CN101490138B

CN101490138B - Microparticle, process for producing microparticle, resin composition loaded with the microparticle and optical film

Info

Publication number: CN101490138B
Application number: CN2007800275144A
Authority: CN
Inventors: 清水健次; 富永美和子; 高崎进治; 保吕信一
Original assignee: Nippon Shokubai Co Ltd
Current assignee: Nippon Shokubai Co Ltd
Priority date: 2006-08-21
Filing date: 2007-08-17
Publication date: 2012-07-18
Anticipated expiration: 2027-08-17
Also published as: CN101490138A; TW200819470A; WO2008023648A1; KR20110133638A; KR20090033251A; KR101382369B1; JP5478066B2; JPWO2008023648A1

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 a kind of particle diameter by the particulate of control to heavens and the resin combination that has used this particulate.

Background technology

In the past, attempted being used in resin or the resin combination of various uses and contained particulate, with the rerum natura that improves this resin or resin combination or operability etc.Optical resin material at the optical applications that is used for LCD (LCD), plasma scope (PDP), electroluminescent display (ELD), transmissive viewing screen (infiltration type ス Network リ one Application) and touch panel etc. has 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 organic matter 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 have also improved the requirement of relative periphery technology, also carry out raising, the mechanical characteristics of particulate self and the 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.Size distribution is wide if this is; 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 this particulate can directly visiblely make the demonstration grade of image display device reduce.

For example, in the patent documentation that discloses the particulate that can be used in optical applications 1, mainly put down in writing preparation method, can obtain the particulate with the purposes relevant particle size of hoping 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 preparing 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 the 2002-166228 communique, Patent right requirement book etc.

Patent documentation 3: the spy opens the 2005-309399 communique, Patent right requirement book etc.

Patent documentation 4: the spy opens the 2004-191956 communique, Patent right requirement book etc.

Summary of the invention

Yet, of patent documentation 1, at the synthesis phase of particulate; In fact highly it is very difficult controlling size distribution; In addition, as pointed among the patent documentation 2-4, even can size distribution be 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 ZGK 5 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; Particulate behind the wet classification is dry, pulverizing, processing moisture content is the operation of the powder particulate of 0.05-2 quality %; With said powder particulate dry type fractionated operation.Like this, through 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 compsn is coated on the base material and is also containing compsn 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 article 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 compsn, 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 stated, 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 be prone to produce scar or this particulate be prone to by visuognosis maybe.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, further be 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 particulate below the 30/0.5g, and further preferred above-mentioned coarse grain subnumber is the particulate below the 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 the median size of particulate of the present invention does not have special qualification, but is preferably 0.1-50 μ m, and more preferably 1-30 μ m further is 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 maybe, when excessive, the possibility that can not get sufficient light diffusion effect is arranged.In addition; The content of particle size distribution, average grain diameter and said fine particle uses and has utilized the accurate particle size distribution device (for example " マ Le チサイザ one II " of ベ Star Network マ Application コ one Le タ one society's system) of Coulter principle to measure, and is that benchmark calculates with the volume.

The shape of particulate of the present invention does not have special qualification, for example, can enumerate out 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 compsn 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 cut, 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 cut, make between particle through 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 cf-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, under the excessive situation of Bulk Specific Gravity, owing to need very big equipment with power and not preferred, on the other hand, under too small situation, owing to be difficult to produce poor that size by particle diameter produces, the step-down of effectiveness of classification meeting 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, because become equipment and power that need be very big and not preferred.

Through wet classification, it is below 200,000 that the content of the coarse particle more than 2 times that offers powder particle and the median size in the dispersion soln that obtains through wet classification of dry classification is preferably every 0.5g.More preferably 100,000/below the 0.5g, further be 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 through wet classification, because preferred through 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 cut " is the value of measuring through 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 under certain state, joining powder in certain volumetrical container, 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 society system)." true specific gravity " of powder particulate is that the powder particulate is filled in certain volumetrical container and then with liquid the space of test portion is replaced fully, from the volume of container, deducted the value that the relation of the quality of the powder particulate of filling in value and the container behind the volume of the liquid that needs this moment calculates, and is to measure the value that machine (the for example セ of Co., Ltd. イシ Application enterprise system) mensuration obtains through true specific gravity.It is the value of benchmark with the volume that the value of above-mentioned particle diameter is measured what obtain through said accurate particle size distribution device (for example ベ Star Network マ Application コ one Le タ one society's system " マ Le チサイザ one II ").

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.

The classifying mechanism of said flow sorting equipment does not have special qualification.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 these and other stage division (sieve or sieve aperture) combines.

As a specific air classifier, can be cited DXF type (Japanese Uni a gusset boots black Kogyo) and other high-precision air classifier; turbine classifier (Tatari a ボ ku ra shifter アイア, Nissin Oh nn ji ni ant nn bag manufactured), high efficiency, precision air classifier (ku ra boots Shin a Hikaru, Seishin social system), Tatari a ボ plastic LEC su (registered trademark ホソ grades Waku by Micron Co., Ltd.) having a grading impeller rotating impeller-type air classifier; elbow nozzle (Oh Hikaru ボ a zip Oh boots Suites, Japanese Iron Ore Industry Co., Ltd.), etc. use of the Coanda effect air classifier (elbow nozzle type classifier (Oh Hikaru ボ a zip Eri boots coat type classifying machine)); Dry sieve high sifter (dry sieve tension イボ Hikaru Tatari one, Japan Hana イ Te boots ku manufactured), the blower phase shifter ( Dry sieve blow a shifter Waku one uni-ro boots a plastic bag, Ltd.) use of the sieve net air classifier.Wherein, because high precision airflow classification device, the wheeled airflow classification device of pivoting leaf and utilized the airflow classification device that attaches the 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); Through producing the high speed gyration airflow to discrete areas and stepped zone leaked-in air; To supplying to when particle in the device gives cf-; Through attracting gas blower (attracting Block ロワ one) that air is discharged from stepped zone, become giving resistance to the cf-of particle, particle is classified into the device of meal and micro mist through the balance of this cf-and resistance.The wheeled airflow classification device of pivoting leaf is meant, has the cylinder (classifying turbine) that rotates freely and outside to the inner suction hole that sucks air of device by device, through high speed rotating generation eddy current in device of above-mentioned impeller; Give cf-through eddy current to the particle that supplies in the device; On the other hand, suck air, make it to become the resistance of cf-from suction hole; Through the balance of this cf-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 of which side wall surface, utilize along the device of the mobile so-called wall attachment effect of this wall; This device is provided with in position arbitrarily: with air-flow (reinforced air (feed air)) injector portion, guiding jet flow (containing particle) of ejection particle in device arrive in the grading room attached wall sheet (coanda block) and according to the classification rib (classification エ Star ジ) of proterties (meal, fine powder (object), micro mist etc.) spacer particle.Jet flow (containing particle) by the ejection of above-mentioned injector portion flows along attaching the wall sheet.This moment mass force (mass force that in fine particle and coarse particle, acts on has difference, and it is farther that coarse particle can fly) and the balance of fluid resistance through acting on particle, 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 peak 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 on the wall in front, is reflected back, to sneak into the possibility of fine powder very high.Yet the particulate that the present invention relates to is of the back to be the particulate that obtains after the wet classification operation, through dry classification, because coarse particle is removed in above-mentioned wet classification operation to a certain extent, the coarse particle that does not therefore reflect back is blended into the situation in the fine powder.Therefore, through 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 stated, 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 of the stream that usually width of classification rib is designed to flow through with the jet flow that contains particle approximately equates.At this, to compare with common used standard rib, above-mentioned elongated ribs forms the distance short (particularly partly being about the half the of standard rib at basal cross section) between the inclined-plane of wedge shape.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.Through 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, further be preferably 200,000/below the 0.5g.

