CN105461847A - Polymer particles and use thereof - Google Patents

Polymer particles and use thereof Download PDF

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Publication number
CN105461847A
CN105461847A CN201510462986.9A CN201510462986A CN105461847A CN 105461847 A CN105461847 A CN 105461847A CN 201510462986 A CN201510462986 A CN 201510462986A CN 105461847 A CN105461847 A CN 105461847A
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Prior art keywords
polymer beads
weight
filtering material
mentioned
medium
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CN201510462986.9A
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Chinese (zh)
Inventor
高桥智之
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Sekisui Kasei Co Ltd
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Sekisui Plastics Co Ltd
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Priority claimed from JP2015050879A external-priority patent/JP2016069621A/en
Application filed by Sekisui Plastics Co Ltd filed Critical Sekisui Plastics Co Ltd
Priority to CN201910477100.6A priority Critical patent/CN110229267B/en
Publication of CN105461847A publication Critical patent/CN105461847A/en
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Abstract

Provided are: polymer particles having excellent dispersibility and dispersion uniformity; a method for producing the polymer particles; and an optical film produced using the polymer particles. The polymer particles have a coefficient of variation in particle diameter of 15.0% or less, and each of the polymer particles contains a surfactant having a polyoxyethylene chain in an amount of 2.0 to 15.0 10-3 g/m2 per unit surface area thereof and also contains another surfactant in an amount of 10.0 10-5 g/m2 or less per unit surface area thereof.

Description

Polymer beads and uses thereof
Technical field
The present invention relates to the polymer beads being suitable for using as the raw material of the optical components such as light diffusion film, anti-dazzle film and uses thereof (resin combination and optical thin film).More specifically, the present invention relates to the few polymer beads of the adhesion amount of the by product (emulsion polymeric product) produced when polyreaction and uses thereof (resin combination and optical thin film).
Background technology
Volume average particle size is that the polymer beads of 1 ~ 100 μm is for the additive (matting agent etc.) of the coating agents such as such as coating, the additive (matting agent etc.) of ink, the main component of caking agent or additive, the additive (lower shrinkage agent etc.) of artificial marble, paper treatment agent, the packing material (for improving the weighting agent of sliding) of the external preparations such as makeup, the column material used in chromatogram, the additive of the toning agent used in electrostatic image development, the antiblocking agent of film, optical component (light diffusion film, the optical thin films such as anti-dazzle film, light diffusion body etc.) the purposes such as light diffusing agent.
This polymer beads can by making the monomer polymerization of polymerizability to manufacture.As the polymerization process of the monomer polymerization for making polymerizability, there will be a known suspension polymerization, seeding polymerization, letex polymerization etc.These polymerization processs use tensio-active agent stably to carry out polyreaction, to suppress the generation of big particle usually.
Such as, in patent documentation 1, as the resin particle (polymer beads) being used as light diffusing agent, disclose a kind of resin particle, it obtains by making vinyl monomer be polymerized in the medium containing tensio-active agent (for not having other tensio-active agents of polyoxyethylene chain in embodiment), and amount of surfactant residual in this resin particle is below 0.05 weight part (being 0.005 ~ 0.036 weight part in embodiment) relative to resin particle 100 weight part.
In addition, in patent documentation 2, as organic particle compounding in redix composition, disclose a kind of organic particle, it has carried out clean to by the organic particle (polymer beads) that letex polymerization or suspension polymerization obtain, surface attachment has tensio-active agent.
In patent documentation 3, as the colored resin particles being used as developing toner for electrostatic latent images, disclose the colored resin particles taken out from the dispersion liquid of colored resin particles by carrying out cleaning.
Patent Document 4 discloses a kind of electrostatic image developing toner, its Charge controlled resin containing binding resin, tinting material and have specific repeating unit, its residual tensio-active agent (for not having other tensio-active agents of polyoxyethylene chain in embodiment) is 1 ~ 1000ppm.
Patent Document 5 discloses a kind of coating composition, it contains organic granular and tensio-active agent, and the content of aforementioned surfactants is 500 ~ 2000ppm relative to aforementioned organic granular.And then, disclose in the embodiment 5 of patent documentation 5 variation coefficient be 6.2%, containing polyoxyethylene diphenylethyllene phenyl ether sulfate ammonium salt (there is a kind in the tensio-active agent of polyoxyethylene chain) 520 ~ 1550ppm (0.1200%) and not containing the organic granular of tensio-active agent without polyoxyethylene chain.Disclose in the embodiment 2 and 4 of patent documentation 5 variation coefficient be 35.5 ~ 37.1%, containing polyoxyethylene diphenylethyllene phenyl ether sulfate ammonium salt 520 ~ 1550ppm (0.0520 ~ 0.1550%) and not containing the organic granular of tensio-active agent without polyoxyethylene chain.In addition, the organic granular containing polyoxyethylene diphenylethyllene phenyl ether sulfate ammonium salt and Sodium Lauryl Sulphate BP/USP (not there is a kind of the tensio-active agent of polyoxyethylene chain) 1950ppm (0.1950%) by summation meter is disclosed in the embodiment 3 of patent documentation 5.
Patent Document 6 discloses a kind of resin particle, it is by containing at least having NO 2base, SO 3polymerizable monomer is made to carry out suspension polymerization in an aqueous medium and obtain under the existence of the letex polymerization hold back agent of the aromatics of Na base and each more than 1 of secondary amino group.
Patent Document 7 discloses a kind of granular substance of polymkeric substance, it makes with (methyl) acrylic monomer is that the polymerizable monomer (A) of main component carries out water system suspension polymerization under being the existence of the compound (B) of insoluble to aforementioned polymeric monomer and forms being insoluble in fact to water.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-233055 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2007-161830 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2011-158889 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2002-189317 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2009-203378 publication
Patent documentation 6: Japanese Unexamined Patent Publication 7-316209 publication
Patent documentation 7: Japanese Unexamined Patent Publication 10-7730 publication
Summary of the invention
the problem that invention will solve
But, as optical thin films such as light diffusion film, anti-dazzle films, have plenty of by the resin composition containing polymer beads and binding agent on film substrate.
When making this optical thin film, in order to stably obtain uniform optical characteristics by the film formed by above-mentioned resin combination on film substrate, need, by before on resin composition to film substrate, to make polymer beads evenly in advance and be stably dispersed in this resin combination (to be specially in binding agent).
But, even if make to use the polymer beads of tensio-active agent manufacture to be evenly dispersed in the mixture of binding agent and organic solvent disclosed in patent documentation 1 ~ 7 to make resin combination, formed in the process of film by made resin composition on above-mentioned film substrate, the dispersion state of the polymer beads sometimes in this resin combination also can become unstable.
Can think that when using polymer beads disclosed in patent documentation 1 ~ 7, the by products such as the emulsion polymeric product produced when polyreaction can remain in polymer particle surface, polymer particles intergranular in a large number.If the by products such as the emulsion polymeric product produced during polyreaction remain in polymer particle surface, polymer particles intergranular in a large number, then the condition of surface of polymer beads changes, in addition, for the residual quantity of the by product of polymer particle surface, polymer particles intergranular, also be not a certain amount of between different batches, therefore the dispersion state of polymer beads becomes unstable.When the dispersion state of polymer beads becomes instability, polymer beads cannot spread on the whole equably being formed at the film on above-mentioned base material film sometimes, and the optical characteristics of optical thin film becomes uneven, cannot stablize the optical characteristics desired by acquisition.
In addition, at this, " emulsion polymeric product " refers in the seeding polymerization of the polymer beads consistent for the manufacture of particle diameter, is generated, has the polymer beads of obviously little than the particle diameter of target polymerization composition granule particle diameter (particle diameter of such as below 300nm) by the letex polymerization in aqueous phase as side reaction.In seeding polymerization, in order to suppress the generation of by product (emulsion polymeric product), be usually polymerized under the existence of stopper, even if but use stopper to be also difficult to the generation preventing by product (emulsion polymeric product) completely.In addition, by increasing the addition of stopper, the effect of the generation suppressing its by product (emulsion polymeric product) can be improved, but then, the amount of the residual monomer in resulting polymers particle can increase (be 1 weight part more than relative to polymer beads 100 weight part), can affect the quality (such as the xanthochromia etc. of polymer beads self) of polymer beads.
The present invention makes in view of the foregoing, and its object is to provides the polymer beads of dispersion stabilization excellence and use its resin combination and optical thin film.
for the scheme of dealing with problems
Present inventors etc. conduct in-depth research in view of the above problems, found that, the state on the surface of polymer beads can affect dispersiveness and dispersion stabilization, want to improve dispersion stabilization, importantly reduce the amount remaining in the by product (emulsion polymeric product) of polymer particle surface and the amount of by product being present in polymer particles intergranular, thus complete the present invention.
The feature of polymer beads of the present invention is, it contains tensio-active agent, the variation coefficient of particle diameter is less than 15.0%, water 15.0g is added in polymer beads 5.0g, ultrasonic cleaner is used to carry out 60 minutes dispersion treatment thus polymer beads is dispersed in water, load internal diameter 24mm centrifuge tube and after using separating centrifuge to carry out centrifugation under k-factor 6943, the rotational time condition of 30 minutes, when reclaiming supernatant liquor, the concentration of the non-volatile component in supernatant liquor is less than 1.0 % by weight.
When polymer beads of the present invention contains by product (emulsion polymeric product), the non-volatile component in the supernatant liquor obtained by aforesaid method is equivalent to by product (emulsion polymeric product).The variation coefficient of the particle diameter of the polymer beads of such scheme is less than 15.0%, and the concentration of non-volatile component in the supernatant liquor obtained by aforesaid method is suppressed to and is less than 1.0 % by weight, the content of the non-volatile components such as by product (emulsion polymeric product) receives suppression.Therefore, be present in polymer particle surface, polymer particles intergranular the non-volatile component such as by product (emulsion polymeric product) amount polymer particles intergranular, batch between difference little, thus, when used in combination with binding agent, the dispersion stabilization in foregoing adhesives is excellent.In addition, when by making the polymer beads of such scheme disperse in a binder, the resin composition obtained is on film substrate, the homogeneously dispersed state of the polymer beads in this resin combination is basic in the process by aforementioned coating formation film remains stable, and the excessive gathering of polymer beads during aforementioned coating is suppressed.Its result, aforementioned polymeric composition granule does not spread unevenly on film substrate, applies the film entirety formed, can give and not have the uneven optical characteristics such as uniform light diffusing, anti-glare for by aforementioned.
In addition, the polymer beads of such scheme is less than 15.0% due to the variation coefficient of particle diameter, therefore when polymer beads being used for the optical component such as anti-dazzle film, light diffusion film, can improve the optical characteristics such as the anti-glare of optical component, light diffusing.
The feature of resin combination of the present invention is, it contains polymer beads of the present invention.
Resin combination of the present invention contains the polymer beads of the present invention of dispersion stabilization excellence, and therefore dispersion stabilization is excellent.
The feature of optical thin film of the present invention is, it is by the coating resin composition containing polymer beads of the present invention and binding agent on film substrate.
Because optical thin film of the present invention is by the coating resin composition of the polymer beads of the present invention containing dispersion stabilization excellence in base material, therefore applying in the film entirety formed by aforementioned, Absorbable organic halogens obtains does not have the uneven optical characteristics such as uniform light diffusing, anti-glare.
the effect of invention
According to the present invention, the polymer beads that dispersion stabilization excellence can be provided and the resin combination using it and optical thin film.
Accompanying drawing explanation
Fig. 1 is the schematic diagram roughly formed that the pressure filter that can use in embodiments of the present invention is shown, (a) of Fig. 1 is the cross-sectional schematic of aforementioned pressure filter, and (b) of Fig. 1 is the schematic top plan view of the inside of the pressure vessel of aforementioned pressure filter.
Fig. 2 is the figure of SEM (scanning electron microscope) image that the polymer beads obtained in embodiment 1 is shown.
Fig. 3 be the solid-liquid separation process of embodiment 1 and matting are shown after the figure of the SEM image of polymer beads that obtains.
description of reference numerals
1 pressure filter
2 pressure vessels
3 filtering materials
R filtering material and the diameter at interface (de-liquid level) being filtered thing
P crude product
The space, upside of S filtering material
Embodiment
The present invention is described in detail below.
[polymer beads]
Polymer beads of the present invention is the polymer beads containing tensio-active agent (tensio-active agent with polyoxyethylene chain and at least one do not had in the tensio-active agent of polyoxyethylene chain), the variation coefficient of particle diameter is less than 15.0%, water 15.0g is added in polymer beads 5.0g, ultrasonic cleaner is used to carry out 60 minutes dispersion treatment thus polymer beads is dispersed in water, load the centrifuge tube of internal diameter 24mm and use separating centrifuge at k-factor 6943, after carrying out centrifugation under the rotational time condition of 30 minutes, when reclaiming supernatant liquor, the concentration of the non-volatile component in supernatant liquor is less than 1.0 % by weight.
The concentration of the non-volatile component in supernatant liquor is more preferably less than 0.5 % by weight, is preferably less than 0.3 % by weight further.Thus, the difference of the amount of the by product (emulsion polymeric product) being present in polymer beads surface each other etc. can be reduced further, therefore by polymer beads and binding agent used in combination time, the dispersion stabilization of the polymer beads in foregoing adhesives can be improved further.
The variation coefficient of the particle diameter of above-mentioned polymer beads is more preferably less than 12.0%, and more preferably less than 10.0%.Thereby, it is possible to improve the dispersion stabilization of above-mentioned polymer beads further.
The content without the tensio-active agent of polyoxyethylene chain of aforementioned polymer particle units surface-area is preferably 10.0 × 10 -5g/m 2below, 7.0 × 10 are more preferably -5g/m 2below, more preferably 5.0 × 10 -5g/m 2below, 3.0 × 10 most preferably are -5g/m 2below.Thereby, it is possible to improve the dispersion stabilization of above-mentioned polymer beads further.
In addition, the content without the tensio-active agent of polyoxyethylene chain in polymer beads such as can calculate by the following method: by the content without the tensio-active agent of polyoxyethylene chain in the polymer beads using liquid chromatography-mass spectrometry (LC-MS-MS) to record respectively divided by the specific surface area of the polymer beads using BET method (nitrogen adsorption method) to record.
The tensio-active agent contained in polymer beads of the present invention is the residue of the tensio-active agent used in the manufacture of this polymer beads.Therefore, as above-mentioned tensio-active agent, the normally used all surface promoting agent of manufacture of polymer beads can be listed, the anionic surfactant without polyoxyethylene chain, the nonionic surfactant without polyoxyethylene chain such as, recorded in [manufacture method of polymer beads] project described later, not there is the cationic surfactant of polyoxyethylene chain, not there is the double ion tensio-active agent of polyoxyethylene chain.In addition, the tensio-active agent contained in polymer beads of the present invention, preferably containing at least one in anionic surfactant and nonionic surfactant, more preferably contains anionic surfactant.When polymer beads of the present invention contains anionic surfactant, dispersion stabilization during polyreaction can be guaranteed.On the other hand, when the tensio-active agent contained in polymer beads of the present invention is only nonionic surfactant, only there is nonionic surfactant when polyreaction, produce when polyreaction sometimes and significantly assemble.
In addition, the tensio-active agent contained in polymer beads of the present invention preferably containing the anionic surfactant without polyoxyethylene chain and at least one do not had in the nonionic surfactant of polyoxyethylene chain, more preferably contains the anionic surfactant without polyoxyethylene chain.When polymer beads of the present invention contains the anionic surfactant without polyoxyethylene chain, dispersion stabilization during polyreaction can be guaranteed.On the other hand, when the tensio-active agent contained in polymer beads of the present invention is only the nonionic surfactant without polyoxyethylene chain, only there is the nonionic surfactant without polyoxyethylene chain when polyreaction, produce when polyreaction sometimes and significantly assemble.
The polymkeric substance forming polymer beads of the present invention is such as the polymkeric substance of vinyl monomer.As above-mentioned vinyl monomer, monofunctional vinyl's base class monomer with 1 ethylenically unsaturated group and the polyfunctional vinyl class monomer with more than 2 ethylenically unsaturated groups can be listed.
As above-mentioned monofunctional vinyl's base class monomer, include, for example out: (methyl) acrylic ester monomer; Styrene monomer (aromatic vinyl base class monomer); The saturated fatty acid vinyl ester monomers such as vinyl-acetic ester, propionate, tertiary ethylene carbonate; The acrylonitrile monomer such as vinyl cyanide, methacrylonitrile; The ethylenically unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, β-crotonic acid, citraconic acid, methylene-succinic acid, toxilic acid, fumaric acid; The ethylenically unsaturated carboxylic acids acid anhydrides such as maleic anhydride; The ethylenically unsaturated dicarboxylic mono alkyl esters such as monobutyl toxilic acid; The ethylenically unsaturated carboxylic acids salts such as the ammonium salt of above-mentioned ethylenically unsaturated carboxylic acids, ethylenically unsaturated dicarboxylic mono alkyl ester or an alkali metal salt; The ethylenically unsaturated carboxylic acids amidess such as acrylamide, Methacrylamide, diacetone acrylamide; The hydroxymethylate and derivative etc. thereof of the ethylenically unsaturated carboxylic acids amidess such as the etherate (such as N-isobutoxymethyl acrylamide) of the alcohols of N hydroxymethyl acrylamide, N-methylol methacrylamide, methylolation diacetone acrylamide and these monomers and carbon number 1 ~ 8.
As above-mentioned (methyl) acrylic ester monomer, can list: the alkyl-acrylates monomers such as methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, n-octyl, vinylformic acid ester in the different ninth of the ten Heavenly Stems, lauryl acrylate, stearyl acrylate ester; The alkyl methacrylate monomers such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, methacrylic acid-2-ethylhexyl, stearyl methacrylate; Glycidyl acrylate, glycidyl methacrylate etc. have (methyl) acrylate of epoxy group(ing) (glycidyl); 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate etc. (methyl) hydroxyalkyl acrylates; Dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate etc. have amino (methyl) acrylate etc.Above-mentioned (methyl) acrylic ester monomer is preferably containing at least one in alkyl-acrylates monomer and alkyl methacrylate monomer.In addition, in this manual, " (methyl) acrylate " refers to acrylate or methacrylic ester, and " (methyl) vinylformic acid " refers to acrylic or methacrylic acid.
As above-mentioned styrene monomer, can list: vinylbenzene, alpha-methyl styrene, Vinyl toluene, vinyl xylene, ethyl vinyl benzene etc.
As above-mentioned polyfunctional vinyl class monomer, include, for example out: (methyl) allyl acrylate, Vinylstyrene, Phthalic acid, diallyl ester, triallyl cyanurate, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate etc.
Above-mentioned vinyl monomer can be used singly or in combination of two or more.
Above-mentioned polymer beads is preferably made up of at least a kind in (methyl) acrylic polymers, styrenic polymer and (methyl) acrylicstyrene analog copolymer.Thereby, it is possible to realize the high polymer beads of light transmission.Above-mentioned (methyl) acrylic polymers is the polymkeric substance of (methyl) acrylic ester monomer, or the multipolymer of (methyl) acrylic ester monomer and the vinyl monomer except (methyl) acrylic ester monomer and styrene monomer.Above-mentioned styrenic polymer is the polymkeric substance of styrene monomer, or the multipolymer of styrene monomer and the vinyl monomer except (methyl) acrylic ester monomer and styrene monomer.In addition, above-mentioned (methyl) acrylicstyrene analog copolymer is the multipolymer of (methyl) acrylic ester monomer and styrene monomer, or the multipolymer of (methyl) acrylic ester monomer, styrene monomer and the vinyl monomer except (methyl) acrylic ester monomer and styrene monomer.From the angle of light diffusing and anti-glare, in the middle of these, above-mentioned polymer beads is preferably made up of (methyl) acrylicstyrene analog copolymer.
