin presoma in the scope of 3-25 quality %, is mixed then.At this moment, there is no particular limitation for the concentration of the aqueous solution of tensio-active agent, gets final product to the concentration in the above-mentioned scope so long as can regulate the concentration of aminoresin presoma.During the concentration less than 3 quality % of above-mentioned aminoresin presoma, the possibility that has the productivity of amino resin crosslinked particle to reduce; When surpassing 25 quality %, have between amino resin crosslinked particle hypertrophyization that obtain, particle to produce the possibility of condensing, the particle diameter owing to not controlling amino resin crosslinked particle has the possibility that becomes the wide amino resin crosslinked particle of size-grade distribution.
As the stirring means in the mixed processes, adopt general stirring means to get final product, be preferably and for example use disc turbine (デ イス Network -PVC Application), fan turbine (Off アApplication -PVC Application), the pull-up (Off in method Wudu アウ De ラ-type), the agitating wing of propeller-type and multistage aerofoil profile etc. carries out stirring method etc.
In second preparation method,, also add inorganic particulate in the mixed solution that can behind mixed processes, obtain in advance as required for the amino resin crosslinked particle that prevents from finally to obtain firmly condenses.About inorganic particulate and addition means thereof etc., the explanation among described first preparation method can similarly be suitable for.
In solidifying the particlized operation, in above-mentioned mixed processes, add catalyzer (being curing catalysts in detail) in the liquid mixture prepared, carry out the curing reaction and the particlized thereof of aminoresin presoma, and generate amino resin crosslinked particle (being the suspension of amino resin crosslinked particle in detail).
As above-mentioned catalyzer (curing catalysts), be preferably acid catalyst.As acid catalyst, the same material of illustrative material among the preferred use and first preparation method in second preparation method, especially preferably uses to have the alkyl benzene sulphonate (ABS) of carbonatoms as the alkyl of 10-18.Have the alkyl benzene sulphonate (ABS) that carbonatoms is the alkyl of 10-18, the special some surface active property of performance generates stable cured resin suspension in as the aqueous solution of the aminoresin presoma of initial stage condenses.Particularly, for example, can list decyl Phenylsulfonic acid, Witco 1298 Soft Acid, tetradecyl Phenylsulfonic acid, hexadecyl Phenylsulfonic acid, octadecyl Phenylsulfonic acid etc.These can only use a kind of, also can two or more and usefulness.
The usage quantity of above-mentioned catalyzer, the aminoresin presoma in the mixed solution that above-mentioned mixed processes obtains of passing through with respect to 100 mass parts is preferably the 0.1-20 mass parts, more preferably 0.5-10 mass parts, more preferably 1-10 mass parts.The usage quantity of above-mentioned catalyzer is when being lower than above-mentioned scope a small amount of, condensation curedly need the long period, and have the steady suspension that can not obtain amino resin crosslinked particle, finally can only obtain with the state of the particle that contains a large amount of thickization of cohesion may.In addition, when being higher than the volume of above-mentioned scope, the catalyzer that is assigned to abovementioned alkyl Phenylsulfonic acid in the amino resin crosslinked particle in the suspension of generation etc. becomes more than the necessary amount, its result, have make the amino resin crosslinked particle plasticization, in condensation cured, be prone between particle cohesion or fusion adhesion, finally can not get having uniform particle diameter amino resin crosslinked particle may.
In addition, similarly, as the usage quantity of above-mentioned catalyzer, with respect to 1 mole as the amino based compound of starting compound, be preferably more than 0.0005 mole, more preferably more than 0.002 mole, 0.005-0.05 mole more preferably.When the amino based compound of the usage quantity of catalyzer with respect to 1 mole is 0.0005 mole of less than, respond need the long period, solidify inadequate may.
Solidify curing reaction and particlized in the particlized operation, in the mixed solution of aminoresin presoma, add above-mentioned catalyzer after, under agitation, add under the suitable temperature of depressing the high temperature more than 0 ℃ low temperature to 100 ℃ and keep getting final product.The addition means of above-mentioned catalyzer has no particular limits, and can suitably select.The terminal point of curing reaction gets final product by sampling or visual judgement.In addition, there is no particular limitation the reaction times of curing reaction.Usually, curing reaction is by being warmed up to 90 ℃ or above temperature and keeping certain hour to finish, but need not one fixing on high temperature is cured, even be cured in the short period of time at low temperatures, as long as the amino resin crosslinked particle in the suspension that obtains is cured to the degree of not swelling in methyl alcohol or acetone, solidify just very abundant.
Solidifying the particlized operation preferably carries out under the stirring by generally well-known whipping appts etc.The median size of the amino resin crosslinked particle in the median size of preferred amino resin crosslinked particle and first preparation method's the curing process is identical.
In second preparation method, can comprise and carry out in the neutral and operation the suspension that contains the amino resin crosslinked particle that obtains by above-mentioned operation.For in and the details of the scope of pH in the operation or the kind of neutralizing agent etc., the explanation among first preparation method can similarly be suitable for.
In second preparation method, also can be provided with after solidifying the particlized operation or and select the separation circuit of this amino resin crosslinked particle in the suspension of the amino resin crosslinked particle that obtains after the operation.And, in second preparation method, so-called separate and select amino resin crosslinked particle from suspension be meant that water-medium from mixed processes separates and selects the amino resin crosslinked particle that obtains by curing.For the method for from suspension, selecting amino resin crosslinked particle (separation method), can suitably use the method identical with first preparation method.
In second preparation method, preferably carry out under 130-190 ℃ temperature, heating the heating process of the amino resin crosslinked particle of selecting through separation circuit.As the condition of heating process, can compatibly use the condition identical with first preparation method's heating process.
The amino resin crosslinked particle that in second preparation method, obtains, preferably with it during from described mixed processes or the water-medium when solidifying the particlized operation separate and dry, pulverize after, with the crushed material that obtains and solvent as suspension, after its wet classification, separation, drying, carry out dry classification.Preferably with the suspension after above-mentioned curing, the particlized operation or through in and the suspension of operation/washing step supply in wet type and the dry classification.Separating particle behind the preferred wet classification carries out drying by heating process as required, pulverizes, make become the powder particulate that moisture content is 0.05-2 quality % after, carry out dry classification.
Then, the particulate (above-mentioned (C)) that contains the organism composite material of inorganic matter and structure thereof and preparation method are described.There is no particular limitation for the polymerization process of the particulate of above-mentioned organism composite material of inorganic matter, can compatibly use the known polymerization process of letex polymerization, suspension polymerization, seeding polymerization, sol-gel polymerizations etc.
As mentioned above, containing the particulate (below, be called complex particles) of organism composite material of inorganic matter, is to contain as the organic polymer skeleton of organism part with as the particle of the polysiloxane skeleton of inorganics part.This complex particles is preferably at intramolecularly has the form (chemical of bonding) that Siliciumatom direct chemical in the polysiloxane skeleton is incorporated into the organosilicon atom at least one carbon atom in the organic polymer skeleton.As concrete form, be preferably by the Siliciumatom in the polysiloxane skeleton and combine with carbon atom in the organic polymer skeleton, become the form of ternary network structure with polysiloxane skeleton and organic polymer skeleton structure.
The material that the skeleton of above-mentioned organic polymer also can be material with side chain, have the material of branched structure, further have crosslinking structure.Form this skeleton organic polymer molecular weight, composition, structure and functional group have or not etc. that there is no particular limitation.As above-mentioned polymkeric substance, for example, be preferably and be selected from least a in the group of forming by polymeric amide, polyimide, polyester, polyethers, urethane, polyureas, polycarbonate, resol, melamine resin and the urea resin of the vinyl based polymer of (methyl) acrylic resin, polystyrene and polyolefine etc., nylon etc.
As the form of organic polymer skeleton, consider from the reason of the hardness that can moderately control complex particles, be preferably polymkeric substance (so-called vinyl based polymer) with the main chain that constitutes by the represented repeating unit of following formula (1).
[Chemical formula 1]
Figure A200780027514D00291
The polysiloxane skeleton is defined as the represented siloxane unit of following chemical formula (2) compound of the network of Chemical bond and the network structure that constitutes continuously.
[Chemical formula 2]
Figure A200780027514D00292
Constitute the SiO of polysiloxane skeleton 2Amount, be preferably 0.1-25 quality %, more preferably 1-10 quality % with respect to the weight of complex particles.As long as the SiO in the polysiloxane skeleton 2Amount in above-mentioned scope, control complex particles hardness will become easy.In addition, during less than 0.1 quality %, have that the flexibility or the elasticity that produce particle reduce, the possibility of inner destroyed etc. the unfavorable condition of particle when externally stress is applied on the resin combination; The possibility that when exceeding above-mentioned scope, have the adhesivity of particle and resin to reduce, the particle in the resin combination becomes and comes off easily.In addition, constitute the SiO of polysiloxane skeleton 2Amount, for by measuring the particle mass percent that the quality before and after the roasting temperature more than 800 ℃ is obtained in the oxidizing atmosphere of air etc.