Above-mentioned particle dispersion liquid can be that the microparticulate for preparing is in advance arrived the particle dispersion liquid in the dispersion medium (water, organic solvent etc.); Under the situation of organic polymer of after particulate contains, stating 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 does not have special qualification, can enumerate sends as an envoy to has used the filtration unit of strainer or sieve, has utilized liquid cyclone device of cf-, mass force etc.Can enumerate as concrete wet classification device and to appear filter core cylinder (cartridge filter) (for example ロキテ Network ノ society system, Japanese ボ one Le society system), utilize cf-to carry out fractionated liquid cyclone (for example ラサ industry society system, イ Application ダストリア society system).

The above-mentioned filter core cylinder of crossing also can use in a plurality of combinations; For example; With the purpose that is reduced to of the operational cost that causes by long lifetime, also can and be used to prolong the strainer combination in post filter life-span with the post filter that satisfies desired filtering accuracy (final filter) and use.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; Because the filter core cylinder of crossing of the SLP type of ロキテ Network ノ society system has as the thickness of the filtering material of the characteristic of deep filter (depth filter) with as the big filtration area of the characteristic of pleat strainer (プリ one Star Off イ Le タ one), 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 cf-fractionated device.For example; Situation with device of cylinder (or circular cone) parts is supplied with particle dispersion liquid from 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 above device, moving.

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 not special qualification.

Though particulate of the present invention obtains the powder particulate dry classification of the rerum natura with 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 enumerate out, after the particle drying behind the wet classification, the pulverizing, carry out the operation of dry classification again particle dispersion liquid wet classification with regulation rerum natura as preferred operation in order to obtain particulate of the present invention.Through 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/particulate below the 0.5g.

Below, describe for the structure and the preparation method of the particulate that the present invention relates to.

The form of the particulate that the present invention relates to does not have special qualification, can be for containing any the particulate in organic polymer, inorganic material, the organism composite material of inorganic matter.Can enumerate out the simple linear polymer of PS, polymethylmethacrylate, Vilaterm, Vestolen PP 7052, polyethylene terephthalate, polybutylene terephthalate, polysulfones, polycarbonate, polymeric amide etc. as above-mentioned organic polymer; Vinylstyrene; Hexatriene; Vinylaether; Divinyl sulfone; Diallyl methyl alcohol; Alkylene diacrylate (alkylenediacrylate); Oligomeric (oligo) or gather alkyl diol diacrylate (polyalkyleneglycoldiacrylate); Oligomeric or gather the alkyl diol dimethacrylate; Alkylene triacrylate (alkylenetriacrylate); The alkylene tetraacrylate; The alkylene trimethacrylate; Alkylene tetramethyl-propenoate; The alkylene bisacrylamide; The two USAF RH-1s 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 through aminocompound (for example benzoguanamine, trimeric cyanamide or urea etc.) and formaldehyde obtains.

As the organism composite material of inorganic matter, can enumerate out: (A) the inorganics microparticulate of the MOX of silicon-dioxide, aluminum oxide, titanium oxide 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 on molecular level, is composited of (organic) ZGK 5, metal oxygen alkane (metalloxane) chain (molecular chain that contains " metal-oxygen-metal " key) and the organic molecule that gather titanoxane (polytitanoxane) etc. or the organoalkoxysilane through methyltrimethoxy silane etc., condensation reaction etc. is particulate; (C) be the organism composite material of inorganic matter that contains organic polymer skeleton and ZGK 5 skeleton that the ZGK 5 of raw material and the reactions such as polymerizable monomer with polymerizable group (for example vinyl, (methyl) acryl etc.) obtain through making with silicon compound with water-disintegrable silyl.

As inorganic material, for example, can enumerate out 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 through seeding polymerization method (シ one De coincidence method) (be more than the 20 quality %, more preferably more than the 30 quality %, further be preferably the particle more than the 50 quality %) with respect to the ratio of the cross-linkable monomer of the full dose of polymerizable monomer; 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 through organic solvent dissolution, swelling.Therefore; The light diffusion layer of after being used to form, stating, 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 effect in the above-mentioned scope fully, thus preferred.

These particles offer the wet classification operation under the state of the particle suspension that preferably when each particle synthetic, obtains.That is, this is poor (for example, the cause that obtains easily of the suspension-s 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 be preferably particle diameter coefficient of variation (size-grade distribution that calculates with volume reference is a benchmark) at the particle below 20%.More preferably below 10%.The value of the coefficient of variation of particle diameter is more little, representes 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 going out by computes.

[mathematical expression 1]

The coefficient of variation of particle diameter (%)=(σ/X) * 100

Wherein, σ representes the standard deviation of particle diameter, and X representes median size.

Among the present invention, the standard deviation of median size and particle diameter is to use described accurate particle size distribution device (for example " マ Le チサイザ one II " of ベ Star Network マ Application コ one Le タ one society's system) to measure, and calculates 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.

< 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 enumerate out 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 through 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: through making amino based compound and formolite reaction to obtain the resinifying operation of aminoresin presoma; The aminoresin presoma that will in said 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 said emulsification process, obtains, to obtain the curing process of amino resin crosslinked particle.

Above-mentioned resinifying operation is to make amino based compound and formolite reaction to generate the operation as the aminoresin presoma of initial stage condensation reaction thing.Solvent when making amino based compound and formolite reaction can make water.As the concrete implementation method of this resinifying operation, preferably can enumerate out: be to add the method that amino based compound reacts under the state of the aqueous solution (Superlysoform) 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 through known whipping appts etc.

In the resinifying operation; Can there be special qualification as the amino based compound of starting raw material; For example; Can enumerate out 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 (シ 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 can use separately, also can two or more and usefulness.

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 %, further be 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 in the resinifying operation, reacts and the mol ratio of formaldehyde (amino based compound (mole)/formaldehyde (mole)) are preferably 1/3.5-1/1.5, and more preferably 1/3.5-1/1.8 further is 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 can the viscosity adjustment of reaction solution in 95-98 ℃ TR that contain as the aminoresin presoma of resultant of reaction 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 aqueous solution that adds emulsifying agent or emulsifying agent in reaction solution so that after the concentration of the aminoresin presoma in the emulsion becomes in the scope of 30-60 quality % in the emulsification process stated concentration get final product.

Therefore, contain the viscosity of reaction solution in 95-98 ℃ TR 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) further is 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 through 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.

Through 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 TR 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 through the operation with this reaction solution cooling etc. gets final product.Thus, can obtain containing the reaction solution of aminoresin presoma.In addition, the reaction times does not have special qualification.

About the aminoresin presoma that obtains in the resinifying operation; The structural unit that comes from amino based compound that constitutes this aminoresin presoma and the mol ratio that comes from the structural unit of formaldehyde (come from the structural unit (mole) of amino based compound/come from the structural unit (mole) of formaldehyde) are preferably 1/3.5-1/1.5; More preferably 1/3.5-1/1.8 further is 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, ETHYLE ACETATE, butylacetate, methyl glycol, glycol monoethyl ether, butanone, toluene, YLENE 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 through 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), after the emulsion that obtains in the emulsification process the stated 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 maybe.On the other hand, the viscosity of reaction solution surpasses 5.5 * 10 ^-2During Pas (55cP), have to after employed impeller etc. applies in the emulsification process stated load excessive, its shearing force is reduced, stirring reaction liquid (making its milkiness) maybe 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 with the operation of the aminoresin presoma emulsification that obtains through the resinifying 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 Z 150PH, CMC 99.5, sodium alginate, ROHM, water-soluble polyacrylate, Vinylpyrrolidone polymer 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 illustrative emulsifying agent of above institute, consider the stability of emulsion, with the interaction of catalyzer etc., Z 150PH more preferably.Z 150PH can be fully saponified thing, also can be partly-hydrolysed thing.In addition, the polymerization degree of Z 150PH does not have special qualification.