The polymkeric substance forming above-mentioned polymer beads is preferably the multipolymer (cross-linked polymer) of above-mentioned monofunctional vinyl's base class monomer and above-mentioned polyfunctional vinyl class monomer.Therefore, from the angle of light diffusing and anti-glare, the polymkeric substance forming above-mentioned polymer beads is particularly preferably (methyl) acrylicstyrene class cross-linking copolymer.Such as, relative to above-mentioned polymkeric substance 100 % by weight, the amount deriving from the Component units of above-mentioned polyfunctional vinyl class monomer in above-mentioned polymkeric substance is preferably in the scope of 5 ~ 50 % by weight.When the amount deriving from the Component units of above-mentioned polyfunctional vinyl class monomer is lower than above-mentioned scope, the degree of crosslinking of above-mentioned polymkeric substance reduces.As a result, polymer beads is mixed with binding agent apply as resin combination time, have that the viscosity that swelling, resin combination occurs polymer beads rises, the anxiety of the workability reduction of coating.And then, the result of the degree of crosslinking reduction of above-mentioned polymkeric substance, polymer beads is mixed with binding agent carry out mix in shaping purposes (so-called mixing purposes) time, shaping time make polymer beads heat time, polymer beads becomes easily fusing or is out of shape.When the amount deriving from the Component units of above-mentioned polyfunctional vinyl class monomer is higher than above-mentioned scope, sometimes confirm to improve less than the effect corresponding to the consumption of above-mentioned polyfunctional vinyl class monomer, production cost can rise.
The gel fraction of polymer beads of the present invention is preferably more than 90%, is more preferably more than 97%.When gel fraction is less than 90%; sufficient solvent resistance cannot be guaranteed; therefore such as when polymer beads is mixed with organic solvent together with binding agent and be coated in film substrate makes the optical thin film such as anti-dazzle film, light diffusion film, there is polymer beads and can be dissolved in organic solvent, fully cannot obtain the anxiety of the optical characteristics such as light diffusing, anti-glare.In addition, in this manual, gel fraction refers to such as by gel fraction that the method recorded in embodiment project records.
The specific refractory power of polymer beads of the present invention is preferably 1.490 ~ 1.600.Thus, the polymer beads of such scheme, when for optical components such as anti-dazzle film, light diffusion films, can realize the optical component with good optical characteristics (such as light transmission, anti-glare, light diffusing etc.).In addition, for the polymer beads passing through to manufacture to the high monomer of monomer (such as styrene monomer) the middle interpolation wetting ability that the specific refractory power of homopolymer is high, due to the specific refractory power low (such as less than 1.488) of the usual homopolymer of monomer that wetting ability is high, therefore high with not adding wetting ability monomer and the polymer beads phase specific refractivity manufactured is lower.Therefore, the polymer beads of this scheme is difficult to realize the polymer beads that specific refractory power is 1.570 ~ 1.600.On the other hand, polymer beads of the present invention is not owing to needing to add the high monomer of wetting ability, therefore, it is possible to easily realize the polymer beads that specific refractory power is 1.570 ~ 1.600.
In addition, the volume average particle size of above-mentioned polymer beads is preferably 0.5 ~ 100 μm, more preferably in the scope of 1 ~ 30 μm.Thus, when polymer beads being used for the optical component such as anti-dazzle film, light diffusion film, the optical characteristics such as the anti-glare of optical component, light diffusing can be improved.In addition, in this manual, the volume average particle size of polymer beads refers to the arithmetical av of the size-grade distribution of the volume reference that the method by recording in Ku Ertefa, such as embodiment project records.
In addition, the levels of residual monomers of above-mentioned polymer beads is preferably less than 1.0 % by weight, is more preferably less than 0.5 % by weight, and more preferably less than 0.2 % by weight.Thus, when using above-mentioned polymer beads to manufacture the products such as optical thin film, residual monomer can be avoided to make, and product is painted, the physical property of reduction product, or residual monomer generation foul smell makes operating environment be deteriorated.
Polymer beads of the present invention is preferably not containing the transparent grain of dyestuff, pigment (pigment dyestuff, mineral dye).Time in polymer beads containing dyestuff, pigment, the transparency of polymer beads can reduce, when using polymer beads of the present invention to make optical thin film, detrimentally affect can be produced to the transmissivity of made optical thin film, anti-glare and diffusion, thus not preferred.
Above-mentioned polymer beads obtains preferably by making seed grain absorption vinyl monomer carry out being polymerized (namely carrying out seeding polymerization) under the existence of tensio-active agent.The polymer beads obtained by seeding polymerization is little due to the deviation of particle diameter, therefore when for optical components such as anti-dazzle film, light diffusion films, can improve the optical characteristics such as the anti-glare of optical component, light diffusing.
[manufacture method of polymer beads]
Polymer beads of the present invention can be manufactured by following manufacture method.
This manufacture method comprises following operation: polymerization process, in the medium of liquid state, under the existence of tensio-active agent, vinyl monomer is polymerized, and obtains the crude product containing the polymer beads and aforementioned medium comprising aforementioned surfactants; Solid-liquid separation process, aforementioned crude product is dropped in strainer, make the medium contained in added aforementioned crude product by the filtering material of aforementioned filter on the one hand, make the polymer beads contained in aforementioned crude product remain on foregoing filtration material on the other hand; Matting, scavenging solution is added in the aforementioned filter remained on by aforementioned polymeric composition granule on foregoing filtration material, make aforementioned scavenging solution and aforementioned polymer particle contacts, make the aforementioned scavenging solution crossed with aforementioned polymer particle contacts by foregoing filtration material, on foregoing filtration material, obtain the polymer beads cleaned through aforementioned scavenging solution thus.This manufacture method is suitable for the method as manufacturing aforementioned polymer beads of the present invention.
Below each operation of this manufacture method is described in detail.
[polymerization process]
In polymerization process, in the medium of liquid state, under the existence of tensio-active agent, vinyl monomer is polymerized, obtains the crude product containing the polymer beads and aforementioned medium comprising aforementioned surfactants.
As the medium (medium contained in crude product) of liquid state, preferred aqueous medium, include, for example out: water; The lower alcohol such as methyl alcohol, ethanol (alcohol of carbon number less than 5); The mixture etc. of water and lower alcohol.
In addition, in above-mentioned polymerization process, above-mentioned tensio-active agent makes the decentralized stabilization of vinyl monomer in the medium of liquid state.As above-mentioned tensio-active agent, the tensio-active agent with polyoxyethylene chain and at least one do not had in the tensio-active agent of polyoxyethylene chain can be used.
As the above-mentioned tensio-active agent with polyoxyethylene chain, the anionic surfactant with polyoxyethylene chain can be used, there is the cationic surfactant of polyoxyethylene chain, the nonionic surfactant with polyoxyethylene chain and there is polyoxyethylene chain double ion tensio-active agent in any number of, in above-mentioned polymerization process, from can guaranteeing that the dispersion of vinyl monomer in the medium of liquid state is more stable and the aspect of the consistent polymer beads of particle diameter can being obtained, the anionic surfactant that preferred use has polyoxyethylene chain and at least one had in the nonionic surfactant of polyoxyethylene chain.As the above-mentioned tensio-active agent with polyoxyethylene chain, more preferably at least use the anionic surfactant with polyoxyethylene chain.Thereby, it is possible to dispersion stabilization when guaranteeing polyreaction.On the other hand, as the above-mentioned tensio-active agent with polyoxyethylene chain, when only use has the nonionic surfactant of polyoxyethylene chain, occur when polyreaction sometimes significantly to assemble.
As the above-mentioned anionic surfactant with polyoxyethylene chain, what can use in the known anionic surfactants such as lipid acid salt form, sulfuric ester salt form, sulfonate type, phosphoric acid ester salt form, phosphate type is any number of, include, for example out: polyoxyethylene alkyl phenyl ether sulfuric acid; The polyoxyethylene alkyl ether sulfate salts such as sodium laureth sulfate; Polyoxyethylene alkyl sulfate; The polyoxyethylene styrene phenyl ether sulfuric acids such as polyoxyethylene styrene phenyl ether sulfuric ester ammonium; The polyoxyethylene alkyl phenyl ether phosphoric acid salt such as ethylene nonyl phenyl ether phosphoric acid salt (such as ethylene nonyl phenyl ether sodium phosphate); Polyoxyethylene styrene phenyl ether phosphoric acid ester; Voranol EP 2001 phosphoric acid ester etc.These anionic surfactants with polyoxyethylene chain can be used singly or in combination of two or more.
As the above-mentioned nonionic surfactant with polyoxyethylene chain, what can use in the known nonionic surfactants such as ester type, ether type, ester-ether type is any number of, include, for example out: the polyoxyethylene sorbitan carboxylic esters such as the polyoxyethylene alkyl phenyl ethers such as Voranol EP 2001, polyoxyethylene octyl phenyl ether such as polyoxyethylene tridecyl ether, polyoxyethylene styrene phenyl ether, polyoxyethylene fatty acid ester, Tween-20, polyoxyethylene alkyl amine, epoxy ethane-epoxy propane block polymer etc.These nonionic surfactants with polyoxyethylene chain can be used singly or in combination of two or more.
The above-mentioned tensio-active agent with polyoxyethylene chain can be used singly or in combination of two or more.As the above-mentioned tensio-active agent with polyoxyethylene chain, be preferably 0.3g/100ml ~ 5.0g/100ml to the solubleness of the water of liquid temperature 25 DEG C, be more preferably 0.5g/100ml ~ 3.0g/100ml.If use above-mentioned solubleness to be less than the tensio-active agent with polyoxyethylene chain of 0.3g/100ml, then in above-mentioned polymerization process, when the medium of above-mentioned liquid state is aqueous medium, there is the vinyl monomer not anxiety of stable dispersion in this aqueous medium, and because this tensio-active agent is insoluble in water, therefore in the aftermentioned matting of cleaning cleaning polyalcohol particle, a large amount of scavenging solutions is needed, not preferred in productivity.On the other hand, above-mentioned solubleness more than the tensio-active agent with polyoxyethylene chain of 5.0g/100ml owing to lacking the effect of hydrophobic grouping, lack the effect making the decentralized stabilization of vinyl monomer in an aqueous medium, if therefore use this to have the tensio-active agent of polyoxyethylene chain, then in above-mentioned polymerization process, when the medium of above-mentioned liquid state is aqueous medium, in order to make the decentralized stabilization of vinyl monomer in this aqueous medium, need a large amount of tensio-active agents with polyoxyethylene chain, not preferred in productivity.
As the above-mentioned tensio-active agent without polyoxyethylene chain, the anionic surfactant without polyoxyethylene chain can be used, not there is the cationic surfactant of polyoxyethylene chain, the nonionic surfactant without polyoxyethylene chain and do not have in the double ion tensio-active agent of polyoxyethylene chain any one, and from above-mentioned polymerization process, can guarantee that the dispersion of vinyl monomer in the medium of liquid state is more stable and can obtain the consistent polymer beads of particle diameter in set out, the anionic surfactant that preferred use does not have polyoxyethylene chain and at least one do not had in the nonionic surfactant of polyoxyethylene chain.As above-mentioned tensio-active agent, more preferably at least use anionic surfactant.Thereby, it is possible to dispersion stabilization when guaranteeing polyreaction.On the other hand, when only using nonionic surfactant as above-mentioned tensio-active agent, occur when polyreaction sometimes significantly to assemble.
As the above-mentioned anionic surfactant without polyoxyethylene chain, what can use in the known anionic surfactants such as lipid acid salt form, sulfuric ester salt form, sulfonate type, phosphoric acid ester salt form is any number of, include, for example out: the fatty acid soaps such as sodium oleate, Viscotrol C potash soap; The alkyl sulfuric ester salt such as lauryl sulfate (such as Sodium Lauryl Sulphate BP/USP, Texapon Special etc.); The alkylbenzene sulfonates such as Sodium dodecylbenzene sulfonate; The dialkyl sulfosuccinates such as sulfonated alkyl naphathalene, sulfonated alkane, two (2-ethylhexyl) sulfosuccinate (sodium salt), dioctyl sulfosuccinate (sodium salt); Alkenyl succinic salt (di-potassium); Alkyl phosphate salt; Naphthalene sulfonic acidformaldehyde condensation product etc.These anionic surfactants without polyoxyethylene chain can be used singly or in combination of two or more.
As the above-mentioned nonionic surfactant without polyoxyethylene chain, what can use in the known nonionic surfactants such as ester type, ether type, ester-ether type is any number of, include, for example out: the carbon number of alkylidene group is polyoxyalkylene alkyl ether, sorbitan carboxylic esters, the glycerol fatty acid esters etc. such as the polyoxy alkylidene tridecyl ether of more than 3.These nonionic surfactants without polyoxyethylene chain can be used singly or in combination of two or more.
As the above-mentioned cationic surfactant without polyoxyethylene chain, what can use in the known cationic surfactants such as amine salt type, quaternary is any number of, and water miscible cationic surfactant is favourable in its process.As the above-mentioned object lesson without the cationic surfactant of polyoxyethylene chain, can list: the alkylamine salts such as lauryl amine acetic ester, stearic amine acetic ester; The alkyl trimethyl ammonium chlorides such as lauryl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, cocoyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride; The alkyldimethylbenzylammonium such as cetalkonium chloride, lauryl dimethyl benzyl ammonium chloride muriate etc.These cationic surfactants without polyoxyethylene chain can be used singly or in combination of two or more.
As the above-mentioned double ion tensio-active agent without polyoxyethylene chain, lauryl dimethyl amine oxide, phosphate ester surfactant, phosphorous acid esters tensio-active agent etc. can be listed.These double ion tensio-active agents without polyoxyethylene chain can be used singly or in combination of two or more.
The above-mentioned tensio-active agent without polyoxyethylene chain can be used singly or in combination of two or more.As the above-mentioned tensio-active agent without polyoxyethylene chain, be preferably more than 0.3g/100ml ~ 15.0g/100ml to the solubleness of the water of liquid temperature 25 DEG C, be more preferably 0.5g/100ml ~ 5.0g/100ml.If use above-mentioned solubleness to be less than the tensio-active agent without polyoxyethylene chain of 0.3g/100ml, then in above-mentioned polymerization process, when the medium of above-mentioned liquid state is aqueous medium, there is the vinyl monomer not anxiety of stable dispersion in this aqueous medium, and because this tensio-active agent is insoluble in water, therefore in the aftermentioned matting of cleaning cleaning polyalcohol particle, a large amount of scavenging solutions is needed, not preferred in productivity.On the other hand, above-mentioned solubleness more than the tensio-active agent without polyoxyethylene chain of 15.0g/100ml owing to lacking the effect of hydrophobic grouping, lack the effect making the decentralized stabilization of vinyl monomer in an aqueous medium, if therefore use this not have the tensio-active agent of polyoxyethylene chain, then in above-mentioned polymerization process, when the medium of above-mentioned liquid state is aqueous medium, in order to make the decentralized stabilization of vinyl monomer in this aqueous medium, need a large amount of tensio-active agents without polyoxyethylene chain, not preferred in productivity.
Consumption for the tensio-active agent in the polymerization of above-mentioned vinyl monomer (is the consumption of the anionic surfactant without polyoxyethylene chain when only using the anionic surfactant without polyoxyethylene chain as tensio-active agent, when using the anionic surfactant without polyoxyethylene chain as tensio-active agent and not there is the tensio-active agent of polyoxyethylene chain for not there is the consumption of the anionic surfactant of polyoxyethylene chain and not there is the summation of consumption of tensio-active agent of polyoxyethylene chain), relative to consumption 100 weight part of vinyl monomer, preferably in the scope of 0.01 ~ 5 weight part.When the consumption of tensio-active agent is lower than above-mentioned scope, there is the anxiety of polymerization stability reduction.In addition, when the consumption of tensio-active agent is higher than above-mentioned scope, uneconomical on cost.
As the polymerization process of vinyl monomer, as long as use the known polymerization process of liquid medium and tensio-active agent to be just not particularly limited, include, for example out the methods such as seeding polymerization, letex polymerization, suspension polymerization.In the middle of these polymerization processs, the minimum and most preferably seeding polymerization of the deviation due to the particle diameter of resulting polymers particle.
Above-mentioned emulsion polymerization refers to and the medium of liquid state, the vinyl monomer being insoluble in this medium and tensio-active agent (emulsifying agent) is mixed, and adds the polymerization process that the polymerization starter that can be dissolved in medium carries out being polymerized wherein.Above-mentioned emulsion polymerization has the little feature of the deviation of the particle diameter of resulting polymers particle.Above-mentioned suspension polymerization refers to carries out mechanical stirring to the aqueous medium such as vinyl monomer and water, makes vinyl monomer suspension carry out the polymerization process be polymerized in an aqueous medium.Above-mentioned suspension polymerization has can obtain the little and feature of the polymer beads that particle diameter ratio is more regular of particle diameter.
Above-mentioned seeding polymerization adds the method that seed (seed) particle comprising the polymkeric substance of vinyl monomer made separately carries out being polymerized.More specifically, above-mentioned seeding polymerization uses the polymer beads comprising the polymkeric substance of vinyl monomer as seed grain, makes above-mentioned seed grain absorb vinyl monomer in an aqueous medium, make the method that vinyl monomer is polymerized in seed grain.The method, by making seed particles grow, can obtain the polymer beads that the original seed grain of particle diameter ratio is large.As mentioned above, as the polymerization process of vinyl monomer, most preferably seeding polymerization, therefore, in this manufacture method, above-mentioned polymerization process is preferably included in liquid medium, under the existence of seed grain and tensio-active agent, make vinyl monomer carry out seeding polymerization, obtains the step of the crude product containing the polymer beads and aforementioned medium comprising aforementioned surfactants.
The following describes the ordinary method of seeding polymerization, but polymerization process is not limited to the method.
In seeding polymerization, first in the emulsion (suspension liquid) containing vinyl monomer, aqueous medium and tensio-active agent, add seed grain.Above-mentioned emulsion can be prepared by known method.Such as, by vinyl monomer and tensio-active agent are added in aqueous medium, utilize the micro-emulsifying machines such as homogenizer, ultrasonic processor, Nanomizer (registered trademark) to disperse, thus can emulsion be obtained.As above-mentioned aqueous medium, the mixture of water or water and organic solvent (such as lower alcohol (alcohol of carbon number less than 5)) can be used.
The consumption of the tensio-active agent in above-mentioned seeding polymerization relative to vinyl monomer 100 weight part preferably in the scope of 0.01 ~ 5 weight part.When the consumption of tensio-active agent is lower than above-mentioned scope, there is the anxiety of polymerization stability reduction.In addition, when the consumption of tensio-active agent is higher than above-mentioned scope, uneconomical on cost.
Seed grain can directly add in emulsion, also can add in emulsion with dispersion form in an aqueous medium.Added to by seed grain after in emulsion, vinyl monomer is absorbed by seed grain.This absorption can be carried out by being stirred under room temperature (about 20 DEG C) by emulsion usually for 1 ~ 12 hour.In addition, in order to promote that vinyl monomer is absorbed by seed grain, emulsion can be heated to about 30 ~ 50 DEG C.
Seed grain occurs swelling because absorbing vinyl monomer.About the mixture ratio of vinyl monomer and seed grain, relative to seed grain 1 weight part, vinyl monomer preferably in the scope of 5 ~ 300 weight parts, more preferably in the scope of 50 ~ 250 weight parts.When the mixture ratio of vinyl monomer is lower than above-mentioned scope, reduced by the increase being polymerized the particle diameter brought, therefore manufacture efficiency and reduce.On the other hand, when the mixture ratio of vinyl monomer is higher than above-mentioned scope, vinyl monomer is not absorbed by seed grain completely, carries out suspension polymerization alone in an aqueous medium, generates the polymer beads of the abnormal particle diameter beyond target sometimes.In addition, with microscopical observation of optics, vinyl monomer can by confirming that the expansion of particle diameter judges by the end that seed grain absorbs.
