CN1745108A - Polymer particle coated with silica, method for producing the same and use of the same - Google Patents

Abstract

A polymer particle coated with silica comprising: a polymer particle derived from a polymerizable vinyl-based monomer; and a silica film covering the polymer particle, which makes a surface of the polymer particle expose so that an aperture ratio of 0.1 to 1 is possessed and a height h of the silica film and a diameter D of the polymer particle coated with silica have a relationship of 0.5<=h/D<1, wherein the silica film includes a polyalkoxysiloxane oligomer condensate.

Description

Be coated with polymer beads of silica gel and its production and use

Technical field

The present invention relates to polymer beads that is coated with in silica gel and its production and use.In more detail, the present invention relates to be coated with polymer beads with good scattering of light/reflexive silica gel and its production and use.But the polymer beads that is coated with silica gel of the present invention is particularly suitable for coating composition, applies the moulding bodies of body, optical element, liquid-crystal display and scattered light.

Background technology

As a kind of coating composition that contains the material of paint component, usually use to be mixed with the various objects of various grains of composition with the scattering of light that obtains to utilize these particles and had.For example, for the mat surface (matting surface) that obtains different moulding bodies, use the coating composition that is mixed with particles of inorganic material such as silica gel particle or organic polymer particles (resin particle) usually.Because the coat film that is formed by aforementioned coating composition has irregular surface, reflected light is scattered on described surface, so the surface is just by delustring.

In addition, in the image display apparatus that in TV, PC, electronic memo, mobile telephone, amusement equipment or the like, uses, a kind of can the scattering transmitted light and catoptrical optical sheet be used as light diffusion sheet or anti-dizzy.For scattering transmitted light or reflected light, the surface of this optical sheet has also formed coat film.Usually use the composition that is mixed with particles of inorganic material or resin particle as the coating composition that forms coat film on this surface.

For example, at the light diffusion sheet that is used for the scattering transmitted light, use usually and be mixed with the composition of particles of inorganic material such as lime carbonate and silica gel or organic polymer particles such as polystyrene and siloxanes as coating composition.

But the shortcoming of particles of inorganic material is that the dispersion stabilization in binder solution is low, particularly in using clear binder such as the binder solution of plexiglass as adhesive resin.

In addition, in being mixed with the coating composition of organic polymer particles, dispersion stabilization is better, but has the insufficient problem of scattering of light.

On the other hand, many optical modules for example throw light on tool housing, lens, light guide plate, CD, projection TV screen and various moulding bodies for example cosmetics containers, vending machine face, signboard, commodity show and the table upper container in, in order to improve their commodity value, appearance characteristics is for example improved their scattering of light by the resin that the above-mentioned use of molding is mixed with optical scatter usually as raw-material goods.In these moulding bodies, use various resins, particularly thermoplastic resin for example polycarbonate resin, polystyrene resin and polyacrylate resin as basic material.

As the optical scatter that is used for moulding bodies, known particles of inorganic material for example glass, lime carbonate and silica gel are arranged usually, perhaps for example polyacrylate resin and polystyrene resin of resin particle.

Yet owing to mixed optical scatter, these moulding bodies exist the problem that transparency descends, and simultaneously, the improvement of scattering of light is also abundant inadequately.

In order to address these problems, Japan's special permission communique the 3rd, 040, the polymer beads that contains terre verte (smectite) is used in No. 705 suggestions, combination particle is used in 10 (1998)-No. 265580 communique suggestions of Japanese kokai publication hei, wherein is dispersed with the silica gel particle that is less than or equal to 500 nanometers in resin particle.

Yet, still can not provide coating body or moulding bodies with abundant scattering of light even be mixed with above-mentioned grains of composition.

Describing in above-mentioned open text, known also have in other polymkeric substance of surface coverage of polymer beads or the combination particle of inorganic materials.

In these reports, be that specific refractory power on the interface between polymer beads and the inorganic materials is greater than the specific refractory power on the interface between the former polymer beads in the advantage that back a kind of combination particle of the surface coverage inorganic materials of polymer beads has.

For example, reported a kind of combination particle in 5 (1993)-No. 170924 communiques of Japanese kokai publication hei in polymer beads surface coverage inorganic materials.This report has been described a kind of combination particle, in this combination particle, is fixed with a kind of have good heat resistance and the material littler than thermoplastic material particle on the particle of thermoplastic material.This combination particle be by rising thermoplastic material particulate temperature to its softening temperature or higher, stir high heat resistance material and thermoplastic material particle simultaneously and the mechanical shear stress that forms obtains.

The combination particle that method by 5 (1993)-No. 170924 communiques of Japanese kokai publication hei obtains has the structure that the thermoplastic material particle surface is evenly covered by high heat resistance material haply, and the scattering of light of this combination particle and reflectivity liken to and be some raising a little of raw-material thermoplastic material particle; Yet, also need further raising.

In addition, owing in aforesaid method the thermoplastic material particle has been used mechanical shear stress, the thermoplastic material particle that therefore requires to use can stand this shearing force, thereby exists the problem that working substance is restricted.

And this method requires to prepare in advance the thermoplastic material particle, wishes further to omit step from the angle of saving manufacturing expense.

Summary of the invention

In order to address the above problem, the inventor furthers investigate, the result finds unexpectedly, by with in the presence of the poly-oxyalkylsiloxane oligopolymer of polymerizable vinyl monomer generation co-polymerization not carrying out the monomeric aqueous suspension polymerization of polymerizable vinyl (aqueous suspensionpolymerization), condensation gathers the oxyalkylsiloxane oligopolymer then, can form the pellosil that obtains from poly-oxyalkylsiloxane oligopolymer, therefore the surface of polymer beads is exposed, the polymer beads that is coated with silica gel that obtains has high scattering of light and reflectivity, thereby has finished the present invention.

In addition, the inventor also finds, by the polymer beads that is coated with silica gel is mixed in coating composition or the moulding bodies, can gives and apply body or good scattering of light and the reflectivity of moulding bodies.

Therefore, the invention provides the polymer beads that is coated with silica gel, this polymer beads contains: the polymer beads that obtains from the polymerizable vinyl monomer; And overlie polymer particulate pellosil, pellosil makes the surface of polymer beads expose with the aperture ratio of 0.1-1, simultaneously, the height h of pellosil and the diameter D that is coated with the polymer beads of silica gel meet following relationship: 0.5≤h/D＜1, wherein, described pellosil contains poly-oxyalkylsiloxane oligomer condensation thing.

The present invention also provides a kind of coating composition, said composition contains polymer beads and the binder solution that is coated with silica gel, this polymer beads contains polymer beads and the overlie polymer particulate pellosil that obtains from the polymerizable vinyl monomer, pellosil makes the surface of polymer beads expose with the aperture ratio of 0.1-1, simultaneously, the height h of pellosil and the diameter D that is coated with the polymer beads of silica gel meet following relationship: 0.5≤h/D＜1, wherein, described pellosil contains poly-oxyalkylsiloxane oligomer condensation thing; Described binder solution contains adhesive resin and solvent.

In addition, the present invention also provides the liquid-crystal display that is coated on coating body on the matrix, is coated on the optical element on the residuite and uses this optical element with aforementioned coating composition with aforementioned coating composition.

And, the present invention also provides the scattering of light moulding bodies, this moulding bodies contains transparent resin and is coated with the polymer beads of silica gel, the described polymer beads that is coated with silica gel contains polymer beads and the overlie polymer particulate pellosil that obtains from the polymerizable vinyl monomer, pellosil makes the surface of polymer beads expose with the aperture ratio of 0.1-1, the height h of pellosil and the diameter D that is coated with the polymer beads of silica gel meet following relationship: 0.5≤h/D＜1, wherein, described pellosil contains poly-oxyalkylsiloxane oligomer condensation thing.

Further, the present invention also provides a kind of preparation to be coated with the method for the polymer beads of pellosil, pellosil makes the surface of polymer beads expose with the aperture ratio of 0.1-1, simultaneously, the height h of pellosil and the diameter D that is coated with the polymer beads of silica gel meet following relationship: 0.5≤h/D＜1, this method comprise the following steps: successively with 100 weight part polymerizable vinyl monomers, the 10-500 weight part not with the poly-oxyalkylsiloxane oligopolymer of polymerizable vinyl monomer reaction, 0.01-10 weight part polymerization starter uniform mixing is to obtain monomer composition; In the presence of suspension stabilizer, carry out the monomeric aqueous suspension polymerization of polymerizable vinyl in the monomer composition to obtain polymer beads; And add acid or alkaline catalysts with the poly-oxyalkylsiloxane oligopolymer of condensation.

Description of drawings

Fig. 1 is the sectional view that is coated with the polymer beads of silica gel of the present invention;

Fig. 2 is the sectional view that is coated with the silica gel particle of polymer beads after calcining of silica gel of the present invention;

Fig. 3 describes the concept map that the present invention measures the method for aperture ratio;

Fig. 4 is the sectional view that expression contains the scattering of light sheet moulding bodies of the polymer beads that is coated with silica gel.

Embodiment

The polymer beads that is coated with silica gel of the present invention has anisotropic structure, and wherein shown in the sectional view of Fig. 1, the surface of the polymer beads 1 of sphere or almost spherical is applied (covering) by pellosil 2, makes that its aperture ratio is 0.1-1.In the figure, mark 3 is meant the polymer beads that is coated with silica gel.With do not have anisotropic particle for example the spherical silica gel particle compare with the combination particle that the surface is applied fully by pellosil owing to have such structure, therefore complicated luminous reflectance and refraction have taken place, the result has represented strong scattering of light and reflectivity.If aperture ratio is less than 0.1, scattering of light and reflection die down; If aperture ratio is greater than 1, described pellosil peels off easily, and both of these case all is inappropriate.Aperture ratio is 0.1-0.8 more preferably.Aperture ratio is equivalent to only about half of particle by 1 the polymer beads that is coated with silica gel and is covered by pellosil.

The method of measuring aperture ratio will be described in the embodiment of back.The polymer beads calcining that we will be coated with silica gel at this obtains silica gel particle with the burning-off polymer beads, with the aperture ratio of described silica gel particle as aperture ratio.Though shrink in calcining owing to pellosil in some cases, perhaps thin position, the end of pellosil takes place damaged, the aperture ratio of saying silica gel particle on stricti jurise is different with the aperture ratio of pellosil, but the inventor confirm to be coated with aperture ratio and the aperture ratio of silica gel particle of pellosil of the polymer beads of silica gel be similar to consistent.

The high h of pellosil and the diameter D that is coated with the polymer beads of silica gel have following relationship: 0.5≤h/D＜1.If h/D equals 1, then scattering of light and reflectivity variation are inappropriate.If h/D is less than 0.5, film peels off easily, also is inappropriate.

The method of measuring h/D will be described in an embodiment.At this, the polymer beads calcining that we will be coated with silica gel obtains silica gel particle with the burning-off polymer beads, with the h/D of described silica gel particle as h/D.Though shrink in calcining owing to pellosil in some cases, perhaps thin position, the end of pellosil takes place damaged, the h/D that says silica gel particle on stricti jurise is different with the h/D of the polymer beads that is coated with silica gel, but the inventor confirm to be coated with h/D and the h/D of silica gel particle of the polymer beads of silica gel be similar to consistent.

