WO2015045448A1 - Polymer particles, process for producing same, and use thereof - Google Patents
Polymer particles, process for producing same, and use thereof Download PDFInfo
- Publication number
- WO2015045448A1 WO2015045448A1 PCT/JP2014/058618 JP2014058618W WO2015045448A1 WO 2015045448 A1 WO2015045448 A1 WO 2015045448A1 JP 2014058618 W JP2014058618 W JP 2014058618W WO 2015045448 A1 WO2015045448 A1 WO 2015045448A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer particles
- surfactant
- medium
- filter medium
- polymer
- Prior art date
Links
- ISDAKFSLYSIQLS-UHFFFAOYSA-M CCC(Cc(cc1)ccc1[O-])C(C)c1ccccc1 Chemical compound CCC(Cc(cc1)ccc1[O-])C(C)c1ccccc1 ISDAKFSLYSIQLS-UHFFFAOYSA-M 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
- G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
Definitions
- the present invention relates to polymer particles suitably used as a raw material for optical members such as a light diffusion film and an antiglare film, uses of the polymer particles (optical film and resin molded product), and a method for producing the polymer particles About.
- Polymer particles having a volume average particle diameter of 1 to 100 ⁇ m are, for example, additives for coating agents such as paints (matting agents etc.), additives for inks (matting agents etc.), main components of adhesives or Additives, artificial marble additives (low shrinkage agents, etc.), paper treatment agents, packing materials for external preparations such as cosmetics (fillers for improving slipperiness), column packing materials used for chromatography, electrostatic charge Used in applications such as toner additives used for image development, anti-blocking agents for films, and light diffusing agents for optical members (optical films such as light diffusing films and antiglare films, light diffusers, etc.) ing.
- additives for coating agents such as paints (matting agents etc.), additives for inks (matting agents etc.), main components of adhesives or Additives, artificial marble additives (low shrinkage agents, etc.), paper treatment agents, packing materials for external preparations such as cosmetics (fillers for improving slipperiness), column packing materials used for chromatography, electrostatic
- Such polymer particles can be produced by polymerizing a polymerizable monomer.
- Known polymerization methods for polymerizing polymerizable monomers include suspension polymerization, seed polymerization, and emulsion polymerization. In these polymerization methods, a surfactant is usually used so that the polymerization reaction is stably performed and the generation of coarse particles is suppressed.
- Patent Document 1 discloses that resin fine particles (polymer particles) used as a light diffusing agent are obtained by polymerizing a vinyl monomer in a medium containing a surfactant and remain in the resin fine particles.
- the amount of the surfactant is 0.05 parts by weight or less (specifically, 0.005 to 0.36 parts by weight) with respect to 100 parts by weight of the resin fine particles.
- Patent Document 2 discloses washing organic particles (polymer particles) having a surface-active agent obtained by emulsion polymerization or suspension polymerization as organic particles blended in an epoxy resin composition. What has been processed is disclosed.
- an optical film such as a light diffusion film or an antiglare film
- a resin composition containing polymer particles and a binder there is one obtained by coating a resin composition containing polymer particles and a binder on a film substrate.
- the resin composition is still on the film substrate.
- the dispersion state of the polymer particles in the resin composition becomes unstable.
- the polymer particles in the resin composition are formed. The dispersion state was not stable, and the polymer particles sometimes aggregated excessively. As a result, polymer particles may not spread over the entire coating film formed on the base film, and desired optical characteristics may not be stably obtained.
- the present invention has been made in view of the above situation, and an object thereof is to provide polymer particles excellent in dispersion stability, a method for producing the same, and an optical film and a resin molded body using the polymer particles. To do.
- the inventors of the present application have found that the surface state of the polymer particles has an influence on the dispersion stability, and the improvement of the dispersion stability involves a production process in the polymer particles. It was found that the content (residual amount) of the surfactant used in 1) needs to be suppressed very slightly (specifically, less than 50 ppm).
- the polymer particles of the present invention are characterized in that the surfactant content is more than 0 ppm and less than 50 ppm.
- the polymer particles of the present invention have a surfactant content of less than 50 ppm, they are excellent in dispersion stability in the binder when used in combination with a binder. Further, when a resin composition obtained by dispersing the polymer particles of the present invention in a binder is applied on a film substrate, the dispersion state of the polymer particles in the resin composition is determined by the coating method. Thus, it is maintained almost stably in the process of forming the coating film, and excessive aggregation of the polymer particles during the coating is suppressed. As a result, the polymer particles spread evenly on the film substrate, and can impart optical characteristics such as stable light diffusibility and antiglare property to the entire coating film formed by the coating.
- the optical film of the present invention is characterized in that a coating resin composition containing the polymer particles of the present invention and a binder is coated on a film substrate.
- the optical film of the present invention is formed by coating a substrate with the coating resin composition containing the polymer particles of the present invention having excellent dispersion stability, the entire coating film formed by the coating , Stable optical properties such as light diffusibility and antiglare properties can be obtained. Therefore, according to the optical film of the present invention, high quality stability can be obtained.
- the resin molded body of the present invention is characterized by molding a molding resin composition containing the polymer particles of the present invention and a transparent resin.
- the resin molded body of the present invention is formed by molding a molding resin composition containing the polymer particles of the present invention having excellent dispersion stability, in the resin molded body, there is no uneven light diffusibility or Optical properties such as antiglare properties can be obtained stably. Therefore, according to the resin molding of the present invention, high quality stability can be obtained.
- a vinyl monomer is polymerized in a liquid medium in the presence of a surfactant, and the polymer particle containing the surfactant and the medium are mixed.
- a polymerization step for obtaining a product and the crude product is charged into a filter, and the medium contained in the charged crude product is passed through the filter medium of the filter while the polymer particles contained in the crude product.
- the amount per hour is Equation (1); X ⁇ 5.50 ⁇ A (1) (In Formula (1), X means the amount (kg / min) per unit time of the medium that has passed through the filter medium, and A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered).
- the amount of the cleaning liquid per unit time that has passed through the filter medium in the cleaning step is the following conditional expression (2): Y ⁇ 8.50 ⁇ A (2) (In Formula (2), Y means the amount (kg / min) per unit time of the cleaning liquid that has passed through the filter medium, and A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered).
- Y means the amount (kg / min) per unit time of the cleaning liquid that has passed through the filter medium
- A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered).
- a washing liquid having a weight 10 times or more of the weight of the polymer particles held on the filter medium is used.
- the amount per unit time of the medium that has passed through the filter medium satisfies the conditional expression (1) in the solid-liquid separation step, and the amount per unit time of the cleaning liquid that has passed through the filter medium in the washing process is the conditional expression ( 2), and in the washing step, a washing liquid having a weight of 10 times or more the weight of the polymer particles held on the filter medium is used. Therefore, the surfactant adhering to the polymer particles in the polymerization step is used. Most can be removed along with the media and cleaning solution. As a result, it is possible to obtain polymer particles excellent in dispersion stability with a very small surfactant content (residual amount).
- the present invention it is possible to provide polymer particles excellent in dispersion stability, a method for producing the same, and an optical film and a resin molded body using the polymer particles.
- FIG. 1 is a schematic diagram showing a schematic configuration of a pressure filter usable in an embodiment of the present invention, (a) is a schematic cross-sectional view of the pressure filter, and (b) is the pressure filter. It is a schematic top view which shows the inside of the pressure vessel of a pressure filter.
- the polymer particles of the present invention are characterized in that the surfactant content is more than 0 ppm and less than 50 ppm.
- the content of the surfactant is preferably as small as possible, preferably more than 0 ppm to 30 ppm, more preferably more than 0 ppm to 20 ppm, more preferably more than 0 ppm to 15 ppm. Is more preferable.
- the content of the surfactant in the polymer particles can be measured using, for example, liquid chromatography mass spectrometry (LC-MS-MS).
- the surfactant contained in the polymer particles of the present invention is the surfactant remaining in the production of the polymer particles.
- any surfactant usually used in the production of polymer particles for example, an anionic surfactant as described in the section of [Method for producing polymer particles] described later, Nonionic surfactants, cationic surfactants, and amphoteric surfactants can be exemplified.
- the surfactant contained in the polymer particles of the present invention contains at least one of an anionic surfactant and a nonionic surfactant.
- the presence of a surfactant in the polymer particles is, for example, measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS).
- TOF-SIMS time-of-flight secondary ion mass spectrometer
- the content (residual amount) of the surfactant used in the production is suppressed to less than 50 ppm, it can be said that the amount of the surfactant on the particle surface is small.
- the polymer particles of the present invention are used by mixing with a binder, there is little difference in the surface state between the polymer particles mixed with the binder, and as a result, the polymer particles of the present invention are dispersed.
- the dispersion state of the polymer particles in the dispersion medium is maintained almost stably. That is, the polymer particles of the present invention are excellent in dispersion stability.
- the polymer particles of the present invention are those in which the content (residual amount) of the surfactant used in the production is suppressed to less than 50 ppm, and the amount of the surfactant on the particle surface is small. Therefore, when the polymer particles of the present invention are used in a mixture with a dispersion medium, the time required for uniform dispersion in the dispersion medium is stable. Further, as described above, the polymer particles of the present invention are obtained by dispersing polymer particles in a binder, for example, because the amount of the surfactant on the particle surface is small and the dispersion stability is excellent.
- the dispersion state of the polymer particles in the resin composition is maintained almost stably in the process of forming a coating film by the coating.
- excessive aggregation of the polymer particles during the coating can be suppressed.
- the polymer particles spread evenly on the film substrate, and can impart optical characteristics such as stable light diffusibility and antiglare property to the entire coating film formed by the coating. For this reason, the optical film produced using the polymer particles of the present invention has excellent quality stability.
- the content of the surfactant on the particle surface is preferably as small as possible.
- the total ionic strength and negative ions of positive ions measured by a time-of-flight secondary ion mass spectrometer are used.
- the ratio of the ionic strength of negative ions derived from the surfactant to the total ionic strength (hereinafter referred to as ionic strength ratio) of 0.01 ⁇ 10 ⁇ 4 to 2.0 ⁇ 10 ⁇ 4 Is preferred.
- ionic strength ratio is obtained by taking the ionic strength of a high fragment as the ionic strength of negative ions derived from the surfactant.
- the polymer particles having the ionic strength ratio within the above range have a very small amount of the surfactant on the particle surface. For this reason, when polymer particles having an ionic strength ratio within the above range are used by being mixed with a binder, the surface states of the polymer particles mixed with the binder are almost the same. When the coalesced particles are used by being dispersed in a dispersion medium, the dispersion state of the polymer particles in the dispersion medium is maintained extremely stably. That is, polymer particles having an ionic strength ratio within the above range are extremely excellent in dispersion stability.
- the polymer particles having an ionic strength ratio within the above range are those in which the amount of the surfactant on the particle surface is extremely small, so that the polymer particles of the present invention are used by mixing with a dispersion medium. In some cases, the time required to uniformly disperse in the dispersion medium is more stable.
- a resin composition obtained by dispersing polymer particles having an ionic strength ratio within the above range in a binder is used on a film substrate, the polymer in the resin composition is used. The dispersed state of the particles is maintained extremely stably in the process of forming the coating film by the coating, and excessive aggregation of the polymer particles during the coating is surely suppressed.
- the polymer particles spread more uniformly on the film substrate and can reliably impart optical properties such as stable light diffusibility and antiglare properties to the entire coating film formed by the coating. .
- the optical film produced using the polymer particles having an ionic strength ratio within the above range is excellent in quality stability.
- the polymer constituting the polymer particles of the present invention is, for example, a vinyl monomer polymer.
- the vinyl monomer include a monofunctional vinyl monomer having one ethylenically unsaturated group and a polyfunctional vinyl monomer having two or more ethylenically unsaturated groups. .
- Examples of the monofunctional vinyl monomer include, for example, (meth) acrylate monomers; styrene monomers (aromatic vinyl monomers); vinyl acetate, vinyl propionate, vinyl versatate, etc. Saturated fatty acid vinyl monomers; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; ethylenic unsaturation such as acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid and fumaric acid Carboxylic acid; Ethylenically unsaturated carboxylic acid anhydride such as maleic anhydride; Ethylenically unsaturated dicarboxylic acid monoalkyl ester such as monobutylmaleic acid; Ethylenically unsaturated carboxylic acid and ethylenically unsaturated dicarboxylic acid monoalkyl ester Ethylenically unsaturated carboxylates such as ammonium salts or alkali metal
- Examples of the (meth) acrylate monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, acrylic acid Alkyl acrylate monomers such as lauryl and stearyl acrylate; alkyl methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and stearyl methacrylate; glycidyl acrylate (Meth) acrylic acid ester having an epoxy group (glycidyl group) such as glycidyl methacrylate; hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl acrylate; dimethyl Amino ethyl me
- the (meth) acrylic acid ester monomer preferably contains at least one of an alkyl acrylate monomer and an alkyl methacrylate monomer.
- (meth) acrylate means acrylate or methacrylate
- (meth) acryl means acryl or methacryl.
- styrenic monomer examples include styrene, ⁇ -methylstyrene, vinyl toluene, and ethyl vinyl benzene.
- polyfunctional vinyl monomer examples include allyl (meth) acrylate, divinylbenzene, diallyl phthalate, triallyl cyanurate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di ( Examples include meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.
- the above-mentioned vinyl monomers may be used alone or in combination of two or more.
- the polymer constituting the polymer particles is preferably any of a (meth) acrylic polymer, a styrene polymer, and a (meth) acryl-styrene polymer.
- the (meth) acrylic polymer is a polymer of a (meth) acrylic acid ester monomer, or a (meth) acrylic acid ester monomer, a (meth) acrylic acid ester monomer, and styrene. It is a copolymer with a vinyl monomer other than the monomer.
- the styrene polymer is a polymer of a styrene monomer or a copolymer of a styrene monomer and a vinyl monomer other than a (meth) acrylate monomer and a styrene monomer. It is a polymer.
- the (meth) acrylic-styrene copolymer is a copolymer of a (meth) acrylic acid ester monomer and a styrene monomer, or a (meth) acrylic acid ester monomer.
- the polymer constituting the polymer particles is preferably a copolymer (crosslinked polymer) of the monofunctional vinyl monomer and the polyfunctional vinyl monomer.
- the amount of the structural unit derived from the polyfunctional vinyl monomer in the polymer is preferably in the range of 5 to 50% by weight with respect to 100% by weight of the polymer.
- the degree of crosslinking of the polymer is lowered.
- the polymer particles when polymer particles are mixed with a binder and applied as a resin composition, the polymer particles may swell and increase the viscosity of the resin composition, which may reduce the coating workability.
- the polymer particles are mixed with the binder and molded when the polymer particles are heated during mixing or molding (so-called kneading application). Particles are easily dissolved or deformed.
- the amount of the structural unit derived from the polyfunctional vinyl monomer is larger than the above range, the improvement in the effect commensurate with the use amount of the polyfunctional vinyl monomer is not recognized, and the production cost increases. There is.
- the gel fraction of the polymer particles of the present invention is preferably 90% or more, and more preferably 97% or more. If the gel fraction is less than 90%, sufficient solvent resistance cannot be ensured.
- polymer particles are mixed with an organic solvent together with a binder and coated on a film substrate to produce an antiglare film or light.
- an optical film such as a diffusion film
- polymer particles are dissolved in an organic solvent, and there is a possibility that optical properties such as light diffusibility and antiglare property cannot be obtained sufficiently.
- a gel fraction shall point out the gel fraction measured, for example by the method as described in the term of an Example.
- the volume average particle diameter of the polymer particles is preferably 0.5 to 100 ⁇ m, more preferably 1 to 30 ⁇ m.
- an optical member such as an antiglare film or a light diffusing film
- optical properties such as antiglare property and light diffusibility of the optical member can be improved.
- the volume average particle diameter of the polymer particles refers to the arithmetic average of the volume-based particle size distribution measured by the Coulter method, for example, the method described in the Examples section.
- the particle diameter variation coefficient (CV) of the polymer particles is preferably 15% or less.
- the polymer particles are preferably obtained by polymerizing (ie, seed polymerizing) a vinyl monomer by absorbing the vinyl monomer in the presence of a surfactant. Since polymer particles obtained by seed polymerization have little variation in particle diameter, when used in an optical member such as an antiglare film or a light diffusing film, the antiglare property and light diffusibility of the optical member, etc. It is possible to improve the optical characteristics.
- the polymer particles of the present invention can be produced by the production method of the present invention.
- a vinyl monomer is polymerized in a liquid medium in the presence of a surfactant, and the polymer particle containing the surfactant and the medium are mixed.
- a polymerization step for obtaining a product and the crude product is charged into a filter, and the medium contained in the charged crude product is passed through the filter medium of the filter while the polymer particles contained in the crude product.
- a solid-liquid separation step for holding the polymer particles on the filter medium, and a cleaning liquid is charged into the filter that holds the polymer particles on the filter medium, the cleaning liquid is brought into contact with the polymer particles, and the polymer particles and A cleaning step of passing the contacted cleaning liquid through the filter medium to obtain polymer particles cleaned with the cleaning liquid on the filter medium.
- a vinyl monomer is polymerized in a liquid medium in the presence of a surfactant to obtain a crude product containing the polymer particles containing the surfactant and the medium.
- the liquid medium (medium contained in the crude product) is preferably an aqueous medium, for example, water; lower alcohols such as methyl alcohol and ethyl alcohol (alcohols having 5 or less carbon atoms); mixtures of water and lower alcohols, etc. Is mentioned.
- the surfactant stabilizes the dispersion of the vinyl monomer in the liquid medium.
- the surfactant any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.
- a liquid medium is used. The dispersion of the vinyl-based monomer can be more stably ensured, and polymer particles having a uniform particle diameter can be obtained, so that at least one of an anionic surfactant and a nonionic surfactant Is preferably used.
- anionic surfactant any known anionic surfactant such as fatty acid salt type, sulfate ester type, sulfonate type and the like can be used.
- anionic surfactant such as fatty acid salt type, sulfate ester type, sulfonate type and the like can be used.
- alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate
- alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate
- alkyl naphthalene sulfonates alkane sulfonates, di (2-ethylhexyl) sulfosuccinate (sodium) Salt), dialkylsulfosuccinate such as dioctylsulfosuccinate (sodium salt); alkenyl succinate (dipotassium salt); alkyl phosphate ester salt
- naphthalene sulfonate formalin condensate polyoxyethylene alkylphenyl Ether sulfates, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether sulfate such as sodium sulfate; polyoxyethylene alkyl sulfates
- nonionic surfactant any known nonionic surfactant such as an ester type, an ether type, and an ester / ether type can be used.
- a polyoxyethylene alkyl such as polyoxyethylene tridecyl ether can be used.
- polyoxyethylene alkylphenyl ether such as polyoxyethylene octylphenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyalkylene alkyl ether such as polyoxyalkylene tridecyl ether having 3 or more carbon atoms in the alkylene group
- poly Oxyethylene fatty acid esters such as polyoxyethylene octylphenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyalkylene alkyl ether such as polyoxyalkylene tridecyl ether having 3 or more carbon atoms in the alkylene group
- poly Oxyethylene fatty acid esters such as polyoxyethylene octylphenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyalkylene alkyl ether such as polyoxyalkylene tridecyl ether having 3 or more carbon atoms in the alkylene group
- cationic surfactant known cationic surfactants such as amine salt type and quaternary ammonium salt type can be used, but water-soluble cationic surfactants are used from the viewpoint of handling. It is advantageous.
- the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate; alkyltrimethylammonium such as lauryltrimethylammonium chloride, hexadecyltrimethylammonium chloride, cocoyltrimethylammonium chloride, and dodecyltrimethylammonium chloride.
- alkyl dimethyl benzyl chlorides such as hexadecyl dimethyl benzyl ammonium chloride and lauryl dimethyl benzyl ammonium chloride;
- These cationic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.
- amphoteric surfactants examples include lauryl dimethylamine oxide, phosphate ester surfactants, phosphite ester surfactants, and the like. These amphoteric surfactants may be used alone or in combination of two or more.
- the above surfactants may be used alone or in combination of two or more.
- the surfactant preferably has a solubility in water at a liquid temperature of 25 ° C. of 0.3 g / 100 ml to 5.0 g / 100 ml, more preferably 0.5 g / 100 ml to 3.0 g / 100 ml. If a surfactant having a solubility of less than 0.3 g / 100 ml is used, the vinyl monomer may not be stably dispersed in the aqueous medium when the liquid medium is an aqueous medium in the polymerization step.
- a surfactant having a solubility exceeding 5.0 g / 100 ml has a poor hydrophobic group effect and a poor effect of stabilizing the dispersion of the vinyl monomer in an aqueous medium.
- a large amount of a surfactant is required to stabilize the dispersion of the vinyl monomer in the aqueous medium. It is not preferable in terms of sex.
- the amount of the surfactant used in the polymerization of the vinyl monomer is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the vinyl monomer.
- the amount of the surfactant used is less than the above range, the polymerization stability may be lowered.
- there is more usage-amount of surfactant than the said range it is uneconomical in terms of cost.
- the polymerization method of the vinyl monomer is not particularly limited as long as it is a known polymerization method using a liquid medium and a surfactant.
- methods such as seed polymerization, emulsion polymerization, suspension polymerization, etc. Is mentioned.
- seed polymerization is most preferred because the resulting polymer particles have the least variation in particle diameter.
- the above emulsion polymerization is a mixture of a liquid medium, a vinyl monomer that is difficult to dissolve in this medium, and a surfactant (emulsifier), and a polymerization initiator that is soluble in the medium is added thereto to perform polymerization.
- the emulsion polymerization is characterized in that there is little variation in the particle diameter of the polymer particles obtained.
- the suspension polymerization is a polymerization method in which a vinyl monomer and an aqueous medium such as water are mechanically stirred to suspend the vinyl monomer in the aqueous medium for polymerization.
- the suspension polymerization is characterized in that polymer particles having a small particle size and a relatively uniform particle size can be obtained.
- the seed polymerization is a method in which, when starting polymerization of a vinyl monomer, seed (seed) particles made of a polymer of a vinyl monomer prepared separately are put into the polymerization. More specifically, in the seed polymerization, polymer particles made of a vinyl monomer polymer are used as seed particles, the vinyl particles are absorbed in the seed particles in an aqueous medium, This is a method of polymerizing a vinyl monomer. In this method, polymer particles having a larger particle diameter than the original seed particles can be obtained by growing the seed particles.
- the polymerization step is performed in a liquid medium in the presence of seed particles and a surfactant.
- the method includes seed polymerizing a vinyl monomer to obtain a crude product including the polymer particles including the surfactant and the medium.
- seed particles are added to an emulsion (suspension) containing a vinyl monomer, an aqueous medium, and a surfactant.
- the emulsion can be prepared by a known method.
- an emulsion can be obtained by adding a vinyl monomer and a surfactant to an aqueous medium and dispersing them with a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer.
- aqueous medium water or a mixture of water and an organic solvent (for example, a lower alcohol (alcohol having 5 or less carbon atoms)) can be used.
- the amount of the surfactant used in the seed polymerization is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the vinyl monomer.
- the amount of the surfactant used is less than the above range, the polymerization stability may be lowered.
- there is more usage-amount of surfactant than the said range it is uneconomical in terms of cost.
- the seed particles may be added to the emulsion as it is, or may be added to the emulsion in a form dispersed in an aqueous medium.