The usage quantity of emulsifying agent, the aminoresin presoma that in above-mentioned resinifying operation, obtains 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 ℃ TR, make its milkiness.More preferably 60-100 ℃, further be preferably 70-95 ℃.The concentration of the aqueous solution of emulsifying agent does not have special qualification, so long as can the concentration adjustment of aminoresin presoma 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) of the aqueous solution of above-mentioned aminoresin presoma and emulsifying agent more forcefully.Specific examples of the stirring device, for example, include a so-called high-speed mixer, homomixer (ホ holds an Miki Thermopreg), TK homomixer (Tokushu Kika Kogyo (Co., Ltd.)), a high speed disperser (high-speed terrestrial イ su bread), the Eibar Rameau Ilsa (Oh, perfect ra ma イ Hikaru ザ one, (strain) Ebara Seisakusho), high-pressure homogenizer ((strains) イ Season mini フ a cloth ma Shin inner re-made ), a static mixer ((strains) Bruno re Tatari Kelly grades Lymph ni a re mini Te boots cloth system) and so on.

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 through 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 further is preferably 1-5 μ m.Like this, make that through 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 finally to obtain condenses securely.As inorganic particulate, particularly, preferably can enumerate out 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 further is preferably 30-300m ²/ g.The particle diameter of inorganic particulate more preferably below the 0.2 μ m, further is preferably below the 0.1 μ m, further is 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 finally to obtain.

In emulsion, add the method for inorganic particulate, do not have special qualification, particularly, for example, can enumerate out 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 that is contained in respect to 100 mass parts is preferably the 1-30 mass parts, and more preferably the 2-28 mass parts further is preferably the 3-25 mass parts.During less than 1 mass parts, the possibility that has the amino resin crosslinked particle that can not prevent fully finally to obtain to condense securely; When surpassing 30 mass parts, the possibility that produces the condensation prod 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; Through 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-s 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 that passes through with respect to 100 mass parts is preferably the 0.1-5 mass parts, and more preferably the 0.3-4.5 mass parts further is preferably the 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, likewise, the usage quantity of above-mentioned catalyzer, the amino based compound as starting compound with respect to 1 mole is preferably more than 0.002 mole, more preferably more than 0.005 mole, further is preferably the 0.01-0.1 mole.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 maybe.

Curing reaction in curing process; Preferably with reaction soln (emulsion) be preferably 15 ℃ (normal temperature) to 80 ℃, more preferably 20-70 ℃, further be 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 ℃, further be preferably under 60-100 ℃ the temperature of scope and carry out.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 through 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, the median size of preferably solidifying the amino resin crosslinked particle obtain through the aminoresin presoma that makes the milkiness state is 0.1-20 μ m, and more preferably 0.5-20 μ m further is preferably 1-5 μ m.

In first preparation method, can comprise in the suspension-s 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-s that contains the amino resin crosslinked particle that obtains through 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.Through in carrying out and operation, can remove above-mentioned acid catalyst (being specially the neutralizing acid catalyzer), for example, after in the heating process stated 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 operation in " neutralization " be that to instigate the pH of the suspension-s that contains amino resin crosslinked particle be more than 5, more preferably making pH is 5-9.When the pH of this suspension-s less than 5 because the residue of acid catalyst, after in the heating process stated etc., the situation of amino resin crosslinked particle variable color is arranged.Through above-mentioned neutralization with the pH that regulates this suspension-s 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 operation in the neutralizing agent that uses, for example, alkaline matter is fit to.As this alkaline matter, for example, can enumerate out yellow soda ash or sodium hydroxide, Pottasium 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 with operation after select the separation circuit of this amino resin crosslinked particle in the suspension-s of the amino resin crosslinked particle that obtains.

As selected from the suspension of the amino resin crosslinked particles method (separation method), a simple method can include isolated by filtration (filter not) method or a centrifuge separator such method is not particularly limited but , may be used any of conventionally known separation method.

And, the amino resin crosslinked particle after selecting from suspension-s, also water etc. washs as required.

In first preparation method, the heating process that preferably amino resin crosslinked particle of selecting through separation circuit is heated under 130-190 ℃ temperature.Through 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) in the amino resin crosslinked particle.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 the situation of operation under, 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 with operation, the Heating temperature that also will make amino resin crosslinked particle is in above-mentioned scope.

Heating means in heating process do not have special qualification, use 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, there is not special qualification heat-up time.

Also can with the amino resin crosslinked particle that in first preparation method, obtains from the water-medium when the said emulsification, separate and dry, pulverize after, the crushed material that obtains is distributed to the suspension-s of processing in the solvent supplies to wet type and dry classification operation.In addition, with the suspension-s behind the curing process (behind the curing process, comprise through in the suspension-s that obtains with operation etc., supply to the suspension-s 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, through the suspension-s behind the wet classification is dry, pulverize, 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 in water-medium, mixing with tensio-active agent through the aminoresin presoma that amino based compound and formolite reaction are obtained; Through in this mixed solution, adding catalyzer; Make said aminoresin presoma in said water-medium particlized and separate out after, said amino resin crosslinked particle is separated and dry the method that the dry thing that obtains is pulverized from said 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 formolite 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, said mixed processes is that the aminoresin presoma that obtains through the resinifying operation is mixed with tensio-active agent in water-medium; Said curing particlized operation is in the mixed solution that contains this aminoresin presoma and tensio-active agent, to add the particlized that catalyzer causes with the curing of carrying out by the aminoresin presoma and separate out, thereby obtains amino resin crosslinked particle.

In second preparation method, begin to solidify through 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 in second preparation method, uses, preferred its kind and the water Combination of group direct ratio suitably set to state after satisfying.For example, more preferably must can generate the amino based compound of water miscible aminoresin presoma with the Superlysoform reaction.

In addition, the aminoresin presoma that in the resinifying operation, obtains is preferably water miscible.The tensio-active agent that in second preparation method, uses uses in order in the water-medium of aminoresin presoma, to give wetting ability, in this tensio-active agent, is not included in employed emulsifying agent among first preparation method.

In the present invention; Above-mentioned wetting ability is used with respect in the quality % of the initial stage condenses of the dripping quantity that in as the aminoresin presoma of initial stage condenses, drips the water of water when producing white opacity under 15 ℃ (below be called the water mixedness) expression; 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-s 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 through 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, non-ionics, amphoterics be can use, aniorfic surfactant or non-ionics or their mixtures are preferably especially.