Then, by making the vinyl monomer by seed grain absorbs be polymerized, polymer beads can be obtained.In addition, also polymer beads can be obtained by the operation repeating to make seed grain absorption vinyl monomer also be polymerized for several times.
In above-mentioned vinyl monomer, polymerization starter can be added as required.For above-mentioned polymerization starter, after above-mentioned polymerization starter can being mixed with vinyl monomer, make the dispersion of obtained mixture in an aqueous medium, also the dispersion making polymerization starter and both vinyl monomers be distributed to respectively to obtain in aqueous medium can be mixed.About the particle diameter of the drop of the vinyl monomer existed in gained emulsion, when being less than the particle diameter of seed grain, vinyl monomer is efficiently absorbed by seed grain, therefore preferably.
As above-mentioned polymerization starter, be not particularly limited, include, for example out: benzoyl peroxide, lauroyl peroxide, adjacent chlorobenzoyl peroxide, O-methoxy benzoyl peroxide, peroxidation 3, the organo-peroxides such as 5,5-trimethyl acetyl, peroxide-2-ethyl hexanoic acid tert-butyl, ditertiary butyl peroxide, 2, 2 '-Diisopropyl azodicarboxylate, 2, 2 '-azo two (2, 4-methyl pentane nitrile), 2, 2 '-azo two (2, 3-nitrile dimethyl), 2, 2 '-azo two (2-methylbutyronitrile), 2, 2 '-azo two (2, 3, 3-trimethylbutyronitrile), 2, 2 '-azo two (2-isopropyl butyronitrile), 1, 1 '-azo two (hexanaphthene-1-nitrile), 2, two (the 4-methoxyl group-2 of 2 '-azo, 4-methyl pentane nitrile), (2-formamyl azo) isopropyl cyanide, 4, 4 '-azo two (4-cyanopentanoic acid), dimethyl-2, the azo-compounds etc. such as 2 '-azobisisobutylonitrile acid esters.Above-mentioned polymerization starter preferably uses relative to vinyl monomer 100 weight part in the scope of 0.1 ~ 1.0 weight part.
The polymerization temperature of above-mentioned seeding polymerization can according to the kind of vinyl monomer, optionally and the kind of the polymerization starter used suitably is selected.The polymerization temperature of above-mentioned seeding polymerization is specifically preferably 25 ~ 110 DEG C, is more preferably 50 ~ 100 DEG C.In addition, the polymerization time of above-mentioned seeding polymerization is preferably 1 ~ 12 hour.The polyreaction of above-mentioned seeding polymerization can be polymerized to inertia non-active gas (such as nitrogen) atmosphere under carry out.In addition, the polyreaction of above-mentioned seeding polymerization preferably vinyl monomer and optionally and use polymerization starter completely by seed grain absorb after heat up carry out.
In above-mentioned seeding polymerization, in order to improve the dispersion stabilization of polymer beads, macromolecular dispersion stabilizer can be added in polymerization reaction system.As above-mentioned macromolecular dispersion stabilizer, include, for example out: polyvinyl alcohol, poly carboxylic acid, cellulose family (Natvosol, carboxymethyl cellulose etc.), polyvinylpyrrolidone etc.In addition, the mineral-type water-soluble high-molecular compounds such as above-mentioned macromolecular dispersion stabilizer and tripoly phosphate sodium STPP can be combinationally used.In the middle of these macromolecular dispersion stabilizers, preferably polyethylene alcohol and polyvinylpyrrolidone.The addition of above-mentioned macromolecular dispersion stabilizer relative to vinyl monomer 100 weight part preferably in the scope of 1 ~ 10 weight part.
In addition, in order to suppress in above-mentioned polyreaction the generation of emulsion polymeric product (polymer beads that particle diameter is too small) in an aqueous medium, the water miscible stoppers such as the nitrites such as Sodium Nitrite, sulfites, hydroquinones, vitamin c class, water-soluble (vitamin) B class, citric acid, Polyphenols can be added in aqueous medium.The addition of above-mentioned stopper relative to vinyl monomer 100 weight part preferably in the scope of 0.02 ~ 0.2 weight part.
In addition, being not particularly limited for for making vinyl monomer be polymerized the polymerization process obtaining seed grain, dispersion polymerization, letex polymerization, emulsifier-free emulsion polymerization (not being used as the letex polymerization of the tensio-active agent of emulsifying agent), seeding polymerization, suspension polymerization etc. can be used.In order to be obtained the roughly uniform polymer beads of particle diameter by seeding polymerization, need to use the roughly uniform seed grain of particle diameter initial, these seed grains are grown roughly in the same way.The roughly uniform seed grain of particle diameter as raw material can carry out being polymerized manufacturing with polymerization processs such as emulsifier-free emulsion polymerization (not using the letex polymerization of tensio-active agent) and dispersion polymerizations by making vinyl monomer.Therefore, as the polymerization process for making vinyl monomer polymerization obtain seed grain, preferred emulsion polymerization, emulsifier-free emulsion polymerization, seeding polymerization and dispersion polymerization.
For obtaining in the polymerization of seed grain, also polymerization starter can be used as required.As aforementioned polymeric initiator, include, for example out: the persulfuric acid salts such as Potassium Persulphate, ammonium persulphate, Sodium Persulfate; The organo-peroxide such as benzoyl peroxide, lauroyl peroxide, adjacent chlorobenzoyl peroxide, O-methoxy benzoyl peroxide, peroxidation 3,5,5-trimethyl acetyl, peroxide-2-ethyl hexanoic acid tert-butyl, ditertiary butyl peroxide; 2,2 '-Diisopropyl azodicarboxylate, 1,1 '-azo bis cyclohexane nitrile, 2, the azo compounds etc. such as 2 '-azo two (2,4-methyl pentane nitrile).Relative in order to obtain vinyl monomer 100 weight part that seed grain uses, the consumption of above-mentioned polymerization starter is preferably in the scope of 0.1 ~ 3 weight part.By the increase and decrease of the consumption of above-mentioned polymerization starter, the weight-average molecular weight of gained seed grain can be adjusted.
For obtaining in the polymerization of seed grain, molecular weight regulator can be used in order to adjust the weight-average molecular weight of gained seed grain.As aforementioned molecular weight conditioning agent, the thio-alcohol such as n octylmercaptan, tertiary lauryl mercaptan can be used; Alpha-methyl styrene dimer; γ-terpenes such as terpinene, limonene; The halogenated hydrocarbons such as chloroform, tetracol phenixin etc.By the increase and decrease of the consumption of above-mentioned molecular weight regulator, the weight-average molecular weight of gained seed grain can be adjusted.
[solid-liquid separation process]
In solid-liquid separation process, in strainer, add aforementioned crude product, make the medium that contains in added aforementioned crude product by the filtering material of aforementioned filter, and the polymer beads contained in aforementioned crude product is remained on foregoing filtration material.
In above-mentioned solid-liquid separation process, the unit time meets following conditional (1) by the amount of the aforementioned medium of foregoing filtration material:
X≤5.50×A···(1)
(in formula (1), the X representation unit time, A represented filtering material and the area (m at interface being filtered thing by the amount (kg/min) of the aforementioned medium of foregoing filtration material 2)).
In above-mentioned solid-liquid separation process, above-mentioned conditional (1) is met by the amount of the aforementioned medium of foregoing filtration material by controlling the unit time, can to remove together with medium and to contain in crude product, the by product (emulsion polymeric product) produced in the polymerization, the optionally tensio-active agent without polyoxyethylene chain used, the optionally macromolecular dispersion stabilizer used, optionally and use polymeric additives (such as stopper) etc. do not need composition, can to reduce in the polymer beads remained on filtering material above-mentioned does not need the residual quantity of composition (being specially the adhesion amount on the surface at polymer beads).
In above-mentioned solid-liquid separation process, be not particularly limited as aforementioned filter, include, for example out as shown in Figure 1, possess the pressure vessel 2 with columned internal space, the inner bottom part being configured in this pressure vessel 2 filtering material 3 and pressurized gas (non-active gas, the air etc. such as nitrogen) is supplied to the pressure filter 1 of the pressurized gas supplying machine (not shown) in pressure vessel.In pressure filter 1 shown in Fig. 1, the area ((b) see Fig. 1) of the bottom surface of the columned internal space of pressure vessel 2 is roughly the same with the area at the interface being filtered thing (crude product P) with filtering material 3.
Use in the solid-liquid separation process of above-mentioned pressure filter 1, such as, crude product P is added with the form of pulp solution in the pressure vessel 2 of pressure filter 1, crude product P being filled by filtering material 3 in pressure vessel 2, pressurizeing to the upside space S of upside space S supplying compressed gas to the filtering material 3 in the inside of pressure vessel 2 of the filtering material 3 in pressure vessel 2 by utilizing pressurized gas supplying machine.Thus, crude product P is pressed to filtering material 3, make the medium of liquid state contained in crude product P by filtering material 3, the medium of this liquid state is discharged to as filtrate outside pressure vessel 2.Further, the filter cake of polymer beads remains on filtering material 3.
As aforementioned pressure vessel 2, such as, be preferably stainless steel and possess the resistance to pressure of more than 0.50MPa.
As filtering material 3, be just not particularly limited as long as can positively trap polymer beads, include, for example out: the filter clothes such as the fabric formed by natural fiber, synthon etc., non-woven fabrics; The wire netting formed by sintering metal; The non-woven fabrics formed by sintering metal; The screen plate (porous plate) formed by natural fiber, glass fibre etc.; The net formed by synthetic resins; Filter paper; Glass fibre filter etc., preferred filter cloth.
In above-mentioned solid-liquid separation process, as long as pressurized conditions when using the upside space S of the filtering material 3 in pressure filter 1 pair of pressure vessel 2 to pressurize meets the pressure of above-mentioned conditional (1), just be not particularly limited, preferably to make the mode be pressed in the scope of 0.01MPa ~ 0.50MPa in pressure vessel 2 pressurize.In addition, in solid separation circuit, the interior pressure of pressure vessel 2 preferably remains substantially certain in the mode meeting above-mentioned conditional (1) from pressurization to solid-liquid separation process terminates, but the interior pressure of pressure vessel 2 after the pressurizing, along with the medium contained in crude product P is by filtering material 3, the pressure in pressure vessel 2 can slowly reduce.Specifically, to be reduced by the medium of filtering material 3 or when almost not having, the compressed air pressure in pressure vessel 2 can spill from bottom, be difficult to pressure when pressure is maintained pressurization in pressure vessel 2, can lower than pressure during aforementioned pressurization.
In addition, in above-mentioned solid-liquid separation process, relative to the amount (being the amount of the medium used in polymerization process when all crude products obtained in polymerization process are added in strainer) 100 % by weight of the medium contained in the crude product P added in strainer (pressure filter 1), preferably make the medium of the amount of more than 70 % by weight by filtering material 3, remove the medium contained in crude product P.In above-mentioned solid-liquid separation process, relative to the amount 100 % by weight of the medium contained in the crude product P added in strainer (pressure filter 1), by making the medium of amount of more than 70 % by weight by filtering material 3, fully can remove together with medium and remain on filtering material 3 accompanying by polymer particle surface, the by product (emulsion polymeric product) produced in the polymerization, the optionally tensio-active agent without polyoxyethylene chain used, the optionally macromolecular dispersion stabilizer used, optionally and use polymeric additives (such as stopper) etc. do not need composition, the above-mentioned residual quantity not needing composition in polymer beads can be reduced.When being less than 70 % by weight by the amount (output) of the medium of filtering material 3 relative to the amount 100 % by weight of the medium contained in crude product P in above-mentioned solid-liquid separation process, there is by product (emulsion polymeric product), the optionally tensio-active agent without polyoxyethylene chain used, the optionally macromolecular dispersion stabilizer used, the optionally anxiety that the polymeric additives (such as stopper) etc. used does not need into point that fully cannot remove and produce in polyreaction.
Such as, in above-mentioned solid-liquid separation process, as strainer, when using pressure filter 1, this solid-liquid separation process preferably terminates in the following moment: relative to the amount (being the amount of the medium used in polymerization process when being added in pressure filter 1 by all crude product P obtained in polymerization process) 100 % by weight of the medium contained in the crude product P added in pressure filter 1, the medium of the amount of more than 70 % by weight by filtering material 3, and less than 2/3 of pressure when the interior pressure of pressure vessel 2 reaches pressurization.Thereby, it is possible to positively reduce the by product (emulsion polymeric product) produced in the polymerization in the polymer beads remaining on filtering material 3, the optionally tensio-active agent without polyoxyethylene chain used, the optionally macromolecular dispersion stabilizer used, optionally and the polymeric additives (such as stopper) etc. used does not need the residual quantity of composition.
[matting]
In matting, scavenging solution is added in the aforementioned filter remained on by aforementioned polymeric composition granule on foregoing filtration material, make aforementioned scavenging solution and aforementioned polymer particle contacts, make the aforementioned scavenging solution crossed with aforementioned polymer particle contacts by foregoing filtration material, on foregoing filtration material, obtain the polymer beads cleaned through aforementioned scavenging solution thus.
In aforementioned matting, the unit time meets following conditional (2) by the amount of the aforementioned scavenging solution of foregoing filtration material:
2.50×A≤Y≤8.50×A···(2)
(in formula (2), the Y representation unit time, A represented filtering material and the area (m at interface being filtered thing by the amount (kg/min) of the aforementioned scavenging solution of foregoing filtration material 2).)。Unit time, when being less than 2.50 × A by the amount Y of the aforementioned scavenging solution of foregoing filtration material, matting can too expend time in, and there is the anxiety of productivity reduction.Unit time by the amount Y of the aforementioned scavenging solution of foregoing filtration material more than 8.50 × A time, the time that polymer beads contacts with scavenging solution is short, therefore the adhering on surface fully cannot removing polymer beads, the by product (emulsion polymeric product) produced in the polymerization, the optionally tensio-active agent without polyoxyethylene chain used, the optionally macromolecular dispersion stabilizer used, optionally and use polymeric additives (such as stopper) etc. do not need composition, there is the worry on the above-mentioned polymer beads not needing composition to remain in a large number finally to obtain.
In addition, unit time in aforementioned matting passes through the amount of the aforementioned scavenging solution of foregoing filtration material preferably, from the cleaning of the aforementioned polymeric composition granule by making aforementioned scavenging solution be undertaken by filtering material to end, on average meet following conditional (3):
2.50×A≤Y≤8.50×A···(3)
(in formula (3), the Y representation unit time, A represented filtering material and the area (m at interface being filtered thing by the amount (kg/min) of the aforementioned scavenging solution of foregoing filtration material 2).)。Unit time in aforementioned matting is when on average meeting above-mentioned conditional (3) by the amount of the aforementioned scavenging solution of foregoing filtration material, the adhering on surface fully can removing polymer beads efficiently, the by product (emulsion polymeric product) produced in the polymerization, the optionally tensio-active agent without polyoxyethylene chain used, the optionally macromolecular dispersion stabilizer used, optionally and use polymeric additives (such as stopper) etc. do not need composition, reduce the above-mentioned residual quantity not needing composition in the polymer beads finally obtained.
Such as, when using pressure filter 1 as shown in Figure 1 in above-mentioned solid-liquid separation process, under the state that the filter cake former state of the polymer beads remained on filtering material 3 is remained on filtering material 3, by cleaning solution supplying in pressure vessel 2, aforementioned filter cake is made to contact with scavenging solution thus, utilize pressurized gas supplying machine to the upside space S supplying compressed gas of the filtering material 3 in pressure vessel 2, thus the upside space S of filtering material 3 is pressurizeed.Thus, aforementioned filter cake contacts with scavenging solution and is cleaned, and then, the scavenging solution after cleaning is discharged to outside pressure vessel 2 as filtrate.It should be noted that, can after supply scavenging solution, pressurize before, slurried by using agitator to be mixed with aforementioned filter cake by the scavenging solution be supplied in pressure vessel 2 to carry out.In addition, can, before the scavenging solution of supply cleaning, agitator be used to repair the crackle of filter cake.Thus, scavenging solution can not walk short circuit, can clean efficiently.
In above-mentioned matting, as long as pressurized conditions when using the upside space S of the filtering material 3 in pressure filter 1 pair of pressure vessel 2 to pressurize meets the pressure of above-mentioned conditional (2), just be not particularly limited, preferably to make the mode be pressed in the scope of 0.01MPa ~ 0.50MPa in pressure vessel 2 pressurize.In addition, the upside space S of filtering material 3 is preferably pressurizeed with the speed of 0.01 ~ 0.30MPa/min.It should be noted that, in matting, the interior pressure of pressure vessel 2 preferably keeps substantially certain in the mode meeting above-mentioned conditional (2) from pressurization to matting terminates, but the interior pressure of pressure vessel 2 after the pressurizing, along with the scavenging solution added in pressure vessel 2 is by filtering material 3, the pressure in pressure vessel 2 can slowly reduce.Specifically, to be reduced by the scavenging solution of filtering material 3 or when almost not having, the compressed air pressure in pressure vessel 2 can spill from bottom, be difficult to pressure when pressure is maintained pressurization in pressure vessel 2, can lower than pressure during aforementioned pressurization.
As the scavenging solution used in aforementioned matting, preferred aqueous medium, include, for example out: water; The lower alcohol such as methyl alcohol, ethanol (alcohol of carbon number less than 5); The mixture etc. of water and lower alcohol, preferably uses the material same with the medium used in above-mentioned polymerization process.
About the weight of the scavenging solution used in matting, no matter whether use at least a kind of tensio-active agent without polyoxyethylene chain at above-mentioned polymerization process, be more than 9 times of the weight (being the total amount of the vinyl monomer used in polymerization process when being added in strainer by all crude products obtained in polymerization process in solid-liquid separation process) of the polymer beads remained on filtering material 3 and less than 18 times.When the weight of the scavenging solution used in matting is less than 9 times of the weight of the polymer beads remained on filtering material 3, contained by polymer beads, the by product (emulsion polymeric product) produced in the polymerization, the optionally tensio-active agent without polyoxyethylene chain used, the optionally macromolecular dispersion stabilizer used, optionally and use polymeric additives (such as stopper) etc. do not need the removal of composition to become insufficient, existence cannot obtain desired polymer beads, and (particularly the content without the tensio-active agent of polyoxyethylene chain of aforementioned polymer particle units surface-area is 10.0 × 10 -5g/m 2following polymer beads) anxiety.
In addition, when using at least a kind not have the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the weight B (kg) of the scavenging solution used in matting is preferably the lower value B of the weight of the scavenging solution that often kind of tensio-active agent without polyoxyethylene chain using in above-mentioned polymerization process is calculated by following calculating formula (4) l(kg) amount esox B l(when using a kind not have the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, equal B l) more than (kg), and the higher limit B of the weight of the scavenging solution calculated by following calculating formula (5) for the often kind of tensio-active agent without polyoxyethylene chain used in above-mentioned polymerization process h(kg) amount esox B h(when using a kind not have the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, equal B h) below.That is, the weight B (kg) of the scavenging solution used in matting preferably meets with lower inequality (6).When using a kind not have the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, be with lower inequality (7) with lower inequality (6).
B L＝(C÷D)×1.8···(4)
B H＝(C÷D)×2.3···(5)
ΣB L≤B≤ΣB H···(6)
B L≤B≤B H···(7)
(in formula (4) and formula (5), C represents a kind of consumption (g) without the tensio-active agent of polyoxyethylene chain, and D represents aforementioned a kind of tensio-active agent solubleness (g/100ml) to the scavenging solution of liquid temperature 25 DEG C without polyoxyethylene chain)
The weight of the scavenging solution used in matting is the lower value B of the weight of the scavenging solution that the often kind of tensio-active agent without polyoxyethylene chain used in above-mentioned polymerization process is calculated by above-mentioned calculating formula (4) l(kg) amount esox B l(kg), time more than, by product (emulsion polymeric product) that adhering on surface in polymer beads, polymer beads, that produce in the polymerization, the optionally tensio-active agent without polyoxyethylene chain used, the optionally macromolecular dispersion stabilizer used, optionally and the polymeric additives (such as stopper) etc. used does not need the content of composition can be reduced further.