- the vinyl monomer is absorbed by the seed particles. This absorption can usually be performed by stirring the emulsion at room temperature (about 20 ° C.) for 1 to 12 hours.
- the emulsion may be heated to about 30 to 50 ° C.
- the seed particles swell by absorbing the vinyl monomer.
- the mixing ratio of the vinyl monomer to the seed particles is preferably in the range of 5 to 300 parts by weight of the vinyl monomer and 1 to 250 parts by weight with respect to 1 part by weight of the seed particles. More preferably, it is within.
- the mixing ratio of the vinyl monomer is smaller than the above range, the increase in particle diameter due to polymerization is small, and thus the production efficiency is lowered.
- the mixing ratio of the vinyl monomer is larger than the above range, the vinyl monomer is not completely absorbed by the seed particles, and is suspension-polymerized independently in an aqueous medium, resulting in an abnormally small particle size. Polymer particles may be produced.
- finish of absorption of the vinyl-type monomer to a seed particle can be determined by confirming expansion of a particle diameter by observation with an optical microscope.
- polymer particles are obtained by polymerizing the vinyl monomer absorbed by the seed particles.
- polymer particle grains by repeating the process of making a seed particle absorb and polymerize a vinyl-type monomer in multiple times.
- a polymerization initiator may be added to the vinyl monomer as necessary.
- the polymerization initiator may be obtained by mixing the polymerization initiator with the vinyl monomer, and then dispersing the obtained mixture in an aqueous medium, or combining both the polymerization initiator and the vinyl monomer. Those separately dispersed in an aqueous medium may be mixed.
- the particle size of the vinyl monomer droplets present in the resulting emulsion is preferably smaller than the particle size of the seed particles because the vinyl monomer is efficiently absorbed by the seed particles.
- the polymerization initiator is not particularly limited.
- benzoyl peroxide lauroyl peroxide, benzoyl peroxide, o-methoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide
- Organic peroxides such as oxide, t-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (2,3-dimethylbutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,3,3) 3-trimethylbutyronitrile), 2,2′-azobis (2-isopropylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonite) ), 2,2′-azobis (4-methoxy-2,4-dimethylvaleron
- the polymerization temperature of the seed polymerization can be appropriately selected according to the type of vinyl monomer and the type of polymerization initiator used as necessary. Specifically, the polymerization temperature of the seed polymerization is preferably 25 to 110 ° C., and more preferably 50 to 100 ° C. The polymerization time for the seed polymerization is preferably 1 to 12 hours.
- the polymerization reaction of the seed polymerization may be performed in an atmosphere of an inert gas (for example, nitrogen) that is inert to the polymerization.
- the seed polymerization is preferably carried out by raising the temperature after the vinyl monomer and the polymerization initiator used as necessary are completely absorbed by the seed particles.
- a polymer dispersion stabilizer may be added to the polymerization reaction system in order to improve the dispersion stability of the polymer particles.
- the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (such as hydroxyethyl cellulose and carboxymethyl cellulose), and polyvinylpyrrolidone.
- the polymer dispersion stabilizer and an inorganic water-soluble polymer compound such as sodium tripolyphosphate may be used in combination.
- polyvinyl alcohol and polyvinyl pyrrolidone are preferred.
- the addition amount of the polymer dispersion stabilizer is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the vinyl monomer.
- nitrites such as sodium nitrite, sulfites, hydroquinones, ascorbic acids, water-soluble Water-soluble polymerization inhibitors such as vitamin Bs, citric acid and polyphenols may be added to the aqueous medium.
- the addition amount of the polymerization inhibitor is preferably in the range of 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the vinyl monomer.
- the polymerization method for obtaining seed particles by polymerizing a vinyl monomer is not particularly limited, but dispersion polymerization, emulsion polymerization, soap-free emulsion polymerization (emulsion polymerization without using a surfactant as an emulsifier). , Seed polymerization, suspension polymerization and the like can be used. In order to obtain polymer particles having a substantially uniform particle size by seed polymerization, it is necessary to first use seed particles having a substantially uniform particle size and grow these seed particles substantially uniformly.
- Seed particles having a substantially uniform particle size as a raw material can be produced by polymerizing a vinyl monomer by a polymerization method such as soap-free emulsion polymerization (emulsion polymerization without using a surfactant) and dispersion polymerization. Accordingly, emulsion polymerization, soap-free emulsion polymerization, seed polymerization, and dispersion polymerization are preferred as polymerization methods for polymerizing vinyl monomers to obtain seed particles.
- a polymerization method such as soap-free emulsion polymerization (emulsion polymerization without using a surfactant) and dispersion polymerization. Accordingly, emulsion polymerization, soap-free emulsion polymerization, seed polymerization, and dispersion polymerization are preferred as polymerization methods for polymerizing vinyl monomers to obtain seed particles.
- a polymerization initiator is used as necessary.
- the polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate; benzoyl peroxide, lauroyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, 3, 5 , 5-trimethylhexanoyl peroxide, tert-butylperoxy-2-ethylhexanoate, organic peroxides such as di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, Examples thereof include azo compounds such as 1′-azobiscyclohexanecarbonitrile and 2,2′-azobis (2,4-dimethylvaleronitrile).
- the amount of the polymerization initiator used is preferably in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the vinyl monomer used to obtain seed particles.
- the weight average molecular weight of the seed particles obtained can be adjusted by adjusting the amount of the polymerization initiator used.
- a molecular weight modifier may be used in order to adjust the weight average molecular weight of the obtained seed particles.
- the molecular weight modifier include mercaptans such as n-octyl mercaptan and tert-dodecyl mercaptan; ⁇ -methylstyrene dimer; terpenes such as ⁇ -terpinene and dipentene; halogenated hydrocarbons such as chloroform and carbon tetrachloride, etc. Can be used.
- the weight average molecular weight of the seed particles obtained can be adjusted by adjusting the amount of the molecular weight modifier used.
- Solid-liquid separation process In the solid-liquid separation step, the crude product is charged into a filter, and the medium contained in the charged crude product is passed through the filter medium of the filter, while the polymer particles contained in the crude product are passed through the filter. Hold on filter media.
- the amount per unit time of the medium that has passed through the filter medium is the following conditional expression (1); X ⁇ 5.50 ⁇ A (1) (In Formula (1), X means the amount (kg / min) per unit time of the medium that has passed through the filter medium, and A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered). Means).
- the surfactant contained in the crude product together with the medium
- the amount of the surfactant remaining in the polymer particles remaining on the filter medium (specifically, the amount of the surfactant adhered on the surface of the polymer particles) can be reduced.
- the filter is not particularly limited.
- the pressure vessel 2 having a cylindrical inner space and an inner bottom portion of the pressure vessel 2 are disposed.
- An example of the pressure filter 1 includes a filter medium 3 and a compressed gas supply device (not shown) that supplies compressed gas (inert gas such as nitrogen, air, etc.) into the pressure vessel.
- compressed gas in the pressure filter 1 shown in FIG. 1, the area of the bottom surface of the cylindrical inner space of the pressure vessel 2 (see FIG. 1B) is the interface between the filter medium 3 and the material to be filtered (crude product P). It is almost the same as the area.
- the crude product P is charged in the form of a slurry solution into the pressure vessel 2 of the pressure filter 1, and is placed on the filter medium 3 in the pressure vessel 2.
- the crude product P is filled, and the compressed gas is supplied to the upper space S of the filter medium 3 in the pressure vessel 2 by the compressed gas supply machine, whereby the upper space S of the filter medium 3 in the pressure vessel 2 is pressurized.
- the crude product P is pressed against the filter medium 3, the liquid medium contained in the crude product P passes through the filter medium 3, and the liquid medium is discharged out of the pressure vessel 2 as a filtrate. Then, a cake of polymer particles remains on the filter medium 3.
- the pressure vessel 2 is preferably made of, for example, stainless steel and has a pressure resistance of 0.50 MPa or more.
- the filter medium 3 is not particularly limited as long as the polymer particles can be reliably collected.
- a filter cloth such as a woven fabric or a nonwoven fabric made of natural fibers or synthetic fibers; a wire mesh made of sintered metal; Nonwoven fabric made of sintered metal; filter plate (perforated plate) made of natural fiber, glass fiber, etc .; net made of synthetic resin: filter paper; glass fiber filter, etc., and filter cloth is preferred.
- the pressurizing condition when pressurizing the upper space S of the filter medium 3 in the pressure resistant vessel 2 using the pressure filter 1 is a pressure satisfying the conditional expression (1).
- the conditional expression (1) it is preferable to pressurize the pressure vessel 2 so that the internal pressure is within a range of 0.01 MPa to 0.50 MPa.
- the internal pressure of the pressure resistant vessel 2 is preferably kept almost constant so as to satisfy the conditional expression (1) from the start of pressurization to the end of the solid-liquid separation step.
- the internal pressure of the container 2 gradually decreases as the medium contained in the crude product P passes through the filter medium 3 after being pressurized.
- the amount of medium contained in the crude product P charged into the filter (pressure filter 1) (when all the crude products obtained in the polymerization step are charged into the filter)
- the amount of the medium used in the polymerization step) is preferably 100% by weight, and the medium contained in the crude product P is preferably removed by passing a medium of 70% by weight or more through the filter medium 3.
- a medium of 70% by weight or more is passed through the filter medium 3 with respect to 100% by weight of the medium contained in the crude product P charged into the filter (pressure filter 1).
- the remaining amount of the surfactant in the polymer particles remaining on the filter medium 3 can be reduced. As a result, it is possible to reduce the amount of cleaning liquid in the cleaning process described later.
- the solid-liquid separation step includes the amount of the medium contained in the crude product P introduced into the pressure filter 1 (
- the amount of the medium is 70% by weight or more with respect to 100% by weight of the medium used in the polymerization step). 3 and it is preferable that the process is terminated when the internal pressure of the pressure vessel 2 becomes 80% or less with respect to the pressure of 100% during pressurization.
- the remaining amount of the surfactant in the polymer particles remaining on the filter medium 3 can be reliably reduced, and the amount of the cleaning liquid in the cleaning step described later can be reduced.
- washing process In the washing step, the washing liquid is put into the filter holding the polymer particles on the filter medium, the washing liquid is brought into contact with the polymer particles, and the washing liquid in contact with the polymer particles passes through the filter medium. As a result, polymer particles washed with the washing liquid are obtained on the filter medium.
- the amount per unit time of the washing liquid that has passed through the filter medium is the following conditional expression (2); Y ⁇ 8.50 ⁇ A (2) (In Formula (2), Y means the amount (kg / min) per unit time of the cleaning liquid that has passed through the filter medium, and A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered). Means).
- Y means the amount (kg / min) per unit time of the cleaning liquid that has passed through the filter medium
- A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered). Means).
- the amount per unit time of the cleaning liquid that has passed through the filter medium in the cleaning step averages from the start to the end of the cleaning of the polymer particles by allowing the cleaning liquid to pass through the filter medium.
- Y means the amount (kg / min) of the cleaning liquid that has passed through the filter medium per unit time
- A means the area (m 2 ) of the interface between the filter medium and the object to be filtered. It is preferable to satisfy.
- the washing liquid is left while the polymer particle cake remaining on the filter medium 3 is held on the filter medium 3 as it is.
- the cake and the cleaning liquid are brought into contact with each other by being supplied into the pressure vessel 2, and the upper space S of the filter medium 3 is pressurized by supplying the compressed gas to the upper space S of the filter medium 3 in the pressure vessel 2 by a compressed gas supply machine. .
- the cake comes into contact with the cleaning liquid and is cleaned, and the cleaned cleaning liquid is discharged out of the pressure vessel 2 as a filtrate.
- the pressurizing condition when the pressurizing filter 1 is used to pressurize the upper space S of the filter medium 3 in the pressure resistant vessel 2 is particularly limited as long as it satisfies the conditional expression (2).
- the upper space S of the filter medium 3 is preferably pressurized at a rate of 0.01 to 0.30 MPa / min.
- the internal pressure of the pressure vessel 2 is kept substantially constant from the start of pressurization to the end of the cleaning step so as to satisfy the conditional expression (2).
- the pressure in the pressure-resistant vessel 2 gradually decreases as the cleaning liquid introduced into the pressure-resistant vessel 2 passes through the filter medium 3 after being pressurized. Specifically, when the cleaning liquid passing through the filter medium 3 is reduced or almost disappeared, the compressed air pressure in the pressure resistant container 2 is released from the bottom, and it becomes difficult to maintain the internal pressure of the pressure resistant container 2 at the pressure at the time of pressurization.
- the pressure at the time of pressurization will be below.
- the cleaning liquid used in the cleaning step is preferably an aqueous medium, and examples thereof include water; lower alcohols such as methyl alcohol and ethyl alcohol (alcohols having 5 or less carbon atoms); and mixtures of water and lower alcohols. It is preferable to use the same medium as used in the polymerization step.
- the weight of the washing liquid used in the washing step is the weight of the polymer particles held on the filter medium 3 (in the case where all the crude products obtained in the polymerization step in the solid-liquid separation step are put into the filter, the polymerization step)
- the total amount of vinyl monomers used in (1) is 10 times or more.
- the weight of the washing liquid used in the washing step is less than 10 times the weight of the polymer particles held on the filter medium 3, the removal of the surfactant contained in the polymer particles becomes insufficient, and the desired polymer There is a possibility that particles (polymer particles having a surfactant content of less than 50 ppm) cannot be obtained.
- the weight of the cleaning liquid used in the cleaning process is preferably equal to or more than the total amount of the lower limit D of the weight of the cleaning liquid calculated by the following calculation formula (4) for each type of surfactant used in the polymerization process.
- the weight of the cleaning liquid used in the cleaning process is equal to or more than the total amount of the lower limit D of the weight of the cleaning liquid calculated by the following calculation formula (4) for each type of surfactant used in the polymerization process, the polymer particles The content of the surfactant in the inside can be further reduced.
- D (E ⁇ F) ⁇ 2000 (4)
- D Lower limit of weight of cleaning solution required for one type of surfactant (g)
- E Amount of the one kind of surfactant used (g)
- F Solubility (g / 100 ml) of the above-mentioned one type of surfactant in the washing liquid having a liquid temperature of 25 ° C.
- the temperature of the cleaning solution used for cleaning is preferably a temperature at which the surfactant is sufficiently eluted, for example, preferably 40 to 80 ° C., and more preferably 50 to 80 ° C.
- a method for heating the cleaning liquid to the above temperature and performing cleaning a method of supplying the heated cleaning liquid to a filter (for example, the pressure vessel 2 of the pressure filter 1) may be used.
- a method of heating the cleaning liquid with a heater jacket disposed around the filter after being supplied to the filter may be used.
- the conductivity of the cleaning liquid that has passed through the filter medium 3 is 2.0 times or less the conductivity of the cleaning liquid before being charged into the filter (pressure filter 1), and the internal pressure of the pressure vessel 2 is It is preferable that the process is terminated when the pressure is 80% or less with respect to the pressure of 100% during pressurization.
- the water that can be absorbed by the polymer particles by passing the cleaning liquid charged into the pressure vessel 2 through the filter medium 3 until the internal pressure of the pressure vessel 2 becomes 80% or less with respect to the pressure of 100% during pressurization.
- the amount can be reduced, and the time required for drying the polymer particles after washing can be shortened.
- the polymer particles obtained in the washing step are dried in a vacuum dryer to almost completely remove the washing liquid, and classified as necessary (preferably, air flow classification) to obtain a weight that can be used as a product. It can be combined particles.
- the amount per unit time of the medium that has passed through the filter medium satisfies the conditional expression (1), and the unit time of the cleaning liquid that has passed through the filter medium in the washing step. Since the amount per hit satisfies the conditional expression (2) and the washing step uses a washing liquid having a weight of 10 times or more the weight of the polymer particles held on the filter medium, the polymer particles are used in the polymerization step. Most of the surfactant adhering to can be removed together with the medium and the cleaning liquid. As a result, it is possible to obtain polymer particles excellent in dispersion stability with a very small surfactant content (residual amount).
- polymerization process is also removed in large quantities by a solid-liquid separation process and a washing
- the polymer particles of the present invention are suitable for optical films such as antiglare films and light diffusion films, and optical members such as light diffusers, and particularly suitable for antiglare members.
- the optical film of the present invention is obtained by coating a coating resin composition containing the polymer particles of the present invention and a binder on a film substrate.
- the optical film of the present invention is obtained, for example, by dispersing the polymer particles in a binder to obtain a coating resin composition, coating the obtained coating resin composition on a film substrate, It is obtained by forming a coating film made of the resin composition for use on the film substrate.
- the binder is not particularly limited as long as it is used in the field according to required properties such as transparency, polymer particle dispersibility, light resistance, moisture resistance and heat resistance.
- the binder include (meth) acrylic resins; (meth) acrylic-urethane resins; urethane resins; polyvinyl chloride resins; polyvinylidene chloride resins; melamine resins; styrene resins; alkyd resins.
- Modified silicone resins; binder resins such as fluororesins such as polyvinylidene fluoride and fluoroolefin vinyl ether polymers.
- the binder resin is preferably a curable resin capable of forming a crosslinked structure by a crosslinking reaction from the viewpoint of improving the durability of the coating resin composition.
- the curable resin can be cured under various curing conditions.
- the curable resin is classified into an ionizing radiation curable resin such as an ultraviolet curable resin and an electron beam curable resin, a thermosetting resin, a hot air curable resin, and the like depending on the type of curing.
- thermosetting resin examples include thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin.
- the ionizing radiation curable resin synthesized from polyfunctional (meth) acrylate resin such as polyhydric alcohol polyfunctional (meth) acrylate; diisocyanate, polyhydric alcohol, and (meth) acrylic acid ester having a hydroxy group And polyfunctional urethane acrylate resins.
- the ionizing radiation curable resin is preferably a polyfunctional (meth) acrylate resin, and more preferably a polyhydric alcohol polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule.
- polyhydric alcohol polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate, etc. That. Two or more kinds of the ionizing radiation curable resins may be used
- polyether resins having an acrylate functional group polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and the like can also be used.
- a photopolymerization initiator is added to the ultraviolet curable resin to form a binder.
- the said photoinitiator it is preferable to use what was suitable for the ultraviolet curable resin to be used.
- Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (Described in JP-A No. 2001-139663), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, active halogen compounds, ⁇ -acyloximes
- Examples include esters.
- acetophenones examples include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropio.
- examples include phenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone.
- benzoins examples include benzoin, benzoin benzoate, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
- benzophenones examples include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone, p-chlorobenzophenone, and the like.
- phosphine oxides examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
- Examples of the ketals include benzylmethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one.
- Examples of the ⁇ -hydroxyalkylphenones include 1-hydroxycyclohexyl phenyl ketone.
- Examples of the ⁇ -aminoalkylphenones include 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone.
- radical photopolymerization initiators include trade names “Irgacure (registered trademark) 651” (2,2-dimethoxy-1,2-diphenylethane-1-one) manufactured by BASF Japan Ltd., manufactured by BASF Japan Ltd. Trade name “Irgacure (registered trademark) 184”, and trade name “Irgacure (registered trademark) 907” (2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) manufactured by BASF Japan Ltd. ) -1-propanone) and the like.
- the amount of the photopolymerization initiator used is usually in the range of 0.5 to 20% by weight, preferably in the range of 1 to 5% by weight with respect to 100% by weight of the binder.
- thermoplastic resin As the binder resin, a thermoplastic resin can be used in addition to the curable resin.
- the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose; homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of vinyl chloride, and vinylidene chloride.
- Vinyl resins such as homopolymers and copolymers; acetal resins such as polyvinyl formal and polyvinyl butyral; homopolymers and copolymers of acrylate esters, homopolymers and copolymers of methacrylate esters, etc.
- Acrylic resin polystyrene resin; polyamide resin; linear polyester resin; polycarbonate resin.
- a rubber binder such as synthetic rubber or natural rubber, an inorganic binder, or the like can be used as the binder.
- the rubber binder resin include ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, and acrylonitrile-butadiene rubber. These rubber-based binder resins may be used alone or in combination of two or more.
- the inorganic binder examples include silica sol, alkali silicate, silicon alkoxide, and phosphate.
- an inorganic or organic-inorganic composite matrix obtained by hydrolysis and dehydration condensation of metal alkoxide or silicon alkoxide can also be used.
- a silicon oxide matrix obtained by hydrolysis and dehydration condensation of a silicon alkoxide such as tetraethoxysilane can be used.
- the amount of the polymer particles in the coating resin composition is preferably 2 parts by weight or more, more preferably 4 parts by weight or more, based on 100 parts by weight of the solid content of the binder, and 6 parts by weight. More preferably, it is the above.
- the amount of the polymer particles 2 parts by weight or more with respect to 100 parts by weight of the solid content of the binder it becomes easy to make the matte property of the coating film formed by the coating resin composition sufficient. Therefore, it becomes easy to make sufficient optical characteristics, such as anti-glare property and light diffusibility, of the film formed by coating the coating resin composition on the film substrate.
- the amount of the polymer particles in the coating resin composition is preferably 300 parts by weight or less, more preferably 200 parts by weight or less, and more preferably 100 parts by weight with respect to 100 parts by weight of the solid content of the binder. More preferably, it is as follows. By making the amount of the polymer particles 300 parts by weight or less with respect to 100 parts by weight of the solid content of the binder, the linear permeability of the coating film formed by the coating resin composition is easily made sufficient.
- the coating resin composition may further contain an organic solvent.
- the organic solvent is added to the coating resin composition so that the coating resin composition for the substrate is coated.
- the coating is not particularly limited as long as the coating is easy.
- organic solvent examples include aromatic solvents such as toluene and xylene; alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene Glycol ethers such as glycol diethyl ether, diethylene glycol dimethyl ether, and propylene glycol methyl ether; 2-methoxyethyl acetate Salts, glycol ether esters such as 2-ethoxyethyl acetate (cellosolve acetate),
- the film substrate is preferably transparent.
- transparent film base materials include polyester polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose (TAC), polycarbonate polymers, and polymethyl methacrylate.
- PET polyethylene terephthalate
- TAC triacetyl cellulose
- polycarbonate polymers polycarbonate polymers
- polymethyl methacrylate polymethyl methacrylate
- a film made of a polymer such as a (meth) acrylic polymer.
- a film made of a polymer such as a vinyl polymer or an amide polymer such as nylon or aromatic polyamide may also be mentioned.
- films made of polymers such as polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers and blends of the above polymers.
- the film substrate those having a particularly low birefringence are preferably used.
- an easy-adhesion layer such as (meth) acrylic resin, copolymerized polyester resin, polyurethane resin, styrene-maleic acid grafted polyester resin, acrylic grafted polyester resin, etc. is further provided on these films is also used as the film substrate. Can be used.
- the thickness of the film substrate can be determined as appropriate, but is generally within the range of 10 to 500 ⁇ m and within the range of 20 to 300 ⁇ m from the viewpoints of strength, workability such as handling, and thin layer properties. It is preferable that it is within a range of 30 to 200 ⁇ m.
- an additive may be added to the film substrate.
- the additive include an ultraviolet absorber, an infrared absorber, an antistatic agent, a refractive index adjuster, and an enhancer.
- the coating resin composition can be applied to a film substrate by bar coating, blade coating, spin coating, reverse coating, diting, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, air Known coating methods such as knife coating and dipping method may be mentioned.