As AS; Can use alkali metal alkyl sulfate like sodium lauryl sulphate, dodecyl sulphate potassium etc.; Alkylsurfuric acid ammonium like 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 one ト) is like the AS of an alkali metal salt of sulfonation paraffin (ス Le ホ Application パラ Off イ Application), the ammonium salt of sulfonation paraffin etc.; Soap like sodium laurate, triethanolamine oleate, sylvic acid trolamine etc.; Like the alkylaryl sulphonate of alkali metal sulfates of X 2073, alkaline phenol hydroxyl ethene (ア Le カリ Off エノ one 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 non-ionics; Can use polyethylene oxide alkyl ethers, 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-s, 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, the concentration of the aqueous solution of tensio-active agent does not have special qualification, 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 the agitating wing of disc turbine (デイス Network タ one PVC Application), fan turbine (Off ア Application タ one PVC Application), method Wudu pull-up (Off アウ De ラ one type), propeller-type and multistage aerofoil profile etc. to carry out stirring method etc.

In second preparation method,, add inorganic particulate in the mixed solution that also can behind mixed processes, obtain in advance as required for the amino resin crosslinked particle that prevents finally to obtain firmly condenses.About inorganic particulate and addition means thereof etc., the explanation among said first preparation method can likewise 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-s 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-s in as the aqueous solution of the aminoresin presoma of initial stage condenses.Particularly, for example, can enumerate out 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 that passes through with respect to 100 mass parts is preferably the 0.1-20 mass parts, and more preferably the 0.5-10 mass parts further is preferably the 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 maybe.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-s 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 maybe.

In addition, likewise, as the usage quantity of above-mentioned catalyzer, the amino based compound as starting compound with respect to 1 mole is preferably more than 0.0005 mole, more preferably more than 0.002 mole, further is preferably the 0.005-0.05 mole.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 maybe.

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 through sampling or visual judgement.In addition, the reaction times of curing reaction does not have special qualification.Usually; Curing reaction is through 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,, solidify just very abundant as long as the amino resin crosslinked particle in the suspension-s that obtains is cured to the degree of not swelling in methyl alcohol or acetone.

Solidifying the particlized operation preferably carries out under the stirring through 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 preparing method's the curing process is identical.

In second preparation method, can comprise and carry out in the neutral and operation the suspension-s that contains the amino resin crosslinked particle that obtains through above-mentioned operation.For in operation in the details of scope or the kind of neutralizing agent etc. of pH, the explanation among first preparation method can likewise be suitable for.

In second preparation method, also can be provided with after solidifying the particlized operation or with operation after select the separation circuit of this amino resin crosslinked particle in the suspension-s of the amino resin crosslinked particle that obtains.And, in second preparation method, so-called separate and select amino resin crosslinked particle from suspension-s be meant that water-medium from mixed processes separates and selects the amino resin crosslinked particle that obtains through curing.For the method for from suspension-s, 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 preparing method's heating process.

The amino resin crosslinked particle that in second preparation method, obtains; Preferably with it during from said 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-s; After its wet classification, separation, drying, carry out dry classification.Preferably with the suspension-s after above-mentioned curing, the particlized operation, or through in and the suspension-s of operation/washing step supply in wet type and the dry classification.Separating particle behind the preferred wet classification carries out drying through 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.The polymerization method of the particulate of above-mentioned organism composite material of inorganic matter does not have special qualification, can compatibly use the known polymerization method of letex polymerization, suspension polymerization, seeding polymerization, sol-gel polymerizations etc.

As stated, 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 ZGK 5 skeleton of inorganics part.This complex particles is preferably at intramolecularly has the form (chemical of bonding) that Siliciumatom direct chemical in the ZGK 5 skeleton is incorporated into the organosilicon atom at least one carbon atom in the organic polymer skeleton.As concrete form, be preferably through the Siliciumatom in the ZGK 5 skeleton and combine with carbon atom in the organic polymer skeleton, become the form of ternary network structure with ZGK 5 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.The having or not etc. of molecular weight, composition, structure and functional group that forms this skeleton organic polymer do not have special qualification.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) vinyl resin, PS 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]

The ZGK 5 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]

Constitute the SiO of ZGK 5 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 ZGK 5 skeleton ₂Amount in above-mentioned scope, control complex particles hardness will become easy.In addition, during less than 0.1 quality %, the possibility of the unfavorable condition that the flexibility or the elasticity that produce particle reduce, particle inside was destroyed etc. when externally stress was applied on the resin combination is arranged; 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 ZGK 5 skeleton ₂Amount, for through 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 through 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 maybe; Surpass 1.0 * 10 ⁴The time, the possibility of the unfavorable condition that the flexibility or the elasticity that produce particle reduce, particle inside was destroyed etc. when externally stress was applied on the resin combination is arranged.

For above-mentioned complex particles, so-called mechanical characteristicies separately such as its hardness or strength at break can suitably change and at random regulate through the ratio that makes ZGK 5 skeleton part or organic polymer skeleton part.

ZGK 5 skeleton in the above-mentioned complex particles, preferably the hydrolysis-condensation reaction of the silicon compound through having hydrolization group obtains.

As having water-disintegrable silicon compound, there is not special qualification, for example, can enumerate out represented silicon compound of following general formula (3) and verivate 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 representes 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 not special qualification, for example,, can enumerate out four functionality silane of tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan, four butoxy silanes etc. as the material of m=0; Material as m=1; Can enumerate out methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, hexyl Trimethoxy silane, decyl Trimethoxy silane, phenyltrimethoxysila,e, benzyl Trimethoxy silane, naphthyl Trimethoxy silane, methyl triacetoxysilane, β-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, 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 enumerate out two functionality silane of dimethyldimethoxysil,ne, dimethyldiethoxysilane, diacetoxy dimethylsilane, diphenyl silanodiol etc.; As the material of m=3, can enumerate out 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 enumerate out methyltrimethoxy silane, phenyltrimethoxysila,e, 3-(methyl) acryloxy propyl trimethoxy silicane, β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan, 3,3,3-three fluoro propyl trimethoxy silicanes etc.

Verivate as the represented silicon compound of above-mentioned general formula (3); There is not special qualification; For example, can enumerate out compound that a part of X replaced by the group that can form inner complex of carboxyl, beta-dicarbonyl etc. or partly hydrolysed above-mentioned silane compound and low condenses of obtaining etc.

Have water-disintegrable silicon compound, also can only use a kind of, also can be two or more suitably combination use.In above-mentioned general formula (3), silane compound and the verivate thereof that only uses m=3 can not get complex particles during as raw material.

Above-mentioned complex particles; At the ZGK 5 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; Have a water-disintegrable silicon compound as above-mentioned, must use silicon compound, as this reactive group with the organic group that contains the polymerizability reactive group that can be formed with the organic polymer skeleton; For example, can enumerate out radical polymerizable group, epoxy group(ing), hydroxyl and amino etc.

As the above-mentioned organic group that contains free-radical polymerised group, for example, can enumerate out represented free-radical polymerised group in formula (4), (5) and (6) etc.:

CH ₂＝C(-R ^a)-COOR ^b- (4)

(wherein, R ^aExpression Wasserstoffatoms 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 Wasserstoffatoms or methyl.)

CH ₂＝C(-R ^d)-R ^e- (6)

(wherein, R ^dExpression Wasserstoffatoms 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 enumerate out acryloxy and methacryloxy etc.; As the silicon compound shown in the above-mentioned general formula (3) with this organic group; For example, can enumerate out 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 enumerate out vinyl, pseudoallyl etc.; As the silicon compound shown in the above-mentioned general formula (3) with this organic group, for example, can enumerate out 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 enumerate out 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 enumerate out 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 enumerate out 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-triethoxysilicane, β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan 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 enumerate out 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 enumerate out 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) absorbing free radical polymerization monomer on the particle of the ZGK 5 skeleton that the hydrolysis-condensation reaction that has through silicon compound obtains, have the monomer of epoxy group(ing), making 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) when above-mentioned silicon compound does not have the organic group of the polymerizability reactive group that can be formed with the organic polymer skeleton that contains free-radical polymerised group, epoxy group(ing), hydroxyl, amino etc.; Make it polyreaction after going up the monomer that absorbs free radical polymerization monomer, have epoxy group(ing) at the particle (seed particles that the ZGK 5 particle is formed below is also referred to as the ZGK 5 particle) of the ZGK 5 skeleton that the hydrolysis-condensation reaction that has through silicon compound obtains, have the monomer of hydroxyl and having the polymerizable monomer with polymerizability reactive group of amino monomer etc. and obtain.