Above-mentioned complex particles, the carbonatoms of this particle surface of trying to achieve by PES and the ratio (the surface atom number is than (C/Si)) of Siliciumatom number are 1.0-1.0 * 10 4The time, when using and adhesivity this resin because having excellent admix in the resin, therefore preferred.Above-mentioned surface atom number is during than (C/Si) less than 1.0, and what have that adhesivity with resin reduces may; Surpass 1.0 * 10 4The time, have that the flexibility or the elasticity that produce particle reduce, the possibility of inner destroyed etc. the unfavorable condition of particle when externally stress is applied on the resin combination.
For above-mentioned complex particles, so-called mechanical characteristicies separately such as its hardness or strength at break can suitably change at random by the ratio that makes polysiloxane skeleton part or organic polymer skeleton part and regulate.
Polysiloxane skeleton in the above-mentioned complex particles, preferably the hydrolysis-condensation reaction of the silicon compound by having hydrolization group obtains.
As having water-disintegrable silicon compound, there is no particular limitation, for example, can list represented silicon compound of following general formula (3) and derivative thereof etc.,
R’ mSiX 4-m (3)
(wherein, R ' also has substituting group, expression is selected from least a group in the group of being made up of alkyl, aryl, aralkyl and unsaturated aliphatic group, and X represents to be selected from least a group in the group of being made up of hydroxyl, alkoxyl group and acyloxy, and m is 0 to 3 integer.)。
As the represented silicon compound of above-mentioned general formula (3), there is no particular limitation, for example, as the material of m=0, can list four functionality silane of tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan, four butoxy silanes etc.; Material as m=1, can list methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, the hexyl Trimethoxy silane, the decyl Trimethoxy silane, phenyltrimethoxysila,e, the benzyl Trimethoxy silane, the naphthyl Trimethoxy silane, methyl triacetoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-glycidoxypropyltrime,hoxysilane, vinyltrimethoxy silane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3,3, the three-functionality-degree silane of 3-three fluoro propyl trimethoxy silicanes etc.; As the material of m=2, can list two functionality silane of dimethyldimethoxysil,ne, dimethyldiethoxysilane, diacetoxy dimethylsilane, diphenyl silanodiol etc.; As the material of m=3, can list a functionality silane of trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl silicane alkanol etc. etc.
Wherein, in the above-mentioned general formula (3), having m and be 1 structure, X is that methoxy or ethoxy, specific refractory power are the silane compound of 1.30-1.60, preferred owing to can access the organism inorganics composite particles of the specific refractory power that is fit on the optical applications.Particularly, can list methyltrimethoxy silane, phenyltrimethoxysila,e, 3-(methyl) acryloxy propyl trimethoxy silicane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3,3,3-three fluoro propyl trimethoxy silicanes etc.
Derivative as the represented silicon compound of above-mentioned general formula (3), there is no particular limitation, for example, can list compound that a part of X replaced by the group that can form inner complex of carboxyl, beta-dicarbonyl etc. or partial hydrolysis above-mentioned silane compound and low condenses of obtaining etc.
Have water-disintegrable silicon compound, also can only use a kind ofly, also can two or morely suitably be used in combination.In above-mentioned general formula (3), when only using the silane compound of m=3 and derivative thereof, can not get complex particles as raw material.
Above-mentioned complex particles, at the polysiloxane skeleton is that intramolecularly is when having the form that Siliciumatom directly is incorporated into the organosilicon atom at least one carbon atom in the organic polymer skeleton, has a water-disintegrable silicon compound as above-mentioned, must use silicon compound with the organic group that contains the polymerizability reactive group that can be formed with the organic polymer skeleton, as this reactive group, for example, can list free-radical polymerised group, epoxy group(ing), hydroxyl and amino etc.
As the above-mentioned organic group that contains free-radical polymerised group, for example, can list represented free-radical polymerised group in following general formula (4), (5) and (6) etc.:
CH 2＝C(-R a)-COOR b- (4)
(wherein, R aExpression hydrogen atom or methyl, R bExpression also can have the organic group that substituent carbonatoms is the divalence of 1-20.)
CH 2＝C(-R c)- (5)
(wherein, R cExpression hydrogen atom or methyl.)
CH 2＝C(-R d)-R e- (6)
(wherein, R dExpression hydrogen atom or methyl, R eExpression also can have the organic group that substituent carbonatoms is the divalence of 1-20.)
As the represented organic group that contains free-radical polymerised group of above-mentioned general formula (4), for example, can list acryloxy and methacryloxy etc.; As the silicon compound shown in the above-mentioned general formula (3) with this organic group, for example, can list γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, γ-acryloxy propyl trimethoxy silicane, γ-acryloxy propyl-triethoxysilicane, γ-methacryloxypropyl triacetoxysilane, γ-methacryloxy ethoxycarbonyl propyl Trimethoxy silane (perhaps being also referred to as γ-trimethoxy-silylpropyl-Beta-methyl acryloyl-oxy benzyl ethyl ether), γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl methyldiethoxysilane, γ-acryloxy propyl group methyl dimethoxysilane etc.They can only use a kind of, also can two or more and usefulness.
As the organic group that contains the free-radical polymerised group shown in the above-mentioned general formula (5), for example, can list vinyl, pseudoallyl etc., as the silicon compound shown in the above-mentioned general formula (3) with this organic group, for example, can list vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, vinyl methyl dimethoxysilane, vinyl methyldiethoxysilane, vinyl methyl diacetoxy silane etc.They can only use a kind of, also can two or more and usefulness.As the organic group that contains the free-radical polymerised group shown in the above-mentioned general formula (6), for example, can list 1-alkenyl or ethenylphenyl, different alkenyl or pseudoallyl phenyl etc., as the silicon compound shown in the above-mentioned general formula (3) with this organic group, for example, can list 1-hexenyl Trimethoxy silane, 1-hexenyl triethoxyl silane, 1-octenyl Trimethoxy silane, 1-decene base Trimethoxy silane, γ-trimethoxy-silylpropyl vinyl ether, ω-trimethoxysilyl undecanoic acid vinyl acetate, to trimethoxysilyl vinylbenzene (to the styryl Trimethoxy silane), 1-hexenyl methyl dimethoxysilane, 1-hexenyl methyldiethoxysilane etc.They can only use a kind of, also can two or more and usefulness.
As silicon compound with the organic group that contains epoxy group(ing), for example, can list 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-triethoxysilicane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.They can only use a kind of, also can two or more and usefulness.As the silicon compound of organic group, for example, can list 3-hydroxypropyl Trimethoxy silane etc. with hydroxyl.They can only use a kind of, also can two or more and usefulness.
As having the silicon compound that contains amino organic group, for example, can list N-β-(aminoethyl)-gamma-amino propyl group methyl dimethoxysilane, N-β-(aminoethyl)-gamma-amino propyl trimethoxy silicane, N-β-(aminoethyl)-γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane etc.They can only use a kind of, also can two or more and usefulness.
In addition, the organic polymer skeleton that is contained in the above-mentioned complex particles, for example, 1) at above-mentioned silicon compound with hydrolization group, when having the organic group of the polymerizability reactive group that can be formed with the organic polymer skeleton that contains free-radical polymerised group or epoxy group(ing) etc., also can pass through 1-1) in the method for the hydrolysis-condensation reaction post polymerization of silicon compound, or 1-2) on the particle of the polysiloxane skeleton that the hydrolysis-condensation reaction that has by silicon compound obtains, absorb free radical polymerization monomer, monomer with epoxy group(ing), make it the polymeric method after having the monomer of hydroxyl and having the polymerizable monomer with polymerizability reactive group of amino monomer etc. and obtain.In addition, 2) do not have at above-mentioned silicon compound and contain free-radical polymerised group, epoxy group(ing), hydroxyl, during the organic group of the polymerizability reactive group that can be formed with the organic polymer skeleton of amino etc., the particle (seed particles that the polysiloxane particle is formed below is also referred to as the polysiloxane particle) of the polysiloxane skeleton that obtains at the hydrolysis-condensation reaction that has by silicon compound is gone up and is absorbed free radical polymerization monomer, monomer with epoxy group(ing), make it polyreaction after having the monomer of hydroxyl and having the polymerizable monomer with polymerizability reactive group of amino monomer etc. and obtain.
As mentioned above, complex particles, can be that intramolecularly has the form (chemical of bonding) that the Siliciumatom direct chemical is combined in the organosilicon atom at least one carbon atom in the organic polymer skeleton for a) polysiloxane skeleton, also can be b) intramolecularly do not have the form (IPN type) of such organosilicon atom, there is no particular limitation, for example, and as above-mentioned 1-1) as described in, when obtaining the organic polymer skeleton, can access and have a) complex particles of form with the polysiloxane skeleton; As above-mentioned 2) shown in the time, can access have b) complex particles of form.In addition, as above-mentioned 1-2) shown in, when obtaining the organic polymer skeleton with the polysiloxane skeleton, can access have simultaneously above-mentioned a) and b) the complex particles of form.
At above-mentioned 1-2) or 2) method in, can be absorbed into the free radical polymerization monomer on the particle with polysiloxane skeleton, preferably with free-radical polymerised vinyl monomer as necessary monomer component.As above-mentioned free-radical polymerised vinyl monomer, for example, get final product so long as intramolecularly contains the compound of at least more than one ethene unsaturated group, there is no particular limitation for its kind etc., can suitably select according to the rerum natura of desirable complex particles.They can only use a kind of, also can two or more and usefulness.