To the polymer beads that be coated with silica gel of the present invention be described by the reference its preparation method below.

At first, the present invention has no particular limits used polymerizable vinyl monomer.The monomeric example of polymerizable vinyl comprises vinylbenzene and derivative thereof, for example vinylbenzene, o-methyl styrene, a vinyl toluene, p-methylstyrene, to ethyl styrene, 2, the 4-dimethyl styrene, align butylstyrene, to t-butyl styrene, to positive hexyl phenenyl ethene, to n-octyl vinylbenzene, align nonyl benzene ethene, align decyl vinylbenzene, align dodecyl vinylbenzene, to methoxy styrene, to styryl phenyl, to chloro-styrene and 3, the 4-dichlorostyrene; Vinyl ester, for example vinyl-acetic ester, propionate and vinyl butyrate; Alpha-methylene aliphatic monocarboxylic acid ester, for example methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, the vinylformic acid n-octyl, dodecyl acrylate, ethyl acrylate, vinylformic acid octadecane ester, lauryl acrylate, vinylformic acid-2-chloroethene ester, phenyl acrylate, α-Lv Bingxisuanjiazhi, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, n octyl methacrylate, methacrylic acid dodecane ester, methacrylic acid-2-ethylhexyl, methacrylic acid octadecane ester, methacrylic acid myrceane ester, phenyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, the vinylformic acid lignocaine ethyl ester, diethylaminoethyl methacrylate; And the derivative of vinylformic acid and methacrylic acid for example vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, 2-hydroxyethyl acrylate, vinylformic acid-2-hydroxypropyl ester, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-2-hydroxypropyl ester.Vinylformic acid, methacrylic acid, toxilic acid and fumaric acid can arbitrarily be selected for use.And these compounds can two kinds or more kinds of being used in combination.

In addition, in the scope that does not influence effect of the present invention, can use separately or two or more are used in combination following material: vinyl ether, for example vinyl methyl ether, EVE, vinyl isobutyl ether; Vinyl ketones, for example ethenyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compound, for example N-vinyl pyrrole, N-vinylcarbazole, N-vinyl indoles and N-vinyl pyrrolidone; With the vinyl naphthalene salts.

In above-claimed cpd, preferred low-cost vinylbenzene, methyl methacrylate etc.

In addition, described polymer beads can for example Ethylene glycol dimethacrylate, polydimethyl vinylformic acid glycol ester and Vinylstyrene carry out crosslinked with the monomer with two or more functional groups.

Particularly when the described polymer beads that is coated with silica gel is used to contain the system of organic solvent, preferably carry out crosslinked to polymer beads.The polymerizable vinyl monomer of per 100 weight parts (monomer with a functional group), the amount of the linking agent of adding (above-mentioned monomer with two or more functional groups) is 1.50 weight parts, is preferably the 3-40 weight part.If the amount that adds is less than 1 weight part, the polymer beads that obtains in some cases will be inappropriate by organic solvent dissolution or swelling.

In the present invention, the poly-oxyalkylsiloxane oligopolymer of the precursor of pellosil not with the polymerizable vinyl monomer reaction (copolymerization does not promptly take place), the available oligopolymer has following structural:

R＝CH ₃，C ₂H ₆，C ₃H ₇，C ₄H ₉ 40＞n＞2

In the said structure formula, the example of oligopolymer comprises polymethoxy siloxane oligomer, polyethoxye siloxane oligomer, poly-propoxy-siloxane oligomer, poly-butoxy siloxane oligomer.In these oligopolymer, polymethoxy siloxane oligomer, poly-butoxy siloxane oligomer are insoluble in water, and have and resin phase separation well, are preferred.Especially, the weight-average molecular weight of polymethoxy siloxane oligomer, poly-butoxy siloxane oligomer is preferably 300-3000, more preferably 300-2000.When weight-average molecular weight less than 300 or all be difficult to form pellosil greater than 3000 the time, be inappropriate.

Use gel chromatograph (GPC) under following condition, to measure weight-average molecular weight:

Pillar: " TSK GEL " (production of Tosoh company)

G-1000H

G-2000H

G-4000H

Eluent: tetrahydrofuran (THF)

Elution rate: 1 ml/min

Eluting temperature: 40 ℃

At the n of above-mentioned molecular formula is the low molecule oxyalkylsiloxane of 1-2 for example in tetramethoxy-silicane and the tetraethoxysilane, because functional group's hydrolysis makes water-soluble enhancing, is difficult to stable existence in monomer droplet, is inappropriate.In addition, because n is equal to or greater than 40 poly-oxyalkylsiloxane oligopolymer and the monomeric consistency of polymerizable vinyl or self condensation reduction in the above-mentioned molecular formula, be inappropriate therefore.

Per 100 weight part polymerizable vinyl monomers, the add-on of poly-oxyalkylsiloxane oligopolymer is preferably the 10-500 weight part, more preferably 20-300 weight.When add-on is difficult to during less than 10 weight parts realize covering state of the present invention, be inappropriate.When add-on is difficult to realize the exposed state of polymer beads during greater than 500 weight parts, be inappropriate.

In addition, in order to give the function that these poly-oxyalkylsiloxane oligopolymer absorb ultraviolet light, can add hydrolyzable alkoxide compound rather than silicon series compound.

In order to make the polymerizable vinyl monomer polymerization, use polymerization starter.The example of polymerization starter comprises oil-soluble superoxide series polymerization starter and is generally used for the azo series initiator of aqueous suspension polymerization.Object lesson comprises superoxide series polymerization starter, for example benzoyl peroxide, lauroyl peroxide, peroxidation decoyl, the adjacent chlorobenzoyl of peroxidation, peroxidation O-methoxy benzoyl, methyl ethyl ketone peroxide, di-isopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide and hydroperoxidation diisopropylbenzene(DIPB); And azo series initiator; for example 2; 2 '-Diisopropyl azodicarboxylate; 2; 2 '-azo two (2; the 4-methyl pentane nitrile); 2,2 '-azo two (2, the 3-nitrile dimethyl); 2; 2 '-azo two (2-methylbutyronitrile); 2; 2 '-azo two (2,3,3-trimethylammonium butyronitrile); 2; 2 '-azo two (2-di-isopropyl butyronitrile); 1; 1 '-azo two (hexamethylene-1-nitrile); 2,2 '-azo two (4-methoxyl group-2,4 methyl pentane nitrile); (2-diazoamino formyl radical) isopropyl cyanide; 4; 4 '-azo two (4-cyanopentanoic acid); and dimethyl-2,2 '-azo-bis-iso-butyl.

In these compounds, consider from the degradation rate of polymerization starter, 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), benzoyl peroxide, lauroyl peroxide etc. are suitable.Per 100 weight part polymerizable vinyl monomers, the consumption of polymerization starter is preferably the 0.01-10 weight part, more preferably the 0.1-5.0 weight part.When polymerization starter during, be difficult to play the polymerization initiation less than 0.15 weight part.On the other hand, when the amount of polymerization starter surpasses 10 weight parts, be uneconomic from cost consideration.

In order to give pellosil painted, can use metal oxide pigment for example titanium oxide, zinc oxide, magnesium oxide, chromic oxide and zirconium white.Yet, because therefore meeting recurring structure changes in sintering or calcining such as organism pigment, metal hydroxides pigment, dyestuff are inappropriate.

Can use known method that polymerizable vinyl monomer, poly-oxyalkylsiloxane oligopolymer, polymerization starter and other component uniform mixing are obtained monomer composition.

Then, be used to make the example of the aqueous medium of monomer composition aqueous suspension polymerization to comprise that water, water and water-soluble solvent are such as the alcoholic acid blending agent.For the stable suspersion aggregated particles, per 100 total weight parts polymerizable vinyl monomers and poly-oxyalkylsiloxane oligopolymer, the consumption of aqueous medium is generally the 100-1000 weight part.

In addition, in order to suppress to produce emulsified particle in the water-based system, can use water-soluble stopper for example nitrite, sulphite, quinhydrones, xitix, water-soluble (vitamin) B family, citric acid and polyphenol.

And, can in aqueous medium, add suspension stabilizer if necessary.The example of suspension stabilizer wherein comprises phosphoric acid salt, for example calcium phosphate, trimagnesium phosphate, aluminum phosphate and zinc phosphate; Pyrophosphate salt, for example Calcium Pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate and zinc pyrophosphate; And the mineral compound dispersion stabilizer that is insoluble in water, for example lime carbonate, magnesiumcarbonate, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, calcium metasilicate, calcium sulfate, barium sulfate and silicon sol.In these compounds, preferred tricalcium phosphate, magnesium pyrophosphate and Calcium Pyrophosphate and the silicon sol that uses by the double decomposition preparation is because use them can obtain the stable polymer particle.

In addition, also might use tensio-active agent for example anion surfactant, cats product, amphoterics and nonionogenic tenside with above-mentioned suspension stabilizer.

Examples of anionic surfactants comprises fatty acid oil for example sodium oleate and Viscotrol C potassium, alkyl sulfuric ester salt is sodium lauryl sulphate and ammonium lauryl sulfate for example, alkylbenzene sulfonate is Sodium dodecylbenzene sulfonate for example, sulfonated alkyl naphathalene, alkylsulfonate, dialkyl group sulfosuccinate, alkyl phosphate salt, naphthalene sulfonic acidformaldehyde condensation product, polyoxyethylene alkyl phenyl ether sulfuric acid, polyxyethylated sulfuric acid etc.

The example of nonionogenic tenside comprises Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty(acid)ester, polyoxy sorbitan fatty(acid)ester, polyoxyethylene alkyl amine, glycerol fatty acid ester, oxygen ethene-oxypropylene block polymer etc.

The example of cats product comprises for example acetate lauryl amine and acetate octadecylamine and quaternary ammonium salt chlorination dodecyl trimethyl ammonium etc. for example of alkylamine salt.

The example of amphoterics comprises dodecyl dimethyl amine oxide and phosphoric acid ester series or phosphorous acid ester series of surfactants etc.

These suspension stabilizers and tensio-active agent can use separately or two or more are used in combination, and consider the polymkeric substance particle diameter that obtains and the dispersion stabilization in the polymerization, suitably adjust the selection and the consumption of suspension stabilizer.Normally, per 100 weight part polymerizable vinyl monomers, the consumption of suspension stabilizer is the 0.5-15 weight part; The aqueous medium of per 100 parts of weight, the add-on of tensio-active agent are the 0.001-0.1 weight part.

Monomer composition is added to carries out aqueous suspension polymerization in the aqueous medium that mixes up.

The dispersed monomer method for compositions comprises and directly joins monomer composition in the aqueous medium, and the whipping force by propeller makes monomer composition be distributed to method in the aqueous medium with monomer droplet, carry out dispersive method etc. with the use homomixer, described homomixer is a kind of dispersion machine or ultrasonic dispersing machine that is constituted, utilized high shear force by rotor and stator.In these methods, when monomer composition utilizing between monomer droplet collision or with the high-pressure type dispersion machine of the surging force of machine wall such as microcosmic fluidisation device or micro mixer in disperse, when perhaps monomer composition being pressed into method in the aqueous medium and disperseing by micropore glass (MPG (Micro PorousGlass)) porous-film, particle diameter is more even, is suitable.