- the binder contained in the coating resin composition is an ionizing radiation curable resin
- the solvent is dried and further irradiated with active energy rays to cure the ionizing radiation.
- the curing resin may be cured.
- Examples of the active energy ray include ultraviolet rays emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp; Electron beams, ⁇ rays, ⁇ rays, ⁇ rays and the like extracted from electron beam accelerators such as a type, a resonant transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used.
- a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp
- Electron beams, ⁇ rays, ⁇ rays, ⁇ rays and the like extracted from electron beam accelerators such as a type
- the thickness of the layer in which the polymer particles are dispersed in the binder formed by application (and curing) of the coating resin composition is not particularly limited and is appropriately determined depending on the particle diameter of the polymer particles. It is preferably in the range of ⁇ 10 ⁇ m, more preferably in the range of 3 to 7 ⁇ m.
- the optical film of the present invention is formed by coating a substrate with the coating resin composition containing the polymer particles of the present invention having excellent dispersion stability, the entire coating film formed by the coating , Stable optical properties such as light diffusibility and antiglare properties can be obtained. Therefore, according to the optical film of the present invention, high quality stability can be obtained.
- optical film of the present invention described above can be suitably used for light diffusion or antiglare, that is, as a light diffusion film or antiglare film.
- the resin molded body of the present invention is formed by molding a molding resin composition containing the polymer particles and a transparent resin.
- the polymer particles function as light diffusing particles. Therefore, the resin molded body of the present invention functions as a light diffuser such as a light diffusing plate and can be used as an LED lighting cover or the like.
- the transparent resin is a base material of the resin molded body.
- a (meth) acrylic resin, a polycarbonate resin, a polystyrene resin, a (meth) acrylic-styrene resin ((meth) acrylic) acid ester and styrene are co-polymerized. Polymer) and the like. Among them, polystyrene resin or (meth) acryl-styrene resin is preferable as the transparent resin.
- the amount of the polymer particles contained in the resin composition is preferably in the range of 0.01 to 5 parts by weight, preferably in the range of 0.1 to 5 parts by weight, with respect to 100 parts by weight of the transparent resin. More preferably. You may add additives, such as a ultraviolet absorber, antioxidant, a heat stabilizer, a light stabilizer, and a fluorescent whitening agent, to the said resin composition.
- the thickness, shape and the like of the resin molded body can be appropriately selected depending on the application of the resin molded body.
- the resin molded body of the present invention can be obtained by melt-kneading the transparent resin and the polymer particles with a single screw extruder or a twin screw extruder. Moreover, the resin composition obtained by melt kneading may be molded into a plate shape via a T die and a roll unit to obtain a resin molded body. Moreover, the resin composition obtained by melt kneading may be pelletized, and the pellet may be formed into a plate shape by injection molding or press molding to obtain a resin molded body.
- the resin molded body of the present invention is formed by molding a molding resin composition containing the polymer particles of the present invention having excellent dispersion stability, in the resin molded body, there is no uneven light diffusibility or Optical properties such as antiglare properties can be obtained stably. Therefore, according to the resin molding of the present invention, high quality stability can be obtained.
- TOF-SIMS the measurement method of the gel fraction of the polymer particles
- the measurement method of the dispersion stabilization time of the polymer particles will be described.
- volume average particle size is measured by Coulter Multisizer III (measurement device manufactured by Beckman Coulter, Inc.). The measurement shall be performed using an aperture calibrated according to the Multisizer TM 3 User's Manual issued by Beckman Coulter, Inc.
- the selection of the aperture used for the measurement is such that when the assumed volume average particle diameter of the polymer particles to be measured is 1 ⁇ m or more and 10 ⁇ m or less, an aperture having a size of 50 ⁇ m is selected, and the assumed volume average of the polymer particles to be measured When the particle diameter is larger than 10 ⁇ m and 30 ⁇ m or less, an aperture having a size of 100 ⁇ m is selected. When the assumed volume average particle diameter of the polymer particles is larger than 30 ⁇ m and not larger than 90 ⁇ m, an aperture having a size of 280 ⁇ m is selected, When the assumed volume average particle diameter of the polymer particles is greater than 90 ⁇ m and 150 ⁇ m or less, an aperture having a size of 400 ⁇ m is selected. When the volume average particle diameter after measurement is different from the assumed volume average particle diameter, the aperture is changed to an aperture having an appropriate size, and measurement is performed again.
- the current (aperture current) is set to ⁇ 800, the gain (gain) is set to 4, and if an aperture having a size of 100 ⁇ m is selected, the current (aperture current) is ⁇ 1600, Gain (gain) is set to 2, and when an aperture having a size of 280 ⁇ m and 400 ⁇ m is selected, Current (aperture current) is set to ⁇ 3200 and Gain (gain) is set to 1.
- the volume average particle diameter of the polymer particles is an arithmetic average in a volume-based particle size distribution of 100,000 particles.
- the coefficient of variation (CV value) of the particle diameter of the polymer particles is calculated by the following formula.
- Coefficient of variation of particle diameter of polymer particles (standard deviation of volume distribution of polymer particles / volume average particle diameter of polymer particles) ⁇ 100
- the volume average particle diameter of the seed particles is measured by a laser diffraction / scattering particle size distribution measuring device (“LS 13 320” manufactured by Beckman Coulter, Inc.) and a universal liquid sample module.
- LS 13 320 manufactured by Beckman Coulter, Inc.
- 0.1 g of seed particles was added to 10 ml of 0.1% by weight nonionic surfactant aqueous solution in a touch mixer (manufactured by Yamato Kagaku Co., Ltd., “TOUCMIXER MT-31”) and an ultrasonic cleaner (Velvok Co., Ltd.). Dispersed using “ULTRASONIC CLEANER VS-150” manufactured by Leer, and used as a dispersion.
- optical parameters required for evaluation based on the Mie theory are set in the software of the laser diffraction / scattering type particle size distribution measuring apparatus.
- the measurement is performed at room temperature, and the volume average particle diameter of the seed particles is determined from the obtained data using the software parameters of the laser diffraction / scattering type particle size distribution measuring apparatus, using the preset optical parameters. (Arithmetic mean diameter in the volume-based particle size distribution) is calculated.
- the refractive index of the seed particles was measured by inputting the refractive index of the polymer constituting the seed particles.
- the polymer constituting the seed particles used in the production of Examples and Comparative Examples described later is polymethyl methacrylate or polyethyl methacrylate
- the known refraction of polymethyl methacrylate and polyethyl methacrylate is known.
- a rate of 1.495 was entered.
- the content of the surfactant in the polymer particles is measured by extracting the polymer particles with a solvent and using a liquid chromatograph mass spectrometer (LC / MS / MS apparatus).
- polymer particles in Examples and Comparative Examples described later are used as surfactants, di (2-ethylhexyl) sulfosuccinate, polyoxyethylene styrenated phenyl ether sulfate (see Formula (A) described later), Using at least one of alkenyl succinate (see formula (C) below) and polyoxyethylene styrenated phenyl ether (see formula (E) below) The content of the surfactant in the polymer particles was measured by the following method.
- Approximately 0.10 g of polymer particles as a sample are precisely weighed in a centrifuge tube, and 5 mL of methanol as an extract is poured with a whole pipette to mix the polymer particles and the extract well. After ultrasonic extraction for 15 minutes, centrifugation is performed at 3500 rpm for 15 minutes, and the resulting supernatant is used as a test solution.
- the amount of the extract is 5 ml.
- the surfactant concentration is calculated from a calibration curve prepared in advance from the peak area value on the obtained chromatogram using an LC / MS / MS apparatus. Further, when the polymer particles contain a plurality of types of surfactants, for each of these surfactants, create a calibration curve, calculate the surfactant concentration using the created calibration curve, and calculate each The total surfactant concentration of the surfactant is defined as the “surfactant concentration ( ⁇ g / ml) in the test solution” in the above calculation formula, and the content of the surfactant in the polymer particles is determined.
- the calibration curve creation method is as follows according to the type of surfactant used in the examples and comparative examples.
- Capillary voltage -20V
- Tube lens voltage -100V
- the polymer particles are measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), and it is confirmed that a peak derived from the surfactant is detected.
- TOF-SIMS time-of-flight secondary ion mass spectrometer
- polymer particles are fixed on a sample stage of a time-of-flight secondary ion mass spectrometer (“TOF-SIMS 5” manufactured by ION-TOF), and measurement is performed under the following measurement conditions.
- TOF-SIMS 5 time-of-flight secondary ion mass spectrometer
- a positive electron gun is used to detect both positive and negative secondary ions, and then it is confirmed that a peak derived from the surfactant is detected.
- anionic surfactant sodium di (2-ethylhexyl) sulfosuccinate is used as the surfactant.
- a secondary ion mass spectrometer a plurality of negative ion fragment peaks derived from sodium di (2-ethylhexyl) sulfosuccinate are detected.
- di (2-ethylhexyl) sulfosuccinate ion (molecular formula: C 20 H 37 SO 7 ⁇ , molecular weight 421) is the highest ion.
- di (2-ethylhexyl) sulfosuccinate ion (molecular formula: C 20 H 37 SO 7 ⁇ , molecular weight 421) is used as an evaluation ion species, and positive ions
- the ratio of the ionic strength of di (2-ethylhexyl) sulfosuccinate ion to the total of the total ionic strength and the total ionic strength of negative ions is determined as the ionic strength ratio.
- Example 8 polyoxyethylene styrenated phenyl ether sulfate ammonium represented by the following formula (A), which is an anionic surfactant, is used as the surfactant.
- A polyoxyethylene styrenated phenyl ether sulfate ammonium represented by the following formula (A)
- a plurality of negative ion fragment peaks derived from polyoxyethylene styrenated phenyl ether ammonium sulfate represented by the following formula (A) are detected.
- styrenated phenyloxy ion represented by the following formula (B) shows the highest ionic strength.
- Example 8 styrenated phenyloxy ion (molecular formula: C 22 H 21 O ⁇ , molecular weight 301) was used as an evaluation ion species, and positive The ratio of the ionic strength of a styrenated phenyloxy ion (molecular formula: C 22 H 21 O ⁇ , molecular weight 301) represented by the following formula (B) to the sum of the total ionic strength of ions and the total ionic strength of negative ions, Obtained as ionic strength ratio.
- n means the number of repeating units of an ethyleneoxy group (—CH 2 CH 2 O—).
- dipotassium alkenyl succinate represented by the following formula (C), which is an anionic surfactant, is used as the surfactant, and measurement using the time-of-flight secondary ion mass spectrometer is performed.
- a plurality of negative ion fragment peaks derived from dipotassium alkenyl succinate represented by the following formula (C) are detected, and the negative ion species having the highest ionic strength is represented by the following formula (D1) or (D2).
- D1 or (D2) was detected (molecular formula: C 20 H 35 O 4 ⁇ , molecular weight 339).
- R means an alkenyl group.
- Example 10 as the surfactant, polyoxyethylene styrenated phenyl ether sulfate ammonium represented by the above formula (A) which is an anionic surfactant and the following formula (nonionic surfactant): E) and polyoxyethylene styrenated phenyl ether represented by the above formula (A) in the time-of-flight secondary ion mass spectrometer. Multiple peaks of negative ion fragments derived from ammonium ether sulfate and polyoxyethylene styrenated phenyl ether represented by the following formula (E) are detected.
- the styrenated phenyloxy ion (molecular formula: C 22 H 21 O ⁇ , molecular weight 301) is an evaluation ion species, and is expressed by the above formula (B) with respect to the sum of the total ionic strength of positive ions and the total ionic strength of negative ions that styrenated phenyloxy ion (molecular formula: C 22 H 21 O -, molecular weight 301) the ratio of the ionic strength of Io Determined as the intensity ratio.
- n means the number of repeating units of an ethyleneoxy group (—CH 2 CH 2 O—)).
- the contents (dissolved solution) in the eggplant flask were weighed with glass fiber filters “GB-140 ( ⁇ 37 mm)” and “GA-200 ( ⁇ 37 mm)” manufactured by ADVANTEC.
- Filtration is performed using a Buchner funnel type filter 3G (glass particle pore diameter 20-30 ⁇ m, volume 30 mL), and the solid content is recovered in the Buchner funnel type filter 3G.
- the solid content collected in the Buchner funnel filter 3G is dried together with the Buchner funnel filter 3G in a vacuum oven at 130 ° C. for 1 hour, and then dried at a gauge pressure of 0.06 MPa for 2 hours. And cool to room temperature.
- the total weight of the Buchner funnel filter 3G, the glass fiber filter, and the solid content was measured in a state where the solid content was contained in the Buchner funnel filter 3G. Then, the weight (g) of the dry powder was obtained by subtracting the weight of the Buchner funnel filter 3G and the glass fiber filter and the weight of the boiling stone from the measured total weight.
- the time required for the rate of change to be within a predetermined range was measured by the following method.
- the viscosity value of the dispersion is measured by the following method using a viscometer (a trace sample viscometer m-VROC manufactured by Nippon Lucas Co., Ltd.). Note that the viscometer is left in the measurement environment for 30 minutes or more in advance before measuring the viscosity value.
- a viscometer a trace sample viscometer m-VROC manufactured by Nippon Lucas Co., Ltd.
- the dispersion liquid to be measured is stirred for 30 minutes with an ultrasonic cleaner and then allowed to stand for 10 minutes, and then the viscosity (mPa ⁇ s) of the dispersion liquid is measured using the viscometer. And the viscosity value V (mPa * s / K) per unit temperature (K) is calculated
- required by the following formula using the measured value (mPa * s) of viscosity, and measured temperature (K). Viscosity value V (mPa ⁇ s / K) Measured value (mPa ⁇ s) ⁇ Measured temperature (K)
- the viscosity value V (mPa ⁇ s / K) of the dispersion is measured every 1 hour from the preparation of the dispersion according to the above viscosity value measurement method.
- the measured dispersion viscosity value V is V T (mPa ⁇ s / K), and the viscosity value 1 hour before the dispersion is V T-1 (mPa ⁇ s / K).
- an aqueous solution in which 0.9 g of potassium persulfate as a polymerization initiator was dissolved in 80 g of water was added to the contents in the separable flask and then polymerized for 12 hours. Reacted.
- the reaction solution after polymerization was filtered through a 400 mesh (mesh size: 32 ⁇ m) wire mesh to prepare a slurry containing 14% by weight of seed particles (referred to as seed particles (1)) composed of polyethyl methacrylate as a solid content.
- seed particles (1) contained in this slurry were true spherical particles having a volume average particle diameter of 0.76 ⁇ m.
- the obtained mixture was added to 1800 g of ion-exchanged water with respect to sodium di (2-ethylhexyl) sulfosuccinate (“RAPISOL (registered trademark) A-80” manufactured by NOF Corporation) as a surfactant and water at a liquid temperature of 25 ° C. (Solubility: 1.5 g / 100 ml) is added to a pure component of 4.5 g and mixed with a homomixer (“TK homomixer MARK 2.5 type” manufactured by PRIMIX Corporation) at 8000 rpm for 10 minutes. And an emulsion was obtained.
- RPISOL sodium di (2-ethylhexyl) sulfosuccinate
- TK homomixer MARK 2.5 type manufactured by PRIMIX Corporation
- the slurry of the seed particles (1) produced in Seed Particle Production Example 1 is added to 12.6 g as a solid content (seed particles), and is allowed to stand at room temperature for 5 hours. Stir. Thereafter, 900 g of an aqueous solution in which 15 g of polyvinyl pyrrolidone (“PVP-90” manufactured by Kuraray Co., Ltd.) as a polymer dispersion stabilizer was dissolved was put into the reactor and polymerized at 55 ° C. for 12 hours with stirring. It was.
- PVP-90 polyvinyl pyrrolidone
- the reaction solution after polymerization is filtered with a 400 mesh (mesh size 32 ⁇ m) wire mesh and contains 14% by weight of seed particles (hereinafter referred to as seed particles (2)) composed of polyethyl methacrylate and polymethyl methacrylate as solids.
- seed particles (2) composed of polyethyl methacrylate and polymethyl methacrylate as solids.
- a slurry was prepared.
- the seed particles (2) contained in this slurry were true spherical particles having a volume average particle diameter of 2.30 ⁇ m.
- Example 1 Production example of polymer particles
- MMA methyl methacrylate
- St styrene
- Solubility 1.5 g / 100 ml
- a homomixer Principals Co., Ltd. “T Put the K Homomixer MARK 2.5 inch ”
- the slurry of seed particles (1) obtained in Seed Particle Production Example 1 was added to a solid content (seed particles) of 4.2 g, and stirred at 30 ° C. for 5 hours.
- slurry (1) a slurry of polymer particles
- the slurry (1) of polymer particles as the crude product P was subjected to pressure filtration and dehydration, and water as an aqueous medium was removed from the slurry (1) of polymer particles as a filtrate.
- the amount of the filtrate is 2.24 kg (70% of the weight of the water used in the polymerization step) or more and the internal pressure of the pressure vessel 2 is 0.064 MPa (80% of the pressure during pressurization) or less.
- Pressurization was terminated.
- a cake of polymer particles was obtained on the filter medium 3.
- the interface between the filter medium 3 (filter cloth) of the pressure filter 1 used in this embodiment and the material to be filtered (that is, the crude product P) is circular, and the diameter thereof is that of the pressure vessel 2. It is 0.115 m, which is the same as the diameter of the bottom surface of the internal space (the diameter indicated by the symbol R in FIG. 1). Therefore, the area A of the interface between the filter medium 3 (filter cloth) of the pressure filter 1 used in this example and the material to be filtered (that is, the crude product P) is 0.0104 m 2 .
- the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.46 kg, and the medium (water) contained in the crude product P is started to pass through the filter medium 3. Then, the time T 1 until the passage of the medium through the filter medium 3 was 55.7 minutes.
- the washing is performed using a washing liquid having a weight 10 times or more the weight of the polymer particles obtained in the polymerization process (total amount of vinyl monomers used in the polymerization process 800 g).
- the test was performed until the electric conductivity of water was 2.0 times or less (specifically, 15 ⁇ S or less), and the internal pressure of the pressure vessel 2 was 0.064 MPa (80% of the pressure during pressurization) or less.
- the weight G 2 of water as the cleaning liquid used in the cleaning step of this example is 12 kg (15 times the weight of the polymer particles obtained in the polymerization step), and the surfactant used in the polymerization step.
- Example 2 Production example of polymer particles
- the inside of the pressure vessel 2 is pressurized to 0.15 MPa
- the amount of the filtrate becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more
- the internal pressure of the pressure vessel 2 is 0.
- the target polymer particles were obtained in the same manner as in Example 1 except that the solid-liquid separation step was terminated when the pressure became .12 MPa (80% of the pressure during pressurization) or less.
- the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.48 kg
- the medium (water) contained in the crude product P starts to pass through the filter medium 3.
- Example 3 Production Example of Polymer Particles
- slurry (2) a slurry of polymer particles
- Solid-liquid separation step instead of the polymer particle slurry (1), the polymer particle slurry (2) is used as the crude product, the inside of the pressure vessel 2 is pressurized to 0.20 MPa, and the filtrate is added.
- the solid-liquid separation step when the amount of water becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more and the internal pressure of the pressure vessel 2 becomes 0.16 MPa (80% of the pressure during pressurization) or less.
- the water as an aqueous medium was removed from the slurry (2) of polymer particles in the same manner as in the solid-liquid separation step of Example 1 except that the process was terminated.
- the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.38 kg, and the medium (water) contained in the crude product P starts to pass through the filter medium 3. Then, the time T 1 from the end of the passage of the medium through the filter medium 3 was 73.9 minutes.
- Example 4 Production Example of Polymer Particles
- the seed particle (1) slurry obtained in seed particle production example 1 is obtained in seed particle production example 2 in place of 4.2 g as the solid content (seed particles).
- Polymer particle slurry (hereinafter referred to as slurry (3)) in the same manner as in the polymerization step of Example 1 except that 18.7 g of the seed particle (2) slurry was used as the solid content (seed particle).
- slurry (3) Polymer particle slurry in the same manner as in the polymerization step of Example 1 except that 18.7 g of the seed particle (2) slurry was used as the solid content (seed particle).
- slurry (3) Polymer particle slurry in the same manner as in the polymerization step of Example 1 except that 18.7 g of the seed particle (2) slurry was used as the solid content (seed particle).
- Solid-liquid separation step instead of the polymer particle slurry (1), the polymer particle slurry (3) is used as the crude product, the inside of the pressure vessel 2 is pressurized to 0.15 MPa, and the filtrate is added.
- the solid-liquid separation step when the amount of water becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more and the internal pressure of the pressure vessel 2 becomes 0.12 MPa (80% of the pressure during pressurization) or less.
- the water as an aqueous medium was removed from the polymer particle slurry (3) in the same manner as in the solid-liquid separation step of Example 1 except that the process was terminated.
- the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.50 kg, and the medium (water) contained in the crude product P is started to pass through the filter medium 3. Then, the time T 1 until the passage of the medium through the filter medium 3 was 49.7 minutes.
- Example 5 Production example of polymer particles
- St styrene
- MMA methyl methacrylate
- a slurry of polymer particles (hereinafter referred to as a slurry) was prepared in the same manner as in the polymerization step of Example 1 except that the amount was 560 g and the blending amount of ethylene glycol dimethacrylate (EGDMA) as a polyfunctional vinyl monomer was 240 g. (4)) was obtained as a crude product.
- EGDMA ethylene glycol dimethacrylate
- Solid-liquid separation step instead of the polymer particle slurry (1), the polymer particle slurry (4) is used as the crude product, the inside of the pressure vessel 2 is pressurized to 0.15 MPa, and the filtrate is added.
- the solid-liquid separation step when the amount of water becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more and the internal pressure of the pressure vessel 2 becomes 0.12 MPa (80% of the pressure during pressurization) or less.
- the water as an aqueous medium was removed from the slurry (4) of polymer particles in the same manner as in the solid-liquid separation process of Example 1 except that the process was terminated.
- the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.48 kg, and the medium (water) contained in the crude product P starts to pass through the filter medium 3. Then, the time T 1 from the end of the passage of the medium through the filter medium 3 was 46.1 minutes.
- Example 6 Production example of polymer particles
- MMA methyl methacrylate
- St styrene
- a slurry of polymer particles (hereinafter referred to as a slurry) was prepared in the same manner as in the polymerization step of Example 1 except that the amount was 560 g and the blending amount of ethylene glycol dimethacrylate (EGDMA) as a polyfunctional vinyl monomer was 240 g. (5)) was obtained as a crude product.
- EGDMA ethylene glycol dimethacrylate
- Solid-liquid separation step instead of the polymer particle slurry (1), the polymer particle slurry (5) is used as a crude product, the inside of the pressure vessel 2 is pressurized to 0.15 MPa, and the filtrate is added.
- the solid-liquid separation step when the amount of water becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more and the internal pressure of the pressure vessel 2 becomes 0.12 MPa (80% of the pressure during pressurization) or less.
- the water as an aqueous medium was removed from the slurry (5) of polymer particles in the same manner as in the solid-liquid separation step of Example 1 except that the process was terminated.
- the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.48 kg, and the medium (water) contained in the crude product P starts to pass through the filter medium 3. Then, the time T 1 until the passage of the medium through the filter medium 3 was 45.3 minutes.