For example, because hydrophobic free-radical polymerised vinyl monomer when above-mentioned monomer component is absorbed on the particle with polysiloxane skeleton, can generate the stable emulsion that makes after above-mentioned monomer component emulsification also disperses, therefore preferred.In addition,, can use cross-linkable monomer as free-radical polymerised vinyl monomer, if use cross-linkable monomer, the adjusting of the mechanical characteristics of the complex particles that can easily obtain, and, also can improve the solvent resistance of complex body particulate.Particularly, can list ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 1,6 hexanediol diacrylate, Vinylstyrene etc.They can only use a kind of, also can two or more and usefulness.
Method as the above-mentioned complex particles of preparation can preferably list the preparation method who comprises hydrolysis described later, condensation operation and polymerization process.Further as required, after hydrolysis, condensation operation, before the polymerization process, can also comprise the monomeric absorption operation of absorbing polymer (above-mentioned 1-2) and 2) situation).In addition, the silicon compound that is used for hydrolysis, condensation operation, the situation of (above-mentioned 2) when being not the silicon compound that has the key element that constitutes the organic polymer skeleton when being to have the key element that can constitute the polysiloxane skeleton), above-mentioned absorption operation as necessary, can be followed this absorption operation and be formed with the organic polymer skeleton in polymerization process.
Said hydrolyzed, condensation operation are meant the operation that above-mentioned silicon compound is hydrolyzed and makes it the reaction of polycondensation in containing the solvent of water.By this operation, can obtain having the particle (polysiloxane particle) of polysiloxane skeleton.Hydrolysis and polycondensation can be adopted together, (cut apart) in batches, arbitrary method such as continuous.When hydrolysis, polycondensation, can preferably use the basic catalyst of ammonia, urea, thanomin, tetramethylammonium hydroxide, alkali metal hydroxide, alkaline-earth metal oxyhydroxide etc. as catalyzer.
In the above-mentioned solvent that contains water, dewater and catalyzer is outer can contain organic solvent.As organic solvent, for example, can list methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, ethylene glycol, propylene glycol, 1, the alcohols of 4-butyleneglycol etc.; The ketone of acetone, ethyl methyl ketone etc.; The ester class of ethyl acetate etc.; (ring) alkanes of octane-iso, hexanaphthene etc.; Benzene, toluene etc. aromatic hydrocarbon based etc.They may be used alone, used in two or more.
In hydrolysis, condensation operation, also can and with the tensio-active agent of anionic, cationic, non-ionic type, or the macromolecule dispersing agent of polyvinyl alcohol, polyvinylpyrrolidone etc.They may be used alone, used in two or more.
Hydrolysis and condensation can be by after will and containing the solvent of catalyzer and water and organic solvent as the above-mentioned silicon compound of raw material, be 0-100 ℃ in temperature, be preferably 0-70 ℃ and stir down and carried out in 30 minutes-100 hours.In addition, be hydrolyzed, condensation reaction is until desirable degree and after preparing particle, also can further add silicon compound in reaction system with it as seed particles, and this seed particles is grown up.
The weight-average molecular weight of polysiloxane particle is preferably 250-10000, more preferably 250-5000.Weight-average molecular weight is in above-mentioned scope the time, absorb the absorption rate height of the polymerizable monomer in the operation, in system, can suppress to come from and not be absorbed and the generation of the coarse particle of residual polymerizable monomer, its result can obtain the content of the coarse particle of median size more than 2 times in complex particles (supplying to dry classification) or the low complex particles of content of fine particle.Further, by this complex particles being supplied in wet classification, the dry classification operation, can obtain the extremely low particle of coarse particle content with high yield.
Absorb operation, as previously mentioned, the silicon compound of with good grounds use should and can be used as the situation of any operation as situation that must operation.Above-mentioned absorption operation so long as in the presence of the polysiloxane particle so that the absorption operation of carrying out under the state that polymerizable monomer exists just there is no particular limitation.Therefore, can add polymerizable monomer in the solvent that is dispersed with the polysiloxane particle, also can add the polysiloxane particle in the solvent that contains polymerizable monomer.Wherein, preferably as the former, add polymerizable monomer in the solvent that is dispersed with the polysiloxane particle in advance; Further, the polysiloxane particle that obtains in hydrolysis, the condensation operation is not selected from reaction solution (polysiloxane particle dispersion) and directly added the method for polymerizable monomer to this reaction solution, because can not make become complexity and productivity of operation good, therefore preferred.
In addition, in absorbing operation, above-mentioned polymerizable monomer is absorbed in the above-mentioned polysiloxane morphology of particles, but set polysiloxane particle and polymerizable monomer concentration or the temperature the when ratio of mixture of above-mentioned polysiloxane and polymerizable monomer, blended treatment process, mode, mixing or time, mixed treatment process, mode etc. separately for the absorption that makes polymerizable monomer promptly carries out, preferably under this condition, carry out.These conditions can consider that suitably its necessity gets final product according to the used polysiloxane particle and the kind of polymerizable monomer etc.And these conditions can only be used a kind of, also can two or more applied in any combination.
The addition of the polymerizable monomer in above-mentioned absorption operation, with respect to the quality of the silicon compound that uses as the raw material of polysiloxane particle, be preferably 0.01-100 in mass doubly, more preferably 0.5-50 is doubly, more preferably 0.5-30 doubly is preferably 1-15 doubly especially.During above-mentioned scope that addition is not enough, the absorbed dose of the polymerizable monomer of polysiloxane particle tails off, and the mechanical characteristics of the complex particles of generation becomes and is difficult to obtain; When exceeding above-mentioned scope, have the polymerizable monomer of the interpolation of making to absorb fully to become on the polysiloxane particle trend of difficulty, have since the residual back of unabsorbed polymerizable monomer produces interparticle cohesion in polymerization stage, the coarse particle that comes from unabsorbed polymerizable monomer becomes be easy to generate may.
In above-mentioned absorption operation, the interpolation time of polymerizable monomer, there is no particular limitation, can add this polymerizable monomer in advance together, also can divide for several times and add, also can be so that speed is reinforced arbitrarily.And, when adding polymerizable monomer, can only add polymerizable monomer, also can add the solution of polymerizable monomer, since carry out more efficiently to add polymerizable monomer to can make in the polysiloxane particle absorption in advance with emulsifying agent emulsification dispersive state in advance to the polysiloxane particle, therefore preferred.
There is no particular limitation for mentioned emulsifier, for example has and have more than one polymerizability tensio-active agent that can the polymeric carbon-to-carbon unsaturated bond etc. in aniorfic surfactant, cationic surfactant, nonionic surface active agent, amphoterics, polymeric surface active agent, the molecule.Wherein, owing to aniorfic surfactant, nonionic surface active agent can make the polysiloxane particle that has absorbed polysiloxane particle or polymerizable monomer, the dispersion state stabilization of polymer particles, therefore preferred.These emulsifying agents, can only use a kind of, also can be two or more and use.
There is no particular limitation for the usage quantity of mentioned emulsifier, particularly, with respect to the total mass of above-mentioned polymerizable monomer, is preferably 0.01-10 quality %, more preferably 0.05-8 quality %, 1-5 quality % more preferably.During the usage quantity less than 0.01 quality % of mentioned emulsifier, the possibility that has the emulsification that can not obtain stable polymerizable monomer to disperse thing; When exceeding 10 quality %, have letex polymerization etc. as side reaction concurrent may.Disperse for above-mentioned emulsification, usually, preferably make above-mentioned polymerizable monomer use uniform mixing machine or ultrasonic homogenizer etc. in water, to become the milkiness state with emulsifying agent.
In addition, when polymerizable monomer was carried out the emulsification dispersion with emulsifying agent, preferably using the quality with respect to polymerizable monomer was 0.3-10 water or water-miscible organic solvent doubly.As above-mentioned water-miscible organic solvent, can list methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, ethylene glycol, propylene glycol, 1, the alcohols of 4-butyleneglycol etc.; The ketone of acetone, ethyl methyl ketone etc.; The ester class of ethyl acetate etc. etc.
Above-mentioned absorption operation preferably stirs in 5 minutes-720 minutes under 0-60 ℃ temperature range and carries out.These conditions can suitably be set according to the used polysiloxane particle or the kind of polymerizable monomer etc., and these conditions can only adopt a kind of or adopt two or more combinations.
In absorbing operation, whether be absorbed into judgement on the polysiloxane particle for monomer component, for example, before adding monomer component and after the absorption stage finishes, by the microscopic examination particle, can be to confirm making particle diameter become judgement greatly and easily by the absorption of monomer component.
Polymerization process is to instigate polymerizability reactive group polyreaction, obtains having the operation of the particle of organic polymer skeleton.Particularly, using as silicon compound when having the material of the organic group that contains the polymerizability reactive group, is to instigate the polymerizability reactive group polymerization of this organic group and the operation that is formed with the organic polymer skeleton; When having passed through the absorption operation, be to instigate the polymerizable monomer polymerization of polymerizability reactive group and the operation that is formed with the organic polymer skeleton with the absorption of making; When satisfying above-mentioned two kinds of situations, can be formed with the operation of organic polymer skeleton according to arbitrary reaction.
