WO2016051814A1 - 重合体粒子、その製造方法、及びその用途 - Google Patents

重合体粒子、その製造方法、及びその用途 Download PDF

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WO2016051814A1
WO2016051814A1 PCT/JP2015/054179 JP2015054179W WO2016051814A1 WO 2016051814 A1 WO2016051814 A1 WO 2016051814A1 JP 2015054179 W JP2015054179 W JP 2015054179W WO 2016051814 A1 WO2016051814 A1 WO 2016051814A1
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polymer particles
surfactant
medium
filter medium
weight
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English (en)
French (fr)
Japanese (ja)
Inventor
智之 ▲高▼橋
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Sekisui Kasei Co Ltd
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Sekisui Plastics Co Ltd
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Priority to JP2015532218A priority Critical patent/JP6560981B2/ja
Priority to KR1020167011141A priority patent/KR101863072B1/ko
Priority to KR1020157020641A priority patent/KR101634940B1/ko
Priority to CN201580000359.1A priority patent/CN105683227B/zh
Priority to TW104130010A priority patent/TWI577440B/zh
Publication of WO2016051814A1 publication Critical patent/WO2016051814A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers

Definitions

  • the present invention relates to polymer particles suitably used as a raw material for optical members such as light diffusing films and antiglare films, a method for producing the same, and uses (optical films) of the polymer particles. More specifically, the present invention relates to polymer particles containing a surfactant having a predetermined amount of polyoxyethylene chains per unit surface area of the polymer particles, a method for producing the same, and uses of the polymer particles (optical film). )
  • 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 vinyl as a resin fine particle (polymer particle) used as a light diffusing agent in a medium containing a surfactant (in the examples, other surfactants having no polyoxyethylene chain).
  • the amount of the surfactant obtained by polymerizing the monomer and remaining in the resin fine particles is 0.05 parts by weight or less (0.005 to 0.036 weight in the examples) with respect to 100 parts by weight of the resin fine particles. Part) is disclosed.
  • 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. Patent Document 2 does not disclose a surfactant having a polyoxyethylene chain, and does not disclose the remaining amount of the surfactant in the washed organic particles.
  • Patent Document 3 discloses colored resin particles taken out from a dispersion of colored resin particles by washing as colored resin particles used as a toner for developing an electrostatic latent image. Patent Document 3 does not disclose a surfactant having a polyoxyethylene chain, and does not disclose the remaining amount of the surfactant in the washed organic particles.
  • Patent Document 4 discloses an electrostatic charge image developing toner containing a binder resin, a colorant, and a charge control resin having a specific repeating unit, and a remaining surfactant (polyoxyethylene chain in the examples).
  • An electrostatic charge image developing toner is disclosed in which the amount of the other surfactant (having no surfactant) is 1 to 1000 ppm.
  • Patent Document 5 discloses a coating composition containing organic particles and a surfactant, wherein the surfactant content is 500 to 2000 ppm with respect to the organic particles. ing. Further, in Example 5 of Patent Document 5, the coefficient of variation is 6.2%, and polyoxyethylene distyryl phenyl ether sulfate ammonium salt (a kind of surfactant having a polyoxyethylene chain) is added from 520 to Organic particles containing 1550 ppm (0.1200%) and no other surfactants are disclosed. In Examples 2 and 4 of Patent Document 5, the coefficient of variation is 35.5 to 37.1%, and polyoxyethylene distyrylphenyl ether sulfate ammonium salt is 520 to 1550 ppm (0.0520 to 0.1550%).
  • polyoxyethylene distyrylphenyl ether sulfate ammonium salt is 520 to 1550 ppm (0.0520 to 0.1550%).
  • Example 3 of Patent Document 5 Polyoxyethylene distyryl phenyl ether sulfate ammonium salt and sodium lauryl sulfate (one of other surfactants having no polyoxyethylene chain) total 1950 ppm (0 .1950%) containing organic particles are disclosed.