As stated, complex particles can be the form (chemical of bonding) that intramolecularly has the Siliciumatom direct chemical and is combined in the organosilicon atom at least one carbon atom in the organic polymer skeleton for a) ZGK 5 skeleton; Also can be b) intramolecularly do not have the form (IPN type) of such organosilicon atom; There is not special qualification, for example, like above-mentioned 1-1) said; When obtaining the organic polymer skeleton, can access and have a) complex particles of form with the ZGK 5 skeleton; As above-mentioned 2) shown in the time, can access have b) complex particles of form.In addition, like above-mentioned 1-2) shown in, when obtaining the organic polymer skeleton with the ZGK 5 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 ZGK 5 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 property unsaturated group, its kind etc. does not have special qualification, 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 ZGK 5 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 enumerate out 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.

As the method for the above-mentioned complex particles of preparation, can preferably enumerate out the preparation method of hydrolysis, condensation operation and the polymerization process stated after comprising.Further as required, after hydrolysis, condensation operation, before the polymerization process, can also comprise the monomeric absorption operation of absorbing polymer property (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 ZGK 5 skeleton); As necessary, then this absorption operation is formed with the organic polymer skeleton in polymerization process with above-mentioned absorption operation.

Said hydrolyzed, condensation operation are meant above-mentioned silicon compound are hydrolyzed in containing the solvent of water and make it the operation of the reaction of polycondensation.Through this operation, can obtain having the particle (ZGK 5 particle) of ZGK 5 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, dewatering can contain organic solvent with catalyzer is outer.As organic solvent, for example, can enumerate out methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, terepthaloyl moietie, Ucar 35,1, the alcohols of 4-butyleneglycol etc.; The ketone of acetone, ethyl methyl ketone etc.; The ester class of ETHYLE ACETATE etc.; (ring) alkanes of octane-iso, hexanaphthene etc.; Benzene, toluene etc. aromatic hydrocarbon based etc.They can use separately, also can two or more and usefulness.

In hydrolysis, condensation operation, also can and with the tensio-active agent of anionic, cationic, non-ionic type, or the macromolecule dispersing agent of Z 150PH, Vinylpyrrolidone polymer etc.They can use separately, also can two or more and usefulness.

Hydrolysis and condensation can through will as the above-mentioned silicon compound of raw material with contain the solvent of catalyzer and water and organic solvent after, be 0-100 ℃ in temperature, be preferably 0-70 ℃ down stirring carried out in 30 minutes-100 hours.In addition, be hydrolyzed, condensation reaction is until desirable degree and after preparing particle, also can further in reaction system, add silicon compound with it as seed particles, and this seed particles is grown up.

The weight-average molecular weight of ZGK 5 particle is preferably 250-10000, more preferably 250-5000.Weight-average molecular weight is in above-mentioned scope the time; The absorption rate that absorbs the polymerizable monomer in the operation is high; In system; Can suppress to come from and be not 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, through 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 ZGK 5 particle so that the absorption operation of carrying out under the state that polymerizable monomer exists does not just have special qualification.Therefore, can add polymerizable monomer in the solvent that is dispersed with the ZGK 5 particle, also can add the ZGK 5 particle in the solvent that contains polymerizable monomer.Wherein, preferably like the former, add polymerizable monomer in the solvent that is dispersed with the ZGK 5 particle in advance; Further, the ZGK 5 particle that obtains in hydrolysis, the condensation operation is not selected and directly added the method for polymerizable monomer to this reaction solution from reaction solution (ZGK 5 particle dispersion), because can not make become complicacy and productivity of operation good, therefore preferred.

In addition; In absorbing operation; Above-mentioned polymerizable monomer is absorbed in the above-mentioned ZGK 5 morphology of particles; But temperature when setting ratio of mixture, blended treatment process, mode, the mixing of ZGK 5 particle and polymerizable monomer concentration or above-mentioned ZGK 5 and polymerizable monomer separately for the absorption that makes polymerizable monomer promptly carries out or time, mixed treatment process, mode etc. are preferably carried out under this condition.These conditions can consider that suitably its necessity gets final product according to the used ZGK 5 particle and the kind of polymerizable monomer etc.And these conditions can only be used a kind of, also can two or more Combination application.

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 ZGK 5 particle, be preferably 0.01-100 in mass doubly, more preferably 0.5-50 is doubly; Further be preferably 0.5-30 doubly, be preferably 1-15 especially doubly.During above-mentioned scope that addition is not enough, the absorbed dose of the polymerizable monomer of ZGK 5 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 ZGK 5 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 maybe.

In above-mentioned absorption operation, the interpolation time of polymerizable monomer does not have special qualification, can add this polymerizable monomer in advance together, can divide for several times yet and add, can be so that speed is reinforced arbitrarily yet.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 ZGK 5 particle absorption in advance with emulsifying agent emulsification dispersive state in advance to the ZGK 5 particle, therefore preferred.

Mentioned emulsifier does not have special qualification, for example has and has more than one polymerizability tensio-active agent that can the polymeric carbon-to-carbon unsaturated bond etc. in aniorfic surfactant, cationic surfactant, non-ionics, amphoterics, polymeric surface active agent, the molecule.Wherein, owing to aniorfic surfactant, non-ionics can make the ZGK 5 particle that has absorbed ZGK 5 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.

The usage quantity of mentioned emulsifier does not have special qualification, particularly, with respect to the total mass of above-mentioned polymerizable monomer, is preferably 0.01-10 quality %, more preferably 0.05-8 quality %, further be preferably 1-5 quality %.During the usage quantity less than 0.01 quality % of mentioned emulsifier, the possibility of the emulsification disperse object that can not obtain stable polymerizable monomer is arranged; When exceeding 10 quality %, have letex polymerization etc. as side reaction concurrent maybe.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 enumerate out methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, terepthaloyl moietie, Ucar 35,1, the alcohols of 4-butyleneglycol etc.; The ketone of acetone, ethyl methyl ketone etc.; The ester class of ETHYLE ACETATE etc. etc.

Above-mentioned absorption operation preferably stirs in 5 minutes-720 minutes under 0-60 ℃ TR and carries out.These conditions can suitably be set according to the used ZGK 5 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 the judgement on the ZGK 5 particle for monomer component, for example, before adding monomer component and after the absorption stage completion; Through the microscopic examination particle, can be to confirm making particle diameter become judgement greatly and easily through 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 situation, 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 after arbitrary or both operation, carry out, and does not have special qualification, usually, and in (when having carried out the absorption operation for after absorbing operation) beginning after the hydrolytic condensation operation.

Polyreaction does not have special qualification, 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 not special qualification, for example, preferably can enumerate out the persulphate of Potassium Persulphate etc.; Hydrogen peroxide, peroxy acetic acid, Lucidol, lauroyl peroxide, adjacent chlorobenzoyl peroxide, O-methoxy Lucidol, peroxo--3; 5; 5-trimethyl acetyl, peroxo-(2 ethyl hexanoic acid) tert-butyl ester, di-t-butyl peroxide, Lucidol, 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 can use separately, also can two or more and usefulness.