Polyreaction can or absorb carrying out of operation midway in the hydrolytic condensation operation, also can carry out after arbitrary or both operation, and there is no particular limitation, usually, and in (when having carried out the absorption operation for after absorbing operation) beginning after the hydrolytic condensation operation.
There is no particular limitation for polyreaction, for example, can adopt the method for the method, irradiation ultraviolet radiation or the radioactive rays that use radical polymerization initiator, any one methods such as method of heating.As above-mentioned radical polymerization initiator, there is no particular limitation, for example, preferably can list the persulphate of Potassium Persulphate etc.; Hydrogen peroxide, peracetic acid, benzoyl peroxide, lauroyl peroxide, adjacent chlorobenzoyl peroxide, O-methoxy benzoyl peroxide, peroxidation-3,5,5-trimethyl acetyl, peroxidation (2 ethyl hexanoic acid) tert-butyl ester, di-t-butyl peroxide, benzoyl peroxide, 1,1-di-tert-butyl peroxide-3,3, the superoxide series initiators class of 5-trimethyl-cyclohexane, tertbutyl peroxide etc.; Diisopropyl azodicarboxylate, azo two cyclohexanenitriles, azo two (2, the 4-methyl pentane nitrile), 2 '-azobis isobutyronitrile, 2,2 '-azo two (2-amidine propane) dihydrochloride, 4,4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azobis isobutyronitrile, 2, the azo based compound class of 2 '-azo two (2, the 4-methyl pentane nitrile) etc. etc.These radical polymerization initiators may be used alone, used in two or more.
The usage quantity of above-mentioned radical polymerization initiator with respect to the total mass of above-mentioned polymerizable monomer, is preferably 0.001-20 quality %, more preferably 0.01-10 quality %, more preferably 0.1-5 quality %.During the usage quantity less than 0.001 quality % of above-mentioned radical polymerization initiator, the situation that has the polymerization degree of polymerizable monomer not rise.About the adding method of above-mentioned radical polymerization initiator with respect to above-mentioned solvent, there is no particular limitation, can adopt methods of all adding in initial (before the reaction beginning) (make radical polymerization initiator with polymerizable monomer emulsification dispersive mode in advance, be absorbed the form of back adding radical polymerization initiator at polymerizable monomer); Add a part in advance at first, add the addition means of surplus continuously, perhaps, the pulsed method of adding by spells, perhaps known method in the past arbitrarily such as the method that they are combined.
The fashionable temperature of reaction of above-mentioned radical polymerization is preferably 40-100 ℃, more preferably 50-80 ℃.Reaction temperature is spent when hanging down, and the trend that the polymerization degree can not rise fully, the mechanical characteristics of polymer particles is difficult to obtain is arranged; On the other hand, when temperature of reaction is too high, the trend that easily causes interparticle cohesion is arranged in polymerization.In addition, the fashionable reaction times of above-mentioned radical polymerization can suitably change according to the kind of used polymerization starter, usually, is preferably 5-600 minute, more preferably 10-300 minute.In the reaction times when too short, the situation that has the polymerization degree not rise fully; When long, the trend that easily causes interparticle cohesion is arranged in the reaction times.
In the present invention, behind the polymerization process, the preparation liquid that contains the polymer particle that obtains directly or with the organic solvent distillation and in the dispersion medium that contains water and/or alcohol after the displacement, can be supplied to above-mentioned wet classification operation; Perhaps also can be with after the polymer particles segregation that generates, the drying, be distributed in water and/or the organic solvent after, be supplied to the wet classification operation.
Because particulate that reduced, narrow particle size distribution that particulate of the present invention is the content of coarse particle and fine particle, as optical applications, for example, the additive of light diffusing agent that contains in the optical resin that uses in light diffusing sheet that uses among the LCD etc. or light guiding plate or PDP, EL indicating meter and the touch panel etc. or antiblocking agent etc. etc. is useful.Certainly, the uses such as antiblocking agent that also can compatibly use as the various films beyond these optical applications.
The resin combination that the present invention relates to is the resin combination that contains particulate of the present invention and clear binder resin.Therefore as mentioned above, particulate of the present invention because not only the content of coarse particle, fine particle also is suppressed to extremely low-levelly, can suitably be used for optical applications.
The content of the particulate in the above-mentioned resin combination suitably determines to get final product according to purposes or desirable optical characteristics, is being used for the situation of optical applications, is preferably more than 1 mass parts to 300 mass parts with respect to the adhesive resin composition of 100 mass parts.More preferably more than 2 mass parts, more preferably more than 5 mass parts; More preferably below 200 mass parts, more preferably below 150 mass parts.When the content of particulate is too much, the possibility of optics with the intensity reduction of parts arranged; When very few, have by adding particulate to be difficult to the situation of the effect (light diffusing etc.) that obtains expecting.
There is no particular limitation for the clear binder resin that is contained in the resin combination of the present invention, can use as the material that adhesive resin uses in this field.For example; (I) to be that resin combination of the present invention is configured as itself tabular for the parts that use resin combination of the present invention to form; during the parts of desirable shape such as sheet (; it is tabular that adhesive resin is configured as; the situation of the substrate resin of sheet-like formed body); as transparent resin; can list the vibrin of polyethylene terephthalate or PEN etc.; acrylic resin; polystyrene resin; polycarbonate resin; polyethersulfone Trees fat; polyurethane series resin; polysulfone resin; polyether resin; the polymethylpentene resin; polyether ketone resin; (methyl) acrylic resin; the polyolefin resin of acrylic resin etc., norcamphane are resin; the amorphousness polyolefin resin; polyamide resin; polyimide resin; and the tri acetyl cellulose resin etc.
In addition, when (II) parts make it integrated parts that form for make resin combination of the present invention stacked (coating, lamination etc.) etc. on the substrate surface of pre-prepd tabular or sheet etc., as the clear binder resin, can use the material same with above-mentioned adhesive resin, for example, can list acrylic resin, acrylic resin, polyvinyl alcohol resin, polyvinyl acetate resins, polystyrene resin, polyvinyl chloride (PVC) RESINS, silicone resin, and urethane resin, vibrin etc.
Resin combination of the present invention except that above-mentioned particulate and clear binder resin, as long as in the scope of not damaging effect of the present invention, can contain other composition as required.As other composition, for example, can enumerate solidifying agent, linking agent, various additive or the stablizer of the rerum natura that is used to improve photostabilization or anti-UV etc. and fire retardant, oxidation inhibitor, UV light absorber etc.These can only use a kind of, also can two or more and usefulness.
By the formed body that resin combination of the present invention obtains,, be the formed body that has possessed good optical characteristics such as light diffusing and photopermeability therefore owing to be that particulate of the present invention is disperseed, is fixed to the formed body in the above-mentioned adhesive resin.Therefore, resin combination of the present invention can be used as various chemical productss component parts raw material and suitably use.In addition, from applying flexibly the good light diffusing that comes from above-mentioned particulate of the present invention or the viewpoint of photopermeability effectively, the anti-dazzle property of the antireflection film of mirroring and image being shown visibly that prevent outdoor light or interior lighting machine can be set in the front of various image display devices, or in image display device, make from the light of light source at the optics of light diffusion film that picture display face spreads equably or light diffusing sheet etc. with compatibly using in the parts.
Above-mentioned optics is not limited to film like (sheet) or tabular with the shape of parts, also can be to be shaped to desirable shapes such as cylinder, centrum, ball.In addition, from guarantee good light diffusion effect, antiglare effect (by suppress, the antiglare effect of the normal reflection of diffusion light) viewpoint, preferably on the surface of optics, be formed with and come from the uneven of above-mentioned particulate of the present invention with parts.
For example, above-mentioned optics parts be such as the film like of light diffusion film or antireflection anti-dazzle film (below, be called " optical thin film ") formed body the time, as its form, can list the form that in a part, has the structure (optical functional layer) that the light diffusion particle fixedly formed by clear binder at least with planar part.For example, can list (i) and will constitute the substrate resin of the clear binder resin of resin combination itself as tabular or sheet etc., form the form (light diffusing sheet etc.) of tabular or film like, (ii) on part or all of pre-prepd tabular or flaky substrate surface, stacked (coating, lamination) contains the layer of above-mentioned resin combination and makes its incorporate form (the surface irregularity film of light diffusion film, anti-dazzle property film etc., light diffusing sheet etc.) etc.The situation of above-mentioned (i), arbitrary form (ii) because particle is disperseed, is fixed in the clear binder resin, can be brought into play good optical characteristics.
In addition, above-mentioned " having planar part " generally is meant, the shape of optics such as tabular, sheet or film like sample ground, surface portion with substantially flat of certain area distributions becomes (comprise and be formed with trickle rough situation on the surface) textural element of the main body of its shape, the mode that is not limited only to relate in the present invention, even be not the textural element of main body, as long as at least a portion of its shape, have the surface portion of substantially flat.
As the preparation method of the optics of the form of above-mentioned (i), can list the forming method that is extruded into sheet, tabular and film like when resin combination of the present invention carried out melting mixing by known forcing machine.At this moment, as required,, also can in above-mentioned resin combination, add the additive of various additives or stablizer and fire retardant etc. and carry out moulding in order to improve the rerum natura of photostabilization or anti-UV etc.In order to obtain the uniform formed body of optical characteristics, above-mentioned resin combination preferably mixes particulate of the present invention in advance and makes its dispersion in the clear binder resin.In addition, similarly above-mentioned additive and resin combination can be pre-mixed.