  • an oily raw material liquid is prepared by dissolving or dispersing a raw material for a toner containing a binder resin, a colorant, a charge control agent, and a release agent in an organic solvent without performing a cleaning treatment.
  • a method for producing toner particles is disclosed that is prepared, granulated while supplying the oily raw material liquid to a spray dryer and spray drying to form colored resin particles.
  • 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 dispersion state of the polymer particles in the resin composition may be non-uniform.
  • the dispersion state of the polymer particles in the resin composition is not stable, and the coating film is formed by the coating.
  • the dispersion state of the polymer particles in the resin composition becomes non-uniform, and the polymer particles sometimes locally aggregate excessively.
  • the polymer particles are not spread uniformly over the entire coating film formed on the base film, the optical properties of the optical film become non-uniform, and the desired optical properties cannot be obtained over the entire optical film. there were.
  • the reason why the dispersion state of the polymer particles in the resin composition is unstable and the dispersion state of the polymer particles in the resin composition is uneven in the process of forming a coating film by the coating is that Since it is considered that there is a variation in the amount of surface residual components on the surface of the coalesced particles and a variation in the surface state due to this, it is desired that the amount of surface residual components on the surface of the polymer particles be constant (uniform).
  • polymer particles composed of at least one of a (meth) acrylic polymer, a styrene polymer, and a (meth) acryl-styrene copolymer have an SP value of 14.3 to 19.4 ( MPa) 1/2 (7.0 to 9.0 (cal / cm 3 ) 1/2 ) and an organic solvent having a high SP value (hereinafter referred to as “high SP value organic solvent”).
  • a monomer having high hydrophilicity is added to the monomer used for the production of the polymer particles. It is conceivable to modify the surface of the coalesced particles. However, if a monomer having high hydrophilicity is added to the monomer used for the production of the polymer particle to give the polymer particle dispersibility in the high SP value organic solvent, the polymer particle Since its composition changes, it becomes difficult to control the refractive index.
  • the additive used in the polymerization (the other interface) Activator, dispersion stabilizer, polymerization inhibitor, etc.) or when the binder resin used in the production is a resin particle containing a by-product (emulsion polymerization product) generated during the polymerization reaction, It becomes difficult to remove other additives such as surfactants and by-products (emulsion polymerization products), which causes non-uniform dispersibility of the colored resin particles in the binder and the organic solvent.
  • the “emulsion polymerization product” refers to a target polymer produced by emulsion polymerization in an aqueous phase, which is a side reaction, in seed polymerization for producing polymer particles having a uniform particle diameter. It means a polymer particle having a remarkably small particle diameter (for example, a particle diameter of 300 nm or less) compared to the particle diameter of the coalesced particle.
  • seed polymerization polymerization is often performed in the presence of a polymerization inhibitor in order to suppress the generation of by-products (emulsion polymerization products). It is difficult to completely prevent the occurrence of polymerization products).
  • the polymerization inhibitor by increasing the addition amount of the polymerization inhibitor, it is possible to enhance the effect of suppressing the generation of the by-product (emulsion polymerization product), but on the other hand, the residual monomer in the resulting polymer particles The amount increases and affects the quality of the polymer particles.
  • the polymer particles are not spread uniformly over the entire coating film formed on the base film, the optical properties of the optical film are non-uniform, and the desired optical properties cannot be obtained over the entire optical film. was there.
  • the dispersibility with respect to the high SP value organic solvent is good, and in the process of forming the coating film by coating the resin composition obtained by dispersing the polymer particles in the binder on the film substrate, a uniform dispersion state
  • the present invention has been made in view of the above situation, and aims to provide polymer particles excellent in dispersibility and dispersion uniformity, a method for producing the same, and an optical film using the polymer particles. To do.