In addition, the temperature of the scavenging solution used in cleaning does not preferably have the temperature of the abundant stripping of tensio-active agent of polyoxyethylene chain, such as, be preferably 40 ~ 80 DEG C, be more preferably 50 ~ 80 DEG C.In addition, as method scavenging solution being heated to said temperature and carrying out cleaning, can to use the cleaning solution supplying through heating to the method for strainer (pressure vessel 2 of such as pressure filter 1), also can use by after cleaning solution supplying to strainer by method that the heating jacket be disposed in around strainer heats scavenging solution.
Above-mentioned matting preferably terminates in the following moment: become less than 2.0 times of the electric conductivity of the scavenging solution before adding to strainer (pressure filter 1) by the electric conductivity of the scavenging solution of filtering material 3, and less than 2/3 of pressure when the interior pressure of pressure vessel 2 becomes pressurization.By adding scavenging solution in pressure vessel 2 until become less than 2.0 times of the electric conductivity of the scavenging solution before adding to strainer (pressure filter 1) by the electric conductivity of the scavenging solution of filtering material 3, can positively reduce contained by the polymer beads that finally obtains, the by product (emulsion polymeric product) produced in the polymerization, the optionally tensio-active agent without polyoxyethylene chain used, the optionally macromolecular dispersion stabilizer used, optionally and the polymeric additives (such as stopper) etc. used does not need the residual quantity of composition.In addition, till pressing less than 2/3 of pressure when becoming pressurization by making the scavenging solution that adds in pressure vessel 2 by filtering material 3 in pressure vessel 2, the amount of moisture that can be absorbed by polymer beads can be reduced, the time needed for drying of the polymer beads after cleaning can be shortened.
The polymer beads obtained in matting is by removing scavenging solution substantially completely with Vacuumdrier drying, and classification (being preferably air classification) as required, can make the polymer beads that can be used as product thus.
According to above-mentioned manufacture method, in solid-liquid separation process, unit time to be satisfied condition formula (1) by the amount of the medium of filtering material, in matting, unit time to be satisfied condition formula (2) by the amount of the scavenging solution of filtering material, and in this matting, use more than 9 times of weight of polymer beads and the scavenging solution of the weight of less than 18 times remaining on filtering material, therefore, containing have polyoxyethylene chain tensio-active agent and do not have polyoxyethylene chain both tensio-active agents tensio-active agent existence under be polymerized time, tensio-active agent major part without polyoxyethylene chain is fully removed together with scavenging solution with medium.Its result, the content (residual quantity) without the tensio-active agent of polyoxyethylene chain that can obtain polymer beads per surface area few (particularly 10.0 × 10 -5g/m 2below), the polymer beads of dispersion stabilization excellence.
And then, according to above-mentioned manufacture method, the by product (emulsion polymeric product) produced in polyreaction, optionally and use macromolecular dispersion stabilizer, optionally and use polymeric additives (such as stopper) etc. do not need composition to be removed in a large number in solid-liquid separation process and matting yet.Therefore, the polymer beads obtained in above-mentioned manufacture method can become these does not need the polymer beads that the amount of composition is also few.Its result, can obtain the polymer beads of the present invention that content (residual quantity) is few, dispersion stabilization is excellent of by product (emulsion polymeric product).
[purposes of polymer beads]
Polymer beads of the present invention is suitable to the optical component such as optical thin film, light diffusion body use such as anti-dazzle film, light diffusion films, is suitable for especially using as anti-dazzle component.
[resin combination]
Resin combination of the present invention contains polymer beads of the present invention.As resin combination of the present invention, can list coating resin combination, molding resin composition etc., resin combination of the present invention is suitable to coating resin combination especially.Above-mentioned coating resin combination preferably also contains binding agent on the basis of polymer beads of the present invention.Above-mentioned molding resin composition is preferably containing polymer beads of the present invention and transparent resin.About coating resin combination, molding resin composition, be described in detail later.
[optical thin film]
Coating resin composition containing polymer beads of the present invention and binding agent forms by optical thin film of the present invention on film substrate.Optical thin film of the present invention is such as by obtaining as follows: make above-mentioned polymer beads disperse to obtain coating resin combination in a binder, by gained coating resin composition on film substrate, above-mentioned film substrate forms the film formed by above-mentioned coating resin combination.
As above-mentioned binding agent, as long as the material used in this field according to transparent, that polymer beads is dispersed, photostabilization, wet fastness and thermotolerance etc. are required characteristic, be just not particularly limited.As above-mentioned binding agent, include, for example out: (methyl) acrylic resin; (methyl) acrylic acid-polyurethane resinoid; Polyurethane based resin; Polyvinyl chloride resin; Polyvinylidene dichloride resinoid; Trimeric cyanamide resinoid; Styrene resin; Alkyd based resin; Phenolic resin; Redix; Polyester resin; The silicone based resins such as alkyl polysiloxane resinoid; The modified organic silicone resins such as (methyl) vinylformic acid-silicone based resin, organosilicon-ol acid resin, polysiloxane-polyurethane resinoid, organosilicon-vibrin; The resin glues such as fluorine-type resin such as poly(vinylidene fluoride), fluoroolefin vinylic-ether polymer.
From the viewpoint of the weather resistance of raising coating resin combination, above-mentioned resin glue preferably can form the curable resin of crosslinking structure by crosslinking reaction.Above-mentioned curable resin can solidify under various condition of cure.Above-mentioned curable resin is categorized as the ionization radial line such as uv curing resin, electron(beam)curing resin curable resin, thermosetting resin, hot blast curable resin etc. according to curing type.
As above-mentioned thermosetting resin, can list: the thermoset polyurethane resin, resol, urea melamine, epoxy resin, unsaturated polyester resin, silicone resin etc. that are formed by acrylic polyol and isocyanate prepolymer.
As above-mentioned ionization radial line curable resin, can list: multifunctional (methyl) acrylate resin of polyvalent alcohol multifunctional (methyl) acrylate etc. and so on; By vulcabond, polyvalent alcohol and have hydroxyl the synthesis such as (methyl) acrylate and so on polyfunctional carbamate acrylate resin etc.As above-mentioned ionization radial line curable resin, preferably multifunctional (methyl) acrylate resin, more preferably has polyvalent alcohol multifunctional (methyl) acrylate of more than 3 (methyl) acryls in 1 molecule.As the polyvalent alcohol in 1 molecule with more than 3 (methyl) acryls multifunctional (methyl) acrylate, specifically can list: trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, 1, 2, 4-hexanaphthene three (methyl) acrylate, five glycerol tri-acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol triacrylate, Dipentaerythritol Pentaacrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, tripentaerythritol triacrylate, tripentaerythritol six acrylate etc.Above-mentioned ionization radial line curable resin can combinationally use two or more.
As above-mentioned ionization radial line curable resin, except these can also use the polyether resin, vibrin, epoxy resin, Synolac, spiral shell acetal (spiroacetal) resin, polybutadiene, polythiol polyenoid resin etc. of the functional group with esters of acrylic acid.
When using uv curing resin in the middle of above-mentioned ionization radial line curable resin, in uv curing resin, add Photoepolymerizationinitiater initiater make binding agent.Above-mentioned Photoepolymerizationinitiater initiater can use any Photoepolymerizationinitiater initiater, preferably use be applicable to use the Photoepolymerizationinitiater initiater of uv curing resin.
As above-mentioned Photoepolymerizationinitiater initiater; can list: acetophenones, bitter almond oil camphor class, benzophenone, phosphinoxides, ketal class, Alpha-hydroxy alkylbenzene ketone, alpha-aminoalkyl benzophenone, Anthraquinones, thioxanthene ketone, azo-compound, peroxide (recording in Japanese Unexamined Patent Publication 2001-139663 publication etc.), 2,3-dialkyl group dione compounds classes, disulfide compound class, fluorine amine compound class, aromatic matte class, salt, borate, active halide, α-acyl group oxime ester etc.
As above-mentioned acetophenones, include, for example out: methyl phenyl ketone, 2,2-diethoxy acetophenones, to dimethyl acetophenone, 1-hydroxyl 3,5-dimethylphenyl ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methylthio group-2-morpholino Propiophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone etc.As above-mentioned bitter almond oil camphor class, include, for example out: bitter almond oil camphor, bitter almond oil camphor benzoic ether, bitter almond oil camphor benzene sulfonate, benzoin tosylate, benzoin methylether, ethoxybenzoin, benzoin iso-propylether etc.As above-mentioned benzophenone, include, for example out: benzophenone, 2,4-dichloro benzophenones, 4,4 '-dichloro benzophenone, p-dichlorobenzene ketone etc.As above-mentioned phosphinoxides, include, for example out: TMDPO etc.As above-mentioned ketal class, include, for example out: the benzylmethylketal classes such as 2,2-dimethoxy-1,2-diphenylethane-1-ketone.As above-mentioned Alpha-hydroxy alkylbenzene ketone, include, for example out: 1-hydroxycyclohexylphenylketone.As above-mentioned alpha-aminoalkyl benzophenone class, include, for example out: 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-(4-morpholinyl)-1-acetone.
As commercially available optical free radical polymerization starter, can list as preference: the trade(brand)name " IRGACURE (registered trademark) 651 " (2 that BASFJapanLtd. manufactures, 2-dimethoxy-1,2-diphenylethane-1-ketone), BASFJapanLtd. manufacture trade(brand)name " IRGACURE (registered trademark) 184 ", BASFJapanLtd. manufacture trade(brand)name " IRGACURE (registered trademark) 907 " (2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-(4-morpholinyl)-1-acetone) etc.
The consumption of above-mentioned Photoepolymerizationinitiater initiater is usual relative to binding agent 100 % by weight in the scope of 0.5 ~ 20 % by weight, preferably in the scope of 1 ~ 5 % by weight.
As above-mentioned resin glue, except above-mentioned curable resin, thermoplastic resin can be used.As above-mentioned thermoplastic resin, can list: the derivatived celluloses such as cellulose acetate, Nitrocellulose, acetic acid butyl cellulose, ethyl cellulose, methylcellulose gum; The vinyl group resin such as homopolymer and multipolymer of the homopolymer of the homopolymer of vinyl-acetic ester and multipolymer, vinylchlorid and multipolymer, vinylidene chloride; The Derlin such as polyvinyl formal, polyvinyl butyral acetal; (methyl) acrylic resin such as homopolymer and multipolymer of the homopolymer of acrylate and multipolymer, methacrylic ester; Polystyrene resin; Polyamide resin; Linear polyester resin; Polycarbonate resin etc.
In addition, as above-mentioned binding agent, the rubber-like such as synthetic rubber, natural rubber binding agent, mineral-type binding agent etc. can also be used except above-mentioned resin glue.As above-mentioned rubber-like resin glue, can list: ethylene-propylene rubber(EPR), polybutadiene rubber, styrene-butadiene rubber(SBR), paracril etc.These rubber-like resin glues may be used singly or in combination of two or more.
As above-mentioned mineral-type binding agent, silicon dioxide gel, alkaline silicate, silicon alkoxide, phosphoric acid salt etc. can be listed.As above-mentioned mineral-type binding agent, metal alkoxide or silicon alkoxide also can be used to be hydrolyzed and dehydrating condensation and the mineral-type that obtains or organo-mineral complexing class matrix.As above-mentioned mineral-type or organic and inorganic compound syzygy matrix, silicon alkoxide, such as tetraethoxysilane etc. can be used to be hydrolyzed and dehydrating condensation and the silica type matrix obtained.These mineral-type binding agents may be used singly or in combination of two or more.
The amount of the polymer beads in above-mentioned coating resin combination is preferably more than 2 weight parts relative to solids component 100 weight part of binding agent, is more preferably more than 4 weight parts, more preferably more than 6 weight parts.By making the amount of above-mentioned polymer beads be more than 2 weight parts relative to solids component 100 weight part of binding agent, easily make the extinction of the film formed by coating resin combination abundant.Therefore, easily make abundant for the optical characteristics such as the anti-glare of the film of coating resin composition on film substrate, light diffusing.The amount of the polymer beads in above-mentioned coating resin combination is preferably below 300 weight parts relative to solids component 100 weight part of binding agent, is more preferably below 200 weight parts, more preferably below 100 weight parts.By making the amount of above-mentioned polymer beads be below 300 weight parts relative to solids component 100 weight part of binding agent, easily make the line transmission of the film formed by coating resin combination abundant.
Above-mentioned coating resin combination also can contain organic solvent.When the base materials such as film substrate described later apply above-mentioned coating resin combination, if above-mentioned organic solvent is by making to contain its coating transfiguration making coating resin combination on base material easily in coating resin combination, be not particularly limited.As above-mentioned organic solvent, such as, can use the aromatic series such as toluene, dimethylbenzene kind solvent; The alcoholic solvents such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, propylene glycol monomethyl ether; The esters solvent such as ethyl acetate, butylacetate; The ketones solvents such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), cyclopentanone, pimelinketone; The glycol ethers such as 2-methyl cellosolve, cellosolvo, butoxy ethanol, glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether; The diol alcohol esters such as acetic acid-2-methoxy-ethyl ester, acetic acid-2-ethoxy-ethyl ester (cellosolve acetate), acetic acid-2-butoxyethyl, propylene glycol methyl ether acetate; The chlorine kind solvents such as chloroform, methylene dichloride (dichloromethane), trichloromethane, methylene dichloride (methylenechloride); The ether solvents such as tetrahydrofuran (THF), diethyl ether, Isosorbide-5-Nitrae-diox, 1,3-dioxolane; The amide solvents etc. such as N-Methyl pyrrolidone, dimethyl formamide, dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE.These organic solvents can be used alone a kind, also can be mixed with two or more.
Above-mentioned film substrate is preferably transparent.As transparent film substrate, include, for example out by the film of the polymer formation such as cellulosic polymer, polycarbonate polymer, polymethylmethacrylate etc. (methyl) acrylic polymers such as the polyester polymers such as polyethylene terephthalate (PET), PEN, Cellulose diacetate, cellulosetri-acetate (TAC).In addition, as transparent film substrate, also can enumerate by the film of the polymer formation such as acylamide polymer such as olefin polymer, vinyl chloride polymer, nylon, aromatic polyamide such as the styrenic polymer such as polystyrene, acrylonitritrile-styrene resin, polyethylene, polypropylene, the polyolefine with ring-type or norbornylene structure, ethylene-propylene copolymer.And then, as transparent film substrate, also can enumerate by the film etc. of the polymer formation such as the blend of acid imide polymkeric substance, sulfone base polymer, polyether sulfone polymkeric substance, polyether-ether-ketone polymer, polyphenylene sulfide base polymer, vinyl alcohol polymer, vinylidene chloride base polymer, vinyl butyral base polymer, aryl nitrone polymkeric substance, polyoxymethylene base polymer, epoxide polymer, above-mentioned polymkeric substance.As above-mentioned film substrate, be suitable for the film substrate using degree of birefringence little especially.In addition, the film these films being provided with further the easy adhesive linkage such as (methyl) acrylic resin, copolyester resinoid, polyurethane based resin, styrene-maleic acid grafted polyester resin, acrylic acid-grafted vibrin also can use as above-mentioned film substrate.
The thickness of above-mentioned film substrate can suitably determine, generally from the workability of intensity, process etc., thin layer angularly in the scope of 10 ~ 500 μm, preferably in the scope of 20 ~ 300 μm, more preferably in the scope of 30 ~ 200 μm.
In addition, additive can be added in film substrate.As above-mentioned additive, include, for example out: UV light absorber, infrared absorbent, static inhibitor, adjustable refractive index agent, toughener etc.
As the method above-mentioned coating resin combination is applied on film substrate, can list: the known coating method such as rod coating, scraper for coating, rotary coating, reverse coating, mould coating, spraying coating, the coating of roller coat cloth, intaglio plate, the coating of nick version, lip coating, airblade coating, pickling process.
When the binding agent contained in above-mentioned coating resin combination is ionization radial line curable resin, after the coating of above-mentioned coating resin combination, make solvent seasoning as required, and then irradiate active energy beam, make ionization radial line curable resin solidify thus.
As above-mentioned active energy beam, such as, can use the ultraviolet that the light sources such as xenon lamp, low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, carbon arc lamp, tungsten lamp send; Cockcroft-the Wal of usual 20 ~ 2000KeV pause type, model De Graff type, resonance variable-pressure, insulating core transformer type, linear pattern, the electron rays accelerators such as that meter of type, the high-frequency type electron rays, alpha-ray, β ray, gamma-rays etc. that send.
The thickness being dispersed with the layer of polymer beads in a binder that coating (and solidification) by coating resin combination is formed is not particularly limited, suitably can determine according to the particle diameter of polymer beads, preferably in the scope of 1 ~ 10 μm, more preferably in the scope of 3 ~ 7 μm.
The optical thin film of the invention described above can be suitable for using or anti-dazzle use as light diffusion, namely uses as light diffusion film or anti-dazzle film.
[resin-formed body]
Polymer beads of the present invention also may be used for resin-formed body.Above-mentioned resin-formed body is by shaping for the molding resin composition containing polymer beads of the present invention and transparent resin.In above-mentioned resin-formed body, above-mentioned polymer beads plays a role as light granule proliferation.Therefore, above-mentioned resin-formed body plays a role as light diffusion bodies such as light diffusing sheets, can be used as LED illumination cover etc.
Above-mentioned transparent resin is the base material of above-mentioned resin-formed body, include, for example out: (methyl) acrylic resin, polycarbonate resin, polystyrene resin, (methyl) acrylic-styrene resin ((methyl) acrylate and cinnamic multipolymer) etc.In the middle of these, preferred polystyrene resin or (methyl) acrylic-styrene resin are as above-mentioned transparent resin.
The amount of the polymer beads contained in above-mentioned resin combination relative to transparent resin 100 weight part preferably in the scope of 0.01 ~ 5 weight part, more preferably in the scope of 0.1 ~ 5 weight part.In above-mentioned resin combination, the additives such as UV light absorber, antioxidant, thermo-stabilizer, photostabilizer, white dyes can be added.
The thickness of above-mentioned resin-formed body and shape etc. suitably can be selected according to the purposes of resin-formed body.
Above-mentioned resin-formed body can by carrying out melting mixing by above-mentioned transparent resin and above-mentioned polymer beads single screw extrusion machine, twin screw extruder etc. and obtaining.In addition, can T mould and roller unit be utilized to be shaped to tabular the resin combination obtained by melting mixing and obtain resin-formed body.In addition, the resin combination pellet that can will be obtained by melting mixing, is shaped to tabular by pellet by injection moulding, compression moulding etc. and obtains resin-formed body.
Above-mentioned resin-formed body obtains shaping for the molding resin composition of the polymer beads of the present invention containing dispersion stabilization excellence, therefore, in this resin-formed body, Absorbable organic halogens ground obtains does not have the uneven optical characteristics such as uniform light diffusing, anti-glare.
Embodiment
Below by embodiment and comparative example, the present invention will be described, but the present invention is not limited thereto.First, illustrate in following examples and comparative example, the measuring method of the volume average particle size of polymer beads and the variation coefficient of particle diameter, the measuring method of the volume average particle size of the seed grain used in the manufacture of polymer beads, the measuring method of the X value (unit time is by the amount (kg/min) of the medium of filtering material) in the solid-liquid separation process of the manufacture of polymer beads, the measuring method of the Y value (unit time is by the amount (kg/min) of the scavenging solution of filtering material) in the matting of the manufacture of polymer beads, the measuring method without the content of the tensio-active agent of polyoxyethylene chain in polymer beads, the calculation method without the content of the tensio-active agent of polyoxyethylene chain of polymer beads per surface area, the measuring method of the content of the by product (emulsion polymeric product) in polymer beads, the measuring method of the gel fraction of polymer beads, the measuring method of the specific refractory power of polymer beads, the measuring method of dispersion behavior displacement of polymer beads and the evaluation method of dispersion stabilization, the measuring method of the levels of residual monomers in polymer beads, and a kind of tensio-active agent without polyoxyethylene chain is to the measuring method of the solubleness of the scavenging solution of liquid temperature 25 DEG C.