As the method for the optics that obtains above-mentioned form (ii), can list on pre-prepd substrate surface the stacked method that contains the layer of resin combination of the present invention.There is no particular limitation for laminating method, and preferably example illustrates coating process or teeming practice etc.As coating process, be coated on the base material as long as will contain the application composition that is coated with that above-mentioned resin combination forms.Resin combination of the present invention, can directly use as being coated with the application composition, preferably above-mentioned resin combination (is for example disperseed, is dissolved into water or organic solvent, the pure series solvent of methyl alcohol, ethanol, Virahol etc., the ketone series solvent of ethylene glycol, propylene glycol etc., the ester series solvent of ethyl acetate etc., and the aromatic hydrocarbons of toluene, dimethylbenzene etc. etc.) in and the application composition that is coated with of preparation uses.There is no particular limitation for base material, for example, can preferably use known in the past water white resin films such as film of polyolefin resin, polyester based resin film, polycarbonate based resin film.As concrete coating method, can list reverse roll coating process, intaglio plate coating method, metal mold coating process (ダ イ コ-ト method), comma coating method (コ Application マ コ-ト method), and the known laminating method of spraying method etc.
After the coating,, make coated film solidify to form the resin combination layer as required with after the solvent seasoning that is contained in the coated film.In addition, from guaranteeing the viewpoint of thermotolerance, weathering resistance, the layer that contains resin combination is preferably that the adhesive resin that makes in this resin combination to be contained solidifies or crosslinked and layer that form.
There is no particular limitation by the thickness of the layer that contains resin combination of the present invention (perhaps being coated with the application composition) that forms by above-mentioned method, and during for above-mentioned smooth diffusion film, the thickness of layer (light diffusion layer) that contains resin combination is preferably below 30 μ m; During for anti-dazzle property film, the thickness of layer (antiglare layer) that contains resin combination is preferably below 20 μ m; The thickness of light diffusing sheet is preferably below 2000 μ m.In the past, during thin thickness, be difficult to show sufficient light diffusing or photopermeability, when using particulate of the present invention or resin combination, even thin thickness also can be brought into play extremely good light diffusing and photopermeability.In addition, the value of above-mentioned smooth diffusion film and anti-dazzle property film thickness is that (that is the value of) thickness, light diffusion layer, antiglare layer does not comprise the thickness of base material to the expression layer that comprises stacked resin combination on the base material.
Particulate of the present invention, not only the content of coarse particle is suppressed to extremely low level, in addition, except that size-grade distribution is precipitous, even particulate of the present invention is the rotten chemically stable particulate that swelling etc. also be difficult to take place in being coated with the application composition, so in aforesaid optics (light diffusion film, anti-dazzle property film, light diffusing sheet etc.), can be formed uniformly trickle uneven.Therefore, use the optics of light diffusion film, anti-dazzle property film and light diffusing sheet etc. that particulate of the present invention obtains, very difficult generation comes from the partial light leak of coarse particle or is difficult to produce the optics foreign matter that causes the face shaping unfavorable condition.Simultaneously, owing to, also can regulate optical characteristics, therefore can suitably be used for optical applications by controlling the median size of particulate of the present invention.
Embodiment
Below, being described more specifically the present invention by enumerating embodiment, the present invention is not limited to following embodiment certainly, also can increase suitable change within the bounds of possibility according to preceding aim described later and implement, and they all are contained in technical scope of the present invention.In addition, unless special the qualification, " part " expression mass parts, " % " expression quality %.
The preparation of particulate
Preparation example 1 (granular of polyorganosiloxane)
Take into account and add 280 parts of ion exchanged waters, 5 part 25% ammoniacal liquor and the mixing solutions of 120 parts of methyl alcohol in the reactor of liquid droping port to being provided with refrigerating unit, temperature, mixed solution under agitation drops into 40 parts of γ-methacryloxypropyl trimethoxy silane by liquid droping port, under 30 ℃ temperature, carry out hydrolysis, the condensation reaction of 2 hours γ-methacryloxypropyl trimethoxy silane, the suspension of preparation granular of polyorganosiloxane.In addition, the weight-average molecular weight of the polysiloxane particle that obtains this moment is 1800 (the 7 times of bodies (amount body) that are equivalent to used silicon compound approximately).
Another approach, with above-mentioned different reactor 2 in, with 400 parts of vinylbenzene, 3 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) is (with light Pure
Figure A200780027514D0044084948QIETU
Industry society system, V-65), 1.5 parts of aniorfic surfactant (LA-10, the first industrial society system) and 400 parts of ion exchanged waters divide in room temperature (25 ℃) lactogenesis by the uniform mixing machine and loose 15 minutes, prepare emulsion (monomer solution).
The preparation of the suspension of described polysiloxane particle begins (γ-methacryloxypropyl trimethoxy silane was added beginning after two hours) after 2 hours, adds above-mentioned emulsion by the liquid droping port of reactor 1.Continue to stir 1 hour, after confirming that the polysiloxane particle is absorbing monomer component, to wherein adding 3500 parts of ion exchanged waters, under nitrogen atmosphere, make reaction soln be warming up to 65 ℃, kept 2 hours down at 65 ± 2 ℃, carry out Raolical polymerizable, obtain polymer particle (organism mineral complex particle) dispersion liquid.The median size that is dispersed in the polymer particle in the dispersion liquid is 10.1 μ m, and the Type B viscosity of dispersion liquid (Brookfield viscometer, Zhu formula Hui She East capital Meter device system) is 3.8mPas, and solid component concentration is 10 quality %.
Preparation example 2-7 (polysiloxane particle)
Remove polysiloxane particle raw material, free radical polymerization monomer, and beyond the change of usage quantity such as table 1, similarly be formulated as the polymer particle dispersion liquid with preparation example 1.The amount of the ion exchanged water that uses when in addition, suitably adjusting the preparation of polysiloxane particle suspension, emulsion, methyl alcohol, tensio-active agent according to the condition of each preparation example.
[mensuration of the median size of polymer particle, the amount of coarse particle]
The 0.5g polymer particle that the polymer particle dispersion liquid that obtains in the above-mentioned preparation example is obtained after by solid-liquid separation, drying is distributed in the 100g ion exchanged water, preparation polymer particle dispersion liquid uses accurate particle size distribution device (trade(brand)name " マ Le チ サ イ ザ-II ", ベ StarNetwork マ Application コ-Le -Co., Ltd.'s system), carries out the mensuration of the particle diameter of polymer particle, calculate median size with volume reference.
In addition, the mensuration of the amount of the coarse particle that is contained in the polymer dispersion liquid (coarse particle with particle diameter more than 2 times of median size) is carried out according to following.
The dried polymer particle of 0.5g is distributed in the 100g methyl alcohol, is mixed with polymer particle dispersion liquid (viscosity: 3mPas, solid component concentration: 0.5 quality %), use the screen cloth (ニ of 1.75-2 sieve aperture doubly with median size Starケ Le system, bundle capital プ ロ セ ス サ-PVC ス Co., Ltd. system) and bell strainer (Filter Over Bell) on have the suction filtration of B device arranged, under reduced pressure filter.Then, (Ri Li System does made, acceleration voltage for SEM, " S-3500N ": 25kV) observe the particle that remains on the screen cloth, the range estimation number goes out the number of the coarse particle more than 2 times of median size with scanning electronic microscope.And observation is to observe whole visual field with 200 times multiplying power.The result uses "〉average diameter * 2 in table 1 " expression.
In addition,, except that the screen cloth that uses 2.25-2.5 sieve aperture doubly, similarly carry out with above-mentioned step with median size for the amount of the coarse particle of the particle diameter more than 2.5 times with median size, the result in table 1 with "〉average diameter * 2.5 " expression.
[SiO 2Content]
In the stoving oven device, with the 1g polymer particle in (under the air atmosphere) roasting under 800 ℃, with the ash content that generates as SiO 2, calculate SiO with respect to the quality of employed polymer particle 2Ratio.
[solid component concentration]
The solid component concentration of polymer particle, with 0.5g polymer beads molecular disperse solution 120 ℃ * 20 minutes (in the vacuum) dryings, with the quality of residual solids component with respect to the ratio of the quality of polymer particle dispersion liquid as solid component concentration.
Solid component concentration (%)=[residual solids component quality/polymer particle dispersion liquid quality] * 100
[Bulk Specific Gravity]
Use powder tstr (ホ ソ カ ワ ミ Network ロ Application system) to measure.
[moisture content]
The 0.5g sized particles is measured as measuring raw material, use Ka Er-Fei Xiu moisture content tester (flat natural pond Industry Co., Ltd system).
[weight-average molecular weight]
Weight-average molecular weight, the use gel permeation chromatograph (GPC, " and HLC-8120GPC ” ， East ソ-Co., Ltd.'s system), measure by following condition determination.In addition, measure sample, regulate sample with tetrahydrofuran (THF) (THF) dilution and make that solids component is 0.8%.