  • the present inventors have found that the surface state of the polymer particles affects the dispersibility and dispersion uniformity, and in order to improve the dispersibility and dispersion uniformity, In order to complete the present invention, it is important to attach an appropriate amount of a surfactant having a polyoxyethylene chain to the surface of the coalesced particles and to keep the content of other surfactants to a predetermined amount or less. It came.
  • the polymer particle of the present invention is a polymer particle containing a surfactant having a polyoxyethylene chain, the coefficient of variation of the particle diameter is 15.0% or less, and per unit surface area of the polymer particle
  • the content of the surfactant having a polyoxyethylene chain is 2.0 to 15.0 ⁇ 10 ⁇ 3 g / m 2
  • the other surfactant polyoxyethylene per unit surface area of the polymer particles.
  • the content of the surfactant other than the surfactant having a chain, that is, the surfactant having no polyoxyethylene chain) is 10.0 ⁇ 10 ⁇ 5 g / m 2 or less.
  • the content of the surfactant having the polyoxyethylene chain per unit surface area of the polymer particle is 2.0 ⁇ 10 ⁇ 3 g / m 2 or more, and the polyoxyethylene chain Since the hydrophilic part derived from the surfactant having an appropriate amount develops on the surface of the polymer particle (the surface of the polymer particle is modified with the hydrophilic part), the hydrophilic composition is hydrophilic in the composition of the polymer particle. Dispersibility in a high SP value organic solvent can be improved without including a hydrophilic portion derived from a highly soluble monomer.
  • the polymer particles having the above-described configuration have a coefficient of variation in particle diameter of 15.0% or less, and the content of the surfactant having the polyoxyethylene chain per unit surface area of the polymer particles is 15.0. ⁇ 10 ⁇ 3 g / m 2 or less, and the content of other surfactants per unit surface area of the polymer particles is suppressed to 10.0 ⁇ 10 ⁇ 5 g / m 2 or less. As a result, there is little difference in the surface state between the polymer particles, so that when used in a mixture with a binder, the dispersion uniformity in the binder is excellent.
  • the polymer particles having the above-described structure have a content of the surfactant having the polyoxyethylene chain per unit surface area of the polymer particles of 2.0 ⁇ 10 ⁇ 3 g / m 2 or more as described above.
  • the dispersibility in the high SP value organic solvent is improved, so there is no variation in the dispersion in the high SP value organic solvent, and the dispersion is uniform in the mixture of the high SP value organic solvent and the binder. The state can be formed, and the dispersion uniformity is excellent.
  • the resin composition obtained by dispersing the polymer particles having the above constitution in a binder (particularly in a mixture of a high SP value organic solvent and a binder) is coated on a film substrate,
  • the uniform dispersion state of the polymer particles in the resin composition is maintained almost stably in the process of forming the coating film by the coating, and excessive aggregation of the polymer particles during the coating is suppressed.
  • the polymer particles spread evenly on the film substrate, and can impart optical characteristics such as uniform light diffusibility and antiglare property to the entire coating film formed by the coating.
  • the polymer particle having the above configuration has a coefficient of variation of the particle diameter of 15.0% or less, when the polymer particle is used for an optical member such as an antiglare film or a light diffusion film, the prevention of the optical member is prevented. Optical properties such as glare and light diffusibility can be improved.
  • 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 applying the coating resin composition containing the polymer particles of the present invention excellent in dispersibility and dispersion uniformity on a base material, and thus formed by the coating. In the entire coating film, uniform optical properties such as uniform light diffusibility and antiglare properties can be obtained.
  • the method for producing polymer particles includes a polymerization step, and further includes a solid-liquid separation step, a washing step, a drying step, and a classification step as necessary.
  • the processes that can affect the uniformity of the amount of residual components on the surface of the polymer particles and the uniformity of the surface condition caused thereby are the solid-liquid separation process and the washing process, and these processes become unstable.