- the inside of the pressure vessel 2 is pressurized to 0.10 MPa, and the conductivity of the filtrate is 2.0 times or less (specifically, 15 ⁇ S or less) of the water before washing, and the pressure vessel A cake of polymer particles on the filter medium 3 was prepared in the same manner as in the cleaning step of Example 1 except that the cleaning was performed until the internal pressure of 2 became 0.08 MPa (80% of the pressure at the time of pressurization) or less.
- the polymer particles after washing were obtained on the filter medium 3.
- the weight G 2 of water as the cleaning liquid used in the cleaning step of this example is 12 kg (15 times the weight of the polymer particles obtained in the polymerization step), and the surfactant used in the polymerization step.
- Example 7 Production example of polymer particles
- MMA methyl methacrylate
- St styrene
- a slurry of particles (hereinafter referred to as slurry (6)) was obtained as a crude product.
- the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.50 kg, and the medium (water) contained in the crude product P is started to pass through the filter medium 3. Then, the time T 1 until the passage of the medium through the filter medium 3 was completed was 77.2 minutes.
- Example 8 Production example of polymer particles
- sodium di (2-ethylhexyl) sulfosuccinate (“Lapisol (registered trademark) A-80” manufactured by NOF Corporation, solubility in water at a liquid temperature of 25 ° C .; 5 g / 100 ml) is replaced with 8 g as a pure component, and ammonium polyoxyethylene styrenated phenyl ether sulfate represented by the above formula (A) (“Hitenol (registered trademark) NF08” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
- a slurry of polymer particles (hereinafter referred to as slurry (7)) was used in the same manner as in the polymerization step of Example 1 except that 8 g was used as a pure component (solubility in water at a liquid temperature of 25 ° C .; 1.2 g / 100 ml).
- Example 9 Production example of polymer particles
- sodium di (2-ethylhexyl) sulfosuccinate (“Lapisol (registered trademark) A-80” manufactured by NOF Corporation, solubility in water at a liquid temperature of 25 ° C .; 5 g / 100 ml) is replaced by 8 g as a pure component
- dipotassium alkenyl succinate represented by the above formula (C) (“Ramtel ASK” manufactured by Kao Corporation, solubility in water at a liquid temperature of 25 ° C .; 1.7 g / A slurry of polymer particles (hereinafter referred to as slurry (8)) was obtained as a crude product in the same manner as in the polymerization step of Example 1 except that 8 g of 100 ml) was used as a pure component.
- Example 10 Production example of polymer particles
- sodium di (2-ethylhexyl) sulfosuccinate (“Lapisol (registered trademark) A-80” manufactured by NOF Corporation, solubility in water at a liquid temperature of 25 ° C .; 5 g / 100 ml) is replaced with 8 g as a pure component, and ammonium polyoxyethylene styrenated phenyl ether sulfate represented by the above formula (A) (“Hitenol (registered trademark) NF08” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 8g as a pure component was used as a polymer dispersion stabilizer ("GOHSENOL (registered trademark) GM-14L” manufactured by Nippon Synthetic Chemical Co., Ltd.).
- GOHSENOL registered trademark
- a slurry of polymer particles hereinafter referred to as slurry (9) was obtained as a crude product.
- the total weight G 1 of the solid-liquid filtrate obtained in the separation step of the present example (medium) is 2.49Kg, start to pass the medium (water) to the filter medium 3 contained in the crude product P Then, the time T 1 from the end of the passage of the medium through the filter medium 3 was 82.5 minutes.
- the weight G 2 of water as a cleaning liquid used in the cleaning process the washing step was 4.0 kg (5 times the weight of the resulting polymer particles in the polymerization process), pressurizing the interior of the pressure vessel 2 to 0.10MPa Without confirming that the conductivity of the filtrate is 2.0 times or less (specifically, 15 ⁇ S or less) of the water before washing, and the internal pressure of the pressure vessel 2 is 0.08 MPa (pressurization).
- the cake of polymer particles on the filter medium 3 is washed in the same manner as in the washing step of Example 1 except that washing is performed until the pressure becomes 80% or less of the pressure at the time of pressure. Polymer particles were obtained.
- washing liquid The water used as a washing liquid is used in an amount of 8.0 kg (10 times the weight of the polymer particles obtained in the polymerization process) or more, and the inside of the pressure vessel 2 is pressurized to 0.20 MPa to conduct the filtrate. Except that cleaning was performed until the rate became 2.0 times or less the conductivity of water before cleaning, and the internal pressure of the pressure vessel 2 became 0.16 MPa (80% of the pressure at the time of pressurization) or less.
- the cake of polymer particles on the filter medium 3 was washed in the same manner as in the washing step 1 to obtain polymer particles after washing on the filter medium 3.
- the number of the slurry of polymer particles obtained in the polymerization step (slurry No.), the composition of the monomer mixture constituting the polymer contained in this slurry (polymer) Composition), measurement result of X value in solid-liquid separation process (amount of medium passing through filter medium per unit time (kg / min)), Y value in cleaning process (amount of cleaning liquid passed through filter medium per unit time ( kg / min)), the amount (kg) of the cleaning liquid (water) used in the cleaning step, the volume average particle size ( ⁇ m) of the obtained polymer particles, and the coefficient of variation (CV value (%)).
- Measurement results the compound name of the surfactant (used in the polymerization step) contained in the obtained polymer particles, the measurement result of the surfactant content (ppm) in the obtained polymer particles, TOF-SIM of the obtained polymer particles Measurement results by (ratio of ionic strength of negative ions derived from surfactant to total ionic strength of positive ions and total ionic strength of negative ions (ionic strength ratio), gel fraction of the resulting polymer particles (%) Measurement results and measurement results of dispersion stabilization time of polymer particles (elapsed time T from the preparation of the dispersion until the rate of change in viscosity value exceeds -1% to less than 1%) The results are shown in Table 1.
- the area A of the interface is 0.0104 (m 2 ). Therefore, in Examples 1 to 10 and Comparative Examples 1 and 2, the upper limit value of the X value represented by the conditional expression (1) (the amount per unit time of the medium that has passed through the filter medium (kg / min)) is 0.0572 kg / min.
- the upper limit value of the Y value (the amount of the cleaning liquid that has passed through the filter medium per unit time (kg / min)) represented by the conditional expression (2) is 0.0884 kg / min.
- the X value in the solid-liquid separation step and the Y value in the washing step are each not more than the above upper limit, and the amount of washing liquid (water) used for washing is not less than 8.0 kg (of the polymer particles).
- the polymer particles obtained in Examples 1 to 10 having a weight of 10 times or more are compared with the amount of the washing liquid (water) used for washing being less than 8.0 kg (less than 10 times the weight of the polymer particles).
- the ionic strength ratio is small. That is, according to the production method of the present invention, it was recognized that the amount of the surfactant used in the polymerization step on the surface of the polymer particles can be reduced by the solid-liquid separation step and the washing step.
- the time until the viscosity value of the dispersion is stabilized that is, the time until the rate of change of the viscosity value exceeds -1% to less than 1%) is short. It was.
- the polymer particles of Examples 1 to 10 having a surfactant content in the range of more than 0 ppm to less than 50 ppm are compared with the polymer particles of Comparative Example 1 having a surfactant content of 156 ppm. It was recognized that the time until the dispersion medium was uniformly dispersed was short.
- Example 11 Production example of optical film
- an ultrasonic cleaner (“ULTRASONIC CLEANER VS-150” manufactured by VervoCrea Inc.) was added. And stirred for 1 minute to disperse the polymer particles in methyl ethyl ketone to obtain a dispersion.
- 2.10 g of acrylic resin (“Acridic (registered trademark) A-811” manufactured by DIC Corporation) was further added, and the mixture was stirred for about 2 minutes with the above ultrasonic cleaner.
- a resin composition was obtained. After this coating resin composition was allowed to stand for 12 hours, 5.40 g of methyl ethyl ketone was added to the coating resin composition, and the mixture was stirred for 1 minute with the ultrasonic cleaner to dilute the coating resin composition.
- the obtained diluted resin composition for coating was coated on a PET film using a 75 ⁇ m slit coater. After coating, the film was placed in a drier maintained at 70 ° C. and left for 1 hour to obtain an optical film.
- Example 12 Production example of optical film
- An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 2 was used instead of 0.15 g of the polymer particles obtained in Example 1.
- Example 13 Production example of optical film
- An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 3 was used instead of 0.15 g of the polymer particles obtained in Example 1.
- Example 14 Production example of optical film
- An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 4 was used instead of 0.15 g of the polymer particles obtained in Example 1.
- Example 15 Production example of optical film
- An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 5 was used instead of 0.15 g of the polymer particles obtained in Example 1.
- Example 16 Production example of optical film
- An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 6 was used instead of 0.15 g of the polymer particles obtained in Example 1.
- Example 17 Production example of optical film
- An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 7 was used instead of 0.15 g of the polymer particles obtained in Example 1.
- Example 18 Production example of optical film
- An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 8 was used instead of 0.15 g of the polymer particles obtained in Example 1.
- Example 19 Production example of optical film
- An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 9 was used instead of 0.15 g of the polymer particles obtained in Example 1.
- Example 20 Production example of optical film
- An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 10 was used instead of 0.15 g of the polymer particles obtained in Example 1.
- Comparative Example 3 Comparative production example of optical film
- An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Comparative Example 1 was used instead of 0.15 g of the polymer particles obtained in Example 1.
- Comparative Example 4 Comparative production example of optical film
- 0.15 g of the polymer particles obtained in Comparative Example 1 0.15 g of the polymer particles obtained in Comparative Example 1 was used, and the standing time of the coating resin composition was changed from 12 hours to 24 hours.
- the optical film was obtained like Example 11 except having changed.
- optical properties of the optical films of Examples 11 to 20 and Comparative Examples 3 to 5 were evaluated by the following method.
- a test piece is obtained by cutting an optical film into a 6 cm ⁇ 6 cm square shape.
- JIS K 7136 the haze of each of the four ends of the upper, lower, left, and right sides of the surface of the test piece coated with the coating resin composition and the central portion (total of 5 locations) manufactured by Nippon Denshoku Industries Co. Measure using "NDH-4000". Then, using the measured maximum value, minimum value, and average value of the haze (%) at five locations, the haze difference (%) is calculated by the following calculation formula, and the haze difference (%) is calculated as follows: Evaluation was based on the evaluation criteria.
- the Example number and surfactant content of the polymer particles used in the production of the optical film, the standing time of the coating resin composition, and the optical Table 3 shows the evaluation results of the optical properties of the film.
- optical film obtained by coating a coating resin composition containing polymer particles having a surfactant content in the range of more than 0 ppm and less than 50 ppm is a surfactant.
- optical films Comparative Examples 3 to 5
- the haze difference is small and the light diffusibility is less uneven. It was recognized that That is, it was confirmed that stable optical characteristics (antiglare property and light diffusibility) can be obtained in an optical film including polymer particles having a surfactant content in the range of more than 0 ppm and less than 50 ppm.
- the polymer particles of Comparative Example 1 having a surfactant content of 50 ppm or more have a stable viscosity when the standing time is 16 hours or more, and are uniformly dispersed in the dispersion medium.
- the standing time of the coating resin composition was set to 24 hours, and the polymer particles were contained in the coating resin composition.
- the haze difference was large and the stable optical characteristic was not acquired.
- the polymer particles of Examples 1 to 10 having a surfactant content in the range of more than 0 ppm to less than 50 ppm and Comparative Example 2 having a surfactant content of 59 ppm are shown in Table 1. From the results shown in the above, it was confirmed that the viscosity was stabilized and dispersed uniformly in the dispersion medium (dispersion state was stabilized) in a short time of 11 to 13 hours. Therefore, in the production of the optical films of Examples 11 to 20 using the polymer particles of Examples 1 to 10 and the production of the optical film of Comparative Example 5 using the polymer particles of Comparative Example 2, the resin composition for coating is used. The standing time of the product was set to 12 hours so that the polymer particles were uniformly dispersed in the coating resin composition.
- Examples 11 to 20 produced using the polymer particles of Examples 1 to 10 having a surfactant content in the range of more than 0 ppm to less than 50 ppm.
- the haze difference was small and stable optical characteristics were obtained.
- the optical film of Comparative Example 5 produced using Comparative Example 2 having a surfactant content of 59 ppm has a large haze difference and stable optical properties compared to the optical films of Examples 11 to 20. Was not obtained.
- polymer particles having a surfactant content in the range of more than 0 ppm to less than 50 ppm are coated on a film substrate with a coating resin composition obtained by dispersing the polymer particles in a binder.
- a coating resin composition obtained by dispersing the polymer particles in a binder In the process of forming a coating film by processing, the dispersion state in the resin composition can be maintained almost stably, and the dispersion stability can be imparted to the optical film with stable optical properties. I can say that.
- an optical film obtained by coating a coating resin composition containing polymer particles having a surfactant content in the range of more than 0 ppm to less than 50 ppm has a small haze difference, and an optical film. It can be said that the characteristics are stable and the quality is excellent.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Optical Elements Other Than Lenses (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Physics & Mathematics (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
Description
X≦5.50×A ・・・(1)
(式(1)中、Xは、前記濾材を通過した前記媒体の単位時間当たりの量(kg/min)を意味し、Aは、濾材と被濾過物との界面の面積(m2)を意味する)を満たし、前記洗浄工程において、前記濾材を通過した前記洗浄液の単位時間当たりの量が、下記条件式(2);
Y≦8.50×A ・・・(2)
(式(2)中、Yは、前記濾材を通過した前記洗浄液の単位時間当たりの量(kg/min)を意味し、Aは、濾材と被濾過物との界面の面積(m2)を意味する。)を満たし、前記洗浄工程では、前記濾材上に保持された重合体粒子の重量の10倍以上の重量の洗浄液を用いることを特徴とする。 In the method for producing polymer particles of the present invention, a vinyl monomer is polymerized in a liquid medium in the presence of a surfactant, and the polymer particle containing the surfactant and the medium are mixed. A polymerization step for obtaining a product, and the crude product is charged into a filter, and the medium contained in the charged crude product is passed through the filter medium of the filter while the polymer particles contained in the crude product. A solid-liquid separation step for holding the polymer particles on the filter medium, and a cleaning liquid is charged into the filter that holds the polymer particles on the filter medium, the cleaning liquid is brought into contact with the polymer particles, and the polymer particles and A unit of passing the filter medium in the solid-liquid separation step by passing the cleaning liquid in contact with the filter medium to obtain polymer particles washed with the cleaning liquid on the filter medium. The amount per hour is Equation (1);
X ≦ 5.50 × A (1)
(In Formula (1), X means the amount (kg / min) per unit time of the medium that has passed through the filter medium, and A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered). The amount of the cleaning liquid per unit time that has passed through the filter medium in the cleaning step is the following conditional expression (2):
Y ≦ 8.50 × A (2)
(In Formula (2), Y means the amount (kg / min) per unit time of the cleaning liquid that has passed through the filter medium, and A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered). In the washing step, a washing liquid having a weight 10 times or more of the weight of the polymer particles held on the filter medium is used.
本発明の重合体粒子は、界面活性剤の含有量が0ppm超~50ppm未満であることを特徴とする。本発明の重合体粒子において、界面活性剤の含有量は、少なければ少ないほど好ましく、0ppm超~30ppmであることが好ましく、0ppm超~20ppmであることがより好ましく、0ppm超~15ppmであることがさらに好ましい。なお、重合体粒子中における界面活性剤の含有量は、例えば、液体クロマトグラフ質量分析法(LC-MS-MS)を用いて測定することができる。 (Polymer particles)
The polymer particles of the present invention are characterized in that the surfactant content is more than 0 ppm and less than 50 ppm. In the polymer particles of the present invention, the content of the surfactant is preferably as small as possible, preferably more than 0 ppm to 30 ppm, more preferably more than 0 ppm to 20 ppm, more preferably more than 0 ppm to 15 ppm. Is more preferable. The content of the surfactant in the polymer particles can be measured using, for example, liquid chromatography mass spectrometry (LC-MS-MS).
本発明の重合体粒子は、本発明の製造方法によって製造できる。 [Production method of polymer particles]
The polymer particles of the present invention can be produced by the production method of the present invention.
重合工程では、液状の媒体中、界面活性剤の存在下で、ビニル系単量体を重合させて、前記界面活性剤を含む重合体粒子と前記媒体とを含む粗生成物を得る。 [Polymerization process]
In the polymerization step, a vinyl monomer is polymerized in a liquid medium in the presence of a surfactant to obtain a crude product containing the polymer particles containing the surfactant and the medium.
固液分離工程では、濾過器に前記粗生成物を投入し、投入した前記粗生成物に含まれる媒体を前記濾過器の濾材に通過させる一方、前記粗生成物に含まれる重合体粒子を前記濾材上に保持させる。 [Solid-liquid separation process]
In the solid-liquid separation step, the crude product is charged into a filter, and the medium contained in the charged crude product is passed through the filter medium of the filter, while the polymer particles contained in the crude product are passed through the filter. Hold on filter media.
X≦5.50×A ・・・(1)
(式(1)中、Xは、前記濾材を通過した前記媒体の単位時間当たりの量(kg/min)を意味し、Aは、濾材と被濾過物との界面の面積(m2)を意味する)を満たす。 In the solid-liquid separation step, the amount per unit time of the medium that has passed through the filter medium is the following conditional expression (1);
X ≦ 5.50 × A (1)
(In Formula (1), X means the amount (kg / min) per unit time of the medium that has passed through the filter medium, and A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered). Means).
洗浄工程では、前記重合体粒子を前記濾材上に保持した前記濾過器に洗浄液を投入し、前記洗浄液を前記重合体粒子と接触させて、前記重合体粒子と接触した前記洗浄液を前記濾材に通過させることによって、前記洗浄液で洗浄された重合体粒子を前記濾材上に得る。 [Washing process]
In the washing step, the washing liquid is put into the filter holding the polymer particles on the filter medium, the washing liquid is brought into contact with the polymer particles, and the washing liquid in contact with the polymer particles passes through the filter medium. As a result, polymer particles washed with the washing liquid are obtained on the filter medium.
Y≦8.50×A ・・・(2)
(式(2)中、Yは、前記濾材を通過した前記洗浄液の単位時間当たりの量(kg/min)を意味し、Aは、濾材と被濾過物との界面の面積(m2)を意味する。)を満たす。前記濾材を通過した前記洗浄液の単位時間当たりの量が、上記条件式(2)を満たさない場合には、重合体粒子と洗浄液とが接している時間が短いために、重合体粒子の表面に付着した界面活性剤が十分に取り除かれず、最終的に得られる重合体粒子に多量の界面活性剤が残存してしまうおそれがある。 In the washing step, the amount per unit time of the washing liquid that has passed through the filter medium is the following conditional expression (2);
Y ≦ 8.50 × A (2)
(In Formula (2), Y means the amount (kg / min) per unit time of the cleaning liquid that has passed through the filter medium, and A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered). Means). When the amount per unit time of the cleaning liquid that has passed through the filter medium does not satisfy the conditional expression (2), the time for which the polymer particles are in contact with the cleaning liquid is short. The attached surfactant is not sufficiently removed, and a large amount of the surfactant may remain in the finally obtained polymer particles.
2.50×A≦Y≦8.50×A ・・・(3)
(式(3)中、Yは前記濾材を通過した前記洗浄液の単位時間当たりの量(kg/min)を意味し、Aは、濾材と被濾過物との界面の面積(m2)を意味する。)を満たすことが好ましい。前記洗浄工程における前記濾材を通過した前記洗浄液の単位時間当たりの量が、平均して、上記条件式(3)を満たす場合、効率よく、重合体粒子の表面に付着した界面活性剤を十分に取り除いて、最終的に得られる重合体粒子における界面活性剤の残存量を減らすことができる。 In addition, the amount per unit time of the cleaning liquid that has passed through the filter medium in the cleaning step averages from the start to the end of the cleaning of the polymer particles by allowing the cleaning liquid to pass through the filter medium. 3);
2.50 × A ≦ Y ≦ 8.50 × A (3)
(In Formula (3), Y means the amount (kg / min) of the cleaning liquid that has passed through the filter medium per unit time, and A means the area (m 2 ) of the interface between the filter medium and the object to be filtered. It is preferable to satisfy. When the amount per unit time of the cleaning liquid that has passed through the filter medium in the cleaning step satisfies the above conditional expression (3), the surfactant adhering to the surface of the polymer particles can be sufficiently removed. The remaining amount of the surfactant in the finally obtained polymer particles can be reduced.
D:1種の界面活性剤に対して必要とされる洗浄液の重量の下限値(g)
E:前記1種の界面活性剤の使用量(g)
F:液温25℃の洗浄液に対する前記1種の界面活性剤の溶解度(g/100ml) D = (E ÷ F) × 2000 (4)
D: Lower limit of weight of cleaning solution required for one type of surfactant (g)
E: Amount of the one kind of surfactant used (g)
F: Solubility (g / 100 ml) of the above-mentioned one type of surfactant in the washing liquid having a liquid temperature of 25 ° C.
本発明の重合体粒子は、防眩フィルムや光拡散フィルム等の光学フィルムや光拡散体等の光学部材用として好適であり、特に防眩部材用として好適である。 [Use of polymer particles]
The polymer particles of the present invention are suitable for optical films such as antiglare films and light diffusion films, and optical members such as light diffusers, and particularly suitable for antiglare members.
本発明の光学フィルムは、本発明の重合体粒子と、バインダーとを含むコーティング用樹脂組成物を、フィルム基材上に塗工してなる。本発明の光学フィルムは、例えば、バインダー中に上記重合体粒子を分散させてコーティング用樹脂組成物を得て、得られたコーティング用樹脂組成物をフィルム基材上に塗工して、上記コーティング用樹脂組成物からなる塗膜を上記フィルム基材上に形成することにより得られる。 [Optical film]
The optical film of the present invention is obtained by coating a coating resin composition containing the polymer particles of the present invention and a binder on a film substrate. The optical film of the present invention is obtained, for example, by dispersing the polymer particles in a binder to obtain a coating resin composition, coating the obtained coating resin composition on a film substrate, It is obtained by forming a coating film made of the resin composition for use on the film substrate.
本発明の樹脂成形体は、上記重合体粒子と透明樹脂とを含む成形用樹脂組成物を成形してなるものである。本発明の樹脂成形体中において、上記重合体粒子は光拡散粒子として機能する。したがって、本発明の樹脂成形体は、光拡散板等の光拡散体として機能し、LED照明カバー等として利用できる。 [Resin molding]
The resin molded body of the present invention is formed by molding a molding resin composition containing the polymer particles and a transparent resin. In the resin molded product of the present invention, the polymer particles function as light diffusing particles. Therefore, the resin molded body of the present invention functions as a light diffuser such as a light diffusing plate and can be used as an LED lighting cover or the like.