Chromatographic column: TSKgelG5000HXL-TSKge12000HXL (East ソ-Co., Ltd.'s system)
Column temperature: 25 ℃
Elutriant: THF
Pump: L6000 (the strain formula can be found System community day and do made)
Flow: 1.0ml/min
Detect: R1 Model 504 (GL サ イ エ Application ス Zhu formula Hui She System)
Sample solution concentration: 0.8%
Standard test specimen calibration curve: use polystyrene standard (TSK polystyrene standard ， East ソ-Co., Ltd.'s system), by 13 calibration curves that sample obtains of Mw=500-1000000.
Figure A200780027514D00471
Embodiment 1
The polymer particle dispersion liquid that obtains in the preparation example 1 is carried out classification (wet classification operation) with the stainless steel wire netting of 20 μ m sieve apertures.Then, the polymer particle dispersion liquid behind the wet classification is passed through natural subsidence and solid-liquid separation.The filter cake that obtains with ion exchanged water and methanol wash after, by 100 ℃ of following vacuum-dryings 5 hours, obtain the dry thing that particle coacervation becomes.By pulverizing by the drying thing, obtain sized particles (rate of recovery 99 quality %).
The Bulk Specific Gravity of the sized particles that obtain this moment is 0.7g/cm 3, particle diameter is 10.1 μ m, moisture content is below the 0.5 quality %.
The sized particles that obtains is put into high precision air classifier (" DFX5 type ", Japanese ニ ユ-マ チ StarNetwork Industrial Co., Ltd system) in, by regulating by the high speed rotating air-flow and attract blower fan to give the centrifugal force of sized particles and the balance of resistance is carried out classification, obtains particulate (dry classification operation) with the rate of recovery of 85 quality % with respect to the sized particles of supplying with.In addition, be 84 quality %s from the rate of recovery of the particulate of polymer particle dispersion liquid recovery this moment.
Embodiment 2
By operation similarly to Example 1, prepare sized particles (rate of recovery is 99 quality %) by the polymer particle dispersion liquid that obtains in the preparation example 2.The Bulk Specific Gravity of the sized particles that obtain this moment is 0.7g/cm 3, particle diameter is 10.1 μ m, moisture content is below the 0.5 quality %.
Then, the sized particles that obtains being put into rotor formula sorting equipment (returns
Figure A200780027514D0048085109QIETU
ロ--formula is divided Grade device, " -ボ プ レ StarNetwork ス 100ATP ", ホ ソ カ ワ ミ Network ロ Application Co., Ltd. system) in; give the centrifugal force of sized particles and the balance of resistance is carried out classification by regulating, obtain particulate (dry classification operation) with respect to supplying with the rate of recovery of sized particles with 85 quality % by the speed of rotation of classification rotor with from the supply of the air of suction hole.In addition, be 84 quality %s from the rate of recovery of the particulate of polymer particle dispersion liquid recovery this moment.
Embodiment 3
Operation similarly to Example 1, (Bulk Specific Gravity is 0.7g/cm to prepare sized particles by the polymer particle dispersion liquid that obtains in the preparation example 3 3, particle diameter is 10.1 μ m, moisture content is below the 0.5 quality %, the rate of recovery is 99 quality %).
This sized particles is put into rotor formula airflow classification device (" -ボ Network ラ シ Off アイ ア TC-15 ", day clear エ Application ジ ニア リ Application グ society system) in, give the centrifugal force of sized particles and the balance of resistance is carried out classification by regulating, obtain particulate (dry classification operation) with respect to supplying with the rate of recovery of sized particles with 85 quality % by the speed of rotation of classification rotor with from the supply of the air of suction hole.In addition, be 84 quality %s from the rate of recovery of the particulate of polymer particle dispersion liquid recovery this moment.
Embodiment 4
Operation similarly to Example 1, (Bulk Specific Gravity is 0.7g/cm to prepare sized particles by the polymer particle dispersion liquid that obtains in the preparation example 3 3, particle diameter is 10.1 μ m, moisture content is below the 0.5 quality %, the rate of recovery is 99 quality %).
This sized particles is put into wall-attachment airflow classification device (コ ア Application ダ formula mood flow point Grade device, " エ Le ボ-ジ The エ Starト EJ-15 ", day iron
Figure A200780027514D0049085127QIETU
Industry Co., Ltd. system, reinforced air: 5kgf uses elongated ribs) in, give the mass force of particulate and carry out classification by adjusting by the balance of the resistance that attracts gas blower to cause, obtain particulate with respect to supplying with the rate of recovery of sized particles with 85 quality %.In addition, be 84 quality %s from the rate of recovery of the particulate of polymer particle dispersion liquid recovery this moment.
Embodiment 5
By operation similarly to Example 1, (Bulk Specific Gravity is 0.7g/cm to prepare sized particles by the polymer particle dispersion liquid that obtains in the preparation example 4 3, particle diameter is 3.7 μ m, moisture content is below the 0.5 quality %, the rate of recovery is 99 quality %).
Then, the sized particles that obtains is put into high precision air classifier (" DFX5 type ", Japanese ニ ユ-マ チ StarNetwork Industrial Co., Ltd system) in, by regulating by the high speed rotating air-flow and attract gas blower to give the centrifugal force of sized particles and the balance of resistance is carried out classification, obtains particulate (dry classification operation) with the rate of recovery of 88 quality % with respect to the sized particles of supplying with.In addition, be 87 quality %s from the rate of recovery of the particulate of polymer particle dispersion liquid recovery this moment.
Embodiment 6
By operation similarly to Example 1, (Bulk Specific Gravity is 0.7g/cm to prepare sized particles by the polymer particle dispersion liquid that obtains in the preparation example 5 3, particle diameter is 25.2 μ m, moisture content is below the 0.5 quality %, the rate of recovery is 99 quality %).
Then, the sized particles that obtains is put into rotor formula sorting equipment (" -ボ プ レ StarNetwork ス 100ATP "; ホ ソ カ ワ ミ Network ロ Application Co., Ltd. system) in; give the centrifugal force of sized particles and the balance of resistance is carried out classification by regulating, obtain particulate (dry classification operation) with the rate of recovery of 85 quality % with respect to the sized particles of supplying with by the speed of rotation of classification rotor with from the supply of the air of suction hole.In addition, be 84 quality %s from the rate of recovery of the particulate of polymer particle dispersion liquid recovery this moment.
Embodiment 7
By operation similarly to Example 1, (Bulk Specific Gravity is 0.7g/cm to prepare sized particles by the polymer particle dispersion liquid that obtains in the preparation example 6 3, particle diameter is 4.2 μ m, moisture content is below the 0.5 quality %, the rate of recovery is 99 quality %).
This sized particles is put into rotor formula airflow classification device (" -ボ Network ラ シ Off アイ ア TC-15 ", day clear エ Application ジ ニア リ Application グ society system) in, give the centrifugal force of sized particles and the balance of resistance is carried out classification by regulating, obtain particulate (dry classification operation) with the rate of recovery of 86 quality % with respect to the sized particles of supplying with by the speed of rotation of classification rotor with from the supply of the air of suction hole.In addition, be 85 quality %s from the rate of recovery of the particulate of polymer particle dispersion liquid recovery this moment.
Embodiment 8
By operation similarly to Example 1, (Bulk Specific Gravity is 0.7g/cm to prepare sized particles by the polymer particle dispersion liquid that obtains in the preparation example 7 3, particle diameter is 12.5 μ m, moisture content is below the 0.5 quality %, the rate of recovery is 99 quality %).
This sized particles is put into wall-attachment airflow classification device (" エ Le ボ-ジ The エ Starト EJ-15 ", day iron
Figure A200780027514D0049085127QIETU
Industry Co., Ltd. system, reinforced air: 5kgf uses elongated ribs) in, give the mass force of particulate and carry out classification by adjusting by the balance of the resistance that attracts gas blower to cause, obtain particulate with respect to the sized particles of supplying with the rate of recovery of 85 quality %.In addition, be 84 quality %s from the rate of recovery of the particulate of polymer particle dispersion liquid recovery this moment.
Comparative Examples 1
The polymer particle dispersion liquid that obtains in the preparation example 1 is carried out classification (wet classification operation) with the stainless steel wire netting of 20 μ m sieve apertures.Then, the polymer particle dispersion liquid behind the wet classification is carried out solid-liquid separation by natural subsidence.The filter cake that obtains with ion exchanged water and methanol wash after, by 100 ℃ of following vacuum-dryings 5 hours, obtain the dry thing that particle coacervation forms.By pulverizing by the drying thing, obtain sized particles.
Comparative Examples 2
After the polymer particle dispersion liquid that obtains in the preparation example 2 carried out classification with the stainless steel wire netting of 20 μ m sieve apertures, further used filter core cylinder (Japanese Port-Le society system, trade(brand)name " ウ Le チ プ リ-Star プ ロ Off アイ Le PUY1UY500 ") processing 1 circulation (パ ス) (wet classification operation).Then, to carry out the separating of polymer particle, washing, drying, pulverize by the dry thing that will obtain and obtain sized particles with the same step of Comparative Examples 1.
Comparative Examples 3
After the polymer particle dispersion liquid that obtains in the preparation example 5 carried out classification with the stainless steel wire netting of 40 μ m sieve apertures, then, to carry out the separating of polymer particle, washing, drying with the same step of Comparative Examples 1, the dry thing that obtains by pulverizing obtains sized particles.