[measuring method of the volume average particle size of polymer beads and the variation coefficient of particle diameter]
The volume average particle size of polymer beads is by Ku Erte Multisizer tM3 (determinators that Beckman Coulter Inc. manufactures) measure.Measure the Multisizer used according to Beckman Coulter Inc.'s distribution tMthe aperture pipe (aperture) that 3 user manuals are calibrated is implemented.
In addition, the aperture pipe used in mensuration is suitably selected according to the size of measured polymer beads.Current (aperture electric current) and Gain (gain) suitably sets according to the size of selected aperture pipe.Such as, when have selected the aperture pipe of the size with 50 μm, Current (aperture electric current) is set as-800, Gain (gain) is set as 4.
As measurement sample, use the sample obtained as follows: utilize TOUCHMIXER (YamatoScientificCo., Ltd. manufacture, " TOUCHMIXERMT-31 ") and ultrasonic cleaner (Velvo-ClearCo., Ltd. manufacture, " ULTRASONICCLEANERVS-150 ") polymer beads 0.1g to be dispersed in 0.1 % by weight nonionic surfactant aqueous solution 10m1 and to make dispersion liquid.In advance not make the degree being mixed into bubble in beaker slowly stir in mensuration, terminate to measure in the moment measured 100,000 polymer beads.The volume average particle size of polymer beads is the arithmetical av in the size-grade distribution of the volume reference of 100,000 particles.
The variation coefficient (CV value) of the particle diameter of polymer beads is calculated by following formula.
The variation coefficient=(volume average particle size of the standard deviation ÷ polymer beads of the size-grade distribution of the volume reference of polymer beads) × 100 of the particle diameter of polymer beads
[measuring method of the volume average particle size of seed grain]
The mensuration of the volume average particle size of the seed grain used in the manufacture of polymer beads is undertaken by laser diffraction/scattering method particle size distribution device (" LS13320 " that Beckman Coulter Inc. manufactures) and universal liquid sample block.
Specifically, use the sample obtained as follows: utilize TOUCHMIXER (YamatoScientificCo., Ltd. manufacture, " TOUCHMIXERMT-31 ") and ultrasonic cleaner (Velvo-ClearCo., Ltd. manufacture, " ULTRASONICCLEANERVS-150 ") the slurry 0.1g containing seed grain to be dispersed in 0.1 % by weight nonionic surfactant aqueous solution 10m1 and to make dispersion liquid.
Be determined at and circulate state that above-mentioned seed grain is disperseed and carrying out under the state that ultrasound unit (ULMULTRASONICMODULE) is started by carrying out pump in universal liquid sample block, calculate the volume average particle size (arithmetic mean diameter in the size-grade distribution of volume reference) of seed grain.Condition determination is as follows.
Medium=water
Specific refractory power=1.333 of medium
The specific refractory power of the specific refractory power=seed grain of solid
PIDS relative concentration: about 40 ~ 55%
[measuring method of X value]
In solid-liquid separation process, measure from make the medium that contains in crude product make aforementioned medium by the time T filtering material by filtering material to end 1(min).Further, the gross weight G of the filtrate (medium) obtained in solid-liquid separation process is measured 1(kg).Then, the amount X (kg/min) of unit time by the medium of filtering material is obtained by following calculating formula.
X(kg/min)＝G 1(kg)/T 1(min)
[measuring method of Y value]
Measure the weight G of the scavenging solution used in matting 2(kg).Further, be determined in matting from make the weight G of scavenging solution of scavenging solution by using in filtering material to matting 2g the scavenging solution of 0.8 times of weight of () is by institute time spent T till filtering material 2(min).Then, the amount Y (kg/min) of unit time by the scavenging solution of filtering material is obtained by following calculating formula.
Y(kg/min)＝0.8×G 2(kg)/T 2(min)
[measuring method without the content of the tensio-active agent of polyoxyethylene chain in polymer beads]
About the content without the tensio-active agent of polyoxyethylene chain in polymer beads, utilize solvent to extract polymer beads, use liquid chromatography mass instrument (LC/MS/MS device) to measure.
It should be noted that, about the mensuration without the content of the tensio-active agent of polyoxyethylene chain in the polymer beads of embodiment described later and comparative example, as LC/MS/MS device, " the LinearIonTrapLC/MS that " UHPLCACCELA " that use ThermoFisherScientific to manufacture and ThermoFisherScientific manufacture nlXQ ".
In addition, about the polymer beads in embodiment described later and comparative example, as the tensio-active agent without polyoxyethylene chain, use at least a kind in two (2-ethylhexyl) sulfosuccinate, lauryl sulfate and alkenyl succinic salt, the content without the tensio-active agent of polyoxyethylene chain in the polymer beads of embodiment and comparative example measures according to method shown below.
The polymer beads accurately taken as sample is about 0.10g to centrifuge tube, injects the methyl alcohol 5mL as extracting solution, fully mixed by polymer beads with extracting solution with whole pipet.After at room temperature carrying out 15 minutes ultrasonic extraction, carry out centrifugation in 15 minutes with rotating speed 3500rpm, using the supernatant that obtains thus as experimental liquid.
Use LC/MS/MS device measures the surfactant concentration without polyoxyethylene chain in this experimental liquid.Then, according to the surfactant concentration (μ g/ml) without polyoxyethylene chain in the experimental liquid recorded, as the weight (sample weight (g)) of the polymer beads of sample and the amount (extracting liquid measure (ml)) of extracting solution, obtained the content (μ g/g) without the tensio-active agent of polyoxyethylene chain in polymer beads by following calculating formula.It should be noted that, extraction liquid measure is 5ml.
Not there is the content (μ g/g) of the tensio-active agent of polyoxyethylene chain
={ surfactant concentration (μ g/ml) in experimental liquid × extraction liquid measure (ml) } ÷ sample weight (g)
In addition, the surfactant concentration without polyoxyethylene chain uses LC/MS/MS device, and the typical curve according to being made in advance by the peak area value on gained spectrogram calculates content.In addition, polymer beads contain multiple not there is the tensio-active agent of polyoxyethylene chain time, not there is for these tensio-active agent production standard curve of polyoxyethylene chain respectively, typical curve according to making calculates the surfactant concentration without polyoxyethylene chain, using the summation without the surfactant concentration of the tensio-active agent of polyoxyethylene chain calculated as " surfactant concentration (μ g/ml) without polyoxyethylene chain in experimental liquid " in above-mentioned calculating formula, obtain the content without the tensio-active agent of polyoxyethylene chain in polymer beads.
Standard curve making method is as follows according to the kind without the tensio-active agent of polyoxyethylene chain used in embodiment and comparative example.
-the standard curve making method of two (2-ethylhexyl) sulfosuccinate-
After about 1000ppm intermediate standard liquid (methanol solution) of preparation two (2-ethylhexyl) sulfosuccinate, dilute the standard curve making reference liquid of preparation 0.1ppm, 0.2ppm, 0.5ppm, 1.0ppm, 2.0ppm further stage by stage with methyl alcohol.Under LC condition determination described later and MS condition determination, measure the standard curve making reference liquid of each concentration, obtain the peak area value of monitoring on the spectrogram of ion m/z=421.3 (precursor ion) → 227.2 (product ion).By each concentration and area value described point, obtain curve of approximation (quafric curve) by method of least squares, it can be used as quantitative typical curve.
-the standard curve making method of lauryl sulfate-
After preparing about 1000ppm intermediate standard liquid (methanol solution) of lauryl sulfate, dilute the standard curve making reference liquid of preparation 0.1ppm, 0.2ppm, 0.5ppm, 1.0ppm, 2.0ppm further stage by stage with methyl alcohol.Under LC condition determination described later and MS condition determination, measure the standard curve making reference liquid of each concentration, obtain the peak area value of monitoring on the spectrogram of ion m/z=421.3 (precursor ion) → 227.2 (product ion).By each concentration and area value described point, obtain curve of approximation (quafric curve) by method of least squares, it can be used as quantitative typical curve.
-the standard curve making method of alkenyl succinic salt-
After about 1000ppm intermediate standard liquid (methanol solution) of preparation alkenyl succinic salt, dilute the standard curve making reference liquid of preparation 0.03ppm, 0.15ppm, 0.60ppm, 1.5ppm, 3.0ppm further stage by stage with methyl alcohol.Under LC condition determination described later and MS condition determination, measure the standard curve making reference liquid of each concentration, obtain the peak area value of monitoring on the spectrogram of ion m/z=339.3 (precursor ion) → 295.2 (product ion).By each concentration and area value described point, obtain curve of approximation (quafric curve) by method of least squares, it can be used as quantitative typical curve.
-LC condition determination-
Determinator: UHPLCACCELA (ThermoFisherScientific manufacture)
HypersilGOLDC181.9 μm (internal diameter 2.1mm, length 100mm) that chromatographic column: ThermoFisherScientific manufactures
-MS condition determination-
Determinator: LinearIonTrapLC/MS nlXQ (ThermoFisherScientific manufacture)
Ionization method (Ionization): (ESI/negative)
Sheath gas (SheathGas): 30arb
Assisted gas (AUXGas): 10arb
Sweep gas (SweepGas): 0arb
Spray voltage (ISprayVoltage): 5.0kV
Capillary temperature (CapillaryTemp): 350 DEG C
Capillary voltage (Capillaryvoltage) :-20V
Sleeve lens voltage (TubelensVoltage) :-100V
Monitoring ion (Monitoringion) (m/Z):
Two (2-ethylhexyl) sulfosuccinate (n=421.3/n2=227.2)
Ethylene nonyl phenyl ether phosphoric acid salt (n=502.3/n2=485.2)
Lauryl sulfate (n=421.3/n2=227.2)
Alkenyl succinic salt (n=339.3/n2=295.2)
Polyoxyethylene styrene phenyl ether sulfuric acid (n=601.4/n2=301.2)
Polyoxyethylene styrene phenyl ether phosphoric acid ester (n=601.4/n2=301.2)
[measuring method of the specific surface area of polymer beads]
The BET method (nitrogen adsorption method) that the specific surface area of polymer beads is recorded by ISO9277 the 1st edition JISZ8830:2001 measures.For the polymer beads as object, the automatic specific surface area/pore distribution measurement device Tristar3000 using Shimadzu Scisakusho Ltd to manufacture measures BET nitrogen adsorption isotherm, uses BET multipoint method to calculate specific surface area according to nitrogen adsorption amount.After implementing to utilize heated air to purge the pre-treatment carried out, use nitrogen, at adsorbate section area 0.162nm as adsorbate 2condition under use vascular unloading technique to measure.Wherein, aforementioned pre-treatment is carried out especially by following operation: heat the container that polymer beads is housed with 65 DEG C, while carry out 20 minutes nitrogen purgings, at room temperature after naturally cooling, while heat this container with 65 DEG C, carry out vacuum outgas until the pressure in aforesaid receptacle becomes below 0.05mmHg.
[calculation method without the content of the tensio-active agent of polyoxyethylene chain of polymer beads per surface area]
According to the content without the tensio-active agent of polyoxyethylene chain in the polymer beads recorded by said determination method and the specific surface area of polymer beads that recorded by said determination method, calculated the content without the tensio-active agent of polyoxyethylene chain of polymer beads per surface area by following calculating formula.
(content without the tensio-active agent of polyoxyethylene chain of polymer beads per surface area) (g/m 2)
=(content without the tensio-active agent of polyoxyethylene chain in polymer beads) (g/1g polymer beads)
Specific surface area (the m of ÷ polymer beads 2/ 1g polymer beads)
[measuring method (solvent dispersion method) of the content of the by product (emulsion polymeric product) in polymer beads]
When polymer beads being dispersed in water and carrying out centrifugation, there is the polymer beads generation sedimentation of target grain size, and the by product contained in polymer beads (emulsion polymeric product) suspends and form supernatant liquor together with a small amount of water.Therefore, measure the content of the by product (emulsion polymeric product) of the seeding polymerization in polymer beads with the form of the content of the non-volatile component in supernatant liquor at this.
[making of supernatant liquor]
First, by the sample bottle that the polymer beads 5.0g obtained in each embodiment and each comparative example loads inner capacities 50ml, water 15.0g is added.Then, by using ultrasonic cleaner (Velvo-ClearCo., Ltd. " ULTRASONICCLEANERVS-150 " that manufacture, oscillation frequency: 50kHz, high frequency output: 150W) carry out 60 minutes dispersion treatment polymer beads is dispersed in water, obtain dispersion liquid.In addition, when polymer beads is difficult to be dispersed in water, can be dispersed in water after moistening for the alcohol (such as ethanol) of polymer beads trace (upper limit 0.8g).
Then, to the centrifuge tube of internal diameter 24mm, (ThermoFisherScientific company manufactures for such as inner capacities 50mL and the centrifuge tube of internal diameter 24mm, trade(brand)name " NALGENE (registered trademark) 3119-0050 ") the above-mentioned dispersion liquid 20.0g of middle loading, this centrifuge tube is fit into rotor, such as angle rotor (anglerotor) (model " RR24A ", Hitachi Koki Co., Ltd manufactures, the centrifuge tube of 8 inner capacities 50mL can be filled), foregoing rotor is fit into separating centrifuge, such as high speed refrigerated centrifuges (high-Speedrefrigeratedcentrifuge) (model " CR22GII ", Hitachi Koki Co., Ltd manufactures), use aforementioned high speed refrigerated centrifuges at k-factor 6943 (when stating angle rotor before use, when rotating speed 4800rpm, k-factor is 6943), after carrying out centrifugation under the rotational time condition of 30 minutes, reclaim supernatant liquor.
[quantitative evaluation of by product (emulsion polymeric product)]
Then, the content of the by product (emulsion polymeric product) contained in the supernatant liquor 5.0g reclaimed is evaluated.That is, first take the sample bottle of supernatant liquor 5.0g to the inner capacities 10ml weighed in advance, the vacuum drying oven putting into temperature 60 C makes moisture evaporate in 5 hours.Measure the weight (g) of the sample bottle comprised through evaporating solid residue, i.e. non-volatile component.
Then, according to comprising the weight (g) of sample bottle of non-volatile component, the weight (g) of sample bottle and loading the weight (g) (=5.0g) of supernatant liquor of sample bottle, calculated the concentration (% by weight) of the non-volatile component (being equivalent to by product (emulsion polymeric product)) in supernatant liquor by following calculating formula.
(concentration of the non-volatile component in supernatant liquor) (% by weight)
={ (comprising the weight of the sample bottle of non-volatile component) (g)-(weight of sample bottle) (g) }
÷ (loading the weight of the supernatant liquor of sample bottle) (g) × 100
[measuring method of the gel fraction of polymer beads]
The gel fraction of polymer beads represents and the degree of crosslinking of polymer beads measures in accordance with the following methods.Namely, first accurate weighing drops into 200mL eggplant-shape bottle as the polymer beads 1.0g of sample and boiling stone 0.03g, after further injection toluene 100mL, aforementioned eggplant-shape bottle installs prolong, aforementioned eggplant-shape bottle is immersed in the oil bath of maintenance 130 DEG C and refluxes 24 hours.
After backflow, to the content (lysate) in aforementioned eggplant-shape bottle, use installed ADVANTEC company manufacture glass fibre filter " GB-140 (φ 37mm) " and " GA-200 (φ 37mm) " and the TOPCorporation weighed manufacture Büchner funnel type filter 3G (glass particle pore diameter 20 ~ 30 μm, capacity 30mL) filter, in aforementioned Büchner funnel type filter 3G, reclaim solids component.Then, the solids component reclaimed in aforementioned Büchner funnel type filter 3G, is removed toluene, is cooled to room temperature after dry 1 hour together with aforementioned Büchner funnel type filter 3G in the vacuum drying oven of 130 DEG C for dry 2 hours under gauge pressure 0.06MPa.
After cooling, under the state comprising aforesaid solid composition in aforementioned Büchner funnel type filter 3G, measure the gross weight of Büchner funnel type filter 3G, glass fibre filter and solids component.Then, the gross weight recorded is deducted Büchner funnel type filter 3G, the weight of glass fibre filter and the weight of boiling stone, obtain the weight (g) of dry powder.
Then, the weight (g) of sample using the weight (g) of dry powder and add in eggplant-shape bottle, calculates gel fraction by following calculating formula.
Gel fraction (% by weight)={ dry powder (g)/sample weight (g) } × 100
[measuring method of the specific refractory power of polymer beads]
The detecting refractive index of polymer beads utilizes Baker process to carry out.First, polymer beads placed by slide glass, drip REFRACTIVE LIQUID (CARGILLE company manufactures: CARGILLE standard refraction liquid, to prepare multiple refractive index n D25 with the interval of refringence 0.002 be the REFRACTIVE LIQUID of 1.538 ~ 1.562).Then, after polymer beads is fully mixed with REFRACTIVE LIQUID, irradiate the light of high-pressure mercury lamp " NX35 " (centre wavelength 589nm) that Iwasaki Electric Co., Ltd. manufactures on one side from below, from top by the profile of observation by light microscope polymer beads.Then, the situation that can't see profile is judged as that REFRACTIVE LIQUID is equal with the specific refractory power of polymer beads.
It should be noted that, as long as utilize the observation of opticmicroscope to observe under the multiplying power of profile that can confirm polymer beads, just no problem, if the polymer beads of particle diameter 5 μm is then suitably the observation multiplying power of about 500 times.By aforesaid operations, because the specific refractory power of polymer beads and REFRACTIVE LIQUID is more close, be more difficult to the profile seeing polymer beads, therefore judge that the specific refractory power being difficult to the REFRACTIVE LIQUID of the profile distinguishing polymer beads is equal with the specific refractory power of this polymer beads.
In addition, when polymer beads seems do not have difference between 2 kinds of REFRACTIVE LIQUIDs that refringence is 0.002, the intermediate value of these 2 kinds of REFRACTIVE LIQUIDs is judged as the specific refractory power of this polymer beads.Such as, when testing with the REFRACTIVE LIQUID of specific refractory power 1.554 and 1.556 respectively, when polymer beads seems do not have difference in two REFRACTIVE LIQUIDs, the intermediate value 1.555 of these REFRACTIVE LIQUIDs is judged to be the specific refractory power of polymer beads.
In addition, said determination is implemented to measure under the environment of testing laboratory's temperature 23 DEG C ~ 27 DEG C.
[measuring method of dispersion behavior displacement of polymer beads and the evaluation method of dispersion stabilization]
When the by product (emulsion polymeric product) contained in polymer beads is few, dispersion behavior (degree of scatter) in dispersion medium becomes stable, the viscosity number of dispersion liquid becomes stable, and the by product contained in polymer beads (emulsion polymeric product) many time, degree of scatter (dispersion behavior) in dispersion medium becomes unstable, and the viscosity number of dispersion liquid becomes unstable.
This be due to, the by product (emulsion polymeric product) of the surface attachment of polymer beads can affect the consistency of polymer particle surface, and, the amount of the by product (emulsion polymeric product) that the surface of each polymer beads is adhered to is different, therefore, when the by product (emulsion polymeric product) contained in polymer beads is many, the dispersion behavior of polymer beads in dispersion medium can become irregular.And then, because by product (emulsion polymeric product) is non-crosslinked/micro-crosslinked polymkeric substance, therefore the by product (emulsion polymeric product) of the surface attachment of polymer beads can ooze out when making polymer beads disperse in organic solvent, makes the viscosity of dispersion liquid increase.With this phenomenon, a large amount of by product (emulsion polymeric product) of the surface attachment of polymer beads also can produce detrimentally affect to the behavior of the dispersion of the polymer beads in dispersion liquid, causes the dispersion behavior of the polymer beads in dispersion liquid irregular.