  • the unnecessary part of the surfactant used for the production of the polymer particles a surfactant having an excess polyoxyethylene chain that does not contribute to the modification of the polymer particle surface, and other used as necessary
  • Surfactant a polymer dispersion stabilizer used as necessary, adversely affecting the amount of residual components on the surface of the polymer particles.
  • the inventor of the present application adjusts the amount per unit time of the medium that has passed through the filter medium in the solid-liquid separation step and the washing step and the amount of the washing solution in the washing step within a predetermined range, thereby achieving dispersion uniformity.
  • the inventors have found that polymer particles having excellent dispersibility can be produced by modifying the surface with a surfactant having a polyoxyethylene chain, and have completed the present invention.
  • a vinyl monomer is polymerized in a liquid medium in the presence of a surfactant containing a surfactant having a polyoxyethylene chain, and the polyoxyethylene chain is polymerized.
  • a polymerization step for obtaining a crude product containing the polymer particles containing the surfactant having the above-mentioned medium and the medium the crude product is charged into a filter, and the medium contained in the charged crude product is filtered into the filter
  • a solid-liquid separation step of allowing the polymer particles contained in the crude product to be retained on the filter medium while passing the filter medium through the filter medium, and supplying the cleaning liquid to the filter holding the polymer particles on the filter medium,
  • the solid-liquid content In step, the amount per unit time of the medium which has passed through the filter media, the following conditional expressions (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): 2.50 ⁇ A ⁇ Y ⁇ 8.50 ⁇ A (2)
  • 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 of 9 to 18 times 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 9 to 18 times the weight of the polymer particles held on the filter medium is used. Therefore, the polymer adhering to the polymer particles in the polymerization step is used.
  • An appropriate amount of a surfactant (which does not contribute to the modification of the polymer particle surface) containing a surfactant having an oxyethylene chain (with an excess polyoxyethylene chain that does not contribute to the modification of the polymer particle surface) together with the medium and the cleaning liquid can be removed. Furthermore, when polymerization is carried out in the presence of a surfactant containing both a surfactant having a polyoxyethylene chain and another surfactant, most of the other surfactant is sufficiently removed together with the medium and the cleaning liquid. can do.
  • the content (residual amount) of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles is an appropriate amount (2.0 to 15.0 ⁇ 10 ⁇ 3 g / m 2 ), Polymer with excellent dispersibility and dispersion uniformity with a very small content (residual amount) of other surfactants per unit surface area of the coalesced particles (10.0 ⁇ 10 ⁇ 5 g / m 2 or less) Particles can be obtained.
  • the surfactant having a polyoxyethylene chain has an SP value of the polyoxyethylene chain of 14.3 to 19.4 (MPa) 1/2 (7.0 to 9.0 (cal / cm 3 ) 1 / 2 ), and the SP value of (meth) acrylic polymer, styrene polymer, and (meth) acrylic-styrene copolymer (14.3 to 19.4 (MPa) 1/2 (7. 0 to 9.0 (cal / cm 3 ) 1/2 )), it is presumed that this is due to the strong connection with the polymer particles and difficulty in removal with water or hot water.
  • polymer particles excellent in dispersibility and dispersion uniformity a method for producing the same, and an optical film using the polymer particles can be provided.
  • 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.
  • 2 is a view showing an SEM (scanning electron microscope) image of the polymer particles obtained in Example 1.
  • FIG. FIG. 3 is a view showing an SEM image of polymer particles obtained after the solid-liquid separation step and the washing step in Example 1.
  • the polymer particle of the present invention is a polymer particle containing a surfactant having a polyoxyethylene chain, the coefficient of variation of the particle diameter is 15.0% or less, and per unit surface area of the polymer particle
  • the content of the surfactant having a polyoxyethylene chain is 2.0 to 15.0 ⁇ 10 ⁇ 3 g / m 2
  • the content of the other surfactant per unit surface area of the polymer particle is 10.0 ⁇ 10 ⁇ 5 g / m 2 or less.