Evaluation result about the content of the stage treatment in embodiment 1-8 and Comparative Examples 1-3, the particulate that obtains and powder particle is illustrated in the table 2.In addition, each evaluation method is as follows.
[mensuration of the median size of particulate, the amount of coarse particle]
The microparticulate that 0.5g is obtained in the foregoing description, Comparative Examples is in 100g methyl alcohol, and preparation polymer particle dispersion liquid uses accurate particle size distribution device (trade(brand)name " マ Le チ サ イ ザ-II ", ベ StarNetwork マ Application コ-Le -Co., Ltd.'s system), carries out the mensuration of particle diameter, calculate median size with volume reference.
The mensuration of the amount of coarse particle 1 (coarse particle with particle diameter more than 2 times of median size) is carried out according to following.(viscosity: 3mPas, solid component concentration: 0.5 quality %) use has the screen cloth (ニ of the 1.75-2 sieve aperture doubly of median size will to measure the microparticulate solution that similarly makes with above-mentioned median size Starケ Le Zhi, East capital プ ロ セ ス サ-PVC ス Co., Ltd.) and bell strainer be provided with the suction filtration device of B, under reduced pressure filter.
Then, the use scanning electronic microscope (Ri Li System does made, acceleration voltage for SEM, " S-3500N ": 25kV), observing residual particle on the screen cloth with whole visual field under 200 times, the number of the coarse particle more than 2 times of range estimation median size (individual/0.5g).
In addition, when measuring the amount (coarse particle 2) of coarse particle of the particle diameter more than 2.5 times, remove the screen cloth in 2.25-2.5 times the aperture of using median size, similarly carry out with above-mentioned step with median size.
[mensuration of the amount of fine particle]
The microparticulate that obtains in 0.5g embodiment and the Comparative Examples in the 100g ion exchanged water, is mixed with particle dispersion liquid, uses accurate particle size distribution device (trade(brand)name " マ Le チ サ イ ザ-II ", ベ StarNetwork マ Application コ-Le -Co., Ltd.'s system), carry out the mensuration (volume reference) of particle diameter and median size.Based on measurement result, calculate the volume % that has the particulate of the particle diameter below 1/2 of 1 numerical value that obtains of rounding up behind the radix point of median size, with the value that obtains as the fine particle amount.
Figure A200780027514D00541
In table 2, " the -ボ プ レ of ホ ソ カ ワ ミ Network ロ Application Co., Ltd. system is used in " rotor formula sorting equipment 1 " expression StarNetwork ス 100ATP ", day " -ボ Network ラ シ Off of clear エ Application ジ ニ ア リ Application グ society system is used in " rotor formula sorting equipment 2 " expression アイ ア TC-15 ".In addition, the meaning of " coarse particle 1 " be have median size the particle diameter more than 2 times particle number (individual/0.5g), the meaning of " coarse particle 2 " be have median size the particle diameter more than 2.5 times particle number (individual/0.5g), the meaning of " product recovery rate " is with respect to the total mass that supplies to the particle in the classification operation in embodiment and Comparative Examples, the ratio of the total quality of the particulate that classified operation reclaims.
Preparation example 8 (amino resin crosslinked particle)
With 75 parts of trimeric cyanamides, 75 parts of benzoguanamines, 290 parts of concentration is that 37% formalin and 1.16 parts of concentration are that 10% aqueous sodium carbonate joins and has prolong, in the reactor of thermometer and liquid droping port, is mixed with the mixture that is used to form the aminoresin presoma.After being warming up to 85 ℃ when stirring this mixture, under this temperature, kept 1.5 hours, obtain the initial stage condenses.Another kind method, 7.5 parts of nonionic surface active agent エ マ Le ゲ Application (registered trademark) 430 (Kao Corp, polyoxyethylene oil alkene ether) are dissolved into the surfactant soln that is mixed with in 2455 parts of ion exchanged waters to be kept down at 50 ℃, stir down, to wherein dropping into described initial stage condenses, obtain the emulsion of aminoresin presoma.90 part 5% the Witco 1298 Soft Acid aqueous solution is put in this emulsion, and condensation under 70-90 ℃ temperature, curing obtain containing the suspension of amino resin crosslinked particle.
Preparation example 9,10 (amino resin crosslinked particle)
Except that the usage quantity of amino based compound, formalin changes to the amount shown in the table 3, similarly to carry out with preparation example 8, preparation contains the suspension of amino resin crosslinked particle.
Figure A200780027514D00561
Preparation example 11 (polystyrene particle)
With 50 parts of vinylbenzene, 50 parts of ethylene glycol dimethacrylates, 5 parts of azos is polymerization starter (V-65 and light Pure
Figure A200780027514D0057085215QIETU
Industry society system), 0.5 part of Tert. Butyl Hydroquinone, 0.5 part of sodium lauryl sulphate and 100 parts of ion exchanged waters mix, and stir and make its emulsification, obtain the aqueous dispersions of polymerizable monomer.
In reactor with cooling line, thermometer and liquid droping port, with 40 parts of particle diameters is that the monodisperse polystyrene latex (solid component concentration 5%) of 1 μ m adds and makes in its ion exchanged water that is distributed to 200 parts, the water dispersion of this seed particles is warmed up to 65 ℃, 2% aqueous solution cost of the aqueous dispersions of whole above-mentioned polymerizable monomers and 200 parts of polyvinyl alcohol was dripped in 5 hours continuously.After being added dropwise to complete, be warmed up to 85 ℃, further under this temperature, kept 3 hours, obtain containing the suspension liquid of polystyrene particle.
Preparation example 12 (polystyrene particle)
As shown in table 4, the combination of change free radical polymerization monomer, suitably regulate the addition of monodisperse polystyrene latex (particle diameter: 0.6 μ m (preparation example 12), 0.7 μ m (preparation example 13)), in addition, similarly make polystyrene latex microparticulate solution with preparation example 11.
Figure A200780027514D00581
Embodiment 9
The polymer dispersion liquid that obtains in the preparation example 3 is carried out filtration treatment (wet classification operation) with a plurality of structures (whole strainer: SLP300 is a ロ キ テ Network ノ society system for prefilter 1:HC-75, prefilter 2:HC-25) of crossing the filter core cylinder combination.
Then, by with the dispersion liquid natural subsidence and solid-liquid separation, the filter cake that obtains with ion exchanged water and methanol wash after, by 100 ℃ of vacuum-dryings 5 hours, obtain the dry thing that particle coacervation becomes.Obtain particle by pulverizing this drying thing.
The Bulk Specific Gravity of the sized particles that obtain this moment is 0.7g/cm 3, particle diameter is 6.9 μ m, and moisture content is below the 0.5 quality %, and the rate of recovery is 97 quality %.
It is put into wall-attachment airflow classification device (エ Le ボ-ジ The エ Starト EJ-15, day iron Industry Co., Ltd. system, reinforced air: 5kgf, use elongated ribs) in, give the mass force of particulate and carry out classification by adjusting, obtain with respect to the particulate (dry classification operation) of the sized particles of supplying with after with the rate of recovery classification of 89 quality % by the balance of the resistance that attracts gas blower to cause.
Embodiment 10
By operation similarly to Example 9, (Bulk Specific Gravity is 0.6g/cm by the polymer dispersed formulations prepared from solutions sized particles that obtains in the preparation example 8 3, particle diameter is 8.5 μ m, moisture content is below the 1.0 quality %, the rate of recovery is 96 quality %).
This sized particles is put into high precision air classifier (DFX5 type, Japanese ニ ユ-マ チ StarNetwork Industrial Co., Ltd system) in, give the centrifugal force of sized particles and carry out classification by regulating, obtain with respect to the particulate (dry classification operation) of the sized particles of supplying with after with the rate of recovery classification of 85 quality % by the balance of the resistance that attracts gas blower to cause by the high speed rotating air-flow.
Embodiment 11
By operation similarly to Example 9, (Bulk Specific Gravity is 0.7g/cm to pulverize particulate by the polymer dispersed formulations prepared from solutions that obtains in the preparation example 11 3, particle diameter is 4.0 μ m, moisture content is below the 0.5 quality %, the rate of recovery is 97 quality %).
This sized particles is put into rotor formula airflow classification device (-ボ Network ラ シ Off アイ ア TC-15, clear エ Application ジ ニ ア リ Application グ She System of day) in, give the centrifugal force of sized particles and the balance of resistance is carried out classification by regulating, obtain with respect to supplying with the particulate (dry classification operation) of sized particles after with the rate of recovery classification of 85 quality % by the speed of rotation of classification rotor with from the supply of the air of suction hole.
Embodiment 12
With method similarly to Example 1, (Bulk Specific Gravity is 0.6g/cm to pulverize particulate by the polymer dispersion liquid preparation that obtains in the preparation example 10 3, particle diameter is 13.1 μ m, moisture content is below the 1.0 quality %, the rate of recovery is 99 quality %).
The pulverizing particulate that obtains is put into wall-attachment airflow classification device (エ Le ボ-ジ The エ Starト EJ-15, day iron Industry Co., Ltd. system, reinforced air: 5kgf, use elongated ribs) in, give the centrifugal force of sized particles and the balance of resistance is carried out classification by regulating, obtain with respect to supplying with the particulate (dry classification operation) of sized particles after with the rate of recovery classification of 85 quality % by the speed of rotation of classification rotor with from the supply of the air of suction hole.