Therefore, the displacement (deviation) as the dispersion behavior in the organic solvent of dispersion medium is determined at this.Specifically, the displacement (deviation) of the viscosity number in 10 viscosity numbers mensuration is determined at by the following method as dispersion behavior displacement.
(1) preparation method of dispersion liquid
Sample hose to 10ml adds polymer beads 0.30g and the methylethylketone 3.00g as dispersion medium, use ultrasonic cleaner (Velvo-ClearCo., Ltd. " ULTRASONICCLEANERVS-150 " that manufacture) stir 1 minute, make polymer beads be dispersed in methylethylketone, obtain dispersion liquid.Acrylic resin (" ACRYDIC (registered trademark) A-811 " that Dainippon Ink Chemicals manufactures) 1.00g is added further in this dispersion liquid, about 2 minutes are stirred with above-mentioned ultrasonic cleaner, polymer beads is dispersed in methylethylketone and acrylic resin, prepares dispersion liquid.
(2) measuring method of viscosity number
The mensuration of the viscosity number of dispersion liquid uses viscometer (the micro-example viscometer m-VROC that NihonRufutoCo., Ltd. manufacture) to be undertaken by method as follows.It should be noted that, above-mentioned viscometer is placed more than 30 minutes in advance before the mensuration of viscosity number under mensuration environment.
The above-mentioned ultrasonic cleaner of the dispersion liquid of determination object is stirred 30 minutes, then, under room temperature atmosphere (testing laboratory's temperature 23 DEG C ~ 27 DEG C) environment in leave standstill after 10 hours, again stir 30 minutes with above-mentioned ultrasonic cleaner, use the viscosity (mPas) of the aforementioned dispersion liquid of above-mentioned viscometer determining.Then, use the measured value (mPas) of viscosity and measure temperature (K), being obtained the viscosity number V (mPas/K) of unit temperature (K) by following calculating formula.
Viscosity number V (mPas/K)=measured value (mPas) ÷ measures temperature (K)
The mensuration of viscosity number repeats 10 times, calculates the minimum value of the mean value of viscosity number, the maximum value of viscosity number and viscosity number.
(3) calculation method of behavior displacement and the evaluation method of dispersion stabilization is disperseed
Then, use the maximum value of the viscosity number in measuring for 10 times, minimum value and mean value, calculated displacement (%), i.e. dispersion behavior displacement (%) of viscosity number by following calculating formula, use its dispersion behavior displacement (%) to evaluate dispersion stabilization according to following judgement criteria.
< disperses the calculating formula > of behavior displacement (%)
V＝{(V MAX-V MIN)/V AVE)}×100
V: dispersion behavior displacement (%)
V mAX: the maximum value (mPas/K) of the viscosity number in measuring for 10 times
V mIN: the minimum value (mPas/K) of the viscosity number in measuring for 10 times
V aVE: the mean value (mPas/K) of the viscosity number in measuring for 10 times
The judgement criteria > of < dispersion stabilization
◎ (very good): dispersion behavior displacement is less than 0.3%
Zero (good): dispersion behavior displacement is more than 0.3% and is less than 1.0%
△ (slightly poor): dispersion behavior displacement is more than 1.0% and is less than 3.0%
× (poor): dispersion behavior displacement is more than 3.0%
[measuring method of the levels of residual monomers of polymer beads]
(1) preparation of test liquid
In test tube, add polymer beads 1g, the dithiocarbonic anhydride 25ml as determination object and interior mark liquid 1ml, at room temperature extract 12 hours.Take gained extracting solution 1.8 μ l and inject.It should be noted that, interior mark liquid is the mixture adding toluene 0.1ml at dithiocarbonic anhydride 75ml.
(2) mensuration of levels of residual monomers
Said sample liquid gas chromatograph is measured, by marker method, amount of monomer is carried out quantitatively.As gas chromatograph, the gas chromatograph of the trade(brand)name " GC-14A " using such as Shimadzu Scisakusho Ltd to manufacture, measures under following condition determination.
< condition determination >
Chromatographic column weighting agent: liquid phase P EG-20M
Support C hromosorbW
Column size: 3mmI.D. × 3000mmL
Detector: FID (hydrogen flame ionization detector)
Carrier gas: nitrogen, air, helium
Carrier gas flux: 30ml/min (nitrogen), 300ml/min (air), 35ml/min (helium)
Column temperature: 105 DEG C
Inlet temperature: 110 DEG C
[a kind of tensio-active agent without polyoxyethylene chain is to the measuring method of the solubleness of the scavenging solution of liquid temperature 25 DEG C]
Liquid solute solubleness in a solvent generally judges with " mist degree ", " gonorrhoea degree " of solution liquid solute dissolved in a solvent, therefore, at this, undertaken a kind of tensio-active agent without polyoxyethylene chain the mensuration of the solubleness (D) of the scavenging solution of liquid temperature 25 DEG C by " transmissivity " of the solution measuring the liquid temperature 25 DEG C of surfactant dissolves in scavenging solution a kind without polyoxyethylene chain.It should be noted that, the part due to liquid solute is not dissolved in solvent and separates out, and causes producing gonorrhoea in the transparent liquid (solution), solution loss of transmission.
Record a kind of tensio-active agent without polyoxyethylene chain below to the determination step of the solubleness (D) of the pure water of the scavenging solution as liquid temperature 25 DEG C.
1) first, in special cuvette, inject the pure water of 4ml, measure the transmissivity T of the pure water under wavelength 380nm water.
2) then, under room temperature atmosphere (25 DEG C), be dissolved in pure water 100g by the tensio-active agent Xg a kind without polyoxyethylene chain and prepare adjustment liquid, 4ml is adjusted liquid and inject special cuvette, measure the transmissivity T of the adjustment liquid under wavelength 380nm s.
3) then, the relative transmittance T of adjustment liquid phase for the transmissivity of pure water is calculated by following formula.
T＝(T s)÷(T water)
Then, while repeat to change X, while calculate the relative transmittance T of adjustment liquid, the value obtaining the X that following formula is set up does not have the solubleness S of the tensio-active agent of polyoxyethylene chain as a kind 0(g/4ml).
T＝(T s)÷(T water)＝0.98
Then, by this solubleness S 0(g/4ml) be converted into by following formula the solubleness D (g/100ml) that a kind does not have the tensio-active agent of polyoxyethylene chain.
D＝S 0×100/4
In addition, transmissivity T waterwith transmissivity T smensuration use ultraviolet-visible pectrophotometer (UV-VISIBLESPECTROPHOTOMETER) (model: UV-2450, Shimadzu Scisakusho Ltd manufacture) to carry out.
[Production Example 1 of seed grain]
Add as water 1250g, the methyl methacrylate 64g as (methyl) acrylic ester monomer of aqueous medium and the n octylmercaptan 0.64g as molecular weight regulator in the removable flask possessing agitator, thermometer and reflux exchanger, while stir the content of removable flask, while carry out nitrogen replacement to the inside of removable flask, temperature in removable flask is warming up to 70 DEG C.And then while temperature in removable flask is remained on 70 DEG C, add in the content in removable flask and make the Potassium Persulphate 0.32g as polymerization starter be dissolved in water 50g and after the aqueous solution that obtains, carry out the polyreaction of 5 hours.
Then, again add methyl methacrylate 256g and the n octylmercaptan 2.56g as molecular weight regulator, be added to after in polymerization liquid, again nitrogen replacement is carried out to the inside of removable flask, temperature in removable flask is warming up to 70 DEG C.While temperature in removable flask is remained on 70 DEG C, add in the content in removable flask and make the Potassium Persulphate 1.28g as polymerization starter be dissolved in water 50g and after the aqueous solution that obtains, carry out 12 hours polyreactions.
Reaction solution after polymerization is filtered with the wire netting of 400 orders (32 μm, aperture), the obtained slurry containing 20 % by weight seed grains formed by polymethylmethacrylate (being called seed grain (1)) by solid component meter.The seed grain (1) contained in this slurry to be volume average particle size the be spheroidal particle of 0.54 μm.
[Production Example 2 of seed grain]
Add as water 1450g, the methyl methacrylate 250g as (methyl) acrylic ester monomer of aqueous medium and the n octylmercaptan 2.5g as molecular weight regulator in the removable flask possessing agitator, thermometer and reflux exchanger, while stir the content of removable flask, while carry out nitrogen replacement to the inside of removable flask, temperature in removable flask is warming up to 70 DEG C.And then while temperature in removable flask is remained on 70 DEG C, add in the content in removable flask and make the Potassium Persulphate 1.25g as polymerization starter be dissolved in water 50g and after the aqueous solution that obtains, carry out 12 hours polyreactions.
Reaction solution after polymerization is filtered with the wire netting of 400 orders (32 μm, aperture), the obtained slurry containing 14 % by weight seed grains formed by polymethylmethacrylate (being called seed grain (2)) by solid component meter.The seed grain (2) contained in this slurry to be volume average particle size the be spheroidal particle of 0.42 μm.
[Production Example 3 of seed grain]
To possess agitator and thermometer 5L reactor in add as water 3300g, the methyl methacrylate 360g as (methyl) acrylic ester monomer of aqueous medium and the n octylmercaptan 3.6g as molecular weight regulator, the slurry of the seed grain (2) manufactured in the Production Example 2 of seed grain is added in the mode counting 35.0g by solids component (seed grain), stir content while carry out nitrogen replacement to inside, temperature in reactor is warming up to 70 DEG C.And then while temperature in reactor is remained on 70 DEG C, add in the content in reactor and make the Potassium Persulphate 1.8g as polymerization starter be dissolved in water 60g and after the aqueous solution that obtains, carry out 12 hours polyreactions.
Reaction solution after polymerization is filtered with the wire netting of 400 orders (32 μm, aperture), the obtained slurry containing 10 % by weight seed grains formed by polymethylmethacrylate (hereinafter referred to as seed grain (3)) by solid component meter.The seed grain (3) contained in this slurry to be volume average particle size the be spheroidal particle of 1.02 μm.
[embodiment 1: the Production Example of polymer beads]
(1) polymerization process
For at methyl methacrylate (MMA) 400g as (methyl) acrylic ester monomer, the benzoyl peroxide 6g as polymerization starter is dissolved and the monomer mixture obtained in vinylbenzene (St) 300g as styrene monomer and ethylene glycol dimethacrylate (EGDMA) 300g as polyfunctional vinyl class monomer, using its with count 10g's by pure composition being added with in the ion exchanged water 1000g of aqueous medium, as do not have polyoxyethylene chain anionic surfactant's (not there is the tensio-active agent of polyoxyethylene chain) two (2-ethylhexyl) sodium sulfosuccinate (Japan Oil Co manufacture, ProductName " RAPISOL (registered trademark) A-80 ", to the solubleness of the water of liquid temperature 25 DEG C, material mixing 1.5g/100ml) obtained, drops into homogeneous mixer (" T.K.HOMOMIXERMARKII2.5 type " that PRIMIXCorporation manufactures) and within 10 minutes, obtains emulsion with rotating speed 10000rpm process.In this emulsion, add the slurry of the seed grain (1) obtained in the Production Example 1 of seed grain in the mode counting 9.6g by solids component (seed grain), stir 5 hours at 30 DEG C, obtain dispersion liquid.
Add in this dispersion liquid be dissolved with by pure composition count 10g, as have polyoxyethylene chain anionic surfactant ethylene nonyl phenyl ether sodium phosphate (Dong Bang KCC manufacture, ProductName " PHOSPHANOL (registered trademark) LO-529 ") and as the Sodium Nitrite 0.60g of stopper the aqueous solution 2000g that obtains, then at 80 DEG C stir 5 hours, then at 105 DEG C stir within 3 hours, carry out polyreaction, obtain the slurry (hereinafter referred to as slurry (1)) of polymer beads as crude product.
(2) solid-liquid separation process
To have the formation shown in Fig. 1 pressure filter 1 pressure vessel 2 in add the slurry (1) of the polymer beads as crude product P, at the filter cloth (ShikishimaCanvasCo. as the filtering material 3 in pressure vessel 2, Ltd. " T713 " that manufacture) upper filled polymer particle slurry (1) after, utilize pressurized gas supplying machine to the upside space S supplying compressed gas of the filtering material 3 in pressure vessel 2, thus the inside (being specially the upside space S of filtering material 3) of pressure vessel 2 is forced into 0.15MPa.Thus, pressure filtration dewatering is carried out to the slurry (1) of the polymer beads as crude product P, the water as aqueous medium is removed with the form of filtrate from the slurry (1) of polymer beads.The amount of filtrate reach more than the 2.10kg weight of the water used in polymerization process (70%) and the interior pressure of pressure vessel 2 reach 0.10MPa (2/3 of pressure during pressurization) below time, terminate pressurization.Thus, filtering material 3 obtains the filter cake of polymer beads.
It should be noted that, the filtering material 3 (filter cloth) of the pressure filter 1 used in the present embodiment is circular with the interface being filtered thing (i.e. crude product P), its diameter is identical with the diameter (diameter represented by the symbol R of Fig. 1) of the bottom surface of the internal space of pressure vessel 2, is 0.115m.Therefore, the filtering material 3 (filter cloth) of the pressure filter 1 used in the present embodiment is 0.0104m with the area A at the interface being filtered thing (i.e. crude product P) 2.
In addition, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment 1for 2.24kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 45.0 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0498kg/min by the amount X of the medium of filtering material.
(3) matting
To keep the state of the filter cake of above-mentioned polymer beads on filtering material 3, after on the filtering material 3 that is supplied to as the water (also using the water of 60 DEG C in the matting of other embodiments and comparative example) of 60 DEG C of scavenging solution in pressure vessel 2, utilize pressurized gas supplying machine to the upside space S supplying compressed gas of the filtering material 3 in pressure vessel 2, thus the inside (being specially the upside space S of filtering material 3) of pressure vessel 2 is forced into 0.10MPa.Carry out pressure filtration dewatering thus, the filter cake of above-mentioned polymer beads is cleaned, and the water after cleaning is removed with the form of filtrate, filtering material 3 obtains the polymer beads after cleaning.Cleaning uses in polymerization process the scavenging solution of more than 10 times weight of the weight of the polymer beads (the total amount 1000g of the vinyl monomer used in polymerization process) obtained, less than 2.0 times (being specially 15 below μ S) of the electric conductivity of the water before the electric conductivity proceeding to filtrate becomes cleaning and the interior pressure of pressure vessel 2 becomes 0.066MPa (2/3 of pressure during pressurization) below.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) as follows.
B L＝(10(g)÷1.5(g/100ml))×1.8＝12.0(kg)
B H＝(10(g)÷1.5(g/100ml))×2.3＝15.3(kg)
The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B labove, aforementioned higher limit B hweight in following scope.
In addition, in the matting of the present embodiment, from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 140.5 minutes.Therefore, in matting, the unit time is 0.0740kg/min by the amount Y of the medium of filtering material.
(4) postprocessing working procedures
[drying process]
Use Vacuumdrier (broken drying machine), under following drying conditions, the moisture value polymer beads after the cleaning obtained by matting being dried to the polymer beads recorded with Karl_Fischer method is less than 1.0 % by weight.
(drying conditions)
Vacuum tightness :-0.1 ~-0.3MPa
Temperature: 50 ~ 60 DEG C
[classification operation (big particle removal)]
Use air classifier (" TURBOCLASSIFIER (registered trademark) TC-15 " that NisshinEngineeringInc. manufactures), to remove the mode with the particle of the particle diameter of more than 2.5 times of the particle diameter of target polymerization composition granule, classification is carried out to the dried polymer beads obtained by drying process, obtain target polymerization composition granule.
(confirmation of by product (emulsion polymeric product))
The SEM image of the polymer beads after the firm polyreaction obtained in embodiment 1 is shown in Fig. 2, and the SEM image of the polymer beads obtained after the solid-liquid separation process and matting of embodiment 1 is shown in Fig. 3.The particle confirmed as particle diameter about the 100 ~ 200nm of by product (emulsion polymeric product) by Fig. 2 is attached to polymer particle surface.Confirm by product (emulsion polymeric product) by Fig. 3 and be not almost attached to polymer particle surface (only adhering to minute quantity).
[embodiment 2: the Production Example of polymer beads]
As anionic surfactant's (not there is the tensio-active agent of polyoxyethylene chain) without polyoxyethylene chain, use Sodium Lauryl Sulphate BP/USP (Kao Corp's manufacture, ProductName " Emal (registered trademark) 2FG ", the solubleness to the water of liquid temperature 25 DEG C of counting 50g by pure composition; 10g/100ml) replace two (2-ethylhexyl) sodium sulfosuccinate counting 10g by pure composition, change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.30kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 50.0 minutes, using the weight G of the water as scavenging solution used in matting 2change to 10.5kg (weight of 10.5 times of the polymer beads obtained in polymerization process), change matting condition using make from make scavenging solution by filtering material 3 to 8.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 150.2 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.0460kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.0559kg/min by the amount Y of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) as follows.
B L＝(50(g)÷10(g/100ml)×1.8＝9.0(kg)
B H＝(50(g)÷10(g/100ml))×2.3＝11.5(kg)
The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 10.5kg (weight of 10.5 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B labove, aforementioned higher limit B hweight in following scope.
[embodiment 3: the Production Example of polymer beads]
As anionic surfactant's (not there is the tensio-active agent of polyoxyethylene chain) without polyoxyethylene chain, use alkenyl succinic dipotassium (Kao Corp's manufacture, ProductName " LATEMUL (registered trademark) ASK ", the solubleness to the water of liquid temperature 25 DEG C of counting 10g by pure composition; 1.7g/100ml) replace two (2-ethylhexyl) sodium sulfosuccinate counting 10g by pure composition, in addition carry out similarly to Example 1 obtaining target polymerization composition granule.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment 1for 2.30kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 40.9 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0562kg/min by the amount X of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) as follows.
B L＝(10(g)÷1.7(g/100ml)×1.8＝10.6(kg)
B H＝(10(g)÷1.7(g/100ml))×2.3＝13.5(kg)
The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B labove, aforementioned higher limit B hweight in following scope.
In addition, in the matting of the present embodiment, from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 132.0 minutes.Therefore, in matting, the unit time is 0.0788kg/min by the amount Y of the medium of filtering material.
[embodiment 4: the Production Example of polymer beads]
As the anionic surfactant with polyoxyethylene chain, use the polyoxyethylene styrene phenyl ether sulfuric ester ammonium (Di-ichi Kogyo Seiyaku Co., Ltd. manufacture, ProductName " HITENOL (registered trademark) NF-08 ") counting 10g by pure composition to replace counting by pure composition the ethylene nonyl phenyl ether sodium phosphate of 10g, the condition changing matting using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 129.0 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment 1for 2.28kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 41.0 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0556kg/min by the amount X of the medium of filtering material.In addition, in matting, the unit time is 0.0806kg/min by the amount Y of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 5: the Production Example of polymer beads]
As the anionic surfactant with polyoxyethylene chain, use the polyoxyethylene styrene phenyl ether phosphoric acid ester (Di-ichi Kogyo Seiyaku Co., Ltd. manufacture, ProductName " PLYSURF (registered trademark) AL ") counting 10g by pure composition to replace counting by pure composition the ethylene nonyl phenyl ether sodium phosphate of 10g, change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.25kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 40.8 minutes, change matting condition using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 133.5 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.0551kg/min by the amount X of the medium of filtering material.In matting, the unit time is 0.0779kg/min by the amount Y of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 6: the Production Example of polymer beads]
As in polymerization process for obtaining the tensio-active agent of emulsion, use and count 20g's by pure composition, as have polyoxyethylene chain anionic surfactant ethylene nonyl phenyl ether sodium phosphate (Dong Bang KCC manufacture, ProductName " PHOSPHANOL (registered trademark) LO-529 ") replace two (2-ethylhexyl) sodium sulfosuccinate counting 10g by pure composition, in polymerization process, ethylene nonyl phenyl ether sodium phosphate is not added (as the aqueous solution adding dispersion liquid to dispersion liquid, the aqueous solution 2000g being dissolved with Sodium Nitrite 0.60g is used to replace being dissolved with counting the ethylene nonyl phenyl ether sodium phosphate of 10g and the aqueous solution 2000g of Sodium Nitrite 0.60g by pure composition), and using the weight G of the water as scavenging solution used in the matting of the present embodiment 2change to 10.0kg (weight of 10.0 times of the polymer beads obtained in polymerization process), change matting condition using make from make scavenging solution by filtering material 3 to 8.0kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 100.6 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment 1for 2.29kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 43.0 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0533kg/min by the amount X of the medium of filtering material.In addition, in matting, the unit time is 0.0795kg/min by the amount Y of the medium of filtering material.