Then, heat that wherein monomer composition is with the form dispersive aqueous medium of spherical monomer droplet, suspension polymerization has been initiated.In polymerization process, preferably aqueous medium to be stirred always, the sedimentation with the floating and aggregated particles that prevents monomer droplet will be leniently carried out in stirring.

In suspension polymerization, polymerization temperature is preferably 30-100 ℃, more preferably 40-80 ℃.The time that polymerization temperature keeps is preferably 0.1-20 hour.

When the boiling point of polymerizable vinyl monomer or poly-oxyalkylsiloxane oligopolymer and polymerization temperature near or when being not less than polymerization temperature, preferred polymeric be reflected at carry out under the air-tight state or use withstand voltage poly-unit for example autoclave carry out adding to depress, polymerizable vinyl monomer and poly-oxyalkylsiloxane oligopolymer just can not volatilize like this.

The poly-oxyalkylsiloxane oligopolymer of condensation just can obtain the polymer beads that is coated with silica gel of the present invention then.The example of the method for condensing of poly-oxyalkylsiloxane oligopolymer comprises that use acid catalyst or alkaline catalysts carry out dehydrating condensation.Can use hydrochloric acid, sulfuric acid, nitric acid, ammonia, sodium hydroxide, potassium hydroxide and ammonium nitrate as acid catalyst and alkaline catalysts.If the preparation container is made with steel or stainless steel, consider preferably to select for use the sodium hydroxide and the ammonia of alkalescence from the corrosive angle.The poly-oxyalkylsiloxane oligopolymer of per 100 weight parts, the add-on of catalyzer is preferably the 0.01-30 weight part, more preferably the 1-15 weight part.

After the condensation, use salt acid degradation suspension stabilizer if necessary, with methods such as suction strainer for example, centrifuge dehydration, centrifugal, pressurizing and dehydratings the polymer beads that is coated with silica gel is separated into moisture filter cake then, the moisture filter cake that obtains washes with water, just obtains being coated with the target polymerization composition granule of silica gel after the drying.

As mentioned above, because the inventive method is not to use high shear force that silica gel particle is coated on the polymer beads,, second-order transition temperature (Tg) also is easy to apply even being lower than 80 ℃ low heat impedance polymer beads.Second-order transition temperature is lower than 80 ℃ polymkeric substance and comprises polyethyl acrylate, the positive butyl ester of polyacrylic acid, polyisobutyl acrylate, polyacrylic acid dodecane ester, polyacrylic acid octadecane ester, polyacrylic acid-2-ethylhexyl, polyethyl methacrylate, Vinalac 5920, polyisobutyl methacrylate, polymethyl acrylic acid dodecane ester, polymethyl acrylic acid octadecane ester, polymethyl acrylic acid-2-ethylhexyl etc.

The present invention has no particular limits the shape and the size of the polymer beads that is coated with silica gel.The volume average particle size that can make the polymer beads that is coated with silica gel according to aforesaid method is the 1-10 micron.

At this, add-on, the agitation condition of agitator or the volume average particle size of the polymer beads that dispersion condition adjustment is coated with silica gel of mixing condition, suspension stabilizer or tensio-active agent that can be by adjusting monomer composition and water.

The polymer beads that the polymer beads of per 100 weight parts, combination particle of the present invention promptly are coated with silica gel preferably contains 10-500 weight part pellosil, more preferably 20-300 weight part.

According to the present invention, can provide specular reflectance (definition provides in an embodiment) to be the polymer beads that is coated with silica gel of 3-13%.14% low when this value is applied by pellosil fully than polymer beads shows that the scattering of light and the reflectivity of the polymer beads that is coated with silica gel of the present invention is fine.When specular reflectance was 5-13%, scattering of light and reflectivity were good especially.

In addition, coating composition of the present invention contains a kind of composition, and the wherein above-mentioned polymer beads that is coated with silica gel mixes with the binder solution that contains adhesive resin and solvent.Because coating composition of the present invention is characterised in that and provides pellosil to make that the part surface of polymer beads is exposed, though its effect is not clear, it is good being coated with the polymer beads of silica gel and the compatibility between the adhesive resin and dispersion stabilization.In addition, complicated luminous reflectance and refraction having taken place in being coated with the polymer beads of silica gel, therefore can represent better scattering of light.

Further, use coating composition of the present invention can obtain the fine and scattering of light of particles dispersed stability and also well apply body.

The volume average particle size of the polymer beads that is coated with silica gel that uses in coating composition is generally the 1-100 micron, is preferably the 3-50 micron, more preferably the 3-30 micron.The measuring method of volume average particle size provides in an embodiment.

When the volume average particle size of the polymer beads that is coated with silica gel during less than 1 micron, might can not get enough light reflectives, be inappropriate.When diameter surpasses 100 microns, might make the degraded appearance that applies body, also be inappropriate.

The adhesive resin of formation binder solution is thermoplastic resin normally, and the example of thermoplastic resin comprises (methyl) acrylic resin, (methyl) alkyl acrylate-styrene copolymer resin, polycarbonate resin, vibrin, polyvinyl resin, acrylic resin, polystyrene resin, silicone resin, urethane resin, Resins, epoxy, melamine resin, vinyl acetate resin, phenol resins, resorcinol resin, paracril etc.

If the element (coating composition that for example is used for optical element) after requiring to apply has good light transmission, can select (methyl) acrylic resin, (methyl) alkyl acrylate-styrene copolymer resin, polycarbonate resin and vibrin for use.These thermoplastic resins can use separately or two or more are used in combination.

The solvent that forms binder solution is not particularly limited, has enough solvabilities and dispersed as long as can guarantee adhesive resin.The example of described solvent comprises one or both or more kinds of varsol, for example normal butane, normal hexane, normal heptane, octane, isononane, n-decane, n-dodecane, pentamethylene, hexanaphthene and tetramethylene; Ketones solvent, for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, isophorone; Esters solvent, for example ethyl acetate and butylacetate; Ether alcohol kind solvent, for example ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and diethylene glycol monoethyl ether; Alcoholic solvent, for example ethanol, Virahol, propyl carbinol and isopropylcarbinol; Aromatic solvents, for example toluene, dimethylbenzene and pyrocatechol, and water etc.

Doing in the binder aqueous solution of solvent with water or pure series material, adhesive resin needn't be dissolved in fully in the solvent and can be dispersed in the solvent with the form of emulsion or dispersion.

In above-mentioned example, consider that from the solvability of adhesive resin and the rate of drying after the coating example of particularly preferred solvent comprises methyl ethyl ketone, pimelinketone, ethyl acetate, butylacetate and toluene.In addition, because the emulsion of water-based emulsion or dispersion, oleic series or polyester series or dispersion is easy to get and the light transmission of resin is also high, thereby be preferred.

In coating composition of the present invention, per 100 weight part adhesive resins, the combined amount that is coated with the polymer beads of silica gel is generally the 1-150 weight part, is preferably the 1-120 weight part.

When being equal to or greater than 1 weight part, combined amount can obtain more satisfied scattering of light and reflectivity.The dispersion stabilization of combination particle and can not reduce when combined amount is equal to or less than 150 weight parts to the tackiness of matrix.

Contain residuite and apply body as in the diffusion sheet of scattering transmitted light, the adhesive resin of per 100 weight parts, the combined amount that is coated with the polymer beads of silica gel in the coating composition is preferably the 20-120 weight part, more preferably the 20-100 weight part.At anti-dizzy that is used for scattered reflection light, combined amount is preferably the 1-30 weight part, more preferably the 5-30 weight part.

In addition, as long as adhesive resin can dissolve or disperse and the polymer beads that is coated with silica gel can disperse fully full and uniformly, combined amount to described solvent has no particular limits, but the adhesive resin of per 100 weight parts is preferably the 100-1000 weight part.When combined amount during less than 100 weight parts, adhesive resin may not dissolve full and uniformly or disperse, and is inappropriate.When combined amount during greater than 1000 weight parts, owing to obviously reducing, the viscosity of coating composition is difficult to prepare uniform coating body (coat film), and be inappropriate.

In coating composition of the present invention, in order to make the coating body have dustproof, opaque or colouring function, can mix mineral dye, for example titanium oxide, zinc oxide, zirconium white, magnesium oxide, ferric oxide, ironic hydroxide, chromic oxide, chromium hydroxide, ultramarine, Prussian blue, manganese violet, ultramarine violet, titanium is deceived (titanium black), carbon black, aluminium powder, mica titanium, pearl white, the mica titanium of iron oxide treatment, the mica titanium of Prussian blue processing, the mica titanium that fuchsin is handled, silica gel, lime carbonate, magnesiumcarbonate, barium sulfate, barium silicate, Calucium Silicate powder, Magnesium Silicate q-agent, calcium phosphate, hydroxylapatite, zeolite, aluminum oxide, talcum, mica, wilkinite (bemonite), kaolin and silk Muscovitum; Perhaps pigment dyestuff, for example aluminium color lake class such as Tartrazol yellow, sunset yellow FCF, brilliant blue FCF, zirconium color lake, barium color lake, helindone red CN, lithol rubin (Lithol Rubine) BCA, Lake red C BA, phthalocyanine blue and permanent orange.

The adhesive resin of per 100 weight parts, the incorporation of pigment is preferably the 1-80 weight part.The effect that will not have pigment when incorporation during less than 1 weight part is for example painted.When add-on will can not get having the coating body of high transmission rate during greater than 80 weight parts.Yet, had better not mix pigment at the coating composition that is used for optical element.

In addition, in the scope that does not reduce effect of the present invention, resin particle (independent polymer beads) or particles of inorganic material (independent particles of inorganic material) can be mixed with coating composition of the present invention.

To describe coating composition below and apply the coating body that various matrix obtain.

Coating body of the present invention is characterised in that aforementioned coating composition is coated on the various matrix.In addition, optical element is characterised in that aforementioned coating composition is coated on the various residuites.

The example of matrix comprises metal (iron, aluminium, zinc etc.), timber, plastics, glass, slate, plaster, stone material, concrete etc.Object lesson comprises the element that constitutes automobile or home electric, and transparent element is the photoconduction dish for example, and the matrix of formation material of construction, various goods, paper and walling material etc.

The matrix that residuite is preferably made by glass or plastics for example comprises the matrix of being made by following material: silica glass, soda glass, polycarbonate, polymethylmethacrylate, polyvinyl chloride, polyester, cellulose acetate butyrate, polyolefine, polystyrene, fluoro-resin, Resins, epoxy, polyacrylic ester, silicon, polyethylene terephthalate, cycloolefine polymer, polyimide etc.

Above-mentioned matrix optimization has heat resistance, anti-crimp tendency, solvent resistance etc.

The shape of the shape of matrix, particularly residuite is preferably sheet.The thickness of flake substrate is preferably the 10-3000 micron.Formation is preferably the 10-300 micron as the thickness of the residuite of the optical sheet of optical element.

As for the method that coating composition is coated on the matrix on the residuite particularly, can select any known method for use.For example can adopt cladding process such as reverse rolling method, extrusion method, scraper coating (comma coater) method, spraying method, gravure cladding process, bar to be coated with method and brushing, roller coat, spraying, cation electric coating, static are coated with etc.