体積平均粒子径は、コールターマルチサイザーIII(ベックマン・コールター株式会社製測定装置)により測定する。測定は、ベックマン・コールター株式会社発行のMultisizerTM 3ユーザーズマニュアルに従って校正されたアパチャーを用いて実施するものとする。 [Measurement method of volume average particle diameter of polymer particles and coefficient of variation of particle diameter]
The volume average particle size is measured by Coulter Multisizer III (measurement device manufactured by Beckman Coulter, Inc.). The measurement shall be performed using an aperture calibrated according to the
種粒子の体積平均粒子径の測定は、レーザー回折・散乱方式粒度分布測定装置(ベックマン・コールター株式会社製「LS 13 320」)およびユニバーサルリキッドサンプルモジュールによって行う。 [Method for measuring volume average particle diameter of seed particles]
The volume average particle diameter of the seed particles is measured by a laser diffraction / scattering particle size distribution measuring device (“LS 13 320” manufactured by Beckman Coulter, Inc.) and a universal liquid sample module.
液体(ノニオン性界面活性剤水溶液)の屈折率B.I.の実部=1.333(水の屈折率)
固体(測定対象の種粒子)の屈折率の実部=種粒子の屈折率
固体の屈折率の虚部=0
固体の形状因子=1
また、測定条件及び測定手順は、以下の通りとする。 <Parameter>
Real part of refractive index BI of liquid (nonionic surfactant aqueous solution) = 1.333 (refractive index of water)
Real part of refractive index of solid (seed particle to be measured) = refractive index of seed particle Imaginary part of refractive index of solid = 0
Solid form factor = 1
Measurement conditions and measurement procedures are as follows.
測定時間:60秒
測定回数:1
ポンプ速度:50~60%
PIDS相対濃度:40~55%程度
超音波出力:8
<測定手順>
オフセット測定、光軸調整、バックグラウンド測定を行った後、上記した分散液を、スポイトを用いて、上記のレーザー回折・散乱方式粒度分布測定装置のユニバーサルリキッドサンプルモジュール内へ注入する。上記のユニバーサルリキッドサンプルモジュール内の濃度が上記のPIDS相対濃度に達し、上記のレーザー回折・散乱方式粒度分布測定装置のソフトウェアが「OK」と表示したら、測定を開始する。なお、測定は、ユニバーサルリキッドサンプルモジュール中でポンプ循環を行うことによって上記種粒子を分散させた状態、かつ、超音波ユニット(ULM ULTRASONIC MODULE)を起動させた状態で行う。 <Measurement conditions>
Measurement time: 60 seconds Number of measurements: 1
Pump speed: 50-60%
PIDS relative concentration: about 40-55% Ultrasonic output: 8
<Measurement procedure>
After performing offset measurement, optical axis adjustment, and background measurement, the above-described dispersion liquid is injected into the universal liquid sample module of the laser diffraction / scattering particle size distribution measuring apparatus using a dropper. When the concentration in the universal liquid sample module reaches the PIDS relative concentration and the software of the laser diffraction / scattering particle size distribution measuring apparatus displays “OK”, the measurement is started. Note that the measurement is performed in a state where the seed particles are dispersed by performing pump circulation in the universal liquid sample module and an ultrasonic unit (ULM ULTRASONIC MODULE) is activated.
固液分離工程において、粗生成物に含まれる媒体を濾材に通過させることを開始してから、前記媒体の濾材の通過を終了させるまでの時間T1(min)を測定する。また、固液分離工程において得られた濾液(媒体)の総重量G1(kg)を計量する。そして、以下の算出式により、濾材を通過した媒体の単位時間当たりの量X(kg/min)を求める。
X(kg/min)=G1(kg)/T1(min) [Measurement method of X value]
In the solid-liquid separation step, a time T 1 (min) from the start of passing the medium contained in the crude product through the filter medium to the end of the passage of the medium through the filter medium is measured. Further, the total weight G 1 (kg) of the filtrate (medium) obtained in the solid-liquid separation step is weighed. And the quantity X (kg / min) per unit time of the medium which passed the filter medium is calculated | required with the following calculation formulas.
X (kg / min) = G 1 (kg) / T 1 (min)
洗浄工程で用いた洗浄液の重量G2(kg)を測定する。また、洗浄工程において、洗浄液を濾材に通過させることを開始してから、洗浄工程に用いた洗浄液の重量G2(g)の0.8倍の重量の洗浄液が濾材を通過するまでに費やした時間T2(min)を測定する。そして、以下の算出式により、濾材を通過した洗浄液の単位時間当たりの量Y(kg/min)を求める。
Y(kg/min)=0.8×G2(kg)/T2(min) [Measurement method of Y value]
The weight G 2 (kg) of the cleaning liquid used in the cleaning process is measured. Further, in the cleaning process, after the cleaning liquid was started to pass through the filter medium, the cleaning liquid having a weight 0.8 times the weight G 2 (g) of the cleaning liquid used in the cleaning process was spent passing through the filter medium. Time T 2 (min) is measured. And the quantity Y (kg / min) per unit time of the washing | cleaning liquid which passed the filter medium is calculated | required with the following calculation formulas.
Y (kg / min) = 0.8 × G 2 (kg) / T 2 (min)
重合体粒子中の界面活性剤の含有量は、重合体粒子を溶媒により抽出し、液体クロマトグラフ質量分析計(LC/MS/MS装置)を用いて測定する。 [Method for measuring content of surfactant in polymer particles]
The content of the surfactant in the polymer particles is measured by extracting the polymer particles with a solvent and using a liquid chromatograph mass spectrometer (LC / MS / MS apparatus).
={試験液中の界面活性剤濃度(μg/ml)×抽出液量(ml)}÷試料重量(g) Surfactant content (μg / g)
= {Surfactant concentration in test solution (µg / ml) x Extraction liquid amount (ml)} ÷ Sample weight (g)
ジ(2-エチルヘキシル)スルホコハク酸塩の約1000ppm中間標準液(メタノール溶液)を調製後、さらにメタノールで段階的に希釈して0.1ppm、0.2ppm、0.5ppm、1.0ppm、2.0ppmの検量線作成用標準液を調製する。各濃度の検量線作成用標準液を後述するLC測定条件及びMS測定条件にて測定し、モニターイオンm/z=421.3(プリカーサーイオン)→227.2(プロダクトイオン)のクロマトグラム上のピーク面積値を得る。各濃度と面積値をプロットして最小二乗法により近似曲線(二次曲線)を求め、これを定量用の検量線とする。 -Preparation of calibration curve for di (2-ethylhexyl) sulfosuccinate-
After preparing about 1000 ppm intermediate standard solution (methanol solution) of di (2-ethylhexyl) sulfosuccinate, it is further diluted stepwise with methanol to 0.1 ppm, 0.2 ppm, 0.5 ppm, 1.0 ppm, and 2. A standard solution for preparing a 0 ppm calibration curve is prepared. A standard solution for preparing a calibration curve at each concentration was measured under the LC measurement conditions and MS measurement conditions described later, and on the chromatogram of monitor ion m / z = 421.3 (precursor ion) → 227.2 (product ion). Obtain the peak area value. Each concentration and area value are plotted to obtain an approximate curve (secondary curve) by the least square method, and this is used as a calibration curve for quantification.
ポリオキシエチレンスチレン化フェニルエーテル硫酸エステル塩の約1000ppm中間標準液(メタノール溶液)を調製後、さらにメタノールで段階的に希釈して0.1ppm、0.5ppm、1.0ppm、2.0ppm、10.0ppmの検量線作成用標準液を調製する。各濃度の検量線作成用標準液を後述するLC測定条件及びMS測定条件にて測定し、モニターイオンm/z=601.4(プリカーサーイオン)→301.2(プロダクトイオン)のクロマトグラム上のピーク面積値を得る。各濃度と面積値をプロットして最小二乗法により近似曲線(二次曲線)を求め、これを定量用の検量線とする。 -Preparation of calibration curve for polyoxyethylene styrenated phenyl ether sulfate ester salt-
After preparing about 1000 ppm intermediate standard solution (methanol solution) of polyoxyethylene styrenated phenyl ether sulfate ester, it is further diluted stepwise with methanol to 0.1 ppm, 0.5 ppm, 1.0 ppm, 2.0 ppm, 10 ppm A standard solution for preparing a calibration curve of 0.0 ppm is prepared. A standard solution for preparing a calibration curve at each concentration was measured under the LC measurement conditions and MS measurement conditions described later, and on the chromatogram of monitor ion m / z = 601.4 (precursor ion) → 301.2 (product ion). Obtain the peak area value. Each concentration and area value are plotted to obtain an approximate curve (secondary curve) by the least square method, and this is used as a calibration curve for quantification.
アルケニルコハク酸塩の約1000ppm中間標準液(メタノール溶液)を調製後、さらにメタノールで段階的に希釈して0.03ppm、0.15ppm、0.60ppm、1.5ppm、3.0ppmの検量線作成用標準液を調製する。各濃度の検量線作成用標準液を後述するLC測定条件及びMS測定条件にて測定し、モニターイオンm/z=339.3(プリカーサーイオン)→295.2(プロダクトイオン)のクロマトグラム上のピーク面積値を得る。各濃度と面積値をプロットして最小二乗法により近似曲線(二次曲線)を求め、これを定量用の検量線とする。 -Method for preparing calibration curve of alkenyl succinate-
After preparing about 1000ppm intermediate standard solution (methanol solution) of alkenyl succinate, further dilute stepwise with methanol to create 0.03ppm, 0.15ppm, 0.60ppm, 1.5ppm, 3.0ppm calibration curves Prepare a standard solution. A standard solution for preparing a calibration curve at each concentration was measured under the LC measurement conditions and MS measurement conditions described later, and on the chromatogram of monitor ion m / z = 339.3 (precursor ion) → 295.2 (product ion). Obtain the peak area value. Each concentration and area value are plotted to obtain an approximate curve (secondary curve) by the least square method, and this is used as a calibration curve for quantification.
ポリオキシエチレンスチレン化フェニルエーテルの約1000ppm中間標準液(メタノール溶液)を調製後、さらにメタノールで段階的に希釈して0.1ppm、0.5ppm、2.5ppm、5.0ppm、10.0ppmの検量線作成用標準液を調製する。各濃度の検量線作成用標準液を後述するLC測定条件及びMS測定条件にて測定し、モニターイオンm/z=980.5(プリカーサーイオン)→963.2(プロダクトイオン)のクロマトグラム上のピーク面積値を得る。各濃度と面積値をプロットして最小二乗法により近似曲線(二次曲線)を求め、これを定量用の検量線とする。 -How to create a calibration curve for polyoxyethylene styrenated phenyl ether-
After preparing about 1000 ppm intermediate standard solution (methanol solution) of polyoxyethylene styrenated phenyl ether, it is further diluted stepwise with methanol to 0.1 ppm, 0.5 ppm, 2.5 ppm, 5.0 ppm, 10.0 ppm. Prepare a standard solution for preparing a calibration curve. A standard solution for preparing a calibration curve at each concentration was measured under the LC measurement conditions and MS measurement conditions described later, and on the chromatogram of monitor ion m / z = 980.5 (precursor ion) → 963.2 (product ion). Obtain the peak area value. Each concentration and area value are plotted to obtain an approximate curve (secondary curve) by the least square method, and this is used as a calibration curve for quantification.
測定装置:UHPLC ACCELA(Thermo Fisher Scientific製)
カラム:Thermo Fisher Scientific製 Hypersil GOLD C18 1.9μm(内径2.1mm、長さ100mm)
カラム温度:40℃
移動相:(A:10mM酢酸アンモニウム/B:アセトニトリル)
移動相条件:(0min=B濃度90%、0→0.5min=B濃度90%→100%、0.5→1min=B濃度100%、1→1.1min=B濃度100%→90%、1.1→3min=B濃度90%)
流量:0.3mL/min
ポンプ温度:室温(25℃)
注入量:2μL
測定時間:3min -LC measurement conditions for di (2-ethylhexyl) sulfosuccinate, polyoxyethylene styrenated phenyl ether sulfate, and polyoxyethylene styrenated phenyl ether-
Measuring apparatus: UHPLC ACCELA (manufactured by Thermo Fisher Scientific)
Column: Hypersil GOLD C18 1.9 μm (inner diameter 2.1 mm, length 100 mm) manufactured by Thermo Fisher Scientific
Column temperature: 40 ° C
Mobile phase: (A: 10 mM ammonium acetate / B: acetonitrile)
Mobile phase conditions: (0 min = B concentration 90%, 0 → 0.5 min = B concentration 90% → 100%, 0.5 → 1 min = B concentration 100%, 1 → 1.1 min = B concentration 100% → 90% 1.1 → 3min = B concentration 90%)
Flow rate: 0.3 mL / min
Pump temperature: room temperature (25 ° C)
Injection volume: 2 μL
Measurement time: 3 min
測定装置:UHPLC ACCELA(Thermo Fisher Scientific製)
カラム:Thermo Fisher Scientific製 Hypersil GOLD C18 1.9μm(内径2.1mm、長さ100mm)
カラム温度:40℃
移動相:(A:10mM酢酸アンモニウム/B:アセトニトリル=25/75)
流量:0.3mL/min
ポンプ温度:室温(25℃)
注入量:2μL
測定時間:5min -LC measurement conditions for alkenyl succinate-
Measuring apparatus: UHPLC ACCELA (manufactured by Thermo Fisher Scientific)
Column: Hypersil GOLD C18 1.9 μm (inner diameter 2.1 mm, length 100 mm) manufactured by Thermo Fisher Scientific
Column temperature: 40 ° C
Mobile phase: (A: 10 mM ammonium acetate / B: acetonitrile = 25/75)
Flow rate: 0.3 mL / min
Pump temperature: room temperature (25 ° C)
Injection volume: 2 μL
Measurement time: 5 min
測定装置:Linear Ion Trap LC/MSn LXQ(Thermo Fisher Scientific製)
イオン化法(Ionization):(ESI/negative)
シースガス(Sheath Gas):30arb
補助ガス(AUX Gas):10arb
スイープガス(Sweep Gas):0arb
スプレー電圧(I Spray Voltage):5.0kV
キャピラリー温度(Capillary Temp):350℃
キャピラリー電圧(Capillary voltage):-20V
チューブレンズ電圧(Tube lens Voltage):-100V
Monitoring ion(m/Z):ジ(2-エチルヘキシル)スルホコハク酸塩(n=421.3/n2=227.2) -MS measurement conditions for di (2-ethylhexyl) sulfosuccinate-
Measuring device: Linear Ion Trap LC / MS n LXQ (manufactured by Thermo Fisher Scientific)
Ionization: (ESI / negative)
Sheath gas: 30 arb
Auxiliary gas (AUX Gas): 10arb
Sweep Gas: 0arb
Spray voltage (I Spray Voltage): 5.0 kV
Capillary temperature: 350 ° C.
Capillary voltage: -20V
Tube lens voltage: -100V
Monitoring ion (m / Z): di (2-ethylhexyl) sulfosuccinate (n = 421.3 / n2 = 227.2)
測定装置:Linear Ion Trap LC/MSn LXQ(Thermo Fisher Scientific製)
イオン化法(Ionization):(ESI/negative)
シースガス(Sheath Gas):30arb
補助ガス(AUX Gas):10arb
スイープガス(Sweep Gas):0arb
スプレー電圧(I Spray Voltage):5.0kV
キャピラリー温度(Capillary Temp):350℃
キャピラリー電圧(Capillary voltage):-20V
チューブレンズ電圧(Tube lens Voltage):-100V
Monitoring ion(m/Z):ポリオキシエチレンスチレン化フェニルエーテル硫酸エステル塩(n=601.4/n2=301.2) -MS measurement conditions for polyoxyethylene styrenated phenyl ether sulfate-
Measuring device: Linear Ion Trap LC / MS n LXQ (manufactured by Thermo Fisher Scientific)
Ionization: (ESI / negative)
Sheath gas: 30 arb
Auxiliary gas (AUX Gas): 10arb
Sweep Gas: 0arb
Spray voltage (I Spray Voltage): 5.0 kV
Capillary temperature: 350 ° C.
Capillary voltage: -20V
Tube lens voltage: -100V
Monitoring ion (m / Z): polyoxyethylene styrenated phenyl ether sulfate ester salt (n = 601.4 / n2 = 301.2)
測定装置:Linear Ion Trap LC/MSn LXQ(Thermo Fisher Scientific製)
イオン化法(Ionization):(ESI/negative)
シースガス(Sheath Gas):30arb
補助ガス(AUX Gas):10arb
スイープガス(Sweep Gas):0arb
スプレー電圧(I Spray Voltage):5.0kV
キャピラリー温度(Capillary Temp):350℃
キャピラリー電圧(Capillary voltage):-20V
チューブレンズ電圧(Tube lens Voltage):-100V
Monitoring ion(m/Z):アルケニルコハク酸塩(n=339.3/n2=295.3) -MS measurement conditions for alkenyl succinate-
Measuring device: Linear Ion Trap LC / MS n LXQ (manufactured by Thermo Fisher Scientific)
Ionization: (ESI / negative)
Sheath gas: 30 arb
Auxiliary gas (AUX Gas): 10arb
Sweep Gas: 0arb
Spray voltage (I Spray Voltage): 5.0 kV
Capillary temperature: 350 ° C.
Capillary voltage: -20V
Tube lens voltage: -100V
Monitoring ion (m / Z): alkenyl succinate (n = 339.3 / n2 = 295.3)
測定装置:Linear Ion Trap LC/MSn LXQ(Thermo Fisher Scientific製)
イオン化法(Ionization):(ESI/negative)
シースガス(Sheath Gas):30arb
補助ガス(AUX Gas):10arb
スイープガス(Sweep Gas):0arb
スプレー電圧(I Spray Voltage):5.0kV
キャピラリー温度(Capillary Temp):350℃
キャピラリー電圧(Capillary voltage):-20V
チューブレンズ電圧(Tube lens Voltage):-100V
Monitoring ion(m/Z):ポリオキシエチレンスチレン化フェニルエーテル(n=980.5/n2=963.2) -MS measurement conditions for polyoxyethylene styrenated phenyl ether-
Measuring device: Linear Ion Trap LC / MS n LXQ (manufactured by Thermo Fisher Scientific)
Ionization: (ESI / negative)
Sheath gas: 30 arb
Auxiliary gas (AUX Gas): 10arb
Sweep Gas: 0arb
Spray voltage (I Spray Voltage): 5.0 kV
Capillary temperature: 350 ° C.
Capillary voltage: -20V
Tube lens voltage: -100V
Monitoring ion (m / Z): polyoxyethylene styrenated phenyl ether (n = 980.5 / n2 = 963.2)
重合体粒子(試料)を飛行時間型二次イオン質量分析計(TOF-SIMS)により測定し、界面活性剤に由来するピークが検出されることを確認する。 [Measurement method of polymer particles by TOF-SIMS]
The polymer particles (sample) are measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), and it is confirmed that a peak derived from the surfactant is detected.
一次イオン:Bi3 2+
一次イオン加速電圧:25kV
測定面積:200μm角 <Measurement conditions>
Primary ion: Bi 3 2+
Primary ion acceleration voltage: 25 kV
Measurement area: 200μm square
200mLナスフラスコに、試料としての重合体粒子1.0gと、沸騰石0.03gとを精秤して投入し、更にトルエン100mLを注加した後、前記ナスフラスコに冷却管を装着し、130℃に保ったオイルバスに前記ナスフラスコを浸けて24時間還流する。 [Method for measuring gel fraction of polymer particles]
In a 200 mL eggplant flask, 1.0 g of polymer particles as a sample and 0.03 g of boiling stone are precisely weighed and added, and further 100 mL of toluene is added, and then a cooling tube is attached to the eggplant flask. The eggplant flask is immersed in an oil bath maintained at ° C. and refluxed for 24 hours.
ゲル分率(重量%)={乾燥粉体(g)/試料重量(g)}×100 And the gel fraction was computed with the following formulas using the weight (g) of dry powder, and the weight (g) of the sample put into the eggplant flask.
Gel fraction (% by weight) = {Dry powder (g) / Sample weight (g)} × 100
分散媒に重合体粒子を分散させてなる分散液の粘度値は、分散液中での重合体粒子の分散状態の変化に伴って変化する。そこで、分散液を調製後、1時間毎に前記分散液の粘度値を測定して、粘度値の変化率を求め、得られた変化率が所定の範囲内となるまでに要する時間、すなわち、分散液中で重合体粒子の分散状態が安定化するのに要する時間(分散安定化時間)を測定した。 [Method for measuring dispersion stabilization time of polymer particles]
The viscosity value of the dispersion liquid in which the polymer particles are dispersed in the dispersion medium changes as the dispersion state of the polymer particles in the dispersion liquid changes. Therefore, after preparing the dispersion, the viscosity value of the dispersion is measured every hour to determine the change rate of the viscosity value, and the time required for the obtained change rate to be within a predetermined range, The time (dispersion stabilization time) required for stabilizing the dispersion state of the polymer particles in the dispersion was measured.
10mlのサンプル管に、重合体粒子0.15gと、分散媒としてのメチルエチルケトン0.90gとを添加し、超音波洗浄器(株式会社ヴェルヴォクリーア製「ULTRASONIC CLEANER VS-150」)を用いて1分間撹拌し、メチルエチルケトン中に重合体粒子を分散させて、分散液を得る。この分散液に、さらに、アクリル系樹脂(DIC株式会社製の「アクリディック(登録商標)A-811」)を2.10g添加し、上記超音波洗浄器で2分程度撹拌して、メチルエチルケトン及びアクリル系樹脂中に重合体粒子を分散させ、分散液を調製する。 (1) Dispersion Preparation Method To a 10 ml sample tube, 0.15 g of polymer particles and 0.90 g of methyl ethyl ketone as a dispersion medium are added, and an ultrasonic cleaner (“ULTRASONIC CLEANER VS manufactured by Velvo Crea Co., Ltd.) is added. -150 ") for 1 minute to disperse the polymer particles in methyl ethyl ketone to obtain a dispersion. To this dispersion, 2.10 g of acrylic resin (“ACRIDIC (registered trademark) A-811” manufactured by DIC Corporation) was further added and stirred for about 2 minutes with the above ultrasonic cleaner, and methyl ethyl ketone and Polymer particles are dispersed in an acrylic resin to prepare a dispersion.
分散液の粘度値の測定は、粘度計(日本ルフト株式会社製の微量サンプル粘度計m-VROC)を用いて、次に示す方法により行う。なお、上記粘度計は、粘度値の測定前に、予め、測定環境下に30分以上放置しておくものとする。 (2) Method for Measuring Viscosity Value The viscosity value of the dispersion is measured by the following method using a viscometer (a trace sample viscometer m-VROC manufactured by Nippon Luft Co., Ltd.). Note that the viscometer is left in the measurement environment for 30 minutes or more in advance before measuring the viscosity value.
粘度値V(mPa・s/K)=測定値(mPa・s)÷測定温度(K) The dispersion liquid to be measured is stirred for 30 minutes with an ultrasonic cleaner and then allowed to stand for 10 minutes, and then the viscosity (mPa · s) of the dispersion liquid is measured using the viscometer. And the viscosity value V (mPa * s / K) per unit temperature (K) is calculated | required by the following formula using the measured value (mPa * s) of viscosity, and measured temperature (K).