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 %, and more preferably 0.01-10 quality % further is 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 not special qualification; Can be employed in methods that initial (before the reaction beginning) all add (make radical polymerization initiator with polymerizable monomer emulsification dispersive mode in advance, be absorbed the form that the back adds 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, the method that perhaps they is combined etc. be known method in the past arbitrarily.

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 is prone to cause 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 is prone to cause interparticle cohesion is arranged in the reaction times.

In the present invention, behind the polymerization process, can with the preparation liquid that contains the polymer particle that obtains directly, or, supply to above-mentioned wet classification operation with the organic solvent distillation and after the dispersion medium displace that contains water and/or alcohol; 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; The additive of light diffusing agent that contains in the optical resin that uses in light diffusing sheet that for example, 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 stated, 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, further be preferably more than 5 mass parts; More preferably below 200 mass parts, further be 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 through adding the situation of the effect (light diffusing etc.) that particulate is difficult to obtain expecting.

The clear binder resin that is contained in the resin combination of the present invention does not have special qualification, in this field, can use as the material that adhesive resin uses.For example; During the parts of desirable shapes such as that the parts that (I) use resin combination of the present invention to form are that resin combination of the present invention is configured as is tabular, sheet itself (; Make adhesive resin be configured as the situation of the substrate resin of tabular, sheet-like formed body); As transparent resin; Can enumerate out the vibrin of polyethylene terephthalate or PEN etc.; The polyolefin resin of vinyl resin, polystyrene resin, polycarbonate resin, polyethersulfone resin, polyurethane series resin, polysulfone resin, polyether resin, polymethylpentene resin, polyether ketone resin, (methyl) acrylic resin, acrylic resin etc., norcamphane is resin, amorphousness polyolefin resin, polyamide resin, polyimide resin and tri acetyl cellulose resin etc.

In addition; When (II) parts make it integrated parts that form on the substrate surface of pre-prepd tabular or sheet etc., making resin combination of the present invention range upon range of (coating, lamination etc.) etc.; As the clear binder resin; Can use the material same with above-mentioned adhesive resin; For example, can enumerate out vinyl resin, acrylic resin, polyvinyl alcohol resin, polyvinyl acetate resins, polystyrene resin, PVC RESINS, silicone resin, and urethane resin, vibrin etc.

Resin combination of the present invention except that above-mentioned particulate and the 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 stablizer and fire retardant, oxidation inhibitor, UV light absorber of the rerum natura that is used to improve photostabilization or anti-UV property etc. 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 mirroring and but the image insight is shown 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 the optics of light diffusion film that picture display face spreads equably or light diffusing sheet etc. with parts in use compatibly.

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 (through 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 use parts be such as light diffusion film or antireflection anti-dazzle film film like (below; Be called " optical thin film ") formed body the time; As its form, can enumerate out 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 enumerate out (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) in the part of pre-prepd tabular or flaky substrate surface or all, range upon range of (coating, lamination) contains the layer of above-mentioned resin combination and make 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 appearance ground, the 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 enumerate out the forming method that is extruded into sheet, tabular and film like when resin combination of the present invention carried out melting mixing through 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 property 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, likewise can above-mentioned additive and resin combination be pre-mixed.

As the method for the optics that obtains above-mentioned form (ii), can enumerate out on pre-prepd substrate surface the range upon range of method that contains the layer of resin combination of the present invention.Laminating method does not have special qualification, and preferably illustration goes out coating process or teeming practice etc.As coating process, be coated on the base material as long as will contain the application compsn 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 compsn; Preferably above-mentioned resin combination is disperseed, is dissolved into water or organic solvent (for example, the pure series solvent of methyl alcohol, ethanol, Virahol etc., the ketone series solvent of terepthaloyl moietie, Ucar 35 etc.; The ester series solvent of ETHYLE ACETATE etc., and the aromatic hydrocarbons of toluene, YLENE etc. etc.) in and the application compsn that is coated with of preparation uses.Base material does not have special qualification, 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 enumerate out reverse roll coating process, intaglio plate coating method, metal mold coating process (ダイコ one ト method), comma coating method (コ Application マコ one 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.

Thickness on the layer that contains resin combination of the present invention (perhaps being coated with the application compsn) that forms through above-mentioned method does not have special limiting, 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 the value of the thickness of the expression layer (that is, light diffusion layer, antiglare layer) that comprises range upon range of resin combination on the base material, does not comprise the thickness of 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 compsn; 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 through controlling the median size of particulate of the present invention.

Embodiment

Below, through enumerating embodiment the present invention being described more specifically, the present invention is not limited to following embodiment certainly, and the aim of stating according to front and back also can increase suitable change within the bounds of possibility to be implemented, and they all are contained in technical scope of the present invention.In addition, only if 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 reaction kettle 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-s of preparation granular of polyorganosiloxane.The weight-average molecular weight of the ZGK 5 particle that obtains this moment in addition, 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 styrene, 3 part 2,2 '-azo two (2; The 4-methyl pentane nitrile) (with the pure pharmaceutical worker's industry of light society system; V-65), 1.5 parts of anionic surfactant (LA-10, the first industrial society system) and 400 parts of ion exchange waters divided diffusing 15 minutes preparation emulsion (monomer solution) in room temperature (25 ℃) lactogenesis by even mixer.

The preparation of the suspension-s of said ZGK 5 particle begins (γ-methacryloxypropyl trimethoxy silane was added beginning after two hours) after 2 hours, adds above-mentioned emulsion through the liquid droping port of reaction kettle 1.Continue to stir 1 hour; After confirming that the ZGK 5 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.Dispersion of the polymer in the dispersion average particle size of 10.1μm, the dispersion B-type viscosity (B type viscometer, Tokyo Keiki Co., Ltd.) was 3.8mPa · s, a solid content concentration of 10 mass%.

Prepare routine 2-7 (ZGK 5 particle)

Remove ZGK 5 particle raw material, free radical polymerization monomer, and beyond the change of usage quantity such as table 1, likewise 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 ZGK 5 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 through solid-liquid separation, drying is distributed in the 100g ion exchanged water; Preparation polymer particle dispersion liquid; Use accurate particle size distribution device (trade(brand)name " マ Le チサイザ one II ", ベ Star Network マ Application コ one Le タ one Co., Ltd.'s system); Carry 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.

0.5g of dried polymer particles are dispersed into 100g of methanol to prepare a polymer particle dispersion (viscosity: 3mPa · s, solid content concentration: 0.5 mass%) having an average particle diameter of 1.75-2 times the sieve mesh screen (ni Tsukeru system, tokyo Thermopreg plastic bi ro su su Center Co., Ltd.) and the bell filter (filtration clock) having a Buchner funnel filtration device, filtration under reduced pressure.Then, and the usefulness SEM (SEM, " S-3500N ", Hitachi's system, accelerating potential: 25kV) observation remains in the particle on the screen cloth, and the range estimation number goes out the number of the corase particles more than 2 times of average grain diameter.And observation is to observe whole visual field with 200 times multiplying power.The result representes with "＞average diameter * 2 " in table 1.

In addition,, except that the screen cloth that uses 2.25-2.5 sieve aperture doubly, likewise 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 society 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 is used gel permeation chromatograph (GPC, " HLC-8120GPC ", eastern ソ one Co., Ltd.'s system), measures by following condition determination.In addition, measure sample, regulate sample with THF (THF) dilution and make that solids component is 0.8%.