Under the complete evaporable drying regime of solvent, the thickness that applies body is preferably the 1-500 micron, more preferably the 1-200 micron.Particularly the thickness of optical sheet is preferably the 1-100 micron.

In the optical sheet as optical element of the present invention, coating composition can be coated in the one or both sides of sheet residuite.In addition, can form many layers, every layer all is the coating body that is coated with coating composition.And, can be at the surface coverage hard coat that applies body to prevent the crack or to improve weathering resistance.

In addition, scattering of light moulding bodies of the present invention contains transparent resin and the above-mentioned polymer beads that is coated with silica gel.Therefore, compare when for example polyacrylate resin is with polystyrene resin, can obtain having the scattering of light moulding bodies of better scattering of light and littler printing opacity reduction amount with using particles of inorganic material or resin particle.And the polymer beads and the consistency between transparent resin that are coated with silica gel are better, can keep light transmission more fully simultaneously.In addition, compare during with the composition particles that uses the polymer beads surface to be applied by pellosil fully, complicated luminous reflectance and refraction have taken place, obtained better scattering of light.Moreover the transmittance of scattered light can reach 80% or higher.Therefore, for example in the liquid-crystal display that uses scattering of light moulding bodies of the present invention,, make current consumption descend owing to reduce from light loss backlight.

At this, term " transparent " comprises " translucent ".And, " transparent " and the unnecessary light of asking through all wavelengths, the luminous energy of specific wavelength has seen through as long as have at least.Light not only comprises visible light, also comprises UV-light and infrared light.

In the present invention, the above-mentioned transparent resin of per 100 weight parts (resin Composition of 100 weight parts does not comprise various additives such as ultraviolet absorbers), the above-mentioned combined amount that is coated with the polymer beads of silica gel is preferably the 0.1-20 weight part.

When combined amount was in this scope, the scattering of light moulding bodies that can obtain more certainly had good scattering of light, little printing opacity reduction amount, and also the transmissivity of scattered light reaches 80% or higher.As mentioned above, scattering of light moulding bodies of the present invention has the following advantages: scattering of light is good, and total light transmission reduction amount reduces, and the transmissivity height of scattered light.

Preferred implementation to scattering of light moulding bodies of the present invention is described below with reference to the accompanying drawings.

Scattering of light moulding bodies of the present invention is characterised in that: the polymer beads that is coated with silica gel 3 shown in Figure 1 mixes as shown in Figure 4 with transparent resin 4, and the transmissivity of the scattered light of expressing with establishing an equation down preferably reaches 80% or higher:

The transmittance of scattered light (%)=total light transmittance (%) * turbidity (%) * 0.01

In scattering of light moulding bodies of the present invention, the transparent resin of per 100 weight parts, the combined amount that is coated with the polymer beads of silica gel is generally the 0.1-20 weight part, is preferably the 0.3-15 weight part, more preferably the 1-15 weight part.When combined amount during greater than 30 weight parts, the preparation of the scattering of light moulding bodies difficulty that becomes is inappropriate.On the other hand, when combined amount during less than 0.1 weight part, being difficult to the transmissivity of scattered light is adjusted to 80% or higher, also is inappropriate.

In the present invention, usually use thermoplastic resin as transparent resin, the example of described thermoplastic resin comprises (methyl) acrylic resin, (methyl) alkyl acrylate-styrene copolymer resin, polycarbonate resin, vibrin, polystyrene resin, acrylic resin etc.

When requiring good transparency, (methyl) acrylic resin, (methyl) alkyl acrylate-styrene copolymer resin, polycarbonate resin and vibrin in the preferred above-mentioned substance.These thermoplastic resins can use separately or two or more are used in combination.

As for the polymer beads that is coated with silica gel, the difference of the particle of use and the specific refractory power of transparent resin is preferably 0.01-0.1, more preferably 0.02-0.1.

When the difference of specific refractory power less than 0.01 the time, make the transmissivity of scattered light less than 80% because can not get enough turbidity, be inappropriate.On the other hand, when the difference of specific refractory power greater than 0.1 the time, the scattering of light of moulding bodies is too high to make total light transmittance obviously reduce, and also is inappropriate.

Added minor amounts of additives for example ultraviolet absorbers, thermo-stabilizer, tinting material, weighting agent etc. in the transparent resin in the past.

In scattering of light moulding bodies of the present invention, described size and the shape that is coated with the polymer beads of silica gel is not particularly limited.When the scattering of light moulding bodies was used as signboard or container, volume average particle size was preferably the 3-50 micron.When the scattering of light moulding bodies for example required the liquid-crystal display of precision profile demonstration and projection TV as optical element, particularly Jing Mi optical element, volume average particle size was preferably the 3-30 micron.

When diameter is the 3-50 micron, can obtain the total light transmittance of more uniform scattered light and Geng Gao, can obtain precision profile when the 3-30 micron, be applicable to the occasion that requires high-accuracy image (for example indicating meter) and particle diameter is less.

In the scope that does not influence effect of the present invention, except the above-mentioned polymer beads that is coated with silica gel, can mix resin particle (independent resin particle) or particles of inorganic material in the scattering of light moulding bodies of the present invention in the past.

Scattering of light moulding bodies of the present invention is normally by mixing, melt and mediate being coated with the polymer beads of silica gel and transparent resin, and for example extrusion molding or jet moulding get the mixture molding by moulding method then.

Embodiment

To be explained in more detail the present invention by embodiment below, but the present invention is not subjected to the restriction of these descriptions.

At first, in an embodiment of the present invention, use following method to measure the transmissivity and the specific refractory power of volume average particle size, second-order transition temperature, specular reflectance, aperture ratio, h/D, heavy dispersiveness, turbidity, total light transmittance, scattered light.

(measuring method of volume average particle size)

Particle diameter is measured with Ku Erte counting process (coulter counter method).

The Ku Erte counting process is the particle size determination method that a kind of utilization is called the electrical resistance method of Coulter principle (Coulter Principle).

In more detail, this method is that electrode is placed on both sides, aperture (pore) that place the mouth pipe of electrolyte solution, make electric current pass through two electrodes, with particle suspension to be measured in electrolyte solution, with the electrolyte solution in the measuring cell suction port pipe, when electrolyte solution is flowed through the aperture, the electrolyte solution that is equivalent to particle volume is replaced, to have a resistance between two electrodes, because the change amount of resistance is directly proportional with the particle volume through the aperture, the change amount of detection and calculated resistance just can obtain the particulate volume average particle size.

In detail, according to " REFERENCEMANUAL FOR THE COULTER MULTISIZER " (1987) of publishing, be that calibrate in 100 microns aperture with diameter by Coulter Electronics Limited, and the mensuration volume average particle size.In more detail, with contact mixer and ultrasonic wave that 0.1 gram particle is pre-dispersed in 10 milliliter 0.1% nonionic surfactant solution, the instrument of being made up of CoulterMultisizer II and Sampling Sdand IIA (being made by Beckman Coulter Inc.) is as particle size measurer, under relax stirring, above-mentioned solution is joined to be placed on the SamplingSdand IIA and to contain 300 milliliters of ISOTON II and (measure and use electrolyte solution with dropper, produce by BeckmanCoulter Inc.) beaker in, adjusting to photodensitometer indication main body value is about 10%, measure 100,000 particulate volume average particle size then.

(measuring method of second-order transition temperature)

The mensuration of second-order transition temperature is carried out with TG/DTA6200 (Seiko Instruments Inc. manufacturing).

Measure

Take by weighing 0.02 gram sample and joining in the aluminum baking oven container (Seiko Instruments Inc. manufacturing), be put on the self-actuated sampler of TG/DTA6200.Under air atmosphere, heat up with 5 ℃/minute speed, to 400 ℃, carry out differential thermal analysis from room temperature (about 25 ℃).

Analyze

From the figure that obtains by the aforesaid operations (longitudinal axis: temperature, transverse axis: can find the flex point that the second-order transition temperature because of polymkeric substance forms the time), select this flex point as second-order transition temperature.Do not having under the situation of second-order transition temperature, temperature linearity rises, and begins degraded up to analyte and flex point also do not occur.

(measuring method of specular reflectance)

The preparation of sample

(NITTO TAPE: made by Nitto Denko Corp.) is bonded on the whole surface of the black and white covering paper (BYK-Gardner GmBH manufacturing) that is cut into 50 * 100 millimeters with double sticky tape, 1 gram particle is placed on the gluing surface, with the cosmetic sponge uniform particles ground longitudinally and is laterally respectively disperseed 10 times, purging whole surperficial 30 seconds from 20 centimetres of places far away of sample removing unnecessary particle with 1.5 kilograms/square centimeter pressurized air again, is that the part of black is measured specular reflectance in background.

Measure

In order to measure specular reflectance,, use VGS-300A and VGS-SENSOR (Nippon Denshoku Industries Co., Ltd. manufacturing) to measure and be stained with the specular reflectance that the particulate surface becomes 60 ° incident light according to JIS Z8741.Measure conduct the specular reflectance here of averaging 5 times.

The meaning of specular reflectance is: scattering of light and light reflective variation when the value of specular reflectance becomes big, scattering of light and light reflective improved when the value of specular reflectance diminished.

(being coated with definite method of the polymer beads of silica gel)

The definite method that is coated with the polymer beads of silica gel is that the dispersion dropping one of polymer beads in water that will be coated with silica gel drips on the glass slide, use sodium lamp to do light source by microscope (using the magnification of lens is 600 times), the polymer beads that is coated with silica gel described in the embodiment detects by an unaided eye.

(measuring method of aperture ratio)

In the measuring method of aperture ratio, at first, the polymer beads that 1 gram is coated with silica gel is packed in 50 milliliters of porcelain crucibles, calcined 2 hours down at 500 ℃ with electric furnace (ISUZU manufacturing), obtain the particle of only forming (following note is made silica gel particle) as shown in Figure 2 by the described silicon gel part that is coated with the polymer beads of silica gel.

Then, with spatula these silica gel particles are taken out from porcelain crucible gently not damaging them, and take pictures with scanning electronic microscope (GMS-820-A:JEOL.Ltd. manufacturing).

Then, take photo in, choose the opening portion photo up of 50 silica gel particles arbitrarily, by using Quantimet (Image-Ana LITE:Omron Co., Ltd. trace analysis manufacturing) is measured the dash area area (S2) and the opening portion area (S1) of silica gel particle as shown in Figure 3 by the profile of the silica gel particle of artificial definite each photo and the profile of opening portion.

Obtain the aperture ratio of each silica gel particle by following equation according to the area of each mensuration, mean value provides in an embodiment.

The dash area area (S2) of opening portion area (the S1)/silica gel particle of aperture ratio=silica gel particle

(mensuration of silica gel particle h/D)

As shown in Figure 2, the diameter that makes silica gel particle is D, and the height of silica gel particle is h, makes to measure h/D with the following method.

According to measure the same measuring method of aperture ratio, with scanning electronic microscope silica gel particle is taken pictures, take photo in, choose 50 take pictures face and the vertical particles of particle opening surface arbitrarily, measure each particulate D and h value with Quantimet, calculate h/D.At this, the h/D value is got the mean value of 50 h/D.