Viscosity value V (mPa · s / K) = Measured value (mPa · s) ÷ Measured temperature (K)
分散液の調製から1時間おきに、上記粘度値の測定方法に従って、分散液の粘度値V(mPa・s/K)を測定する。測定した分散液の粘度値VをVT(mPa・s/K)とし、この分散液の1時間前の粘度値をVT-1(mPa・s/K)として、下記算出式により、変化率W(%)を求める。
W=((VT-1-VT)/VT-1)×100 (3) Dispersion stabilization time measurement method The viscosity value V (mPa · s / K) of the dispersion is measured every 1 hour from the preparation of the dispersion according to the above viscosity value measurement method. The measured dispersion viscosity value V is V T (mPa · s / K), and the
W = ((V T−1 −V T ) / V T−1 ) × 100
攪拌機、温度計及び還流コンデンサーを備えたセパラブルフラスコに、水性媒体としての水1000gと、(メタ)アクリル酸エステル系単量体としてのメタクリル酸エチル180gと、分子量調整剤としてのn-オクチルメルカプタン3.6gとを仕込み、セパラブルフラスコの内容物を攪拌しながらセパラブルフラスコの内部を窒素置換し、セパラブルフラスコの内温を55℃に昇温した。さらにセパラブルフラスコの内温を55℃に保ちながら、重合開始剤としての過硫酸カリウム0.9gを水80gに溶解させた水溶液を、セパラブルフラスコ内の内容物に添加した後、12時間重合反応させた。重合後の反応液を400メッシュ(目開き32μm)の金網で濾過し、固形分としてポリメタクリル酸エチルからなる種粒子(種粒子(1)という)を14重量%含有するスラリーを作製した。このスラリーに含まれる種粒子(1)は、体積平均粒子径が0.76μmの真球状粒子であった。 [Seed Particle Production Example 1]
In a separable flask equipped with a stirrer, a thermometer and a reflux condenser, 1000 g of water as an aqueous medium, 180 g of ethyl methacrylate as a (meth) acrylic acid ester monomer, and n-octyl mercaptan as a molecular weight regulator 3.6 g was charged, the inside of the separable flask was purged with nitrogen while stirring the contents of the separable flask, and the internal temperature of the separable flask was raised to 55 ° C. Furthermore, while maintaining the internal temperature of the separable flask at 55 ° C., an aqueous solution in which 0.9 g of potassium persulfate as a polymerization initiator was dissolved in 80 g of water was added to the contents in the separable flask and then polymerized for 12 hours. Reacted. The reaction solution after polymerization was filtered through a 400 mesh (mesh size: 32 μm) wire mesh to prepare a slurry containing 14% by weight of seed particles (referred to as seed particles (1)) composed of polyethyl methacrylate as a solid content. The seed particles (1) contained in this slurry were true spherical particles having a volume average particle diameter of 0.76 μm.
攪拌機及び温度計を備えた5Lの反応器に、(メタ)アクリル酸エステル系単量体としてのメタクリル酸メチル450gと、分子量調整剤としてのn-オクチルメルカプタン4.5gと、重合開始剤としての2,2’-アゾビスイソブチロニトリル4.5gとを混合した。得られた混合物を、イオン交換水1800gに界面活性剤としてのジ(2-エチルヘキシル)スルホコハク酸ナトリウム(日油株式会社製の「ラピゾール(登録商標)A-80」、液温25℃の水に対する溶解度;1.5g/100ml)を純分として4.5g添加したものに混合し、ホモミキサー(プライミクス株式会社製の「T.KホモミキサーMARK 2.5型」)にて8000rpmで10分間処理し、乳化液を得た。 [Seed Particle Production Example 2]
In a 5 L reactor equipped with a stirrer and a thermometer, 450 g of methyl methacrylate as a (meth) acrylic acid ester monomer, 4.5 g of n-octyl mercaptan as a molecular weight regulator, and a polymerization initiator 2,2′-Azobisisobutyronitrile (4.5 g) was mixed. The obtained mixture was added to 1800 g of ion-exchanged water with respect to sodium di (2-ethylhexyl) sulfosuccinate (“RAPISOL (registered trademark) A-80” manufactured by NOF Corporation) as a surfactant and water at a liquid temperature of 25 ° C. (Solubility: 1.5 g / 100 ml) is added to a pure component of 4.5 g and mixed with a homomixer (“TK homomixer MARK 2.5 type” manufactured by PRIMIX Corporation) at 8000 rpm for 10 minutes. And an emulsion was obtained.
(1)重合工程
(メタ)アクリル酸エステル系単量体としてのメタクリル酸メチル(MMA)280gと、スチレン系単量体としてのスチレン(St)280gと、多官能ビニル系単量体としてのエチレングリコールジメタクリレート(EGDMA)240gと、重合開始剤としての2,2’-アゾイソブチロニトリル4gと、重合開始剤としての過酸化ベンゾイル4gとを溶解して得られた単量体混合物を、水性媒体としてのイオン交換水800gにアニオン性界面活性剤としてのジ(2-エチルヘキシル)スルホコハク酸ナトリウム(日油株式会社製の「ラピゾール(登録商標)A-80」、液温25℃の水に対する溶解度;1.5g/100ml)を純分として8g添加したものと混合し、ホモミキサー(プライミクス株式会社製の「T.KホモミキサーMARK 2.5型」)に入れて10000rpmで10分間処理して乳化液を得た。この乳化液に、種粒子の製造例1で得られた種粒子(1)のスラリーを、固形分(種粒子)として4.2gとなるように加え、30℃で5時間撹拌し、分散液を得た。 [Example 1: Production example of polymer particles]
(1) Polymerization step 280 g of methyl methacrylate (MMA) as a (meth) acrylic acid ester monomer, 280 g of styrene (St) as a styrene monomer, and ethylene as a polyfunctional vinyl monomer A monomer mixture obtained by dissolving 240 g of glycol dimethacrylate (EGDMA), 4 g of 2,2′-azoisobutyronitrile as a polymerization initiator, and 4 g of benzoyl peroxide as a polymerization initiator, 800 g of ion-exchanged water as an aqueous medium, sodium di (2-ethylhexyl) sulfosuccinate as an anionic surfactant (“Lapizol (registered trademark) A-80” manufactured by NOF Corporation), water at a liquid temperature of 25 ° C. Solubility: 1.5 g / 100 ml) is added to the pure 8 g added and mixed with a homomixer (Primics Co., Ltd. “T Put the K Homomixer MARK 2.5 inch ") to obtain an emulsion solution for 10 minutes at 10000 rpm. To this emulsion, the slurry of seed particles (1) obtained in Seed Particle Production Example 1 was added to a solid content (seed particles) of 4.2 g, and stirred at 30 ° C. for 5 hours. Got.
図1に示す構成を有する加圧濾過器1の耐圧容器2に、粗生成物Pとして重合体粒子のスラリー(1)を投入して、耐圧容器2内の濾材3としての濾布(敷島カンバス株式会社製の「T713」)上に重合体粒子のスラリー(1)を充填した後、圧縮気体供給機によって耐圧容器2内における濾材3の上側空間Sに圧縮気体を供給することによって耐圧容器2の内部(具体的には、濾材3の上側空間S)を、0.08MPaに加圧した。これにより、粗生成物Pとしての重合体粒子のスラリー(1)を加圧濾過・脱水して、重合体粒子のスラリー(1)から水性媒体としての水を濾液として除去した。濾液の量が2.24kg(重合工程で使用した水の重量の70%)以上となり、耐圧容器2の内圧が、0.064MPa(加圧時の圧力の80%)以下となった時点で、加圧を終了した。これにより、濾材3上に重合体粒子のケーキが得られた。なお、本実施例で使用した加圧濾過器1の濾材3(濾布)と被濾過物(すなわち、粗生成物P)との界面は、円形状であり、その直径は、耐圧容器2の内部空間の底面の径(図1の符号Rで示す径)と同じ、0.115mである。よって、本実施例で使用した加圧濾過器1の濾材3(濾布)と被濾過物(すなわち、粗生成物P)との界面の面積Aは、0.0104m2である。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.46kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は55.7分であった。 (2) Solid-liquid separation step The slurry (1) of polymer particles as the crude product P is charged into the pressure resistant container 2 of the
濾材3上に上記重合体粒子のケーキを保持させたままで、洗浄液としての水を耐圧容器2内の濾材3上に供給した後、圧縮気体供給機によって耐圧容器2内における濾材3の上側空間Sに圧縮気体を供給することによって耐圧容器2の内部(具体的には、濾材3の上側空間S)を、0.08MPaに加圧した。これにより、加圧濾過・脱水が行われて、上記重合体粒子のケーキが洗浄されると共に、洗浄後の水が濾液として除去され、濾材3上に洗浄後の重合体粒子が得られた。洗浄は、重合工程で得られた重合体粒子(重合工程で使用したビニル系単量体の合計量800g)の重量の10倍以上の重量の洗浄液を用い、濾液の導電率が、洗浄前の水の導電率の2.0倍以下(具体的には、15μS以下)となり、耐圧容器2の内圧が、0.064MPa(加圧時の圧力の80%)以下となるまで行った。なお、本実施例の洗浄工程で用いた洗浄液としての水の重量G2は、12kg(重合工程で得られた重合体粒子の15倍の重量)であり、上記重合工程で使用した界面活性剤の種類毎に上記算出式(4)により算出した洗浄液の重量の下限値Dの合計量10.7kg(8(g)÷1.5(g/100ml)×2000=10667(g))よりも多い重量であった。また、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、9.6kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、230.8分であった。 (3) Washing step After the cake of the polymer particles is held on the
洗浄工程により得られた洗浄後の重合体粒子を、真空乾燥機で乾燥させ、気流分級機(日清エンジニアリング株式会社製の「ターボクラシファイア(TC-15)」)を用いて分級し、目的の重合体粒子を得た。 (4) Post-treatment step The polymer particles after washing obtained in the washing step are dried with a vacuum dryer, and an airflow classifier ("Turbo Classifier (TC-15)" manufactured by Nissin Engineering Co., Ltd.) is used. To obtain the desired polymer particles.
固液分離工程において、耐圧容器2の内部を0.15MPaに加圧して、濾液の量が2.24kg(重合工程で使用した水の重量の70%)以上となり、耐圧容器2の内圧が0.12MPa(加圧時の圧力の80%)以下となった時に、当該固液分離工程を終了した以外は、実施例1と同様にして、目的の重合体粒子を得た。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.48kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は46.6分であった。なお、本実施例の洗浄工程で用いた洗浄液としての水の重量G2は、12kg(重合工程で得られた重合体粒子の15倍の重量)であり、上記重合工程で使用した界面活性剤の種類毎に上記算出式(4)により算出した洗浄液の重量の下限値Dの合計量10.7kg(8(g)÷1.5(g/100ml)×2000=10667(g))よりも多い重量であった。また、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、9.6kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、355.6分であった。 [Example 2: Production example of polymer particles]
In the solid-liquid separation step, the inside of the pressure vessel 2 is pressurized to 0.15 MPa, the amount of the filtrate becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more, and the internal pressure of the pressure vessel 2 is 0. The target polymer particles were obtained in the same manner as in Example 1 except that the solid-liquid separation step was terminated when the pressure became .12 MPa (80% of the pressure during pressurization) or less. The total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.48 kg, and the medium (water) contained in the crude product P starts to pass through the
(1)重合工程
種粒子の製造例1で得られた種粒子(1)のスラリーの使用量を、固形分(種粒子)として16.7gとした以外は、実施例1の重合工程と同様にして、重合体粒子のスラリー(以下、スラリー(2)という)を、粗生成物として得た。 [Example 3: Production Example of Polymer Particles]
(1) Polymerization step Similar to the polymerization step of Example 1, except that the amount of the slurry of seed particles (1) obtained in Seed Particle Production Example 1 was changed to 16.7 g as the solid content (seed particles). Thus, a slurry of polymer particles (hereinafter referred to as slurry (2)) was obtained as a crude product.
粗生成物として、重合体粒子のスラリー(1)に代えて、重合体粒子のスラリー(2)を使用し、耐圧容器2の内部を0.20MPaに加圧し、濾液の量が2.24kg(重合工程で使用した水の重量の70%)以上となり、耐圧容器2の内圧が0.16MPa(加圧時の圧力の80%)以下となった時に固液分離工程を終了した以外は、実施例1の固液分離工程と同様にして、重合体粒子のスラリー(2)から水性媒体としての水を除去した。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.38kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は73.9分であった。 (2) Solid-liquid separation step Instead of the polymer particle slurry (1), the polymer particle slurry (2) is used as the crude product, the inside of the pressure vessel 2 is pressurized to 0.20 MPa, and the filtrate is added. The solid-liquid separation step when the amount of water becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more and the internal pressure of the pressure vessel 2 becomes 0.16 MPa (80% of the pressure during pressurization) or less. The water as an aqueous medium was removed from the slurry (2) of polymer particles in the same manner as in the solid-liquid separation step of Example 1 except that the process was terminated. The total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.38 kg, and the medium (water) contained in the crude product P starts to pass through the
耐圧容器2の内部を0.20MPaに加圧し、濾液の導電率が、洗浄前の水の導電率の2.0倍以下(具体的には、15μS以下)となり、耐圧容器2の内圧が、0.16MPa(加圧時の圧力の80%)以下となるまで洗浄を行った以外は、実施例1の洗浄工程と同様にして、濾材3上の重合体粒子のケーキを洗浄し、濾材3上に洗浄後の重合体粒子を得た。なお、本実施例の洗浄工程で用いた洗浄液としての水の重量G2は、12kg(重合工程で得られた重合体粒子の15倍の重量)であり、上記重合工程で使用した界面活性剤の種類毎に上記算出式(4)により算出した洗浄液の重量の下限値Dの合計量10.7kg(8(g)÷1.5(g/100ml)×2000=10667(g))よりも多い重量であった。また、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、9.6kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、346.6分であった。 (3) Washing process The inside of the pressure vessel 2 is pressurized to 0.20 MPa, and the electrical conductivity of the filtrate is 2.0 times or less (specifically, 15 μS or less) of the water before washing, and the pressure vessel A cake of polymer particles on the
洗浄工程により得られた洗浄後の重合体粒子を、真空乾燥機で乾燥させ、気流分級機(日清エンジニアリング株式会社製の「ターボクラシファイア(TC-15)」)を用いて分級し、目的の重合体粒子を得た。 (4) Post-treatment step The polymer particles after washing obtained in the washing step are dried with a vacuum dryer, and an airflow classifier ("Turbo Classifier (TC-15)" manufactured by Nissin Engineering Co., Ltd.) is used. To obtain the desired polymer particles.
(1)重合工程
種粒子として、種粒子の製造例1で得られた種粒子(1)のスラリーを固形分(種粒子)として4.2gに代えて、種粒子の製造例2で得られた種粒子(2)のスラリーを固形分(種粒子)として18.7g使用したこと以外は、実施例1の重合工程と同様にして、重合体粒子のスラリー(以下、スラリー(3)という)を、粗生成物として得た。 [Example 4: Production Example of Polymer Particles]
(1) Polymerization step As seed particles, the seed particle (1) slurry obtained in seed particle production example 1 is obtained in seed particle production example 2 in place of 4.2 g as the solid content (seed particles). Polymer particle slurry (hereinafter referred to as slurry (3)) in the same manner as in the polymerization step of Example 1 except that 18.7 g of the seed particle (2) slurry was used as the solid content (seed particle). Was obtained as a crude product.
粗生成物として、重合体粒子のスラリー(1)に代えて、重合体粒子のスラリー(3)を使用し、耐圧容器2の内部を0.15MPaに加圧し、濾液の量が2.24kg(重合工程で使用した水の重量の70%)以上となり、耐圧容器2の内圧が0.12MPa(加圧時の圧力の80%)以下となった時に固液分離工程を終了した以外は、実施例1の固液分離工程と同様にして、重合体粒子のスラリー(3)から水性媒体としての水を除去した。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.50kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は49.7分であった。 (2) Solid-liquid separation step Instead of the polymer particle slurry (1), the polymer particle slurry (3) is used as the crude product, the inside of the pressure vessel 2 is pressurized to 0.15 MPa, and the filtrate is added. The solid-liquid separation step when the amount of water becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more and the internal pressure of the pressure vessel 2 becomes 0.12 MPa (80% of the pressure during pressurization) or less. The water as an aqueous medium was removed from the polymer particle slurry (3) in the same manner as in the solid-liquid separation step of Example 1 except that the process was terminated. The total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.50 kg, and the medium (water) contained in the crude product P is started to pass through the
耐圧容器2の内部を0.20MPaに加圧し、濾液の導電率が、洗浄前の水の導電率の2.0倍以下(具体的には、15μS以下)となり、耐圧容器2の内圧が、0.16MPa(加圧時の圧力の80%)以下となるまで洗浄を行った以外は、実施例1の洗浄工程と同様にして、濾材3上の重合体粒子のケーキを洗浄し、濾材3上に洗浄後の重合体粒子を得た。なお、本実施例の洗浄工程で用いた洗浄液としての水の重量G2は、12kg(重合工程で得られた重合体粒子の15倍の重量)であり、上記重合工程で使用した界面活性剤の種類毎に上記算出式(4)により算出した洗浄液の重量の下限値Dの合計量10.7kg(8(g)÷1.5(g/100ml)×2000=10667(g))よりも多い重量であった。また、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、9.6kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、119.7分であった。 (3) Washing process The inside of the pressure vessel 2 is pressurized to 0.20 MPa, and the electrical conductivity of the filtrate is 2.0 times or less (specifically, 15 μS or less) of the water before washing, and the pressure vessel A cake of polymer particles on the
洗浄工程により得られた洗浄後の重合体粒子を、真空乾燥機で乾燥させ、気流分級機(日清エンジニアリング株式会社製の「ターボクラシファイア(TC-15)」)を用いて分級し、目的の重合体粒子を得た。 (4) Post-treatment step The polymer particles after washing obtained in the washing step are dried with a vacuum dryer, and an airflow classifier ("Turbo Classifier (TC-15)" manufactured by Nissin Engineering Co., Ltd.) is used. To obtain the desired polymer particles.
(1)重合工程
上記単量体混合物において、スチレン系単量体としてのスチレン(St)を配合せず、(メタ)アクリル酸エステル系単量体としてのメタクリル酸メチル(MMA)の配合量を560gとし、多官能ビニル系単量体としてのエチレングリコールジメタクリレート(EGDMA)の配合量を240gとしたこと以外は、実施例1の重合工程と同様にして、重合体粒子のスラリー(以下、スラリー(4)という)を、粗生成物として得た。 [Example 5: Production example of polymer particles]
(1) Polymerization step In the monomer mixture, styrene (St) as a styrene monomer is not blended, and the amount of methyl methacrylate (MMA) as a (meth) acrylic ester monomer is blended. A slurry of polymer particles (hereinafter referred to as a slurry) was prepared in the same manner as in the polymerization step of Example 1 except that the amount was 560 g and the blending amount of ethylene glycol dimethacrylate (EGDMA) as a polyfunctional vinyl monomer was 240 g. (4)) was obtained as a crude product.
粗生成物として、重合体粒子のスラリー(1)に代えて、重合体粒子のスラリー(4)を使用し、耐圧容器2の内部を0.15MPaに加圧し、濾液の量が2.24kg(重合工程で使用した水の重量の70%)以上となり、耐圧容器2の内圧が0.12MPa(加圧時の圧力の80%)以下となった時に固液分離工程を終了した以外は、実施例1の固液分離工程と同様にして、重合体粒子のスラリー(4)から水性媒体としての水を除去した。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.48kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は46.1分であった。 (2) Solid-liquid separation step Instead of the polymer particle slurry (1), the polymer particle slurry (4) is used as the crude product, the inside of the pressure vessel 2 is pressurized to 0.15 MPa, and the filtrate is added. The solid-liquid separation step when the amount of water becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more and the internal pressure of the pressure vessel 2 becomes 0.12 MPa (80% of the pressure during pressurization) or less. The water as an aqueous medium was removed from the slurry (4) of polymer particles in the same manner as in the solid-liquid separation process of Example 1 except that the process was terminated. The total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.48 kg, and the medium (water) contained in the crude product P starts to pass through the
耐圧容器の内部を0.15MPaに加圧し、濾液の導電率が、洗浄前の水の導電率の2.0倍以下(具体的には、15μS以下)となり、耐圧容器2の内圧が、0.12MPa(加圧時の圧力の80%)以下となるまで洗浄を行った以外は、実施例1の洗浄工程と同様にして、濾材3上の重合体粒子のケーキを洗浄し、濾材3上に洗浄後の重合体粒子を得た。なお、本実施例の洗浄工程で用いた洗浄液としての水の重量G2は、12kg(重合工程で得られた重合体粒子の15倍の重量)であり、上記重合工程で使用した界面活性剤の種類毎に上記算出式(4)により算出した洗浄液の重量の下限値Dの合計量10.7kg(8(g)÷1.5(g/100ml)×2000=10667(g))よりも多い重量であった。また、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、9.6kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、263.7分であった。 (3) Washing process The inside of the pressure vessel is pressurized to 0.15 MPa, and the conductivity of the filtrate becomes 2.0 times or less (specifically, 15 μS or less) of the water before washing, and the pressure vessel 2 The cake of polymer particles on the
洗浄工程により得られた洗浄後の重合体粒子を、真空乾燥機で乾燥させ、気流分級機(日清エンジニアリング株式会社製の「ターボクラシファイア(TC-15)」)を用いて分級し、目的の重合体粒子を得た。 (4) Post-treatment step The polymer particles after washing obtained in the washing step are dried with a vacuum dryer, and an airflow classifier ("Turbo Classifier (TC-15)" manufactured by Nissin Engineering Co., Ltd.) is used. To obtain the desired polymer particles.
(1)重合工程
上記単量体混合物において、(メタ)アクリル酸エステル系単量体としてのメタクリル酸メチル(MMA)を配合せず、スチレン系単量体としてのスチレン(St)の配合量を560gとし、多官能ビニル系単量体としてのエチレングリコールジメタクリレート(EGDMA)の配合量を240gとしたこと以外は、実施例1の重合工程と同様にして、重合体粒子のスラリー(以下、スラリー(5)という)を、粗生成物として得た。 [Example 6: Production example of polymer particles]
(1) Polymerization step In the monomer mixture, methyl methacrylate (MMA) as a (meth) acrylic acid ester monomer is not blended, and the blending amount of styrene (St) as a styrene monomer is changed. A slurry of polymer particles (hereinafter referred to as a slurry) was prepared in the same manner as in the polymerization step of Example 1 except that the amount was 560 g and the blending amount of ethylene glycol dimethacrylate (EGDMA) as a polyfunctional vinyl monomer was 240 g. (5)) was obtained as a crude product.