Embodiment 13
With method similarly to Example 1, (Bulk Specific Gravity is 0.6g/cm to pulverize particulate by the polymer dispersion liquid preparation that obtains in the preparation example 9 3, particle diameter is 2.0 μ m, moisture content is below the 1.0 quality %, the rate of recovery is 99 quality %).
The pulverizing particulate that obtains is put into high precision air classifier (DFX5 type, Japanese ニ ユ-マ チ StarNetwork Industrial Co., Ltd system) in, gives the centrifugal force of sized particles and carry out classification, obtain with respect to the particulate of the sized particles of supplying with after with the rate of recovery classification of 80 quality % by the balance of the resistance that attracts gas blower to cause by regulating by the high speed rotating air-flow.
Embodiment 14
With method similarly to Example 1, (Bulk Specific Gravity is 0.7g/cm to pulverize particulate by the polymer dispersion liquid preparation that obtains in the preparation example 12 3, particle diameter is 6.5 μ m, moisture content is below the 0.5 quality %, the rate of recovery is 99 quality %).
The pulverizing particulate that obtains is put into wall-attachment airflow classification device (エ Le ボ-ジ The エ Starト EJ-15, day iron Industry Co., Ltd. system, reinforced air: 5kgf, use elongated ribs) in, give the centrifugal force of sized particles and the balance of resistance is carried out classification by regulating, obtain with respect to supplying with the particulate of sized particles after with the rate of recovery classification of 87 quality % by the speed of rotation of classification rotor with from the supply of the air of suction hole.
Embodiment 15
With method similarly to Example 1, (Bulk Specific Gravity is 0.7g/cm to pulverize particulate by the polymer dispersion liquid preparation that obtains in the preparation example 13 3, particle diameter is 9.3 μ m, moisture content is below the 0.5 quality %, the rate of recovery is 99 quality %).
The pulverizing particulate that obtains is put into rotor formula airflow classification device (-ボ Network ラ シ Off アイ ア TC-15, day is エ Application ジ ニ ア リ Application グ society system clearly) in, give the centrifugal force of sized particles and the balance of resistance is carried out classification by regulating, obtain with respect to supplying with the particulate of sized particles after with the rate of recovery classification of 83 quality % by the speed of rotation of classification rotor with from the supply of the air of suction hole.
Comparative Examples 4
With method similarly to Example 1, (Bulk Specific Gravity is 0.7g/cm to pulverize particulate by the polymer dispersion liquid preparation that obtains in the preparation example 12 3, particle diameter is 6.5 μ m, moisture content is below the 0.5 quality %, the rate of recovery is 99 quality %).
The pulverizing particulate that obtains is put into wall-attachment airflow classification device (エ Le ボ-ジ The エ Starト EJ-15, day iron Industry Co., Ltd. system, reinforced air: 5kgf, use elongated ribs) in, give the centrifugal force of sized particles and the balance of resistance is carried out classification by regulating, obtain with respect to supplying with the particulate of sized particles after with the rate of recovery classification of 75 quality % by the speed of rotation of classification rotor with from the supply of the air of suction hole.
Comparative Examples 5
Except that not carrying out wet classification, with method similarly to Example 1, (Bulk Specific Gravity is 0.7g/cm to pulverize particulate by the polymer dispersion liquid preparation that obtains in the preparation example 3 3, particle diameter is 6.9 μ m, moisture content is that 0.5 quality % is following).
The pulverizing particulate that obtains is put into rotor formula airflow classification device (-ボ Network ラ シ Off アイ ア TC-15, day clear エ Application ジ ニア リ Application グ society system) in, give the centrifugal force of sized particles and the balance of resistance is carried out classification by regulating, obtain with respect to supplying with the particulate (the 1st dry classification) of sized particles after with the rate of recovery classification of 90 quality % by the speed of rotation of classification rotor with from the supply of the air of suction hole., repeat same dry classification operation, obtain with respect to supplying with the particulate (dry classification for the second time) of sized particles after with the rate of recovery classification of 90 quality % thereafter.
Evaluation result about the content of the stage treatment in embodiment 9-13 and Comparative Examples 4, resulting particulate and powder particle is as shown in table 5.In addition, each evaluation method as mentioned above.
Figure A200780027514D00631
In addition, Comparative Examples 5 example of secondary that be repetitions as the dry classification of classification operation.Only repeat dry classification and can not remove coarse particle fully.And,, find that product recovery rate has the trend of reduction, only carries out dry classification and is difficult to obtain industrial product yield by repeating dry classification.
The preparation of embodiment 16 anti-dazzle films
Each resin particle that obtains in 3 mass parts embodiment 1,9,10 and the Comparative Examples 4 and the toluene of 20 mass parts are mixed fully.The acrylic acid series ionizing radiation cured resin, 2 mass parts Photoepolymerizationinitiater initiaters (the チ バ ス ペ シ that add 40 mass parts ヤLe テ イケ ミ カ Le society system, " イ Le ガ キ ユア (registered trademark) 907 "), 23 mass parts ethyl methyl ketones, 2 mass parts ethylene glycol monobutyl ether, and levelling agent (PVC StarNetwork ケ ミ-society's system, BYK320) in this mixed solution, stir fully and be mixed with coating fluid.
At thickness is tri acetyl cellulose film (Fuji's description Off of 80 μ m イLe ム She System, " Off ジ StarNetwork (registered trademark) ") single face on, apply this coating fluid by scraping strip coating machine.By the coated film that will obtain with 80 ℃ moisture eliminator drying after, with high-pressure mercury light irradiation 300mJ/cm 3Ultraviolet ray, resinous principle is solidified makes anti-dazzle film.
Stick the film of black in the inside of each anti-dazzle film, shine 10000cd/cm in position from this film 2m 3Luminescent lamp, by the fog-level of following its reflected image of benchmark evaluation.The result is as shown in table 6.
Zero: the profile that can not distinguish luminescent lamp.
*: the profile that can distinguish luminescent lamp clearly.
In addition,, use the wide light comb of mapping determinator (ス ガ Try Omen Machine Co., Ltd. system, ICB-IDD) and 0.5mm, measure according to JIS K7105 and see through visibility (image visibility) for each anti-dazzle film.
Further each anti-dazzle film is attached to the liquid-crystal display (15 inches XGA, TFT-TN mode, the front face brightness: 350cd/m that are connected in PC 2, positive contrast gradient: 300 to 1, surfaces A G: on surface nothing), by the ambiguity of following benchmark evaluation literal.The result is as shown in table 6.
Zero: the profile of literal is not fuzzy fully.
*: the soft edge of literal, can feel very strong inharmonious sense.
Table 6
Particle Average diameter * 2 coarse particlees (individual/0.5g) Anti-dazzle property Transparent visibility Literal is fuzzy
Embodiment 1 500 ○ 40 ○
Embodiment 9 10 ○ 44 ○
Embodiment 10 200 ○ 42 ○
Comparative Examples 4 1200 ○ 18 ×
As can be seen from Table 6, the anti-dazzle film that uses the particle of embodiment 1,9 and 10 to obtain all has good anti-dazzle property, and visuognosis degree (literal is fuzzy).On the other hand, though use the anti-dazzle film of the particle preparation of the many Comparative Examples 4 of the amount of 2 times the coarse particle that surpasses median size to have anti-dazzle property, but the coarse particle that is contained in the anti-dazzle film can work as lens, because this coarse particle produces scar on film surface, its result becomes literal and is difficult to distinguish.
Industrial applicibility
Particulate of the present invention is that particle diameter exceeds the corase particles of proper range or the content of small particle is lowered to low-level particulate. Therefore, use the various film for optical use of this particulate preparation or sheet (anti-glare sheet, light diffusion film etc.) to be difficult to produce the reduction that comes from the shortcoming of corase particles or come from the transparency of small particle. In addition, uneven owing to being formed uniformly in the face, can bring into play good optical characteristics (for example anti-glare or light diffusing).

Claims (8)

1, a kind of particulate is characterized in that, in this particulate, the coarse particle with particle diameter more than 2 times of median size be 1000/below the 0.5g.
2, particulate according to claim 1, wherein, described particulate is the organism mineral complex that contains organic polymer skeleton and polysiloxane skeleton.
3, the preparation method of a kind of claim 1 or 2 described particulates is characterized in that, this method comprises: with solid component concentration is that 0.5-50 quality %, Type B viscosity are the operation of the particle dispersion liquid wet classification of 0.5-20mPas; With particulate drying, the pulverizing behind the wet classification, making moisture content is the operation of the powder particulate of 0.05-2 quality %; With described powder particulate dry type fractionated operation.
4, a kind of resin combination is characterized in that, this resin combination contains claim 1 or 2 described particulates.
5, a kind of application composition that is coated with is characterized in that, this is coated with the application composition and contains the described resin combination of claim 4.
6, a kind of optical thin film is characterized in that, this optical thin film is by being coated to the described application composition that is coated with of claim 5 on the base material and obtaining.
7, optical thin film according to claim 6, wherein, described optical thin film is as the light diffusion film.
8, optical thin film according to claim 6, wherein, described optical thin film is as anti-dazzle film.
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