(heavy dispersed evaluation)

Be injected in the 50 ml sample pipes 40 milliliters of coating compositions that prepare and cover lid, with whizzer with centrifugal 10 minutes of the speed of 3000rpm so that liquid portion is separated fully with solid part, sample hose is horizontally installed in rotation electromagnetic shaker (Taiyo Scientific Industrial Co., Ltd. make) on, vibrations are 10 minutes under 60 times/minute vibrations condition.

State after with the naked eye determining to shake does not have the note of cluster of grains to do zero, and also have the note of cluster of grains to do *.

(mensuration of total light transmittance, turbidity, specular reflectance, scattered light transmissivity)

Apply total light transmittance and turbidity turbidometer (Nippon DenshokuIndustries Co., " NDH-2000 " that Ltd. makes of body and moulding bodies; According to JIS K7105) measure.

In addition, according to JIS Z8741, use VGS-300A and VGS-SENSOR (NipponDenshoku Industries Co., the Ltd. makes) specular reflectance when incident light is 60 ° with the coated side that applies body to measure.Measure the conduct specular reflectance value herein of averaging 5 times.

Moreover the transmissivity of scattered light is the ratio that is occupied by scattered light in the total light transmittance, the transmissivity of scattered light by under establish an equation and obtain:

The transmittance of scattered light (%)=total light transmittance (%) * turbidity (%) * 0.01

(measuring method of specific refractory power)

1, the measuring method of polymer beads specific refractory power

0.001 gram polymer beads is placed on the glass slide, with 0.2 milliliter of liquid state organics particles dispersed is prepared sample strip, liquid state organics wherein has the specific refractory power of choosing arbitrarily from publication " ATAGO RefractometerDatabook " (ATAGO Co., Ltd. delivers).

Then, each sample strip is placed on the opticmicroscope observes with the sodium light lamp as light source, determine the disappearance of particle outline under the specific refractory power known temperature of each liquid state organics, the specific refractory power of the liquid state organics of Shi Yonging then is taken as the particulate specific refractory power herein.

Above-mentioned publication has been described liquid state organics and specific refractory power thereof, for example:

Chaff amine (17 ℃) ... specific refractory power: 1.4900 and

P-Diethylbenzene ... specific refractory power: 1.4948,

Refractive index value is got behind the radix point 4.When not showing temperature (as p-Diethylbenzene), 20 ℃ of existence and disappearances of definite particle outline down.

Among the preparation embodiment below, the monomer composition that use prepares separately in each preparation embodiment, every kind of monomer is carried out radical polymerization obtain polymer beads, when polysiloxane oligomers condensation of no use, take out polymer beads, to remove polysiloxane oligomers fully, be used for above-mentioned detecting refractive index with toluene wash then.

2. the measuring method of transparent resin specific refractory power

Transparent resin is worn into particle (every 1 milligram or littler approximately), measure specific refractory power according to method as above-mentioned polymer beads.

(being coated with the embodiment and the comparative example of the polymer beads of silica gel)

Embodiment 1

The magnesium pyrophosphate that 5 grams are obtained by metathesis restrains water as suspension stabilizer and 200 to be mixed and obtains dispersion medium, this dispersion medium is joined in 500 milliliters of separable flasks, and 0.04 gram sodium lauryl sulphate is added in the dispersion medium as stopper as tensio-active agent and 0.02 gram SODIUMNITRATE.

Respectively 70 gram methyl methacrylates are restrained MKCsilicate MS57 (Mitsubishi Chemical Co. as simple function polymerizable vinyl monomer, 30, Ltd. make: molecular-weight average 1300-1500, R in the aforementioned structure is a methyl, n average out to 15-18) as poly-oxyalkylsiloxane oligopolymer, 0.25 gram 2,2 '-azo two (2, the 4-methyl pentane nitrile) makes monomer composition as the polymerization starter uniform dissolution.

The gained monomer composition is joined in the above-mentioned dispersion medium, and (ULTRATURRAX T-25, IKA makes) stirred for 10 seconds so that monomer composition is fully disperseed under 8000rpm speed with homogeneous mixer.Stirring arm, thermometer and reflux exchanger are connected on the separable flask, and the air nitrogen replacement in the flask places 60 ℃ of waters bath with thermostatic control.Continue stirred flask inside with 200rpm speed, when the adding in the separable flask has the temperature of the dispersion medium of monomer composition to reach 60 ℃, the polymerizable vinyl monomer is carried out 10 hours suspension polymerization, add 2 gram sodium hydroxide then with the poly-oxyalkylsiloxane oligopolymer of condensation.

Then, flask is shifted out water bath with thermostatic control, the reaction soln in the flask under agitation is cooled to room temperature, adds hydrochloric acid slurry pH value is adjusted to 2 to decompose suspension stabilizer, so obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes.The particle that obtains B suction filtration lifts away from sub-exchanged water washing with 1.2 and removes suspension stabilizer, obtains target particles after the drying.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 5.8 microns, and the second-order transition temperature of the polymer beads that obtains from the polymerizable vinyl monomer is 105 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 2

According to method similarly to Example 1, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, the amount that the amount of different is methyl methacrylate changes 30 grams, MKC silicate MS57 into changes 70 grams, 2 into, the amount of 2 '-azo two (2, the 4-methyl pentane nitrile) changes 0.15 gram into.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 116.3 microns, and the second-order transition temperature of the polymer beads that obtains from the polymerizable vinyl monomer is 105 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 3

According to method similarly to Example 1, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, different MKC silicate MS 51 (the Mitsubishi Chemical Co. that are to use, Ltd. make: molecular-weight average 500-700, R in the aforementioned structure is a methyl, n average out to 5-10) as poly-oxyalkylsiloxane oligopolymer.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 6.4 microns, and the second-order transition temperature of the polymer beads that obtains from the polymerizable vinyl monomer is 105 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 4

According to method similarly to Example 1, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, different MKC silicate MS 58B 15 (the Mitsubishi Chemical Co. that are to use, Ltd. make: molecular-weight average 1600-1800, R in the aforementioned structure is a methyl, n average out to 11-13) as poly-oxyalkylsiloxane oligopolymer.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 17.1 microns, and the second-order transition temperature of the polymer beads that obtains from the polymerizable vinyl monomer is 105 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 5

According to method similarly to Example 1, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, different is to use vinylbenzene as the polymerizable vinyl monomer.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 12.5 microns, and the second-order transition temperature of the polymer beads that obtains from the polymerizable vinyl monomer is 84 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 6

According to method similarly to Example 1, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, different is to use n-butyl acrylate as the polymerizable vinyl monomer.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 19.5 microns, and the second-order transition temperature of the polymer beads that obtains from the polymerizable vinyl monomer is-54 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Comparative Examples 1

The magnesium pyrophosphate that 18 grams are obtained by metathesis restrains water as suspension stabilizer and 900 to be mixed and obtains dispersion medium, this dispersion medium is packed in 2 liters of stainless steel beakers, 0.18 gram sodium lauryl sulphate is added in the dispersion medium as dispersion stabilizer as tensio-active agent and 0.1 gram SODIUMNITRATE.

Respectively 270 gram methyl methacrylates are made monomer composition as simple function polymerizable vinyl monomer, 30 gram Ethylene glycol dimethacrylate and 0.3 gram Diisopropyl azodicarboxylate as the polymerization starter uniform dissolution.

The gained monomer composition is joined in the above-mentioned dispersion medium, under 4000rpm speed, stirred for 10 seconds so that monomer composition fully disperses with homogeneous mixer (TK homogeneous mixer, Tokushu Kika Kogyo Co.Ltd. makes).Dispersion medium is joined in the polymerizer that agitator and thermometer are housed, continue down to stir 5 hours to finish suspension polymerization at 50 ℃.

The cooling back adds salt acid degradation suspension stabilizer in suspension, polymer beads separation, washing, drying under reduced pressure are obtained pearl polymerization composition granule (volume average particle size is 13.1 microns).Because the pearl polymerization composition granule has crosslinking structure, it is stable that particle begins the still definite vitrifying of thermal destruction in the time of 260 ℃.

(Aerosil makes, volume average particle size: 16 nanometers) to obtain surface-coated the combination particle of silica gel particle (volume average particle size is 13.6 microns) was arranged with hydridization device (Nara KikaiKogyo Co.Ltd. manufacturing) processing 5 minutes under 50 ℃, 14000rpm condition with 21 gram pearl polymerization composition granules and 9 gram aerosil (Aerosil) R972.Particulate specular reflectance and specific refractory power are as shown in table 1.

Comparative Examples 2

According to method similarly to Example 1, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, the amount that the amount of different is methyl methacrylate changes 97 grams, MKC silicate MS57 into changes 3 grams, 2 into, the amount of 2 '-azo two (2, the 4-methyl pentane nitrile) changes 0.45 gram into.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 15 microns, and the second-order transition temperature of the polymer beads that obtains from the polymerizable vinyl monomer is 105 ℃.Because the particle that obtains has only small portion to be covered by silica gel, so pellosil can be peeled off under some situation.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 7

According to method similarly to Example 1, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, different is that the polymerizable vinyl monomer is used 56 gram methyl methacrylates and 14 gram Ethylene glycol dimethacrylate instead.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 15 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 8

According to method similarly to Example 7, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, different is that methyl methacrylate changes vinylbenzene into, Ethylene glycol dimethacrylate changes Vinylstyrene into.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 6 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 9

According to method similarly to Example 7, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, different MKC silicate MS 58 B15 (the Mitsubishi Chemical Co. that are to use, Ltd. make, molecular-weight average is 1600-1800) as poly-oxyalkylsiloxane oligopolymer, the agitation condition of homogeneous mixer is that 10000rpm stirred 10 seconds.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 5 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature certificate of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 10

According to method similarly to Example 7, obtain the polymer beads that is coated with silica gel that polymer beads surface exposes, the agitation condition that the amount that the amount of different is magnesium pyrophosphate changes 7.5 grams, tensio-active agent sodium lauryl sulphate into changes 0.06 gram, homogeneous mixer into is that 10000rpm stirred 60 seconds.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 3 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 11

According to method similarly to Example 7, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, different is that 56 gram vinylbenzene change 28 gram vinylbenzene and 28 gram methyl methacrylates into.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 6 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature certificate of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Comparative Examples 3

The 500 gram deionized waters that are dissolved with 0.05 gram sodium lauryl sulphate are joined in the polymerizer that stirring arm and thermometer are housed, 50 gram calcium triphosphates are joined also disperse to obtain dispersion in the solution.Join in this dispersion being dissolved into as the mixed solution that obtains in monomeric 85 gram vinylbenzene of polymerizable vinyl and the 15 gram Vinylstyrenes, disperse drop is adjusted to about 6 microns with T.K mixing tank (Tokushu Kika Kogyo Co.Ltd. manufacturing) by 0.5 gram benzoyl peroxide and 0.5 gram Diisopropyl azodicarboxylate.Under agitation polymerizer inside is heated to 65 ℃ then to carry out suspension polymerization, then cooling.Filtering suspension liquid obtains the pearl polymerization composition granule after washing and the drying.The volume average particle size of the polymer beads that obtains is 6 microns, because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Comparative Examples 4

Method according to same with Comparative Examples 3 obtains the pearl polymerization composition granule, and different is that vinylbenzene changes methyl methacrylate into, and Vinylstyrene changes Ethylene glycol dimethacrylate into, and the particle diameter of drop changes 15 microns into simultaneously.The sphere polymers particulate volume average particle size that obtains is 15 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Comparative Examples 5

(preparation of polymkeric substance toluene solution)

144.5 gram tetramethoxy-silicanes, 23.6 gram γ-methacrylic acid oxygen propyl trimethoxy silicanes, 19 gram water, 30 gram methyl alcohol and 5 gram Amberlist 15 (Rohm and Haas Japan make Zeo-karb) are joined in 300 milliliters of four-hole boiling flasks that agitator, thermometer and condenser be housed, stir down at 65 ℃ and made it reaction in 2 hours.The reaction mixture cool to room temperature, use by condenser to add the distillation tower replacement condenser that spout is made, under atmospheric pressure 2 hours temperature is raised to 80 ℃, keep this temperature until there is not methyl alcohol to flow out further to react.Once more behind the cool to room temperature, it is 1800 polymerisable polysiloxane that elimination Amberlist 15 obtains number-average molecular weight.