粗生成物として、重合体粒子のスラリー(1)に代えて、重合体粒子のスラリー(5)を使用し、耐圧容器2の内部を0.15MPaに加圧し、濾液の量が2.24kg(重合工程で使用した水の重量の70%)以上となり、耐圧容器2の内圧が0.12MPa(加圧時の圧力の80%)以下となった時に固液分離工程を終了した以外は、実施例1の固液分離工程と同様にして、重合体粒子のスラリー(5)から水性媒体としての水を除去した。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.48kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は45.3分であった。 (2) Solid-liquid separation step Instead of the polymer particle slurry (1), the polymer particle slurry (5) is used as a crude product, the inside of the pressure vessel 2 is pressurized to 0.15 MPa, and the filtrate is added. The solid-liquid separation step when the amount of water becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more and the internal pressure of the pressure vessel 2 becomes 0.12 MPa (80% of the pressure during pressurization) or less. The water as an aqueous medium was removed from the slurry (5) of polymer particles in the same manner as in the solid-liquid separation step of Example 1 except that the process was terminated. The total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.48 kg, and the medium (water) contained in the crude product P starts to pass through the
耐圧容器2の内部を0.10MPaに加圧し、濾液の導電率が、洗浄前の水の導電率の2.0倍以下(具体的には、15μS以下)となり、耐圧容器2の内圧が、0.08MPa(加圧時の圧力の80%)以下となるまで洗浄を行った以外は、実施例1の洗浄工程と同様にして、濾材3上の重合体粒子のケーキを洗浄し、濾材3上に洗浄後の重合体粒子を得た。なお、本実施例の洗浄工程で用いた洗浄液としての水の重量G2は、12kg(重合工程で得られた重合体粒子の15倍の重量)であり、上記重合工程で使用した界面活性剤の種類毎に上記算出式(4)により算出した洗浄液の重量の下限値Dの合計量10.7kg(8(g)÷1.5(g/100ml)×2000=10667(g))よりも多い重量であった。また、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、9.6kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、183.6分であった。 (3) Cleaning step The inside of the pressure vessel 2 is pressurized to 0.10 MPa, and the conductivity of the filtrate is 2.0 times or less (specifically, 15 μS or less) of the water before washing, and the pressure vessel A cake of polymer particles on the
洗浄工程により得られた洗浄後の重合体粒子を、真空乾燥機で乾燥させ、気流分級機(日清エンジニアリング株式会社製の「ターボクラシファイア(TC-15)」)を用いて分級し、目的の重合体粒子を得た。 (4) Post-treatment step The polymer particles after washing obtained in the washing step are dried with a vacuum dryer, and an airflow classifier ("Turbo Classifier (TC-15)" manufactured by Nissin Engineering Co., Ltd.) is used. To obtain the desired polymer particles.
(1)重合工程
上記単量体混合物において、(メタ)アクリル酸エステル系単量体としてのメタクリル酸メチル(MMA)を配合せず、スチレン系単量体としてのスチレン(St)の配合量を560gとし、多官能ビニル系単量体として、エチレングリコールジメタクリレート(EGDMA)240gに代えて、ジビニルベンゼン(DVB)240gを配合したこと以外は、実施例1の重合工程と同様にして、重合体粒子のスラリー(以下、スラリー(6)という)を、粗生成物として得た。 [Example 7: Production example of polymer particles]
(1) Polymerization step In the monomer mixture, methyl methacrylate (MMA) as a (meth) acrylic acid ester monomer is not blended, and the blending amount of styrene (St) as a styrene monomer is changed. 560 g, a polymer similar to the polymerization step of Example 1 except that 240 g of divinylbenzene (DVB) was blended in place of 240 g of ethylene glycol dimethacrylate (EGDMA) as the polyfunctional vinyl monomer. A slurry of particles (hereinafter referred to as slurry (6)) was obtained as a crude product.
粗生成物として、重合体粒子のスラリー(1)に代えて、重合体粒子のスラリー(6)を使用し、耐圧容器2の内部を0.10MPaに加圧し、濾液の量が2.24kg(重合工程で使用した水の重量の70%)以上となり、耐圧容器2の内圧が0.08MPa(加圧時の圧力の80%)以下となった時に固液分離工程を終了した以外は、実施例1の固液分離工程と同様にして、重合体粒子のスラリー(6)から水性媒体としての水を除去した。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.50kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は77.2分であった。 (2) Solid-liquid separation process
As a crude product, instead of the polymer particle slurry (1), the polymer particle slurry (6) was used, the inside of the pressure vessel 2 was pressurized to 0.10 MPa, and the amount of filtrate was 2.24 kg ( Except that the solid-liquid separation process was completed when the pressure of the pressure vessel 2 became equal to or greater than 70% of the weight of water used in the polymerization process and the internal pressure of the pressure vessel 2 became equal to or less than 0.08 MPa (80% of the pressure during pressurization). In the same manner as in the solid-liquid separation step of Example 1, water as an aqueous medium was removed from the slurry (6) of polymer particles. The total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.50 kg, and the medium (water) contained in the crude product P is started to pass through the
耐圧容器2の内部を0.15MPaに加圧し、濾液の導電率が、洗浄前の水の導電率の2.0倍以下(具体的には、15μS以下)となり、耐圧容器2の内圧が、0.12MPa(加圧時の圧力の80%)以下となるまで洗浄を行った以外は、実施例1の洗浄工程と同様にして、濾材3上の重合体粒子のケーキを洗浄し、濾材3上に洗浄後の重合体粒子を得た。なお、本実施例の洗浄工程で用いた洗浄液としての水の重量G2は、12kg(重合工程で得られた重合体粒子の15倍の重量)であり、上記重合工程で使用した界面活性剤の種類毎に上記算出式(4)により算出した洗浄液の重量の下限値Dの合計量10.7kg(8(g)÷1.5(g/100ml)×2000=10667(g))よりも多い重量であった。また、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、9.6kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、151.9分であった。 (3) Washing process The inside of the pressure vessel 2 is pressurized to 0.15 MPa, and the conductivity of the filtrate becomes 2.0 times or less (specifically, 15 μS or less) of the water before washing, and the pressure vessel A cake of polymer particles on the
洗浄工程により得られた洗浄後の重合体粒子を、真空乾燥機で乾燥させ、気流分級機(日清エンジニアリング株式会社製の「ターボクラシファイア(TC-15)」)を用いて分級し、目的の重合体粒子を得た。 (4) Post-treatment step The polymer particles after washing obtained in the washing step are dried with a vacuum dryer, and an airflow classifier ("Turbo Classifier (TC-15)" manufactured by Nissin Engineering Co., Ltd.) is used. To obtain the desired polymer particles.
(1)重合工程
アニオン性界面活性剤として、ジ(2-エチルヘキシル)スルホコハク酸ナトリウム(日油株式会社製の「ラピゾール(登録商標)A-80」、液温25℃の水に対する溶解度;1.5g/100ml)を純分として8gに代えて、上記式(A)で表されるポリオキシエチレンスチレン化フェニルエーテル硫酸エステルアンモニウム(第一工業製薬株式会社製の「ハイテノール(登録商標)NF08」、液温25℃の水に対する溶解度;1.2g/100ml)を純分として8g使用したこと以外は、実施例1の重合工程と同様にして、重合体粒子のスラリー(以下、スラリー(7)という)を、粗生成物として得た。 [Example 8: Production example of polymer particles]
(1) Polymerization Step As an anionic surfactant, sodium di (2-ethylhexyl) sulfosuccinate (“Lapisol (registered trademark) A-80” manufactured by NOF Corporation, solubility in water at a liquid temperature of 25 ° C .; 5 g / 100 ml) is replaced with 8 g as a pure component, and ammonium polyoxyethylene styrenated phenyl ether sulfate represented by the above formula (A) (“Hitenol (registered trademark) NF08” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) A slurry of polymer particles (hereinafter referred to as slurry (7)) was used in the same manner as in the polymerization step of Example 1 except that 8 g was used as a pure component (solubility in water at a liquid temperature of 25 ° C .; 1.2 g / 100 ml). Was obtained as a crude product.
粗生成物として、重合体粒子のスラリー(1)に代えて、重合体粒子のスラリー(7)を使用した以外は、実施例1の固液分離工程と同様にして、重合体粒子のスラリー(7)から水性媒体としての水を除去した。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.44kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は60.1分であった。 (2) Solid-liquid separation step As the crude product, the same procedure as in the solid-liquid separation step of Example 1 was performed except that the polymer particle slurry (7) was used instead of the polymer particle slurry (1). Then, water as an aqueous medium was removed from the slurry (7) of polymer particles. The total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.44 kg, and the medium (water) contained in the crude product P is started to pass through the
実施例1の洗浄工程と同様にして、濾材3上の重合体粒子のケーキを洗浄し、濾材3上に洗浄後の重合体粒子を得た。なお、本実施例の洗浄工程で用いた洗浄液としての水の重量G2は、15.0kg(重合工程で得られた重合体粒子の18.75倍の重量)であり、上記重合工程で使用した界面活性剤の種類毎に上記算出式(4)により算出した洗浄液の重量の下限値Dの合計量13.3kg(8(g)÷1.2(g/100ml)×2000=13333(g))よりも多い重量であった。た。また、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、12.0kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、311.7分であった。 (3) Washing Step In the same manner as in the washing step of Example 1, the polymer particle cake on the
洗浄工程により得られた洗浄後の重合体粒子を、真空乾燥機で乾燥させ、気流分級機(日清エンジニアリング株式会社製の「ターボクラシファイア(TC-15)」)を用いて分級し、目的の重合体粒子を得た。 (4) Post-treatment step The polymer particles after washing obtained in the washing step are dried with a vacuum dryer, and an airflow classifier ("Turbo Classifier (TC-15)" manufactured by Nissin Engineering Co., Ltd.) is used. To obtain the desired polymer particles.
(1)重合工程
アニオン性界面活性剤として、ジ(2-エチルヘキシル)スルホコハク酸ナトリウム(日油株式会社製の「ラピゾール(登録商標)A-80」、液温25℃の水に対する溶解度;1.5g/100ml)を純分として8gに代えて、上記式(C)で表されるアルケニルコハク酸ジカリウム(花王株式会社製の「ラムテルASK」、液温25℃の水に対する溶解度;1.7g/100ml)を純分として8g使用したこと以外は、実施例1の重合工程と同様にして、重合体粒子のスラリー(以下、スラリー(8)という)を、粗生成物として得た。 [Example 9: Production example of polymer particles]
(1) Polymerization Step As an anionic surfactant, sodium di (2-ethylhexyl) sulfosuccinate (“Lapisol (registered trademark) A-80” manufactured by NOF Corporation, solubility in water at a liquid temperature of 25 ° C .; 5 g / 100 ml) is replaced by 8 g as a pure component, and dipotassium alkenyl succinate represented by the above formula (C) (“Ramtel ASK” manufactured by Kao Corporation, solubility in water at a liquid temperature of 25 ° C .; 1.7 g / A slurry of polymer particles (hereinafter referred to as slurry (8)) was obtained as a crude product in the same manner as in the polymerization step of Example 1 except that 8 g of 100 ml) was used as a pure component.
粗生成物として、重合体粒子のスラリー(1)に代えて、重合体粒子のスラリー(8)を使用した以外は、実施例1の固液分離工程と同様にして、重合体粒子のスラリー(8)から水性媒体としての水を除去した。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.49kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は62.0分であった。 (2) Solid-Liquid Separation Step As the crude product, the same procedure as in the solid-liquid separation step of Example 1 was performed except that the polymer particle slurry (8) was used instead of the polymer particle slurry (1). Then, water as an aqueous medium was removed from the slurry (8) of polymer particles. The total weight G 1 of the solid-liquid filtrate obtained in the separation step of the present example (medium) is 2.49Kg, start to pass the medium (water) to the
実施例1の洗浄工程と同様にして、濾材3上の重合体粒子のケーキを洗浄し、濾材3上に洗浄後の重合体粒子を得た。なお、本実施例の洗浄工程で用いた洗浄液としての水の重量G2は、12.0kg(重合工程で得られた重合体粒子の15倍の重量)であり、上記重合工程で使用した界面活性剤の種類毎に上記算出式(4)により算出した洗浄液の重量の下限値Dの合計量9.4kg(8(g)÷1.7(g/100ml)×2000=9412(g))よりも多い重量であった。また、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、9.6kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、250.7分であった。 (3) Washing Step In the same manner as in the washing step of Example 1, the polymer particle cake on the
洗浄工程により得られた洗浄後の重合体粒子を、真空乾燥機で乾燥させ、気流分級機(日清エンジニアリング株式会社製の「ターボクラシファイア(TC-15)」)を用いて分級し、目的の重合体粒子を得た。 (4) Post-treatment step The polymer particles after washing obtained in the washing step are dried with a vacuum dryer, and an airflow classifier ("Turbo Classifier (TC-15)" manufactured by Nissin Engineering Co., Ltd.) is used. To obtain the desired polymer particles.
(1)重合工程
アニオン性界面活性剤として、ジ(2-エチルヘキシル)スルホコハク酸ナトリウム(日油株式会社製の「ラピゾール(登録商標)A-80」、液温25℃の水に対する溶解度;1.5g/100ml)を純分として8gに代えて、上記式(A)で表されるポリオキシエチレンスチレン化フェニルエーテル硫酸エステルアンモニウム(第一工業製薬株式会社製の「ハイテノール(登録商標)NF08」、液温25℃の水に対する溶解度;1.2g/100ml)を純分として8g使用し、高分子分散安定剤としてのポリビニルアルコール(日本合成化学株式会社製の「ゴーセノール(登録商標)GM-14L」)40gに代えて、ノニオン性界面活性剤としての上記式(E)で表されるポリオキシエチレンスチレン化フェニルエーテル(第一工業製薬株式会社製の「ノイゲン(登録商標)EA-167」、液温25℃の水に対する溶解度;1.1g/100ml)を純分として8g使用したこと以外は、実施例1の重合工程と同様にして、重合体粒子のスラリー(以下、スラリー(9)という)を、粗生成物として得た。 [Example 10: Production example of polymer particles]
(1) Polymerization Step As an anionic surfactant, sodium di (2-ethylhexyl) sulfosuccinate (“Lapisol (registered trademark) A-80” manufactured by NOF Corporation, solubility in water at a liquid temperature of 25 ° C .; 5 g / 100 ml) is replaced with 8 g as a pure component, and ammonium polyoxyethylene styrenated phenyl ether sulfate represented by the above formula (A) (“Hitenol (registered trademark) NF08” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 8g as a pure component was used as a polymer dispersion stabilizer ("GOHSENOL (registered trademark) GM-14L" manufactured by Nippon Synthetic Chemical Co., Ltd.). ]) In place of 40 g, polyoxyethylene styrenated phenyl represented by the above formula (E) as a nonionic surfactant Example 1 except that 8 g of ether (“Neugen® EA-167” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solubility in water at a liquid temperature of 25 ° C .; 1.1 g / 100 ml) was used as a pure component. In the same manner as in the polymerization step, a slurry of polymer particles (hereinafter referred to as slurry (9)) was obtained as a crude product.
粗生成物として、重合体粒子のスラリー(1)に代えて、重合体粒子のスラリー(9)を使用した以外は、実施例1の固液分離工程と同様にして、重合体粒子のスラリー(9)から水性媒体としての水を除去した。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.44kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は65.8分であった。 (2) Solid-liquid separation step As the crude product, the same procedure as in the solid-liquid separation step of Example 1 was conducted except that the polymer particle slurry (9) was used instead of the polymer particle slurry (1). Then, water as an aqueous medium was removed from the slurry (9) of polymer particles. The total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.44 kg, and the medium (water) contained in the crude product P is started to pass through the
実施例1の洗浄工程と同様にして、濾材3上の重合体粒子のケーキを洗浄し、濾材3上に洗浄後の重合体粒子を得た。なお、本実施例の洗浄工程で用いた洗浄液としての水の重量G2は、30.0kg(重合工程で得られた重合体粒子の37.5倍の重量)であり、上記重合工程で使用した界面活性剤の種類毎に上記算出式(4)により算出した洗浄液の重量の下限値Dの量の合計量27.9kg({8(g)÷1.2(g/100ml)×2000}+{8(g)÷1.1(g/100ml)×2000}=13333+14545=27878(g))よりも多い重量であった。また、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、24.0kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、633.2分であった。 (3) Washing Step In the same manner as in the washing step of Example 1, the polymer particle cake on the
洗浄工程により得られた洗浄後の重合体粒子を、真空乾燥機で乾燥させ、気流分級機(日清エンジニアリング株式会社製の「ターボクラシファイア(TC-15)」)を用いて分級し、目的の重合体粒子を得た。 (4) Post-treatment step The polymer particles after washing obtained in the washing step are dried with a vacuum dryer, and an airflow classifier ("Turbo Classifier (TC-15)" manufactured by Nissin Engineering Co., Ltd.) is used. To obtain the desired polymer particles.
(1)重合工程
実施例1の重合工程と同様にして、重合体粒子のスラリー(以下、スラリー(1)という)を、粗生成物として得た。 [Comparative Example 1: Comparative production example of polymer particles]
(1) Polymerization step In the same manner as in the polymerization step of Example 1, a slurry of polymer particles (hereinafter referred to as slurry (1)) was obtained as a crude product.
耐圧容器2の内部を0.10MPaに加圧して、濾液の量が2.24kg(重合工程で使用した水の重量の70%)以上となり、耐圧容器2の内圧が0.08MPa(加圧時の圧力の80%)以下となった時に、当該固液分離工程を終了した以外は、実施例1の固液分離工程と同様にして、重合体粒子のスラリー(1)から水性媒体としての水を除去した。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.49kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は82.5分であった。 (2) Solid-liquid separation process The inside of the pressure vessel 2 is pressurized to 0.10 MPa, the amount of the filtrate becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more, and the internal pressure of the pressure vessel 2 is A slurry of polymer particles (1) was obtained in the same manner as in the solid-liquid separation step of Example 1, except that the solid-liquid separation step was terminated when the pressure became 0.08 MPa (80% of the pressure during pressurization) or less. ) To remove water as an aqueous medium. The total weight G 1 of the solid-liquid filtrate obtained in the separation step of the present example (medium) is 2.49Kg, start to pass the medium (water) to the
洗浄工程で用いる洗浄液としての水の重量G2を4.0kg(重合工程で得られた重合体粒子の5倍の重量)とし、耐圧容器2の内部を0.10MPaに加圧して、濾液の導電率が洗浄前の水の導電率の2.0倍以下(具体的には、15μS以下)となることを確認せず、耐圧容器2の内圧が、0.08MPa(加圧時の圧力の80%)以下となるまで洗浄を行った以外は、実施例1の洗浄工程と同様にして、濾材3上の重合体粒子のケーキを洗浄し、濾材3上に洗浄後の重合体粒子を得た。なお、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、3.2kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、74.1分であった。 (3) the weight G 2 of water as a cleaning liquid used in the cleaning process the washing step was 4.0 kg (5 times the weight of the resulting polymer particles in the polymerization process), pressurizing the interior of the pressure vessel 2 to 0.10MPa Without confirming that the conductivity of the filtrate is 2.0 times or less (specifically, 15 μS or less) of the water before washing, and the internal pressure of the pressure vessel 2 is 0.08 MPa (pressurization). The cake of polymer particles on the
(1)重合工程
実施例1の重合工程と同様にして、重合体粒子のスラリー(以下、スラリー(1)という)を、粗生成物として得た。 [Comparative Example 2: Comparative production example of polymer particles]
(1) Polymerization step In the same manner as in the polymerization step of Example 1, a slurry of polymer particles (hereinafter referred to as slurry (1)) was obtained as a crude product.
耐圧容器2の内部を0.25MPaに加圧して、濾液の量が2.24kg(重合工程で使用した水の重量の70%)以上となり、耐圧容器2の内圧が0.20MPa(加圧時の圧力の80%)以下となった時に、当該固液分離工程を終了した以外は、実施例1の固液分離工程と同様にして、重合体粒子のスラリー(1)から水性媒体としての水を除去した。なお、本実施例の固液分離工程で得られた濾液(媒体)の総重量G1は2.45kgであり、粗生成物Pに含まれる媒体(水)を濾材3に通過させることを開始してから、前記媒体の濾材3の通過を終了させるまでの時間T1は19.5分であった。 (2) Solid-liquid separation process The inside of the pressure vessel 2 is pressurized to 0.25 MPa, the amount of the filtrate becomes 2.24 kg (70% of the weight of water used in the polymerization step) or more, and the internal pressure of the pressure vessel 2 is A slurry of polymer particles (1) was obtained in the same manner as in the solid-liquid separation step of Example 1 except that the solid-liquid separation step was terminated when the pressure became 0.20 MPa (80% of the pressure during pressurization) or less. ) To remove water as an aqueous medium. The total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.45 kg, and the medium (water) contained in the crude product P is started to pass through the
洗浄液としての水を8.0kg(重合工程で得られた重合体粒子の10倍の重量)以上使用し、耐圧容器2の内部を0.20MPaに加圧して、濾液の導電率が洗浄前の水の導電率の2.0倍以下となり、耐圧容器2の内圧が、0.16MPa(加圧時の圧力の80%)以下となるまで洗浄を行った以外は、実施例1の洗浄工程と同様にして、濾材3上の重合体粒子のケーキを洗浄し、濾材3上に洗浄後の重合体粒子を得た。なお、本実施例の洗浄工程で用いた洗浄液としての水の重量G2は、12.0kg(重合工程で得られた重合体粒子の15倍の重量)であり、上記重合工程で使用した界面活性剤の種類毎に上記算出式(4)により算出した洗浄液の重量の下限値Dの合計量10.7kg(8(g)÷1.5(g/100ml)×2000=10667(g))よりも多い重量であった。また、本実施例の洗浄工程において、洗浄液を濾材3に通過させることを開始してから、9.6kg(洗浄工程で用いた洗浄液としての水の重量G2の0.8倍の重量)の洗浄液が濾材3を通過するまでに費やした時間T2(min)は、80.2分であった。 (3) Washing process The water used as a washing liquid is used in an amount of 8.0 kg (10 times the weight of the polymer particles obtained in the polymerization process) or more, and the inside of the pressure vessel 2 is pressurized to 0.20 MPa to conduct the filtrate. Except that cleaning was performed until the rate became 2.0 times or less the conductivity of water before cleaning, and the internal pressure of the pressure vessel 2 became 0.16 MPa (80% of the pressure at the time of pressurization) or less. The cake of polymer particles on the
10mlのサンプル管に、実施例1で得られた重合体粒子0.15gと、メチルエチルケトン0.90gとを添加し、超音波洗浄器(株式会社ヴェルヴォクリーア製「ULTRASONIC CLEANER VS-150」)を用いて1分間撹拌し、メチルエチルケトン中に重合体粒子を分散させて、分散液を得る。この分散液に、さらに、アクリル系樹脂(DIC株式会社製の「アクリディック(登録商標)A-811」)を2.10g添加し、上記超音波洗浄器で2分程度撹拌して、コーティング用樹脂組成物を得た。このコーティング用樹脂組成物を12時間静置させた後、コーティング用樹脂組成物にメチルエチルケトン5.40gを添加し、上記超音波洗浄器にて1分間撹拌して、コーティング用樹脂組成物の希釈液を得た。 [Example 11: Production example of optical film]
To a 10 ml sample tube, 0.15 g of the polymer particles obtained in Example 1 and 0.90 g of methyl ethyl ketone were added, and an ultrasonic cleaner (“ULTRASONIC CLEANER VS-150” manufactured by VervoCrea Inc.) was added. And stirred for 1 minute to disperse the polymer particles in methyl ethyl ketone to obtain a dispersion. To this dispersion, 2.10 g of acrylic resin (“Acridic (registered trademark) A-811” manufactured by DIC Corporation) was further added, and the mixture was stirred for about 2 minutes with the above ultrasonic cleaner. A resin composition was obtained. After this coating resin composition was allowed to stand for 12 hours, 5.40 g of methyl ethyl ketone was added to the coating resin composition, and the mixture was stirred for 1 minute with the ultrasonic cleaner to dilute the coating resin composition. Got.
実施例1で得られた重合体粒子0.15gに代えて、実施例2で得られた重合体粒子0.15gを使用した以外は、実施例11と同様にして、光学フィルムを得た。 [Example 12: Production example of optical film]
An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 2 was used instead of 0.15 g of the polymer particles obtained in Example 1.