Chromatographic column: TSKgelG5000HXL-TSKgel2000HXL (eastern ソ one Co., Ltd.'s system)

Column temperature: 25 ℃

Elutriant: THF

Pump: L6000 (Hitachi Co., Ltd's system)

Flow: 1.0ml/min

Detect: R1 Model 504 (GL サイエ Application ス Co., Ltd. system)

Sample solution concentration: 0.8%

Standard specimen calibration curve: use polystyrene standard (TSK polystyrene standard, eastern ソ one Co., Ltd.'s system), by 13 calibration curves that sample obtains of Mw=500-1000000.

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, through 100 ℃ of following vacuum-dryings 5 hours, obtain the dry thing that particle coacervation becomes.Through pulverizing by the drying thing, obtain sized particles (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 "; Japan ニユ one マチ Star Network Industrial Co., Ltd system) in; Through regulating by the high speed rotating air-flow and attract blower fan to give the cf-of sized particles, obtain particulate (dry classification operation) with the recovery of 85 quality % with respect to the sized particles of supply with the balance of resistance is carried out classification.In addition, be 84 quality %s from the recovery of the particulate of polymer particle dispersion liquid recovery this moment.

Embodiment 2

Through the operation same, prepare sized particles (recovery is 99 quality %) by the polymer particle dispersion liquid that obtains in the preparation example 2 with embodiment 1.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 is put in the rotor formula grading plant (returning translocation ロ one タ same form grading plant, " タ one ボプレ Star Network ス 100ATP ", ホソカワミ Network ロ Application Co., Ltd. system); Give the centrifugal force of sized particles with 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 supply sized particles by the rotary speed of classification rotor with from the supply of the air of suction hole.In addition, be 84 quality %s from the recovery of the particulate of polymer particle dispersion liquid recovery this moment.

Embodiment 3

Likewise operate with embodiment 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 recovery is 99 quality %).

This sized particles is put in the rotor formula airflow classification device (" タ one ボ Network ラシ Off アイア TC-15 ", day clear エ Application ジニアリ Application グ society system); Give the cf-of sized particles with the balance of resistance is carried out classification through regulating, obtain particulate (dry classification operation) with the recovery of 85 quality % with respect to the supply sized particles 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 recovery of the particulate of polymer particle dispersion liquid recovery this moment.

Embodiment 4

Likewise operate with embodiment 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 recovery is 99 quality %).

The pulverized particles were introduced into the Coanda-type air classifier (Coanda-type air flow classification device, "Oh Hikaru ボ a zip Oh boots coat EJ-15", Japan Iron Ore Industry Co., Ltd., feeding air: 5kgf, with a thin edge), by adjusting giving particle inertia force and the resistance caused by the suction blower balance of graded crushed particles relative to the supply of the recovery of 85% by mass to obtain particles.In addition, be 84 quality %s from the recovery of the particulate of polymer particle dispersion liquid recovery this moment.

Embodiment 5

Through the operation same with embodiment 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 recovery is 99 quality %).

Then; The sized particles that obtains is put into high precision air classifier (" DFX5 type "; Japan ニユ one マチ Star Network Industrial Co., Ltd system) in; Through regulating by the high speed rotating air-flow and attract gas blower to give the cf-of sized particles, obtain particulate (dry classification operation) with the recovery of 88 quality % with respect to the sized particles of supply with the balance of resistance is carried out classification.In addition, be 87 quality %s from the recovery of the particulate of polymer particle dispersion liquid recovery this moment.

Embodiment 6

Through the operation same with embodiment 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 recovery is 99 quality %).

Then; The sized particles that obtains is put into rotor formula sorting equipment (" タ one ボプレ Star Network ス 100ATP "; ホソカワミ Network ロ Application Co., Ltd. system) in; Give the cf-of sized particles with the balance of resistance is carried out classification through regulating, obtain particulate (dry classification operation) with the recovery of 85 quality % with respect to the sized particles of supply 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 recovery of the particulate of polymer particle dispersion liquid recovery this moment.

Embodiment 7

Through the operation same with embodiment 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 recovery is 99 quality %).

This sized particles is put into rotor formula airflow classification device (" タ one 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 cf-of sized particles with the balance of resistance is carried out classification through regulating, obtain particulate (dry classification operation) with the recovery of 86 quality % with respect to the sized particles of supply 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 recovery of the particulate of polymer particle dispersion liquid recovery this moment.

Embodiment 8

Through the operation same with embodiment 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 recovery is 99 quality %).

The pulverized particles into the Coanda-type air classifier ("Oh, Hikaru ボ a zip Eri boots Suites EJ-15", Japanese Iron Ore Industries, Ltd., feeding air: 5kgf, using thin edge), by adjusting imparting particulate inertial force and the attractive balance of the resistance caused by the blower grading, relative to the supply of pulverized particles of the recovery of 85% by mass to obtain particles.In addition, be 84 quality %s from the 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 through natural subsidence.The filter cake that obtains with ion exchanged water and methanol wash after, through 100 ℃ of following vacuum-dryings 5 hours, obtain the dry thing that particle coacervation forms.Through 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 one Le society system, trade(brand)name " ウ Le チプリ one 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 through the dry thing that will obtain and to obtain sized particles with Comparative Examples 1 same step.

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 Comparative Examples 1 same step, the dry thing that obtains through 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; Preparation polymer particle dispersion liquid; Use accurate particle size distribution device (trade(brand)name " マ Le チサイザ one II ", ベ Star Network マ Application コ one Le タ one Co., Ltd.'s system); Carry 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.To measure the microparticulate solution (viscosity: 3mPas that likewise makes with above-mentioned average grain diameter; Solid component concentration: 0.5 quality %) use the screen cloth (ニ Star ケ Le system, Tokyo プロセスサ one PVC ス Co., Ltd.) of 1.75-2 sieve aperture doubly and the suction filtration device that bell filter is provided with Buchner funnel, under reduced pressure filter with average grain diameter.

Then, the use SEM (SEM, " S-3500N ", Hitachi's system, accelerating potential: 25kV), observing residual particle on the screen cloth with whole visual field under 200 times, the number of the corase particles more than 2 times of range estimation average grain diameter (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, likewise carry out with above-mentioned step with median size.

[mensuration of the amount of fine particle]

With the microparticulate that obtains in 0.5g embodiment and the Comparative Examples in the 100g ion exchanged water; Be mixed with particle dispersion liquid; Use accurate particle size distribution device (trade(brand)name " マ Le チサイザ one II ", ベ Star Network マ Application コ one Le タ one Co., Ltd.'s system), carry out the mensuration (volume reference) of particle diameter and median size.Be the basis to measure the 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.

In table 2; " the タ one ボプレ Star Network ス 100ATP " of ホソカワミ Network ロ Application Co., Ltd. system used in " rotor formula sorting equipment 1 " expression, and day " the タ one ボ Network ラシ Off アイア TC-15 " of clear エ Application ジニアリ Application グ society system used in " rotor formula sorting equipment 2 " expression.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 in embodiment and Comparative Examples, supplies to the particle in the classification operation, the ratio of the total quality of the particulate that classified operation reclaims.

Preparation example 8 (amino resin crosslinked particles)

With 75 parts of trimeric cyanamides, 75 parts of benzoguanamines, 290 parts of concentration is that 37% Superlysoform and 1.16 parts of concentration are that 10% aqueous sodium carbonate joins and has prolong, in the reaction kettle of TM 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 non-ionics エマ Le ゲ Application (registered trademark) 430 (Kao Corp, T 46155 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 said 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-s of amino resin crosslinked particle.