Then, 200 gram toluene are joined as organic solvent in 1 liter of flask that agitator, additional port, thermometer, condenser and nitrogen inlet are housed, import nitrogen, under agitation flask interior is heated to 110 ℃.Then, being mixed with the above-mentioned polymerisable polysiloxane of 20 grams, 80 gram methyl methacrylates, 10 gram ethyl acrylates, 60 gram vinylbenzene, 30 gram butyl acrylates and 6 grams 2, the solution of 2 '-Diisopropyl azodicarboxylate dropwise adds by additional port in 2 hours.Dripping the back continues to stir 1 hour under uniform temp, added 0.4 gram 1 in per 30 minutes, 1 '-two (tert-butyl peroxide)-3,3, the 5-trimethyl-cyclohexane adds twice altogether, heats and carries out copolymerization in 2 hours, obtain the toluene solution of polymkeric substance, the number-average molecular weight that wherein is dissolved in the polymkeric substance of toluene is 12000.Solid matter accounts for 49.5 weight % in the solution that obtains.

(preparation of dispersion)

496 gram butylacetates and 124 gram methyl alcohol are joined in 1 liter of flask that agitator, two additional port (additional port 1 and 2) and thermometer are housed, and internal temperature transfers to 20 ℃.Then, in 1 hour time, under the condition of stirred flask inside, dropwise add mixed liquor A and B respectively by additional port 1 and 2, wherein mixed liquor A contains above-mentioned polymkeric substance toluene solution of 10 grams and 100 gram tetramethoxy-silicanes, and mixed liquid B contains 30 gram water, 30 gram 25% ammoniacal liquor and 60 gram methyl alcohol.Adding the back continues to stir 2 hours under uniform temp.Then, in 1 hour, dropwise add the mixed solution that contains 37 above-mentioned polymkeric substance toluene solutions of gram and 37 gram butylacetates by additional port 1.Add the back and under uniform temp, stir continuation 2 hours.Then, under 110 mmhg pressures flask interior is warming up to 100 ℃, ammonia, methyl alcohol, toluene and butylacetate are distilled away until solid content and become 30 weight %, obtain polymkeric substance and silica gel fine particle and are dispersed in dispersion in the butylacetate.With ion exchanged water the solid content of dispersion is diluted to 1 weight %, the fine grain median size (volume diameter) that obtains laser diffraction/scatter-type particle size dispersion survey meter (trade(brand)name " LS230 ", Coulter Inc. makes) to measure, measurement result is 0.18 micron (180 nanometer).

(preparation of silica gel combination copolymer particulate)

To be dissolved with 0.5 gram polyvinyl alcohol (PVA-205 Kuraray Co., Ltd. 900 gram deionized waters manufacturing) join in the flask that agitator, rare gas element ingress pipe, reflux exchanger and thermometer are housed, add then by mixing the mixture that 75 gram methyl methacrylates, 19 gram ethylene glycol dimethacrylate, the 20 above-mentioned dispersion liquids of gram and 1 gram Diisopropyl azodicarboxylate obtain, under 3000rpm, stir 5 minutes with the preparation unit for uniform suspension with TK mixing tank (TokushuKika Kogyo Co.Ltd. manufacturing).

Then, be blown into nitrogen, suspension is heated to 75 ℃, continue to stir 5 hours to carry out polyreaction under this temperature, reaction mixture obtains combination particle with suspension filtered, washing and drying.Combination particle has silica gel particle and is dispersed in structure from the polymer beads that the polymerizable vinyl monomer obtains.The volume average particle size of the polymer beads that obtains is 12 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.The particulate specular reflectance is as shown in table 1.

Comparative Examples 6

Method according to same with Comparative Examples 4 obtains polymer beads, and the particle diameter of different is drop changes 5 microns into.The volume average particle size of the polymer beads that obtains is 5 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature certificate of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Comparative Examples 7

According to the method identical with Comparative Examples 4, obtain terre verte dispersive composition grain, different is with 5 gram lipotropy terre verte (trade(brand)names " SAM ", Coap Chemical makes) be dispersed in the monomer composition of Comparative Examples 4, the particle diameter of drop changes 6 microns (the mixing tank agitation condition is that 10000rpm stirred 10 seconds) into.The volume average particle size of the polymer beads that obtains is 6 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 12

According to method similarly to Example 7, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, different is that Ethylene glycol dimethacrylate changes Vinylstyrene into.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 20 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 13

According to the method identical with embodiment 7, obtain the polymer beads of the covering silica gel that the polymer beads surface exposes, different is to use 56 gram vinylbenzene and 20 gram Vinylstyrenes as the polymerizable vinyl monomer.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 12 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature certificate of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 14

According to the method identical with embodiment 12, obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes, different MKC silicate MS 58B 15 (the Mitsubishi ChemicalCo. that are to use, Ltd. make, molecular-weight average is 1600-1800) as poly-oxyalkylsiloxane oligopolymer.The volume average particle size of the polymer beads that is coated with silica gel that obtains is 15 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature certificate of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Comparative Examples 8

The 500 gram deionized waters that are dissolved with 0.05 gram sodium lauryl sulphate are joined in the polymerizer that stirring arm and thermometer are housed, 50 gram calcium triphosphates are joined solution and disperse to form dispersion.Join in the polymerizer being dissolved into as the mixed solution that obtains in monomeric 80 gram vinylbenzene of polymerizable vinyl and the 20 gram Vinylstyrenes, disperse drop is adjusted to about 12 microns with T.K mixing tank (Tokushu Kika Kogyo Co.Ltd. manufacturing) by 0.5 gram benzoyl peroxide and 0.5 gram Diisopropyl azodicarboxylate.Under agitation be heated to then in the polymerizer be 65 ℃ to carry out suspension polymerization, then the cooling.Suspension filtered, washing and drying are obtained the pearl polymerization composition granule.The volume average particle size of the polymer beads that obtains is 12 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Comparative Examples 9

Obtain the pearl polymerization composition granule according to the method identical with Comparative Examples 8, different is that the polymerizable vinyl monomer changes 80 gram methyl methacrylates and 20 gram Vinylstyrenes into.The volume average particle size of the polymer beads that obtains is 20 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 15

Obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes according to the method identical with embodiment 13, different is in the polymer beads part as in Example 13 after the polymerization, to be used to solidify the catalyzer that gathers the oxyalkylsiloxane oligopolymer and change 2 gram tart thionamic acid sodium into from 2 gram sodium hydroxide, solidification value is 80 ℃.The volume average particle size of the polymer beads that obtains is 20 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 16

Obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes according to the method identical with embodiment 13, different is that 56 gram methyl methacrylates and 14 gram Vinylstyrenes change 35 gram methyl methacrylates, 21 gram vinylbenzene and 14 gram Ethylene glycol dimethacrylate into.The volume average particle size of the polymer beads that obtains is 20 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Embodiment 17

Obtain the polymer beads that is coated with silica gel that the polymer beads surface exposes according to the method identical, in different is methyl methacrylate is 20 grams, Vinylstyrene be 5 grams, poly-oxyalkylsiloxane oligopolymer be 75 grams, 4 gram sodium-chlor add as dispersion medium the water with embodiment 13.The volume average particle size of the polymer beads that obtains is 15 microns.Because the polymer moieties that obtains from the polymerizable vinyl monomer has crosslinking structure, particle begins the still definite second-order transition temperature of thermal destruction in the time of 260 ℃.Particulate specular reflectance, aperture ratio, h/D and specific refractory power are as shown in table 1.

Table 1

	Specular reflectance (%)	Aperture ratio	h/D	Specific refractory power
					Embodiment
1	11.3	0.56	0.78	1.490
					Embodiment 2	10.6	0.16	0.92	1.490
Embodiment 3	11.7	0.61	0.72	1.490
					Embodiment 4	11.9	0.69	0.70	1.490
Embodiment 5	9.6	0.58	0.77	1.590
					Embodiment 6	10.9	0.52	0.79	1.480
Embodiment 7	10.9	0.55	0.79	1.490
					Embodiment 8	9.5	0.59	0.76	1.590
Embodiment 9	11.1	0.61	0.73	1.490
					Embodiment 10	11.7	0.62	0.72	1.490
Embodiment 11	10.2	0.60	0.69	1.530
					Embodiment 12	10.1	0.65	0.64	1.510
Embodiment 13	9.9	0.48	0.65	1.590
					Embodiment 14	11.5	0.63	0.74	1.510
Embodiment 15	9.8	0.67	0.67	1.510
					Embodiment 16	10.4	0.72	0.78	1.520
Embodiment 17	10.4	0.18	0.93	1.510
					Comparative Examples 1	14.7	-	-	1.490
Comparative Examples 2	15.1	1	0.36	1.490
					Comparative Examples 3	13.7	-	-	1.590
Comparative Examples 4	15.0	-	-	1.490
					Comparative Examples 5	14.5	-	-	1.510
Comparative Examples 6	14.7	-	-	1.490
					Comparative Examples 7	14.4	-	-	1.490
Comparative Examples 8	13.7	-	-	1.590
					Comparative Examples 9	14.1	-	-	1.510
Silica gel particle	16.9	-	-	-

Silica gel particle: TOKUSEAL U (Tokuyama Corp. makes, particle diameter: 14 microns)

Can obtain following results from embodiment 1-17 and Comparative Examples 1-9.

Can see in the data of table 1 from embodiment 1-6 and Comparative Examples 1, when the polymer beads that is coated with silica gel that exposes when the surface was compared with the unexposed polymer beads that is coated with silica gel in surface, the former had scattering of light and reflectivity that little specular reflectance is become reconciled.

Can see that from Comparative Examples 2 when pellosil overlie polymer particulate scope was little, pellosil can come off, and can not get enough scattering of light and reflectivity.

Can see that from embodiment 6 method of the present invention is not restricted to the kind of polymer beads, even when second-order transition temperature is low, still can obtain being coated with the polymer beads of silica gel.

Can see from embodiment 7-17, even under the situation that polymer beads is crosslinked, still can obtain being coated with the polymer beads of silica gel.

Can see just having possessed good scattering of light and reflectivity behind the silicon-coating glued membrane from embodiment 7-17 and Comparative Examples 3-4,6-9.

Can see that from embodiment 7-11 and Comparative Examples 5 particle that is formed with pellosil has better scattering of light and reflectivity than silica gel particle dispersive situation.