  • the polymer particles having the above structure are dispersed in a high SP value organic solvent without including a hydrophilic part derived from a highly hydrophilic monomer in the composition of the polymer constituting the polymer particles. Can be improved. Furthermore, as described above, the polymer particles having the above-described structure are used by being mixed with a binder (particularly, a mixture of a high SP value organic solvent and a binder) because there is little difference in the surface state between the polymer particles. In some cases, the dispersion uniformity is excellent in the binder (particularly in a mixture of a high SP value organic solvent and a binder).
  • the polymer particles having the above-described structure are excellent in quality stability because the temporal change in the surface state of the polymer particles and the difference in the surface state between production lots of the polymer particles are small.
  • the dispersion state difference between production lots of the resin composition is small, and the dispersion stability is excellent.
  • the polymer particles having the above structure are prepared by adding 15.0 g of water to 5.0 g of the polymer particles and dispersing the polymer particles in water by performing a dispersion treatment for 60 minutes using an ultrasonic cleaner. After centrifuging in a centrifuge tube under conditions of K-factor 6943 and rotation time of 30 minutes using a centrifuge, when the supernatant liquid is recovered, the non-volatile components in the supernatant liquid (polymer particles are produced by seed polymerization).
  • the concentration of the by-product is preferably less than 1.0% by weight, more preferably less than 0.5% by weight, More preferably, it is less than 0.3% by weight.
  • the polymer particles are bonded to the binder (particularly, the high SP value organic solvent and the binder).
  • the dispersion uniformity of the polymer particles in the binder can be further improved.
  • the content of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles is more preferably 3.0 to 15.0 ⁇ 10 ⁇ 3 g / m 2 . Thereby, the dispersibility with respect to the high SP value effective solvent of the said polymer particle can further be improved. Further, the content of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles is more preferably 4.0 to 15.0 ⁇ 10 ⁇ 3 g / m 2 . Thereby, the dispersion uniformity of the polymer particles can be further improved.
  • the content of the other surfactant per unit surface area of the polymer particles is more preferably 7.0 ⁇ 10 ⁇ 5 g / m 2 or less, and 5.0 ⁇ 10 ⁇ 5 g / m 2 or less. More preferably, it is 3.0 ⁇ 10 ⁇ 5 g / m 2 or less. Thereby, the dispersion uniformity of the polymer particles can be further improved.
  • the coefficient of variation of the particle diameter of the polymer particles is more preferably 12.0% or less, and further preferably 10.0% or less. Thereby, the dispersion uniformity of the polymer particles can be further improved.
  • the content of the surfactant having a polyoxyethylene chain and other surfactants in the polymer particles is measured by, for example, liquid chromatography / mass spectrometry (LC-MS-MS). It can be calculated by dividing the content of the surfactant having a polyoxyethylene chain and the other surfactant by the specific surface area of the polymer particles measured using the BET method (nitrogen adsorption method), respectively. .
  • LC-MS-MS liquid chromatography / mass spectrometry
  • 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, having a polyoxyethylene chain as described in the section of [Method for producing polymer particles] described later.
  • An anionic surfactant, a nonionic surfactant having a polyoxyethylene chain, a cationic surfactant having a polyoxyethylene chain, and an amphoteric surfactant having a polyoxyethylene chain can be mentioned.
  • the surfactant contained in the polymer particles of the present invention preferably contains at least one of an anionic surfactant and a nonionic surfactant, and more preferably contains an anionic surfactant.
  • the polymer particles of the present invention contain an anionic surfactant, the dispersion stability during the polymerization reaction can be ensured.
  • the surfactant contained in the polymer particles of the present invention is only a nonionic surfactant, only the nonionic surfactant is present during the polymerization reaction, and significant aggregation occurs during the polymerization reaction. There is a case.
  • the surfactant having a polyoxyethylene chain contained in the polymer particle of the present invention contains at least one of an anionic surfactant having a polyoxyethylene chain and a nonionic surfactant having a polyoxyethylene chain. It is preferable to include an anionic surfactant having a polyoxyethylene chain.