実施例1で得られた重合体粒子0.15gに代えて、実施例3で得られた重合体粒子0.15gを使用した以外は、実施例11と同様にして、光学フィルムを得た。 [Example 13: Production example of optical film]
An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 3 was used instead of 0.15 g of the polymer particles obtained in Example 1.
実施例1で得られた重合体粒子0.15gに代えて、実施例4で得られた重合体粒子0.15gを使用した以外は、実施例11と同様にして、光学フィルムを得た。 [Example 14: Production example of optical film]
An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 4 was used instead of 0.15 g of the polymer particles obtained in Example 1.
実施例1で得られた重合体粒子0.15gに代えて、実施例5で得られた重合体粒子0.15gを使用した以外は、実施例11と同様にして、光学フィルムを得た。 [Example 15: Production example of optical film]
An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 5 was used instead of 0.15 g of the polymer particles obtained in Example 1.
実施例1で得られた重合体粒子0.15gに代えて、実施例6で得られた重合体粒子0.15gを使用した以外は、実施例11と同様にして、光学フィルムを得た。 [Example 16: Production example of optical film]
An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 6 was used instead of 0.15 g of the polymer particles obtained in Example 1.
実施例1で得られた重合体粒子0.15gに代えて、実施例7で得られた重合体粒子0.15gを使用した以外は、実施例11と同様にして、光学フィルムを得た。 [Example 17: Production example of optical film]
An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 7 was used instead of 0.15 g of the polymer particles obtained in Example 1.
実施例1で得られた重合体粒子0.15gに代えて、実施例8で得られた重合体粒子0.15gを使用した以外は、実施例11と同様にして、光学フィルムを得た。 [Example 18: Production example of optical film]
An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 8 was used instead of 0.15 g of the polymer particles obtained in Example 1.
実施例1で得られた重合体粒子0.15gに代えて、実施例9で得られた重合体粒子0.15gを使用した以外は、実施例11と同様にして、光学フィルムを得た。 [Example 19: Production example of optical film]
An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 9 was used instead of 0.15 g of the polymer particles obtained in Example 1.
実施例1で得られた重合体粒子0.15gに代えて、実施例10で得られた重合体粒子0.15gを使用した以外は、実施例11と同様にして、光学フィルムを得た。 [Example 20: Production example of optical film]
An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Example 10 was used instead of 0.15 g of the polymer particles obtained in Example 1.
実施例1で得られた重合体粒子0.15gに代えて、比較例1で得られた重合体粒子0.15gを使用した以外は、実施例11と同様にして、光学フィルムを得た。 [Comparative Example 3: Comparative production example of optical film]
An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Comparative Example 1 was used instead of 0.15 g of the polymer particles obtained in Example 1.
実施例1で得られた重合体粒子0.15gに代えて、比較例1で得られた重合体粒子0.15gを使用し、コーティング用樹脂組成物の静置時間を12時間から24時間に変更した以外は、実施例11と同様にして、光学フィルムを得た。 [Comparative Example 4: Comparative production example of optical film]
Instead of 0.15 g of the polymer particles obtained in Example 1, 0.15 g of the polymer particles obtained in Comparative Example 1 was used, and the standing time of the coating resin composition was changed from 12 hours to 24 hours. The optical film was obtained like Example 11 except having changed.
実施例1で得られた重合体粒子0.15gに代えて、比較例2で得られた重合体粒子0.15gを使用した以外は、実施例11と同様にして、光学フィルムを得た。 [Comparative Example 5: Comparative Production Example of Optical Film]
An optical film was obtained in the same manner as in Example 11 except that 0.15 g of the polymer particles obtained in Comparative Example 2 was used instead of 0.15 g of the polymer particles obtained in Example 1.
光学フィルムを6cm×6cmの正方形状にカットしたものを試験片とする。試験片のコーティング用樹脂組成物が塗工された面の上下左右の4つの端部及び中央部(計5箇所)のそれぞれのヘイズを、JIS K 7136に従って、日本電色工業株式会社製の「NDH-4000」を使用して測定する。そして、測定した5箇所のヘイズ(%)の最大値、最小値、及び平均値を用いて、以下の算出式により、ヘイズ差(%)を算出し、そのヘイズ差(%)を、以下の評価基準により評価した。 [Evaluation method of optical characteristics]
A test piece is obtained by cutting an optical film into a 6 cm × 6 cm square shape. According to JIS K 7136, the haze of each of the four ends of the upper, lower, left, and right sides of the surface of the test piece coated with the coating resin composition and the central portion (total of 5 locations) manufactured by Nippon Denshoku Industries Co. Measure using "NDH-4000". Then, using the measured maximum value, minimum value, and average value of the haze (%) at five locations, the haze difference (%) is calculated by the following calculation formula, and the haze difference (%) is calculated as follows: Evaluation was based on the evaluation criteria.
R={(HzMAX-HzMIN)/HzAVE)}×100
R:ヘイズ差(%)
HzMAX:5箇所のヘイズ(%)の最大値
HzMIN:5箇所のヘイズ(%)の最小値
HzAVE:5箇所のヘイズ(%)の平均値
<評価基準>
◎:ヘイズ差が0.5%未満
○:ヘイズ差が0.5%以上1.0%未満
△:ヘイズ差が1.0%以上3.0%未満
×:ヘイズ差が3.0以上 <Calculation formula of haze difference (%)>
R = {(Hz MAX −Hz MIN ) / Hz AVE )} × 100
R: Haze difference (%)
Hz MAX : Maximum value of 5 hazes (%) Hz MIN : Minimum value of 5 hazes (%) Hz AVE : Average value of 5 hazes (%) <Evaluation Criteria>
◎: Haze difference is less than 0.5% ○: Haze difference is 0.5% or more and less than 1.0% △: Haze difference is 1.0% or more and less than 3.0% ×: Haze difference is 3.0 or more
2 耐圧容器
3 濾材
R 濾材と被濾過物との界面(脱液面)の径
P 粗生成物
S 濾材の上側空間
DESCRIPTION OF
Claims (14)
- 界面活性剤の含有量が0ppm超~50ppm未満であることを特徴とする重合体粒子。 Polymer particles, wherein the surfactant content is more than 0 ppm and less than 50 ppm.
- 請求項1に記載の重合体粒子であって、
飛行時間型2次イオン質量分析計により測定される、正イオンの総イオン強度及び負イオンの総イオン強度の合計に対する、前記界面活性剤に由来する負イオンのイオン強度の比が、0.01×10-4~2.00×10-4であることを特徴とする重合体粒子。 The polymer particles according to claim 1,
The ratio of the ionic strength of the negative ions derived from the surfactant to the sum of the total ionic strength of the positive ions and the total ionic strength of the negative ions, measured by a time-of-flight secondary ion mass spectrometer, is 0.01. A polymer particle having a size of × 10 −4 to 2.00 × 10 −4 . - 請求項1又は2に記載の重合体粒子であって、
前記界面活性剤が、アニオン性界面活性剤及びノニオン性界面活性剤の少なくとも一方を含むことを特徴とする重合体粒子。 The polymer particles according to claim 1 or 2,
The polymer particles, wherein the surfactant contains at least one of an anionic surfactant and a nonionic surfactant. - 請求項1~3のいずれか1つに記載の重合体粒子であって、
当該重合体粒子を構成する重合体が、(メタ)アクリル系重合体、スチレン系重合体、及び、(メタ)アクリル-スチレン系共重合体のうちの何れかであることを特徴とする重合体粒子。 The polymer particles according to any one of claims 1 to 3,
The polymer constituting the polymer particles is any one of a (meth) acrylic polymer, a styrene polymer, and a (meth) acryl-styrene copolymer. particle. - 請求項1~4のいずれか1つに記載の重合体粒子であって、
粒子径の変動係数が15%以下であることを特徴とする重合体粒子。 Polymer particles according to any one of claims 1 to 4, comprising
Polymer particles having a coefficient of variation in particle diameter of 15% or less. - 請求項1~5のいずれか1つに記載の重合体粒子であって、
ゲル分率90%以上であることを特徴とする重合体粒子。 The polymer particles according to any one of claims 1 to 5,
A polymer particle having a gel fraction of 90% or more. - 請求項1~6のいずれか1つに記載の重合体粒子であって、
界面活性剤の存在下で、ビニル系単量体を種粒子に吸収させて重合することによって得られることを特徴とする重合体粒子。 The polymer particles according to any one of claims 1 to 6,
Polymer particles obtained by polymerizing a vinyl monomer by absorbing the vinyl monomer in the presence of a surfactant. - 請求項1~7のいずれか1つに記載の重合体粒子であって、
光学部材用であることを特徴とする重合体粒子。 Polymer particles according to any one of claims 1 to 7, comprising
Polymer particles for optical members. - 請求項1~8のいずれか1つに記載の重合体粒子であって、
防眩部材用であることを特徴とする重合体粒子。 The polymer particles according to any one of claims 1 to 8,
Polymer particles for use in an antiglare member. - 請求項1~7のいずれか1つに記載の重合体粒子と、バインダーとを含むコーティング用樹脂組成物を、フィルム基材上に塗工してなることを特徴とする光学フィルム。 An optical film obtained by coating a coating resin composition containing the polymer particles according to any one of claims 1 to 7 and a binder on a film substrate.
- 請求項10に記載の光学フィルムであって、
防眩用であることを特徴とする光学フィルム。 The optical film according to claim 10,
An optical film characterized by being used for antiglare. - 請求項1~7のいずれか1つに記載の重合体粒子と、透明樹脂とを含む成形用樹脂組成物を、成形してなることを特徴とする樹脂成形体。 8. A resin molded article obtained by molding a molding resin composition comprising the polymer particles according to any one of claims 1 to 7 and a transparent resin.
- 重合体粒子の製造方法であって、
液状の媒体中、界面活性剤の存在下で、ビニル系単量体を重合させて、前記界面活性剤を含む重合体粒子と前記媒体とを含む粗生成物を得る重合工程と、
濾過器に前記粗生成物を投入し、投入した前記粗生成物に含まれる媒体を前記濾過器の濾材に通過させる一方、前記粗生成物に含まれる重合体粒子を前記濾材上に保持させる固液分離工程と、
前記重合体粒子を前記濾材上に保持した前記濾過器に洗浄液を投入し、前記洗浄液を前記重合体粒子と接触させて、前記重合体粒子と接触した前記洗浄液を前記濾材に通過させることによって、前記洗浄液で洗浄された重合体粒子を前記濾材上に得る洗浄工程とを含み、
前記固液分離工程において、前記濾材を通過した前記媒体の単位時間当たりの量が、下記条件式(1);
X≦5.50×A ・・・(1)
(式(1)中、Xは、前記濾材を通過した前記媒体の単位時間当たりの量(kg/min)を意味し、Aは、濾材と被濾過物との界面の面積(m2)を意味する)を満たし、
前記洗浄工程において、前記濾材を通過した前記洗浄液の単位時間当たりの量が、下記条件式(2);
Y≦8.50×A ・・・(2)
(式(2)中、Yは、前記濾材を通過した前記洗浄液の単位時間当たりの量(kg/min)を意味し、Aは、濾材と被濾過物との界面の面積(m2)を意味する。)を満たし、
前記洗浄工程では、前記濾材上に保持された重合体粒子の重量の10倍以上の重量の洗浄液を用いることを特徴とする重合体粒子の製造方法。 A method for producing polymer particles, comprising:
A polymerization step in which a vinyl monomer is polymerized in the presence of a surfactant in a liquid medium to obtain a crude product including the polymer particles including the surfactant and the medium;
The crude product is charged into a filter, and the medium contained in the charged crude product is allowed to pass through the filter medium of the filter, while the polymer particles contained in the crude product are retained on the filter medium. A liquid separation step;
By introducing a cleaning liquid into the filter holding the polymer particles on the filter medium, bringing the cleaning liquid into contact with the polymer particles, and passing the cleaning liquid in contact with the polymer particles through the filter medium, A washing step of obtaining polymer particles washed with the washing liquid on the filter medium,
In the solid-liquid separation step, the amount per unit time of the medium that has passed through the filter medium is the following conditional expression (1);
X ≦ 5.50 × A (1)
(In Formula (1), X means the amount (kg / min) per unit time of the medium that has passed through the filter medium, and A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered). Meaning)
In the washing step, the amount per unit time of the washing liquid that has passed through the filter medium is the following conditional expression (2):
Y ≦ 8.50 × A (2)
(In Formula (2), Y means the amount (kg / min) per unit time of the cleaning liquid that has passed through the filter medium, and A represents the area (m 2 ) of the interface between the filter medium and the object to be filtered). Means)
In the washing step, a washing liquid having a weight 10 times or more of the weight of the polymer particles held on the filter medium is used. - 請求項13に記載の重合体粒子の製造方法であって、
前記重合工程が、液状の媒体中、種粒子及び界面活性剤の存在下で、ビニル系単量体をシード重合させて、前記界面活性剤を含む重合体粒子と前記媒体とを含む粗生成物を得ることを含むことを特徴とする重合体粒子の製造方法。 It is a manufacturing method of the polymer particles according to claim 13,
The polymerization step comprises seeding a vinyl monomer in the presence of seed particles and a surfactant in a liquid medium, and a crude product containing the polymer particles containing the surfactant and the medium. A process for producing polymer particles, comprising obtaining
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015538928A JP6410266B2 (en) | 2013-09-30 | 2014-03-26 | Method for producing polymer particles |
KR1020167008406A KR101790509B1 (en) | 2013-09-30 | 2014-03-26 | Polymer particles, process for producing same, and use thereof |
CN201480054204.1A CN105593248B (en) | 2013-09-30 | 2014-03-26 | Polymer beads, its manufacturing method, and application thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-204577 | 2013-09-30 | ||
JP2013204577 | 2013-09-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015045448A1 true WO2015045448A1 (en) | 2015-04-02 |
Family
ID=52742608
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/058618 WO2015045448A1 (en) | 2013-09-30 | 2014-03-26 | Polymer particles, process for producing same, and use thereof |
Country Status (4)
Country | Link |
---|---|
JP (4) | JP6410266B2 (en) |
KR (1) | KR101790509B1 (en) |
CN (1) | CN105593248B (en) |
WO (1) | WO2015045448A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017056529A1 (en) * | 2015-09-30 | 2017-04-06 | 積水化成品工業株式会社 | Polymer particles and use thereof |
JP2017179335A (en) * | 2016-03-29 | 2017-10-05 | 積水化成品工業株式会社 | Polymer particle, manufacturing method and application thereof |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5889603A (en) * | 1981-11-24 | 1983-05-28 | Denki Kagaku Kogyo Kk | Manufacture of copolymer |
JPH041202A (en) * | 1990-04-18 | 1992-01-06 | Agency Of Ind Science & Technol | Production of fine polymer bead having heat sensitive characteristics |
JPH06289660A (en) * | 1993-04-06 | 1994-10-18 | Konica Corp | Carrier for electrostatic charge image developing |
JPH08100022A (en) * | 1994-09-30 | 1996-04-16 | Nippon Zeon Co Ltd | Production of highly pure polymer |
JP2006233055A (en) * | 2005-02-25 | 2006-09-07 | Jsp Corp | Light-diffusing agent and method for producing light-diffusing agent and light-diffusing sheet |
JP2008007666A (en) * | 2006-06-30 | 2008-01-17 | Jsr Corp | Optical material composition, method for producing the same, and optical material molded article |
JP2009138034A (en) * | 2007-12-03 | 2009-06-25 | Nippon Shokubai Co Ltd | Particles and method for manufacturing the same |
JP2009538965A (en) * | 2006-05-31 | 2009-11-12 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for reducing fluorosurfactant content of fluoropolymer dispersion using anion exchange resin treated with anionic surfactant |
JP2011252054A (en) * | 2010-06-01 | 2011-12-15 | Asahi Glass Co Ltd | Method for producing aqueous fluorine-containing polymer dispersion and aqueous fluorine-containing polymer dispersion |
JP2012224735A (en) * | 2011-04-19 | 2012-11-15 | Sumitomo Chemical Co Ltd | Resin composition, optical film, and liquid crystal display device |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6372713A (en) * | 1986-09-12 | 1988-04-02 | Nitto Electric Ind Co Ltd | Production of solvent-resistant fine particle of uniform particle diameter |
JPH0791348B2 (en) * | 1987-01-30 | 1995-10-04 | 日本合成ゴム株式会社 | Method for producing crosslinked polymer particles |
JPH07173217A (en) * | 1993-12-17 | 1995-07-11 | Kanegafuchi Chem Ind Co Ltd | Production of resin powder |
JPH07238105A (en) * | 1994-08-19 | 1995-09-12 | Japan Synthetic Rubber Co Ltd | Particle of highly crosslinked polymer and production thereof |
JP2005239837A (en) * | 2004-02-25 | 2005-09-08 | Toyo Ink Mfg Co Ltd | Light diffusion coating film-forming coating material and light diffusion sheet |
JP5212853B2 (en) * | 2006-05-19 | 2013-06-19 | 綜研化学株式会社 | Light diffusing polymer particles, production method thereof, and light diffusing sheet containing the light diffusing polymer particles |
JP5000613B2 (en) * | 2008-09-30 | 2012-08-15 | 株式会社日本触媒 | Organic particle-containing composition |
JP5634031B2 (en) * | 2009-03-27 | 2014-12-03 | 株式会社日本触媒 | POLYMER PARTICLE AND POLYMER PARTICLE-CONTAINING COMPOSITION USING THE SAME |
JP5417102B2 (en) * | 2009-09-18 | 2014-02-12 | 積水化成品工業株式会社 | Polymer particles and method for producing the same |
JP2011075704A (en) * | 2009-09-29 | 2011-04-14 | Mitsubishi Chemicals Corp | Toner for developing electrostatic charge image |
JP5500981B2 (en) * | 2009-12-28 | 2014-05-21 | 積水化成品工業株式会社 | Resin particles for light diffusion film, method for producing the same, and light diffusion film |
WO2011142482A1 (en) * | 2010-05-12 | 2011-11-17 | Canon Kabushiki Kaisha | Toner |
US9890223B2 (en) * | 2010-09-28 | 2018-02-13 | Sekisui Plastics Co., Ltd. | Resin particles and process for producing same, antiglare film, light-diffusing resin composition, and external preparation |
-
2014
- 2014-03-26 WO PCT/JP2014/058618 patent/WO2015045448A1/en active Application Filing
- 2014-03-26 JP JP2015538928A patent/JP6410266B2/en active Active
- 2014-03-26 CN CN201480054204.1A patent/CN105593248B/en active Active
- 2014-03-26 KR KR1020167008406A patent/KR101790509B1/en active IP Right Review Request
-
2018
- 2018-09-18 JP JP2018173414A patent/JP2019052306A/en active Pending
-
2020
- 2020-05-22 JP JP2020090130A patent/JP6913210B2/en active Active
-
2021
- 2021-07-08 JP JP2021113459A patent/JP2021183692A/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5889603A (en) * | 1981-11-24 | 1983-05-28 | Denki Kagaku Kogyo Kk | Manufacture of copolymer |
JPH041202A (en) * | 1990-04-18 | 1992-01-06 | Agency Of Ind Science & Technol | Production of fine polymer bead having heat sensitive characteristics |
JPH06289660A (en) * | 1993-04-06 | 1994-10-18 | Konica Corp | Carrier for electrostatic charge image developing |
JPH08100022A (en) * | 1994-09-30 | 1996-04-16 | Nippon Zeon Co Ltd | Production of highly pure polymer |
JP2006233055A (en) * | 2005-02-25 | 2006-09-07 | Jsp Corp | Light-diffusing agent and method for producing light-diffusing agent and light-diffusing sheet |
JP2009538965A (en) * | 2006-05-31 | 2009-11-12 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for reducing fluorosurfactant content of fluoropolymer dispersion using anion exchange resin treated with anionic surfactant |
JP2008007666A (en) * | 2006-06-30 | 2008-01-17 | Jsr Corp | Optical material composition, method for producing the same, and optical material molded article |
JP2009138034A (en) * | 2007-12-03 | 2009-06-25 | Nippon Shokubai Co Ltd | Particles and method for manufacturing the same |
JP2011252054A (en) * | 2010-06-01 | 2011-12-15 | Asahi Glass Co Ltd | Method for producing aqueous fluorine-containing polymer dispersion and aqueous fluorine-containing polymer dispersion |
JP2012224735A (en) * | 2011-04-19 | 2012-11-15 | Sumitomo Chemical Co Ltd | Resin composition, optical film, and liquid crystal display device |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017056529A1 (en) * | 2015-09-30 | 2017-04-06 | 積水化成品工業株式会社 | Polymer particles and use thereof |
CN108137719A (en) * | 2015-09-30 | 2018-06-08 | 积水化成品工业株式会社 | Polymer beads and its purposes |
JPWO2017056529A1 (en) * | 2015-09-30 | 2018-07-26 | 積水化成品工業株式会社 | Polymer particles and uses thereof |
EP3357934A4 (en) * | 2015-09-30 | 2019-05-01 | Sekisui Plastics Co., Ltd. | Polymer particles and use thereof |
JP2020128536A (en) * | 2015-09-30 | 2020-08-27 | 積水化成品工業株式会社 | Polymer particle and application thereof |
CN108137719B (en) * | 2015-09-30 | 2021-05-14 | 积水化成品工业株式会社 | Polymer particles and use thereof |
US11098167B2 (en) | 2015-09-30 | 2021-08-24 | Sekisui Plastics Co., Ltd. | Polymer particles and use thereof |
CN113336976A (en) * | 2015-09-30 | 2021-09-03 | 积水化成品工业株式会社 | Polymer particles and use thereof |
CN113336976B (en) * | 2015-09-30 | 2023-10-31 | 积水化成品工业株式会社 | Polymer particles and use thereof |
JP2017179335A (en) * | 2016-03-29 | 2017-10-05 | 積水化成品工業株式会社 | Polymer particle, manufacturing method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN105593248A (en) | 2016-05-18 |
JP2019052306A (en) | 2019-04-04 |
KR20160049545A (en) | 2016-05-09 |
JP6410266B2 (en) | 2018-10-24 |
CN105593248B (en) | 2019-06-28 |
JP6913210B2 (en) | 2021-08-04 |
JPWO2015045448A1 (en) | 2017-03-09 |
JP2021183692A (en) | 2021-12-02 |
JP2020158772A (en) | 2020-10-01 |
KR101790509B1 (en) | 2017-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6612417B2 (en) | Polymer particles and uses thereof | |
CN113336976B (en) | Polymer particles and use thereof | |
JP2021183692A (en) | Polymer particle and use thereof | |
JP6668489B2 (en) | Polymer particle dispersion, polymer particles used therefor, dispersant and dispersion medium, and uses thereof | |
JP6550456B2 (en) | Polymer particle, method for producing polymer particle, and use thereof | |
JP6231030B2 (en) | POLYMER PARTICLE, METHOD FOR PRODUCING POLYMER PARTICLE, AND USE THEREOF | |
JPWO2021171669A5 (en) | ||
WO2021171669A1 (en) | Polymer particles and use thereof | |
WO2022181349A1 (en) | Fine resin particles and composition containing fine resin particles | |
JP2017179335A (en) | Polymer particle, manufacturing method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14848507 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015538928 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20167008406 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14848507 Country of ref document: EP Kind code of ref document: A1 |