Can see that from embodiment 1-17 the h/D value of silica gel particle has suitable scattering of light and reflectivity in the scope of 0.5≤h/D＜1 time.When h/D value pellosil less than 0.5 time comes off scattering of light and reflectivity variation when h/D is 1 easily from polymer beads.

(embodiment of coating composition and Comparative Examples)

Embodiment 18

With 100 weight parts by the polymer beads that is coated with silica gel of embodiment 7 preparation and polyacrylate resin (trade(brand)name " BR106 " by 100 weight parts, Mitsubishi Rayon Co., Ltd makes) be dissolved in the mixed coating composition that gets of the binder solution that obtains in the solvent (toluene 180 weight parts, ethyl acetate 90 weight parts, butylacetate 30 weight parts) of 300 weight parts as adhesive resin.

Use 75 microns applicator that the gained coating composition is coated on the poly-terephthalic acid ethyl ester residuite film of 100 micron thickness, drying makes light diffusion sheet.

Measure the turbidity and the total light transmittance on the light diffusion sheet surface that makes respectively by preceding method, the result is as shown in table 2.

Embodiment 19

Make light diffusion sheet, the different polymer beads that is coated with silica gel that is to use 20 weight parts to make according to the method identical by example 8 with embodiment 18.Measure the turbidity and the total light transmittance on this light diffusion sheet surface, the result is as shown in table 2.

Embodiment 20

Make light diffusion sheet according to the method identical, the different polymer beads that are coated with silica gel of 70 weight parts that are to use by example 10 preparations with embodiment 18.The turbidity and the total light transmittance on the light diffusion sheet surface that mensuration makes, the result is as shown in table 2.

Embodiment 21

Make light diffusion sheet according to the method identical with embodiment 18, different is that the described add-on that is coated with the polymer beads of silica gel changes 150 weight parts into.The turbidity and the total light transmittance on the light diffusion sheet surface that mensuration makes, the result is as shown in table 2.

Comparative Examples 11

Make light diffusion sheet according to the method identical with embodiment 18, different is to replace the polymer beads that is coated with silica gel with the polymer beads that Comparative Examples 3 obtains, and usage quantity is 3 grams/300 gram methyl methacrylates.The turbidity and the total light transmittance on the light diffusion sheet surface that mensuration makes, the result is as shown in table 2.

Comparative Examples 12

Make light diffusion sheet according to the method identical with embodiment 18, different is to replace the polymer beads that is coated with silica gel with the polymer beads that Comparative Examples 4 obtains.The turbidity and the total light transmittance on the light diffusion sheet surface that mensuration makes, the result is as shown in table 2.

Comparative Examples 13

Make light diffusion sheet, the different polymer beads that is coated with silica gel that is to use Comparative Examples 5 to obtain according to the method identical with embodiment 18.The turbidity and the total light transmittance on the light diffusion sheet surface that mensuration makes, the result is as shown in table 2.

Comparative Examples 14

Make light diffusion sheet, the different polymer beads that is coated with silica gel that is to use Comparative Examples 7 to obtain according to the method identical with embodiment 18.The turbidity and the total light transmittance on the light diffusion sheet surface that mensuration makes, the result is as shown in table 2.

Table 2

	Turbidity (100%)	Total light transmittance (100%)
			Embodiment 18	94.11	88.55
Embodiment 19	94.36	86.75
			Embodiment 20	95.12	86.02
Embodiment 21	94.53	85.78
			Comparative Examples 11	0.54	96.28
Comparative Examples 12	92.66	81.12
			Comparative Examples 13	91.32	93.21
Comparative Examples 14	93.23	80.87

From Comparative Examples 11-14 in the data of table 2 as can be seen, normally, total light transmittance reduces when turbidity increases, and turbidity minimizing (especially as Comparative Examples 11) when total light transmittance increases.In other words, increase turbidity and generally mean the reduction total light transmittance, increase total light transmittance and mean the reduction turbidity.

Yet as can seeing with the comparison of Comparative Examples 12-14, in the example of the optical sheet of embodiment 18-21, turbidity and total light transmittance be making moderate progress than Comparative Examples all.

As implied above, mix the coating composition that obtains by the polymer beads that is coated with silica gel that uses part to expose polymer beads, the optical sheet that obtains (optical element) all is good on scattering of light (turbidity) and total light transmittance.Therefore we know that this is well suited for the situation of light diffusion sheet, for example, are configured in prism sheet in the liquid crystal indicator and the light diffusion sheet between the light pipe.

Embodiment 22

With 10 weight parts by the polymer beads that is coated with silica gel of embodiment 9 preparation and (trade(brand)name " Biron 200 " the Toyobo Co. of the vibrin as adhesive resin by 100 weight parts, Ltd. make) mix the binder solution mixing that obtains with the solvent (toluene 180 weight parts, ethyl acetate 90 weight parts, butylacetate 30 weight parts) of 300 weight parts, make coating composition through homodisperse.

Use 20 microns applicator this coating composition to be coated on the poly-terephthalic acid ethyl ester residuite film of 100 micron thickness, drying makes anti-dizzy.The measurement result of turbidity, total light transmittance and the specular reflectance on the anti-dizzy surface that obtains is as shown in table 3.

Embodiment 23

Make anti-dizzy according to the method identical, the different polymer beads that is coated with silica gel that in embodiment 10, obtains that is to use 5 weight parts with embodiment 22.The measurement result of turbidity, total light transmittance and the specular reflectance on the anti-dizzy surface that obtains is as shown in table 3.

Embodiment 24

Make anti-dizzy according to the method identical, the different polymer beads that is coated with silica gel that in embodiment 11, obtains that is to use 20 weight parts with embodiment 22.The measurement result of turbidity, total light transmittance and the specular reflectance on the anti-dizzy surface that obtains is as shown in table 3.

Comparative Examples 15

Make anti-dizzy according to the method identical with embodiment 22, the different polymer beads that are to use Comparative Examples 6 to obtain replace the polymer beads that is coated with silica gel that is used for embodiment 22.The measurement result of turbidity, total light transmittance and the specular reflectance on the anti-dizzy surface that obtains is as shown in table 3.

Comparative Examples 16

According to method similarly to Example 22, make anti-dizzy, the different polymer beads that is coated with silica gel that is to use Comparative Examples 5 to obtain.The measurement result of turbidity, total light transmittance and the specular reflectance on the anti-dizzy surface that obtains is listed in table 3.

Comparative Examples 17

Make anti-dizzy according to the method identical, the different polymer beads that is coated with silica gel that is to use Comparative Examples 7 to obtain with embodiment 22.The measurement result of turbidity, total light transmittance and the specular reflectance on the anti-dizzy surface that obtains is as shown in table 3.

Table 3

	Turbidity (%)	Total light transmittance (%)	Specular reflectance (%)
				Embodiment 22	32.56	92.76	20.45
Embodiment 23	33.72	92.45	25.37
				Embodiment 24	34.17	91.78	21.69
Comparative Examples 15	30.21	90.81	42.34
				Comparative Examples 16	30.21	90.93	38.22
Comparative Examples 17	31.22	89.97	33.64

As can be seen from Table 3, comparing all in the turbidity in the optical sheet of embodiment 22-24 and total light transmittance and the Comparative Examples is improved, and specular reflectance also obviously reduces.

As implied above; the polymer beads that is coated with silica gel by use mixes the coating composition that obtains; having pellosil in the described polymer beads that is coated with silica gel makes polymer beads partly expose; therefore the scattering of light (turbidity) and the total light transmittance of the optical sheet (optical element) that obtains all are fine, and very little specular reflectance can be arranged.Therefore we know that this is well suited for anti-dizzy situation, for example, and outermost anti-dizzy of being configured in the liquid crystal indicator.

Embodiment 24

With 50 weight parts by the polymer beads that is coated with silica gel of embodiment 7 preparation and the binder aqueous solution (trade(brand)name " Bironal MD1200 " of 400 weight parts, Toyobo Co., Ltd. make) (about 30 weight parts of adhesive resin) mixing, make coating composition through homodisperse, use in the wherein said binder aqueous solution vibrin as adhesive resin and make water and ethanol as solvent.Use 75 microns applicator that this coating composition is coated in (BYK-Garder manufacturing) on the black and white covering paper, drying makes the coating body.Measure the specular reflectance that gained applies the surface.

In addition, determine the heavy dispersed of prepared coating composition.The result is as shown in table 4.

Embodiment 25

Make coating composition, the polymer beads that is coated with silica gel that the different embodiment that is to use 10 weight parts 8 obtains according to the method identical with embodiment 24.In addition, as embodiment 24, measure specular reflectance and definite heavy dispersed.The result is as shown in table 4.

Embodiment 26

Make coating composition according to the method identical, the different polymer beads that are coated with silica gel that obtain by embodiment 11 that are to use 100 weight parts with embodiment 24.In addition, as embodiment 24, measure specular reflectance and definite heavy dispersed.The result is as shown in table 4.

Comparative Examples 18

Make coating composition according to the method identical with embodiment 24, the different polymer beads that obtained by Comparative Examples 5 that are to use 10 weight parts replace the polymer beads that is coated with silica gel of embodiment 24.In addition, as embodiment 24, measure specular reflectance and definite heavy dispersed.The result is as shown in table 4.

Comparative Examples 20

Make coating composition according to the method identical, the different polymer beads that are coated with silica gel that obtain by Comparative Examples 5 that are to use 10 weight parts with embodiment 24.In addition, as embodiment 24, measure specular reflectance and definite heavy dispersed.The result is as shown in table 4.

Comparative Examples 21

Make coating composition according to the method identical with embodiment 24, different is not have to mix the polymer beads that is coated with silica gel.In addition, as embodiment 24, measure specular reflectance and definite heavy dispersed.The result is as shown in table 4.

Comparative Examples 22

Make coating composition according to the method identical, the different polymer beads that are coated with silica gel that obtain by Comparative Examples 7 that are to use 20 weight parts with embodiment 24.In addition, as embodiment 24, measure specular reflectance and definite heavy dispersed.The result is as shown in table 4.

Embodiment 27

With 50 weight parts by the combination particle of embodiment 1 preparation and the binder aqueous solution (trade(brand)name " Bironal MD1200 " of 400 parts of weight, Toyobo Co., Ltd. make) (about 120 weight parts of adhesive resin) mixing, make coating composition through homodisperse, wherein said binder aqueous solution use vibrin as tackiness agent and make water and ethanol as solvent.Use 75 microns applicator that this coating composition is coated in (BYK-Garder manufacturing) on the black and white covering paper, drying makes the coating body.Measure the specular reflectance that gained applies the surface.

In addition, determine the heavy dispersed of prepared coating component.The result is as shown in table 4.

Embodiment 28

Make coating composition according to the method identical, the different particles that obtain by embodiment 3 that are to use 50 weight parts with embodiment 27.Measure the specular reflectance that gained applies the surface.

In addition, determine the heavy dispersed of prepared coating composition.The result is as shown in table 4.

Embodiment 29

Make coating composition according to the method identical, the different particles that obtain by embodiment 4 that are to use 50 weight parts with embodiment 27.Measure the specular reflectance that gained applies the surface.