Preparation example 9,10 (amino resin crosslinked particles)

Except that the usage quantity of amino based compound, Superlysoform changes to the amount shown in the table 3, likewise to carry out with preparation example 8, preparation contains the suspension-s of amino resin crosslinked particle.

Preparation example 11 (polystyrene particles)

With 50 parts of styrene, 50 parts of ethylene glycol dimethacrylates, 5 parts of azos is polymerization initiator (V-65; With the pure pharmaceutical worker of light industry society system), 0.5 part of TBHQ, 0.5 part of lauryl sodium sulfate and 100 parts of ion exchange waters mix; Stirring makes its emulsification, obtains the aqueous dispersions of polymerizable monomer.

In reaction kettle with cooling line, TM 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 Z 150PH 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 particles)

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, likewise make polystyrene latex microparticulate solution with preparation example 11.

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, through with the dispersion liquid natural subsidence and solid-liquid separation, the filter cake that obtains with ion exchanged water and methanol wash after, through 100 ℃ of vacuum-dryings 5 hours, obtain the dry thing that particle coacervation becomes.Should obtain particle by the drying thing through pulverizing.

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 recovery is 97 quality %.

Throw into the Coanda-type air classifier (Oh Hikaru ボ a zip Eri boots Suites EJ-15, Japan Iron Ore Industries, Ltd., feeding air: 5kgf, using thin edge), by adjusting imparting particulate inertia forces and by the suction blower caused balance of resistance grading, pulverized to obtain particles with respect to the supply of 89 mass% recovery after classification of fine particles (dry classification step).

Embodiment 10

Through the operation same with embodiment 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 recovery is 96 quality %).

This sized particles is put into high precision air classifier (DFX5 type; Japan ニユ one マチ Star Network Industrial Co., Ltd system) in; Give the cf-of sized particles and carry out classification through regulating, obtain with respect to the particulate (dry classification operation) of the sized particles of supplying with after with the 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

Through the operation same with embodiment 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 recovery is 97 quality %).

This sized particles is put into rotor formula airflow classification device (タ one 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 with the balance of resistance is carried out classification by regulating, obtain with respect to the particulate (dry classification operation) of supply sized particles after with the rate of recovery classification of 85 quality % by the rotary speed of classification rotor with from the supply of the air of suction hole.

Embodiment 12

With the method same with embodiment 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 recovery is 99 quality %).

The obtained pulverized particles into the Coanda-type air classifier (Oh Hikaru ボ a zip Oh boots coat EJ-15, Japan Iron Ore Industry Co., Ltd., feeding air: 5kgf, with a thin edge), by adjusting the classification rotor rotational speed to and from supply air suction hole to give pulverized particles balance the centrifugal force and resistance grading, pulverized to obtain particles with respect to the supply of 85% by mass recovery of the classified particles (dry classification step).

Embodiment 13

With the method same with embodiment 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 recovery is 99 quality %).

The pulverizing particulate that obtains is put into high precision air classifier (DFX5 type; Japan ニユ one マチ Star Network Industrial Co., Ltd system) in; Give the cf-of sized particles and carry out classification through regulating, obtain with respect to the particulate of the sized particles of supplying with after with the recovery classification of 80 quality % by the balance of the resistance that attracts gas blower to cause by the high speed rotating air-flow.

Embodiment 14

With the method same with embodiment 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 recovery is 99 quality %).

The obtained pulverized particles into the Coanda-type air classifier (Oh Hikaru ボ a zip Oh boots coat EJ-15, Japan Iron Ore Industry Co., Ltd., feeding air: 5kgf, with a thin edge), by adjusting the classification rotor rotational speed to and from supply air suction hole to give pulverized particles balance the centrifugal force and resistance grading, pulverized to obtain particles with respect to the supply of 87 mass% recovery particles after classification.

Embodiment 15

With the method same with embodiment 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 recovery is 99 quality %).

The pulverizing particulate that obtains is put into rotor formula airflow classification device (タ one 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 cf-of sized particles with the balance of resistance is carried out classification through regulating, obtain with respect to the particulate of supply sized particles after with the 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

The obtained pulverized particles into the Coanda-type air classifier (Oh Hikaru ボ a zip Oh boots coat EJ-15, Japan Iron Ore Industry Co., Ltd., feeding air: 5kgf, with a thin edge), by adjusting the classification rotor rotational speed to and from supply air suction hole to give pulverized particles balance the centrifugal force and resistance grading, pulverized to obtain particles with respect to the supply of recovery of 75% by mass of the particles after classification.

Comparative Examples 5

Except that not carrying out the wet classification, with the method same with embodiment 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 below the 0.5 quality %).

The pulverizing particulate that obtains is put into rotor formula airflow classification device (タ one 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 cf-of sized particles with the balance of resistance is carried out classification through regulating, obtain with respect to the particulate (the 1st dry classification) of supply sized particles after with the 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 supply with the particulate (for the second time dry classification) of sized particles after with the 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 stated.

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 the product yield in the industry through 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.Add 40 mass parts acrylic acid series ionizing radiation cured resin, 2 mass parts Photoepolymerizationinitiater initiaters (チバスペシヤ 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 Star Network ケミ one society's system, BYK320) in this mixed solution, stir fully and be mixed with coating fluid.

Be on the single face of tri acetyl cellulose film (Fuji description Off イ Le system society system, " Off ジタ Star Network (registration mark) ") of 80 μ m at thickness, apply this coating fluid by scraping strip coating machine.Through with the coated film that obtains 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, through 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, for the anti-glare film, using a mapping tester (manufactured by Suga Test Instruments Co., Ltd., ICB-IDD) and 0.5mm wide comb, in accordance with JIS K7105 determined through visibility (image visibility).

Further each anti-dazzle film is attached to liquid-crystal display (15 inches XGA, TFT-TN mode, the front face brightness: 350cd/m that is connected in PC ², positive contrast gradient: 300 to 1, surfaces A G: on surface nothing), through 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	×

Can find out that from table 6 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 coarse particle 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-dazzle property sheet, light diffusion film etc.) to be difficult to produce the reduction that comes from the shortcoming of coarse particle 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-dazzle property or light diffusing).

Claims

1. particulate; This particulate is the particulate that is used for light diffusion film, anti-dazzle property film or light diffusing sheet; It 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; Fine particle with particle diameter below 1/2 times of median size is below the 10 volume %, and the median size of said particulate is 0.1-50 μ m.

2. particulate according to claim 1, wherein, said particulate is the organism mineral complex that contains organic polymer skeleton and ZGK 5 skeleton.

3. the preparation method of claim 1 or 2 described particulates, it 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; Particulate behind the wet classification is dry, pulverizing, processing 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, median size are the operation of the powder particulate of 1-50 μ m; Use airflow classification device with said powder particulate dry type fractionated operation.

4. a resin combination is characterized in that, this resin combination contains claim 1 or 2 described particulates.

5. one kind is coated with the application compsn, it is characterized in that, this is coated with the application compsn and contains the described resin combination of claim 4.

6. an optical thin film is characterized in that, this optical thin film is through being coated to the described application compsn that is coated with of claim 5 on the base material and obtaining.

7. optical thin film according to claim 6, wherein, said optical thin film is as the light diffusion film.

8. optical thin film according to claim 6, wherein, said optical thin film is as anti-dazzle film.