[embodiment 7: the Production Example of polymer beads]
Do not use vinylbenzene (St), the consumption of methyl methacrylate (MMA) is changed to 700g, change matting condition using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 143.8 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment 1for 2.31kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 43.2 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0535kg/min by the amount X of the medium of filtering material.In addition, in matting, the unit time is 0.0723kg/min by the amount Y of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 8: the Production Example of polymer beads]
Do not use methyl methacrylate (MMA), the consumption of vinylbenzene (St) is changed to 900g, the consumption of ethylene glycol dimethacrylate (EGDMA) is changed to 100g, change matting condition using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 137.5 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment 1for 2.30kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 44.0 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0523kg/min by the amount X of the medium of filtering material.In addition, in matting, the unit time is 0.0756kg/min by the amount Y of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 9: the Production Example of polymer beads]
The slurry adding the seed grain (3) obtained in the Production Example 3 of seed grain in the mode counting 4.7g by solids component (seed grain) replaces adding in the mode counting 9.6g by solids component (seed grain) slurry of seed grain (1), the condition of change matting using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 130.0 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment 1for 2.45kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 45.0 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0544kg/min by the amount X of the medium of filtering material.In addition, in matting, the unit time is 0.0800kg/min by the amount Y of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 10: the Production Example of polymer beads]
Use by pure composition count 10g, as the polyoxyethylene styrene phenyl ether (Di-ichi Kogyo Seiyaku Co., Ltd. manufacture, ProductName " NOIGEN (registered trademark) EA-167 ") of the nonionic surfactant with polyoxyethylene chain replace by pure composition count 10g, as the ethylene nonyl phenyl ether sodium phosphate of anionic surfactant with polyoxyethylene chain, the condition of change solid-liquid separation process is to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.29kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 51.0 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.0499kg/min by the amount X of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process).
In addition, in the matting of the present embodiment, from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 170.0 minutes.Therefore, in matting, the unit time is 0.0612kg/min by the amount Y of the medium of filtering material.
[embodiment 11: the Production Example of polymer beads]
Using as have polyoxyethylene chain anionic surfactant ethylene nonyl phenyl ether sodium phosphate (Dong Bang KCC manufacture, ProductName " PHOSPHANOL (registered trademark) LO-529 ") change to 25g by the addition of pure composition from 10g, change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.35kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 43.3 minutes, change matting condition using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 126.8 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.0543kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.0820kg/min by the amount Y of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 12: the Production Example of polymer beads]
Using as have polyoxyethylene chain anionic surfactant ethylene nonyl phenyl ether sodium phosphate (Dong Bang KCC manufacture, ProductName " PHOSPHANOL (registered trademark) LO-529 ") change to 5g by the addition of pure composition from 10g, the condition changing matting using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 135.5 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment 1for 2.32kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 45.5 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0510kg/min by the amount X of the medium of filtering material.In addition, in matting, the unit time is 0.0768kg/min by the amount Y of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 13: the Production Example of polymer beads]
Using the weight G of the water as scavenging solution used in matting 2change to 12.1kg (weight of 12.1 times of the polymer beads obtained in polymerization process), change matting condition using make from make scavenging solution by filtering material 3 to 9.68kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 110.0 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.In the matting of the present embodiment, the unit time is 0.0880kg/min by the amount Y of the medium of filtering material.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment 1for 2.37kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 43.2 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0549kg/min by the amount X of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2(=12.1kg) is at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 14: the Production Example of polymer beads]
Change matting condition using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 357.4 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.In the matting of the present embodiment, in matting, the unit time is 0.0291kg/min by the amount Y of the medium of filtering material.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment 1for 2.34kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 50.2 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0466kg/min by the amount X of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 15: the Production Example of polymer beads]
Using the weight G of the water as scavenging solution used in matting 2change to 12.0kg (weight of 12.0 times of the polymer beads obtained in polymerization process), change matting condition using make from make scavenging solution by filtering material 3 to 9.60kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 109.0 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.In matting, the unit time is 0.0881kg/min by the amount Y of the medium of filtering material.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment 1for 2.30kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 41.5 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0554kg/min by the amount X of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2(=12.0kg) is at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 16: the Production Example of polymer beads]
Be used as the polyvinyl alcohol of macromolecular dispersion stabilizer (PVA) (the Nippon Synthetic Chemical Industry Co., Ltd manufacture, ProductName " GOHSENOLGM-14L ") 40g replace by pure composition count 10g, as the ethylene nonyl phenyl ether sodium phosphate of anionic surfactant with polyoxyethylene chain, the condition of change solid-liquid separation process is to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.35kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 53.3 minutes, change matting condition using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 145.2 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.0441kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.0716kg/min by the amount Y of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 17: the Production Example of polymer beads]
Do not use vinylbenzene (St), the consumption of methyl methacrylate (MMA) is changed to 700g, change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.30kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 58.2 minutes, change matting condition using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 140.5 minutes, in addition carry out similarly to Example 16, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.0395kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.0740kg/min by the amount Y of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[embodiment 18: the Production Example of polymer beads]
Do not use methyl methacrylate (MMA), the consumption of vinylbenzene (St) is changed to 700g, change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.31kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 56.2 minutes, change matting condition using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 143.5 minutes, in addition carry out similarly to Example 16, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.0411kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.0725kg/min by the amount Y of the medium of filtering material.
In addition, a kind that uses is not had to the tensio-active agent of polyoxyethylene chain in above-mentioned polymerization process, the lower value B of the weight of the scavenging solution calculated by aforementioned calculating formula (4) and (5) land higher limit B (kg) h(kg) similarly to Example 1.The weight G of the water as scavenging solution used in the matting of the present embodiment 2for 13.0kg (weight of 13.0 times of the polymer beads obtained in polymerization process), be at aforementioned minimum value B lmore than (=12.0 (kg)), aforementioned higher limit B hweight in (=15.3 (kg)) scope below.
[comparative example 1: the Production Example of polymer beads]
Change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.33kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 47.5 minutes, omit matting (the weight G of the water as scavenging solution used in matting 2be considered as 0), in addition carry out similarly to Example 1, obtain target polymerization composition granule.In solid-liquid separation process, the unit time is 0.0491kg/min by the amount X of the medium of filtering material.
[comparative example 2: the Production Example of polymer beads]
Change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.41kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 45.0 minutes, using the weight G of the water as scavenging solution used in matting 2change to 5.0kg (weight of 5.0 times of the polymer beads obtained in polymerization process), change matting condition using make from make scavenging solution by filtering material 3 to 4.0kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 48.6 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.0536kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.0823kg/min by the amount Y of the medium of filtering material.
[comparative example 3: the Production Example of polymer beads]
Change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.39kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 47.7 minutes, using the weight G of the water as scavenging solution used in matting 2change to 5.0kg (weight of 5.0 times of the polymer beads obtained in polymerization process), change matting condition using make from make scavenging solution by filtering material 3 to 4.0kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 55.2 minutes, in addition carry out similarly to Example 4, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.0501kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.0725kg/min by the amount Y of the medium of filtering material.
[comparative example 4: the Production Example of polymer beads]
Using as have polyoxyethylene chain anionic surfactant ethylene nonyl phenyl ether sodium phosphate (Dong Bang KCC manufacture, ProductName " PHOSPHANOL (registered trademark) LO-529 ") change to 40g by the addition of pure composition from 10g, using the weight G of the water as scavenging solution used in matting 2change to 5.0kg (weight of 5.0 times of the polymer beads obtained in polymerization process), change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.30kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 42.8 minutes, change matting condition using make from make scavenging solution by filtering material 3 to 4.0kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 49.7 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.0537kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.0805kg/min by the amount Y of the medium of filtering material.
[comparative example 5: the Production Example of polymer beads]
Change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.25kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 21.8 minutes, change matting condition using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 93.3 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.1032kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.1115kg/min by the amount Y of the medium of filtering material.
[comparative example 6: the Production Example of polymer beads]
Change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.25kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 17.7 minutes, change matting condition using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 118.3 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.
In solid-liquid separation process, the unit time is 0.1271kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.0879kg/min by the amount Y of the medium of filtering material.
[comparative example 7: the Production Example of polymer beads]
Change matting condition using make from make scavenging solution by filtering material 3 to 10.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 90.0 minutes, in addition carry out similarly to Example 1, obtain target polymerization composition granule.In matting, the unit time is 0.1156kg/min by the amount Y of the medium of filtering material.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of this comparative example 1for 2.33kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 55.2 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0422kg/min by the amount X of the medium of filtering material.
[comparative example 8: the Production Example of polymer beads]
Using the weight G of the water as scavenging solution used in matting 2change to 3.0kg (weight of 3.0 times of the polymer beads obtained in polymerization process), change matting condition using make from make scavenging solution by filtering material 3 to 2.4kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 27.3 minutes, in addition carry out similarly to Example 6, obtain target polymerization composition granule.
It should be noted that, the gross weight G of the filtrate (medium) obtained in the solid-liquid separation process of this comparative example 1for 2.25kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1it is 40.2 minutes.Therefore, in solid-liquid separation process, the unit time is 0.0560kg/min by the amount X of the medium of filtering material.In matting, the unit time is 0.0880kg/min by the amount Y of the medium of filtering material.
[comparative example 9: the Production Example of polymer beads]
Polymer beads is prepared according to the embodiment 5 of patent documentation 5 (Japanese Unexamined Patent Publication 2009-203378 publication).Namely, first in the four-hole boiling flask possessing prolong, thermometer and dropping mouth, ion exchanged water 529g, 25 % by mole of ammonia soln 1.6g and methyl alcohol 118g are loaded, in this mixed solution, add 3-methacryloxypropyl trimethoxy silane (Shin-Etsu Chemial Co., Ltd's manufacture, KBM-503) 25g from dripping mouth while stirring, organopolysiloxane particles is prepared in hydrolysis, the condensation of carrying out 3-methacryloxypropyl trimethoxy silane.After autoreaction starts 2 hours, the emulsion of the organopolysiloxane particles obtained is sampled, measure volume average particle size by the measuring method recorded in [measuring method of the volume average particle size of polymer beads and the variation coefficient of particle diameter], result volume average particle size is 1.9 μm.
Then, to using as have polyoxyethylene chain anionic surfactant polyoxyethylene styrene phenyl ether sulfate ammonium salt (Di-ichi Kogyo Seiyaku Co., Ltd. manufacture, ProductName " HITENOL (registered trademark) NF-08 ") 20.0g (by pure composition about about 19g) dissolves with ion exchanged water 1750g and in the solution that obtains, add and be dissolved with vinylbenzene (St) 600g, 1, 6-hexanediol dimethacrylate (HDDMA) 400g, 2, 2 '-azo two (2, 4-methyl pentane nitrile) (Wako Pure Chemical Industries, Ltd. manufactures, V-65) solution of 20g, within 5 minutes, emulsion is prepared with 6000rpm emulsion dispersion by TKHOMOMIXER (PRIMIXCorporation (old Tokushu Kika Kogyo K.K) manufacture), gained monomer emulsion is added in the emulsion of organopolysiloxane particles, stir further.After monomer emulsion adds 2 hours, to reaction solution sampling microscopic examination, results verification absorbs monomer to organopolysiloxane particles and there occurs hypertrophyization.
Then, reaction solution is warming up to 65 DEG C under nitrogen atmosphere, at 65 DEG C, keeps the radical polymerization carrying out monomer for 2 hours.After reaction solution is cooled, filter, leaching polymerisate.Now, the solid component concentration of regenerant (polymerisate of institute's leaching) is 67 % by weight.
In regenerant, add ion exchanged water 1kg makes solid component concentration be 40 % by weight, stirs after 30 minutes, and filtered and recycled is through the polymerisate of cleaning.Now, after cleaning, the solid component concentration of regenerant is 60 % by weight.
Within 6 hours, organo-mineral complexing particle is obtained by dry at 100 DEG C for regenerant drying machine after cleaning.For gained organo-mineral complexing particle, measured the variation coefficient of volume average particle size and particle diameter by aforesaid measuring method, result volume average particle size is 3.82 μm, the variation coefficient of particle diameter is 7.22%.Further, for the content of gained organo-mineral complexing particle by aforesaid measuring method chart surface-active agent, result is 1940 weight ppm (0.19 % by weight).
In addition, the filtration of the 1st time, use quantitative paper (AdvantecToyoKaisha, Ltd. manufacture, quantitative paper No.5C) replace filter cloth as filtering material 3, change the condition of solid-liquid separation process to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 0.80kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 18.5 minutes, carry out in addition equally with the solid-liquid separation process of embodiment 1.The weight G of the water as scavenging solution that the filtration of the 2nd time will use in matting 2change to 1.0kg (weight of 1.0 times of the polymer beads obtained in polymerization process) to make solid component concentration be 40 % by weight, change matting condition using make from make scavenging solution by filtering material 3 to 0.8kg (the weight G of the water as scavenging solution used in matting 2the weight of 0.8 times) scavenging solution by institute time spent T till filtering material 3 2(min) be 28.9 minutes, use quantitative paper (AdvantecToyoKaisha, Ltd. manufacture, quantitative paper No.5C) to replace filter cloth as filtering material 3, to carry out in addition equally with the matting of embodiment 1.
In solid-liquid separation process, the unit time is 0.0432kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.0277kg/min by the amount Y of the medium of filtering material.
[comparative example 10: the Production Example of polymer beads]
Polymer beads is prepared according to the embodiment 4 of patent documentation 7 (Japanese Unexamined Patent Publication 10-7730 publication).Namely, first, in the flask possessing agitator, non-active gas ingress pipe, reflux exchanger and thermometer, in pure water 3600g, add polyoxyethylene styrene phenyl ether sulfate ammonium salt (Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture, ProductName " HITENOL (registered trademark) the NF-08 ") 2.0g as the anionic surfactant with polyoxyethylene chain and make it dispersed.Then, add previously prepared good monomer mixed solution wherein, stir 5 minutes by homogeneous mixer (" T.K.HOMOMIXERMARKII2.5 type " that PRIMIXCorporation manufactures) with the rotating speed of 8000rpm, prepare uniform suspension liquid thus.
Monomer mixed solution is prepared by (ProductName " TIPAQUE (registered trademark) CR-60-2 ", Ishihara Sangyo Kaisha, Ltd. manufacture) 80g, 2,2 '-Diisopropyl azodicarboxylate 4.0g and the thiosalicylic acid 4.0g of compounding titanium oxide in the polymerizable monomer composition comprising methyl methacrylate 300g and ethylene glycol dimethacrylate 20g.
Then, while be blown into nitrogen limit to be heated to 75 DEG C, Keep agitation carries out suspension polymerization in 5 hours at such a temperature, then cools.
Then, the condition of solid-liquid separation process is changed to make the gross weight G of the filtrate (medium) obtained in solid-liquid separation process 1for 2.77kg, from make the medium (water) that contains in crude product P by filtering material 3 to terminating aforementioned medium by the time T filtering material 3 1be 38.2 minutes, in addition implement solid separation circuit similarly to Example 1, implement drying process according to step similarly to Example 1, obtain target polymerization composition granule (not implementing matting and classification operation) thus.
In solid-liquid separation process, the unit time is 0.0725kg/min by the amount X of the medium of filtering material.
The image analysis carrying out made polymer beads is observed by SEM, result can be inferred, the concentration (content of by product) of the non-volatile component in the supernatant liquor that the centrifugal separation recorded by this specification sheets is obtained 1.50 ~ 2.00 % by weight scope.
[comparative example 11: the Production Example of polymer beads]
Polymer beads is prepared according to the embodiment 1 of patent documentation 6 (Japanese Unexamined Patent Publication 7-316209 publication).Namely, first agitator is being possessed, non-active gas ingress pipe, in the flask of reflux exchanger and thermometer, polyoxyethylene styrene phenyl ether sulfate ammonium salt (Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture as the anionic surfactant with polyoxyethylene chain is added in pure water 3600g, ProductName " HITENOL (registered trademark) NF-08 ") 2.0g make it dispersed, as letex polymerization hold back agent, further interpolation is as C.I.10410 (Nippon Kayaku K. K's manufacture of dark brown matching stain, ProductName " Kayanol (registered trademark) MillingBrown4GW ") 0.04g make it dissolve.Then, add previously prepared good monomer mixed solution wherein, 5 minutes are stirred with the rotating speed of 8000rpm, thus obtained uniform suspension liquid by homogeneous mixer (" T.K.HOMOMIXERMARKII2.5 type " that PRIMIXCorporation manufactures).
Monomer mixed solution is by compounding vinylbenzene 320g, n-butyl acrylate (BA) 80g and 2,2 '-Diisopropyl azodicarboxylate 2.0g and obtain.
Then, while be blown into nitrogen limit to be heated to 75 DEG C, Keep agitation carries out suspension polymerization in 5 hours at such a temperature, then cools.
Then, after gained resin particle slurry is filtered, dry, obtain target polymerization composition granule thus.Do not record the details of filter progress (solid-liquid separation process) and drying process in the embodiment 1 of patent documentation 6, in this comparative example, implement filter progress (solid-liquid separation process) and drying process as follows.Namely, after gained resin particle slurry is dewatered with the separating centrifuge (TanabeWilltecInc. manufacture, machine models: CO-20) in the basket portion (basket) with diameter 485mm × degree of depth 275mm implement solid-liquid separation process in 10 minutes with rotating speed 2000rpm, implement drying process according to step similarly to Example 1, obtain target polymerization composition granule (not implementing classification operation) thus.
The image analysis carrying out made polymer beads is observed, the existence of the visible by product of result (emulsification) by SEM.And can infer, concentration (content of the by product) scope 1.40 ~ 1.90% of the non-volatile component in the supernatant liquor that the centrifugal separation recorded by this specification sheets is obtained.
[comparative example 12: the Production Example of polymer beads]
Polymer beads is prepared according to the embodiment 5 of patent documentation 6 (Japanese Unexamined Patent Publication 7-316209 publication).Namely, the addition of the C.I.10410 (Nippon Kayaku K. K's manufacture, ProductName " Kayanol (registered trademark) MillingBrown4GW ") as letex polymerization hold back agent is changed to 40g, in addition equally with comparative example 11 to carry out, obtain polymer beads.
The image analysis carrying out made polymer beads is observed, the existence of the visible by product of result (emulsification) by SEM.And can infer, the concentration (content of by product) of the non-volatile component in the supernatant liquor that the centrifugal separation recorded by this specification sheets is obtained 1.10 ~ 1.60 % by weight scope.
[comparative example 13: the Production Example of polymer beads]
The consumption of each material is reduced to 1/4, changes size and the rotating speed in the basket portion in separating centrifuge, in addition with the reference example 4 of patent documentation 1 (Japanese Unexamined Patent Publication 2006-233055 publication) with embodiment 6 is same carries out, prepare polymer beads.
Namely, first in the reactor (autoclave) possessing discoideus agitating vane, trisodium phosphate 33g is added and after making it dissolve in pure water 2000g, add pulverous magnesium chloride hexahydrate 59g, stir under room temperature atmosphere and obtain magnesium pyrophosphate slurry with the form of clouding agent in 30 minutes.