In addition, determine the heavy dispersed of prepared coating composition.The result is as shown in table 4.

Embodiment 30

According to making coating composition with the mutually same method of embodiment 21, the different particles that obtain by embodiment 6 that are to use 50 weight parts.Measure the specular reflectance that gained applies the surface.

In addition, determine the heavy dispersed of prepared coating composition.The result is as shown in table 4.

Table 4

	Specular reflectance (%)	Heavy dispersed evaluation
			Embodiment 24	19.88	○
Embodiment 25	27.54	○
			Embodiment 26	15.23	○
Embodiment 27	20.17	○
			Embodiment 28	19.38	○
Embodiment 29	18.42	○
			Embodiment 30	20.53	○
Comparative Examples 18	36.43	×
			Comparative Examples 19	35.92	×
Comparative Examples 20	78.98	-
			Comparative Examples 21	29.96	×

As can be seen from Table 4, coating composition of the present invention has better heavy dispersiveness, in other words, good dispersion stabilization is arranged also in water-based system.

(embodiment of moulding bodies and Comparative Examples)

Embodiment 31

The polymer beads that is coated with silica gel that 30 grams are obtained by embodiment 12 joins 300 gram methyl-methacrylate resin (MG-5, Sumitomo Chemical Co., Ltd makes, specific refractory power 1.49) in, mixed 3 minutes with food mixer, be injected into afterwards in the jet molding machine, obtain long 100 millimeters, wide 50 millimeters and thick 2 millimeters moulding bodies through jet molding.

Measure the transmissivity of total light transmittance, turbidity and the scattered light of moulding bodies respectively with preceding method.Result such as table 5.

Embodiment 32

Make the moulding bodies of scattering of light according to the method identical with embodiment 31, different is with respect to 300 gram methyl-methacrylate resins, and the described addition that is coated with the polymer beads of silica gel is 45 grams.In addition, as embodiment 31, measure the transmissivity of total light transmittance, turbidity and scattered light.The result is as shown in table 5.

Embodiment 33

Make the moulding bodies of scattering of light according to the method identical with embodiment 31, different is with respect to 300 gram methyl-methacrylate resins, the polymer beads that is coated with silica gel that uses 3 grams to be obtained by embodiment 14.In addition, as embodiment 31, measure the transmissivity of total light transmittance, turbidity and scattered light.The result is as shown in table 5.

Embodiment 34

Make the moulding bodies of scattering of light according to the method identical with embodiment 31, different is with respect to 300 gram methyl-methacrylate resins, the polymer beads that is coated with silica gel that uses 30 grams to be obtained by embodiment 15.In addition, as embodiment 31, measure the transmissivity of total light transmittance, turbidity and scattered light.The result is as shown in table 5.

Comparative Examples 21

Make the moulding bodies of scattering of light according to the method identical with embodiment 31, different is with respect to 300 gram methyl-methacrylate resins, uses 3 grams to replace the polymer beads that is coated with silica gel by the polymer beads that Comparative Examples 8 obtains.In addition, as example 31, measure the transmissivity of total light transmittance, turbidity and scattered light.The result is as shown in table 5.

Comparative Examples 22

Make the moulding bodies of scattering of light according to the method identical with embodiment 31, different is with respect to 300 gram methyl-methacrylate resins, uses 30 grams to replace the polymer beads that is coated with silica gel by the polymer beads that Comparative Examples 9 obtains.In addition, as embodiment 31, measure the transmissivity of total light transmittance, turbidity and scattered light.The result is as shown in table 5.

Comparative Examples 23

Make the moulding bodies of scattering of light according to the method identical with embodiment 31, different is with respect to 300 gram methyl-methacrylate resins, uses the polymer beads that is coated with silica gel that 45 grams obtain by Comparative Examples 5 as the polymer beads that is coated with silica gel.In addition, as embodiment 31, measure the transmissivity of total light transmittance, turbidity and scattered light.The result is as shown in table 5.

Comparative Examples 24

Make the moulding bodies of scattering of light according to the method identical with example 31, different is not have to use the polymer beads that is coated with silica gel, only uses methyl-methacrylate resin.In addition, as embodiment 31, measure the transmissivity of total light transmittance, turbidity and scattered light.The result is as shown in table 5.

Embodiment 35

Make the moulding bodies of scattering of light according to the method identical, the different combination particle that obtain by embodiment 15 that are to use with embodiment 31.In addition, as embodiment 31, measure the transmissivity of total light transmittance, turbidity and scattered light.The result is as shown in table 5.

Embodiment 36

Make the moulding bodies of scattering of light according to the method identical, the different polymer beads that are coated with silica gel that obtain by embodiment 16 that are to use with embodiment 31.In addition, as embodiment 31, measure the transmissivity of total light transmittance, turbidity and scattered light.The result is as shown in table 5.

Embodiment 37

Make the moulding bodies of scattering of light, the different polymer beads that is coated with silica gel that is to use 45 grams to obtain according to the method identical by embodiment 17 with embodiment 31.In addition, as embodiment 31, measure the transmissivity of total light transmittance, turbidity and scattered light.The result is as shown in table 5.

Embodiment 38

The polymer beads that is coated with silica gel that 3 grams are obtained by embodiment 5 joins 300 gram methyl-methacrylate resin (MG-5, Sumitomo Chemical Co., Ltd makes, specific refractory power 1.49) in, mixed 3 minutes with food mixer, be injected into the jet molding machine afterwards, obtain long 100 millimeters, wide 50 millimeters and thick 2 millimeters moulding bodies through jet molding.

Measure the transmissivity of total light transmittance, turbidity and the scattered light of moulding bodies respectively with preceding method.The result is as shown in table 5.

Table 5

	Total light transmittance (%)	Turbidity (%)	Scattered light transmissivity (%)
				Embodiment 31	83.17	97.55	81.13
Embodiment 32	81.79	98.77	80.78
				Embodiment 33	89.25	90.21	80.51
Embodiment 34	82.95	98.23	81.48
				Embodiment 35	83.52	97.39	81.34
Embodiment 36	81.21	98.56	80.04
				Embodiment 37	84.23	95.48	80.42
Embodiment 38	88.93	91.83	81.66
				Comparative Examples 21	81.56	87.78	71.59
Comparative Examples 22	76.32	94.38	72.03
				Comparative Examples 23	76.21	96.59	73.61
Comparative Examples 24	92.34	0.83	0.77

As shown in table 5; because comparing with the moulding bodies that is mixed with common polymer beads or combination particle, the moulding bodies of scattering of light of the present invention kept higher total light transmittance and the turbidity of Geng Gao; therefore the transmissivity of scattered light reaches 80% or higher, and scattered light is seen through effectively as can be known simultaneously.

The polymer beads that is coated with silica gel of the present invention has good scattering of light and reflectivity, can use to utilize these characteristics in many occasions are for example painted.And, because the polymer beads that is coated with silica gel of the present invention has good scattering of light and reflectivity, and produce particle and do not need to use strong mechanical shear stress with producing the method that is coated with the polymer beads of silica gel of the present invention, so can easily apply polymer beads with low Tg with pellosil.

In addition, because coating body of the present invention has lower specular reflectance, be effective in the field that needs delustring and anti-dazzle.Particularly because optics constituent element of the present invention has good transmittance and scattering of light, be effective in cover for luminaire, photoconduction dish and the projection TV screen for example in the field of high scattering of light of needs and high transmission rate.

And, the moulding bodies that contains the scattering of light of the polymer beads that is coated with silica gel of the present invention can be used as optics constituent element for example throw light on tool housing, lens, light guide plate, CD, projection TV screen, and cosmetics containers, vending machine face, signboard, commodity show and the table upper container in.

Claims (12)

1. polymer beads that is coated with silica gel, this polymer beads contains:

The polymer beads that obtains from the polymerizable vinyl monomer; And

Cover the pellosil of described polymer beads, described pellosil makes the surface of polymer beads expose with the aperture ratio of 0.1-1, the height h of pellosil and the diameter D that is coated with the polymer beads of silica gel meet following relationship: 0.5≤h/D＜1, wherein, described pellosil contains the condenses of poly-oxyalkylsiloxane oligopolymer.

2. coating composition, this coating composition contains polymer beads and the binder solution that is coated with silica gel, this polymer beads that is coated with silica gel contains from polymerizable vinyl monomer polymer beads that obtains and the pellosil that covers described polymer beads, described pellosil makes the surface of polymer beads expose with the aperture ratio of 0.1-1, the height h of pellosil and the diameter D that is coated with the polymer beads of silica gel meet following relationship: 0.5≤h/D＜1, described pellosil contains the condenses of poly-oxyalkylsiloxane oligopolymer, wherein, this binder solution contains adhesive resin and solvent.

3. coating composition according to claim 2, wherein, per 100 weight part adhesive resins, the combined amount that is coated with the polymer beads of silica gel is the 1-150 weight part.

4. one kind applies body, and wherein, the described coating composition of claim 2 is coated on the matrix.

5. optical element, wherein, the described coating composition of claim 2 is coated on the residuite.

6. optical element according to claim 5, wherein, per 100 weight part adhesive resins, the combined amount that is coated with the polymer beads of silica gel is the 20-120 weight part.

7. liquid-crystal display, wherein, this liquid-crystal display uses the described optical element of claim 6.

8. scattering of light moulding bodies, this scattering of light moulding bodies contains transparent resin and is coated with the polymer beads of silica gel, wherein, the described polymer beads that is coated with silica gel contains polymer beads and the overlie polymer particulate pellosil that obtains from the polymerizable vinyl monomer, this pellosil makes the surface of polymer beads expose with the aperture ratio of 0.1-1, the height h of pellosil and the diameter D that is coated with the polymer beads of silica gel meet following relationship: 0.5≤h/D＜1, and described pellosil contains the condenses of poly-oxyalkylsiloxane oligopolymer.

9. scattering of light moulding bodies according to claim 8, wherein, the difference of the specific refractory power of described polymer beads that is coated with silica gel and transparent resin is 0.01-0.10, and the scattered light transmittance of being expressed by following equation reaches 80% or higher:

The transmittance of scattered light (%)=total light transmittance (%) * turbidity (%) * 0.01

10. scattering of light moulding bodies according to claim 8, wherein, per 100 weight part transparent resins, the combined amount that is coated with the polymer beads of silica gel is the 0.1-20 weight part.

11. method for preparing the polymer beads that is coated with pellosil, this pellosil makes the surface of polymer beads expose with the aperture ratio of 0.1-1, the height h of pellosil and the diameter D that is coated with the polymer beads of silica gel meet following relationship: 0.5≤h/D＜1, this method comprises the following steps: successively

With 100 weight part polymerizable vinyl monomers, 10-500 weight part not with the poly-oxyalkylsiloxane oligopolymer and the 0.01-10 weight part polymerization starter uniform mixing of polymerizable vinyl monomer reaction, obtain monomer composition;

In the presence of suspension stabilizer, make the polymerizable vinyl monomer aqueous suspension polymerization in the monomer composition, obtain polymer beads; And

Add acid or alkaline catalysts, make poly-oxyalkylsiloxane oligomer condensation.

12. preparation according to claim 1 is coated with the method for the polymer beads of silica gel, wherein, the weight-average molecular weight of described poly-oxyalkylsiloxane oligopolymer is 300-3000.

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