Then, to this containing adding Sodium dodecylbenzene sulfonate (SDBS) 10 % by weight aqueous solution 11.0g as the anionic surfactant without polyoxyethylene chain in the slurry of reaction product and after making it disperse, add previously prepared good monomer mixed solution, stir 15 minutes to carry out differential by utilizing homogeneous mixer (" T.K.HOMOMIXERMARKII2.5 type " that PRIMIXCorporation manufactures) with the rotating speed of 10000rpm and fall apart.
Monomer mixed solution is by compounding vinylbenzene 500g, Vinylstyrene 10g, peroxide-2-ethyl hexanoic acid tert-butyl 1.5g and tert-butyl peroxide-2-ethylhexyl carbonate 0.5g and obtaining.
Then, after purging with nitrogen in reactor, the discoideus agitating vane of diameter 120mm is stirred with rotating speed 250rpm, while be warming up to 90 DEG C with 1 and a half hours, keep carrying out polyreaction in 8 hours at 90 DEG C after, be cooled to 30 DEG C with 4 hours.In the resin particle slurry after polyreaction, add the nitric acid 80ml of 10% purity, carry out stir process and clouding agent is dissolved.
Then, the separating centrifuge with basket portion is used to implement solid-liquid separation process and matting to gained resin particle slurry.In this comparative example, as the basket portion of separating centrifuge, the basket portion of diameter 485mm × degree of depth 275mm is used to replace the basket portion of the diameter 250mm × degree of depth 150mm used in the embodiment 6 of patent documentation 1, therefore in order to make the centrifugal force of separating centrifuge identical with the embodiment 6 of patent documentation 1 (thus the effect of the centrifugation of separating centrifuge is equal) rotating speed of separating centrifuge be changed to 2150rpm to implement solid-liquid separation process and cleaning and dewatering.That is, within 5 minutes, solid-liquid separation process is implemented by being dewatered with rotating speed 2150rpm with the separating centrifuge (TanabeWilltecInc. manufacture, mechanical model: CO-20) in basket portion with diameter 485mm × degree of depth 275mm by the resin particle slurry of gained.Then, while make separating centrifuge rotate with rotating speed 2150rpm, while spray supply as the electric conductivity 20 μ S of rinse water, the water 2.5kg (being equivalent to the weight of 5.0 times of resin particle) of 40 DEG C with water-jet to dewatered cake, cleaning and dewatering is carried out to resin particle.Then, through drying process, obtain polymer beads (not implementing classification operation).
In solid-liquid separation process, the unit time is 0.0592kg/min by the amount X of the medium of filtering material, and in matting, the unit time is 0.0702kg/min by the amount Y of the medium of filtering material.
[embodiment 19: the Production Example of optical thin film]
The polymer beads 0.20g obtained in the embodiment 1 and butylacetate 1.00g as organic solvent is added in the sample hose of 10ml, use ultrasonic cleaner (Velvo-ClearCo., Ltd. " ULTRASONICCLEANERVS-150 " is manufactured) stir 1 minute, in the butylacetate that polymer beads is dispersed in as organic solvent, obtain dispersion liquid.Acrylic resin (" ACRYDIC (registered trademark) A-817 " that Dainippon Ink Chemicals manufactures, containing as the toluene of organic solvent and butylacetate 49.0 ~ 51.0 % by weight) 1.50g is added further in this dispersion liquid, stir about 2 minutes with above-mentioned ultrasonic cleaner, obtain coating resin combination.After this coating is left standstill 4 hours with resin combination, in coating resin combination, add the butylacetate 5.50g as organic solvent, stir 1 minute with above-mentioned ultrasonic cleaner, obtain the diluent of coating resin combination.
The coating machine of 75 μm of slits is used to be coated in by the diluent of the coating resin combination of gained in the PET film (Fuji Photo Film Co., Ltd.'s manufacture, trade(brand)name " used in copy machines FUJIX (registered trademark) OHP film ") of thickness 100 μm.After coating, put into the drying machine that temperature remains on 70 DEG C and place 1 hour, obtain optical thin film thus.
[embodiment 20: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 2 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 21: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 3 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 22: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 4 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 23: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 5 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 24: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 6 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 25: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 7 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 26: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 8 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 27: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 9 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 28: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 10 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 29: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 11 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 16, obtain optical thin film.
[embodiment 30: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 12 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 31: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 13 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 32: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 14 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 33: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 15 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 34: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 16 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 35: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 17 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[embodiment 36: the Production Example of optical thin film]
Use the polymer beads 0.20g obtained in embodiment 18 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 14: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 1 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 15: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 2 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 16: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 3 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 17: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 4 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 18: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 5 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 19: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 6 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 20: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 7 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 21: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 8 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 22: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 9 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 23: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 10 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 24: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 11 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 25: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 12 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
[comparative example 26: the comparison Production Example of optical thin film]
Use the polymer beads 0.20g obtained in comparative example 13 to replace the polymer beads 0.20g obtained in embodiment 1, in addition carry out similarly to Example 19, obtain optical thin film.
For the optical thin film of embodiment 19 ~ 36 and comparative example 14 ~ 26, by method evaluation optical characteristics shown below.
[evaluation method of optical characteristics (number of the deviation of mist degree)]
The optical thin film of the square shape of 6cm × 6cm will be cut into as test film.To 4 ends up and down and central part (the totally 5 places) mist degree everywhere in the face of coating resin combination that is coated with of test film, " NDH-4000 " that use Japanese electricity Se Industrial Co., Ltd to manufacture according to JISK7136 measures.Then, use the maximum value of the mist degree (%) at 5 measured places, minimum value and mean value, calculate mist degree difference (%) by following calculating formula, evaluate its mist degree difference (%) according to following judgement criteria.
The calculating formula > of < mist degree difference (%)
R＝{(Hz MAX-Hz MIN)/Hz AVE)}×100
R: mist degree difference (%)
Hz mAX: the maximum value of 5 place's mist degrees (%)
Hz mIN: the minimum value of 5 place's mist degrees (%)
Hz aVE: the mean value of 5 place's mist degrees (%)
< judgement criteria >
◎: mist degree difference is less than 0.5%
Zero: mist degree difference is more than 0.5% and is less than 1.0%
△: mist degree difference is more than 1.0% and is less than 3.0%
×: mist degree difference is more than 3.0%
About embodiment 1 ~ 18 and comparative example 1 ~ 13, table 1 and table 3 illustrate the numbering (seed grain numbering) of the seed grain used in polymerization process, the composition (monomer composition) of the monomer used in polymerization process, the tensio-active agent without polyoxyethylene chain used in polymerization process and there is the kind of tensio-active agent of polyoxyethylene chain, the kind of the macromolecular dispersion stabilizer used in polymerization process, the measurement result of the X value (unit time is by the amount (kg/min) of the medium of filtering material) in solid-liquid separation process, the measurement result of the Y value (unit time is by the amount (kg/min) of the scavenging solution of filtering material) in matting, the amount (kg) of the scavenging solution (water) used in matting, the measurement result of the volume average particle size (μm) of the polymer beads of gained and the variation coefficient (CV value (%)) of particle diameter, the measurement result of the specific refractory power of the polymer beads of gained, and the measurement result of the gel fraction of the polymer beads of gained (%).
In addition, about the polymer beads obtained in embodiment 1 ~ 18 and comparative example 1 ~ 13, table 2 and table 4 illustrate the specific surface area (m of polymer beads 2/ g) measurement result, the measurement result of the content (% by weight) without the tensio-active agent of polyoxyethylene chain in polymer beads, polymer beads per surface area polymer beads in the content (× 10 without the tensio-active agent of polyoxyethylene chain -3g/m 2) measurement result, the measurement result of dispersion behavior displacement (%) of polymer beads, the evaluation result of the dispersion stabilization of polymer beads, the measurement result of content of by product (emulsion polymeric product) in polymer beads and polymer beads in the measurement result of levels of residual monomers.In addition, about the optical thin film of embodiment 19 ~ 36 and comparative example 14 ~ 26, table 2 and table 4 illustrate the measurement result of mist degree difference (%) of optical thin film and the evaluation result of the optical characteristics of optical thin film in the lump.
In addition, in table 1 ~ 4, " other tensio-active agents " represents the tensio-active agent without polyoxyethylene chain.In addition, in table 1 and table 3, DSS represents two (2-ethylhexyl) sodium sulfosuccinate, and LS represents Sodium Lauryl Sulphate BP/USP, and ASK represents alkenyl succinic dipotassium, POEPS represents ethylene nonyl phenyl ether sodium phosphate, ASPSE represents polyoxyethylene styrene phenyl ether sulfuric ester ammonium, and POESE represents polyoxyethylene styrene phenyl ether phosphoric acid ester, and PSE represents polyoxyethylene styrene phenyl ether, PVA represents polyvinyl alcohol, and SDBS represents Sodium dodecylbenzene sulfonate.
[table 1]
[table 2]
[table 3]
[table 4]
The filtering material 3 (filter cloth) of pressure filter 1 (see Fig. 1) used in the solid-liquid separation process of embodiment 1 ~ 18 and comparative example 1 ~ 10 and matting is 0.0104 (m with the area A at the interface of filtrate (i.e. crude product P) 2).Therefore, in embodiment 1 ~ 18 and comparative example 1 ~ 10, the higher limit meeting the X value (unit time is by the amount (kg/min) of the medium of filtering material) of aforementioned condition formula (1) is 0.0572kg/min.In addition, the lower value meeting the Y value (unit time is by the amount (kg/min) of the scavenging solution of filtering material) of above-mentioned conditional (2) is 0.0260kg/min, higher limit is 0.0884kg/min.
From the result shown in table 1 ~ 4, in the middle of the polymer beads obtained in the embodiment comparative example employing the tensio-active agent without polyoxyethylene chain, for the amount of scavenging solution (water) used in cleaning be the weight of polymer beads more than 9 times (more than 9kg), be specially 10.0 ~ 13.0 times embodiment 1 ~ 18 in the polymer beads that obtains, the content without the tensio-active agent of polyoxyethylene chain of polymer beads per surface area is 10.0 × 10 -5g/m 2below, 0.88 ~ 8.38 × 10 are specially -5g/m 2less, and the weight of polymer beads is less than for the amount eliminating the scavenging solution (water) used in the comparative example 1 of matting (amount of scavenging solution (water) being equivalent to use in cleaning is the situation of 0) and cleaning 9 times (being less than 9kg), be specially 5.0 times comparative example 2,3,5 in the polymer beads that obtains, the content without the tensio-active agent of polyoxyethylene chain of polymer beads per surface area is greater than 10.0 × 10 -5g/m 2, be specially 131.76 ~ 413.62 × 10 -5g/m 2, be more.Therefore confirm: the manufacture method according to the amount of scavenging solution (water) used in cleaning being more than 9 times of the weight of polymer beads, the tensio-active agent without polyoxyethylene chain that uses in the polymerization process adhesion amount in the per surface area of polymer particle surface can be reduced.
In addition, amount for the scavenging solution (water) used in cleaning is more than 9 times (more than 9kg) of the weight of polymer beads, be specially the polymer beads obtained in the embodiment 1 ~ 18 of 10.0 ~ 13.0 times, the measured value of the content of by product (emulsion polymeric product) is less than 1.0 % by weight, be specially 0.05 ~ 0.82 % by weight, less, and for eliminating (amount being equivalent to the scavenging solution (water) used in cleaning is the situation of 0) comparative example 1 of matting, 10 ~ 12 are less than 9 times (being less than 9kg) of the weight of polymer beads with the amount of the scavenging solution (water) of use in cleaning, be specially the comparative example 2 ~ 4 of 1.0 ~ 5.0 times, 8, 9, the polymer beads obtained in 13, the measured value of the content of by product (emulsion polymeric product) is more than 1.0 % by weight, be specially 1.35 ~ 4.33 % by weight, more.Therefore confirm: the manufacture method of more than 9 times according to the amount of the scavenging solution used in cleaning (water) being the weight of polymer beads, the content of the by product (emulsion polymeric product) in polymer beads can be reduced.
In addition, for the polymer beads of X value for obtaining in the embodiment 1 ~ 18 that meets the higher limit 0.0572 (kg/min) of aforementioned condition formula (1) and (be specially 0.0460 ~ 0.0566 (kg/min)) below, the measured value of the content of by product (emulsion polymeric product) is less than 1.0 % by weight, be specially 0.05 ~ 0.82 % by weight, less, and X value is greater than to the comparative example 5 of the higher limit 0.0572 (kg/min) (being specially 0.0592 ~ 0.0725 (kg/min)) meeting aforementioned condition formula (1), 6, the polymer beads obtained in 10, the measured value of the content of by product (emulsion polymeric product) is that more than 1.0 % by weight (being specially 1.75 ~ 2.33 % by weight) are more.Therefore confirm: the manufacture method meeting aforementioned condition formula (1) according to X value, the content of the by product (emulsion polymeric product) in polymer beads can be reduced.
In addition, Y value is met to the polymer beads obtained in the embodiment 1 ~ 18 of aforementioned condition formula (2) (being specially 0.0291 ~ 0.0881 (kg/min)), the measured value of the content of by product (emulsion polymeric product) is less than 1.0 % by weight, be specially 0.05 ~ 0.82 % by weight, less, and Y value is greater than to the comparative example 5 of the higher limit 0.0884kg/min (being specially 0.1115 ~ 0.1156 (kg/min)) meeting aforementioned condition formula (2), the polymer beads obtained in 7, the measured value of the content of by product (emulsion polymeric product) is more than 1.0 % by weight (being specially 1.89 ~ 2.33 % by weight), more.Therefore confirm, meet the manufacture method of aforementioned condition formula (2) according to Y value, the content of the by product (emulsion polymeric product) in polymer beads can be reduced.
In addition confirm: the content without the tensio-active agent of polyoxyethylene chain for polymer beads per surface area is 10.0 × 10 -5g/m 2(be specially 0.88 ~ 8.38 × 10 below -5g/m 2) the polymer beads of embodiment 1 ~ 18, be greater than 10.0 × 10 with the content without the tensio-active agent of polyoxyethylene chain of polymer beads per surface area -5g/m 2(be specially 10.19 ~ 413.62 × 10 -5g/m 2) the polymer beads of comparative example 1 ~ 7,13 compare, dispersion stabilization is excellent.
In addition confirm: the content without the tensio-active agent of polyoxyethylene chain containing polymer beads per surface area for coating is 10.0 × 10 -5g/m 2the optical thin film of the embodiment 19 ~ 36 of the coating resin combination of the polymer beads of following examples 1 ~ 18, is greater than 10.0 × 10 with the content without the tensio-active agent of polyoxyethylene chain of coating containing polymer beads per surface area -5g/m 2the optical thin film of comparative example 14 ~ 20,26 of coating resin combination of polymer beads of comparative example 1 ~ 7,13 compare, mist degree difference is few, and the degree of irregularity of light diffusing is little.That is, the content without the tensio-active agent of polyoxyethylene chain confirmed containing polymer beads per surface area is 10.0 × 10 -5g/m 2the optical thin film of following polymer beads can obtain evenly optical characteristics (anti-glare and light diffusing).This represents that the content without the tensio-active agent of polyoxyethylene chain of polymer beads per surface area is 10.0 × 10 -5g/m 2the dispersion stabilization of following polymer beads is excellent.
In addition, painted as seen from dyestuff of the optical thin film of the comparative example 20 and comparative example 21 that employ the polymer beads of comparative example 11 containing dyestuff (C.I.10410) and comparative example 12.In addition, employ its polymer beads of polymer beads obtained in the comparative example 12 of stopper (letex polymerization hold back agent) in a large number self to also show painted (partially yellow).
In addition confirm, compared with the polymer beads that the polymer beads that the measured value of the content of by product (emulsion polymeric product) is less than the embodiment 1 ~ 18 of 1.0 % by weight (being specially 0.05 ~ 0.82 % by weight) and the measured value of the content of by product (emulsion polymeric product) are the comparative example 1 ~ 13 of more than 1.0 % by weight (being specially 1.35 ~ 4.33 % by weight), dispersion stabilization is excellent.
In addition confirm, measured value for the content of coating containing by product (emulsion polymeric product) is less than the optical thin film of the embodiment 19 ~ 36 of the coating resin combination of the polymer beads of the embodiment 1 ~ 18 of 1.0 % by weight, compared with being the optical thin film of the comparative example 14 ~ 24,26 of the coating resin combination of the polymer beads of the comparative example 1 ~ 13 of more than 1.0 % by weight with the measured value of the content of coating containing by product (emulsion polymeric product), mist degree difference is few, and the degree of irregularity of light diffusing is little.That is, confirm: the optical thin film that the measured value of the content containing by product (emulsion polymeric product) is less than the polymer beads of 1.0 % by weight can obtain evenly optical characteristics (anti-glare and light diffusing).The measured value of the content of this vice product (emulsion polymeric product) is less than the dispersion stabilization excellence of the polymer beads of 1.0 % by weight.
In addition, the gel fraction of the polymer beads of comparative example 12 is low, and dispersion stabilization is also low, the light diffusing degree of irregularity of the optical thin film (optical thin film of comparative example 21) of the coating resin combination of coating containing this polymer beads is large.Can think, the polymer beads of comparative example 12 makes levels of residual monomers, and many (polymer beads of embodiment 1 ~ 18 is less than 1 % by weight, is specially 0.22 ~ 0.50 % by weight because using letex polymerization hold back agent in a large number, and comparative example 12 is 2.34 % by weight), and be zon-crosslinked polymeric composition granule, when therefore disperseing in organic solvent, produce the extract component from polymer beads, result dispersion stabilization reduces, and the degree of irregularity of the light diffusing of the optical thin film of the coating resin combination of coating containing this polymer beads increases.

Claims (12)

1. a polymer beads, is characterized in that, it contains tensio-active agent,
The variation coefficient of particle diameter is less than 15.0%,
Water 15.0g is added in polymer beads 5.0g, ultrasonic cleaner is used to carry out 60 minutes dispersion treatment thus polymer beads is dispersed in water, load internal diameter 24mm centrifuge tube and after using separating centrifuge to carry out centrifugation under k-factor 6943, the rotational time condition of 30 minutes, when reclaiming supernatant liquor, the concentration of the non-volatile component in supernatant liquor is less than 1.0 % by weight.
2. polymer beads according to claim 1, is characterized in that, volume average particle size is in the scope of 1 ~ 30 μm.
3. polymer beads according to claim 1 and 2, is characterized in that, the content without the tensio-active agent of polyoxyethylene chain of the per surface area of described polymer beads is 10.0 × 10 -5g/m 2below.
4. polymer beads according to claim 1 and 2, is characterized in that, described tensio-active agent contains the anionic surfactant without polyoxyethylene chain and at least one do not had in the nonionic surfactant of polyoxyethylene chain.
5. polymer beads according to claim 1 and 2, it is characterized in that, this polymer beads is made up of at least a kind in (methyl) acrylic polymers, styrenic polymer and (methyl) acrylicstyrene analog copolymer.
6. polymer beads according to claim 1 and 2, is characterized in that, gel fraction is more than 90%.
7. polymer beads according to claim 1 and 2, is characterized in that, specific refractory power is 1.490 ~ 1.600.
8. polymer beads according to claim 1 and 2, is characterized in that, it is for optical component.
9. polymer beads according to claim 1 and 2, is characterized in that, it is for anti-dazzle component.
10. a resin combination, it contains the polymer beads according to any one of claim 1 ~ 9.
11. 1 kinds of optical thin films, is characterized in that, it is by the coating resin composition of the polymer beads according to any one of claim 1 ~ 9 and binding agent on film substrate.
12. optical thin films according to claim 11, is characterized in that, it is for anti-dazzle.
CN201510462986.9A 2014-09-30 2015-07-31 Polymer particles and use thereof Pending CN105461847A (en)

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