  • an anionic surfactant having a polyoxyethylene chain When the polymer particles of the present invention contain an anionic surfactant having a polyoxyethylene chain, the dispersion stability during the polymerization reaction can be ensured.
  • the surfactant having a polyoxyethylene chain contained in the polymer particles of the present invention is only a nonionic surfactant having a polyoxyethylene chain, it has a polyoxyethylene chain present during the polymerization reaction. Only the nonionic surfactant in which the surfactant has a polyoxyethylene chain is present, and significant aggregation may occur during the polymerization reaction.
  • 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 particles are preferably composed of at least one of a (meth) acrylic polymer, a styrene polymer, and a (meth) acryl-styrene copolymer.
  • 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 particles are preferably composed of a (meth) acryl-styrene copolymer from the viewpoint of light diffusibility and antiglare property.
  • the polymer constituting the polymer particles is preferably a copolymer (crosslinked polymer) of the monofunctional vinyl monomer and the polyfunctional vinyl monomer. Therefore, the polymer constituting the polymer particles is particularly preferably a (meth) acryl-styrene cross-linked copolymer from the viewpoint of light diffusibility and antiglare property.
  • 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. When the quantity of the structural unit derived from the said polyfunctional vinyl-type monomer is less than the said range, the crosslinking degree of the said polymer will become low.
  • 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. Furthermore, as a result of the low degree of crosslinking of the polymer, 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. When 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 refractive index of the polymer particles of the present invention is preferably 1.490 to 1.600.
  • the polymer particles having the above-described structure exhibit good optical characteristics (for example, light transmittance, antiglare property, light diffusibility, etc.) when used for an optical member such as an antiglare film or a light diffusion film.
  • polymer particles produced by adding a highly hydrophilic monomer to a monomer having a high refractive index of a homopolymer for example, a styrene monomer
  • the refractive index of a homopolymer is generally low (for example, 1.488 or less), the refractive index is lower than that of polymer particles produced without adding a highly hydrophilic monomer. Therefore, it is difficult to realize polymer particles having a refractive index of 1.570 to 1.600 with such a polymer particle.
  • the polymer particles of the present invention do not require the addition of a highly hydrophilic monomer, so that polymer particles having a refractive index of 1.570 to 1.600 can be easily realized.
  • 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 polymer particles are preferably obtained by polymerization in the presence of a surfactant, particularly in the presence of a surfactant containing a surfactant having a polyoxyethylene chain. Obtained by absorbing the monomer into seed particles and polymerizing (ie, seed polymerizing) in the presence of a surfactant, particularly in the presence of a surfactant comprising a surfactant having a polyoxyethylene chain. More preferably. 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 containing a surfactant having a polyoxyethylene chain, and the polyoxyethylene chain is polymerized.
  • a polymerization step for obtaining a crude product containing the polymer particles containing the surfactant having the above-mentioned medium and the medium the crude product is charged into a filter, and the medium contained in the charged crude product is filtered into the filter
  • a solid-liquid separation step of allowing the polymer particles contained in the crude product to be retained on the filter medium while passing the filter medium through the filter medium, and supplying the cleaning liquid to the filter holding the polymer particles on the filter medium,
  • the production method of the present invention is suitable as a method for producing the above-described polymer particles of the present invention.
  • the vinyl monomer is polymerized in the presence of a surfactant containing a surfactant having a polyoxyethylene chain in a liquid medium to contain the surfactant having the polyoxyethylene chain.
  • a crude product containing polymer particles and the medium is obtained.
  • 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 having a polyoxyethylene chain include an anionic surfactant having a polyoxyethylene chain, a cationic surfactant having a polyoxyethylene chain, a nonionic surfactant having a polyoxyethylene chain, and Any of the zwitterionic surfactants having a polyoxyethylene chain can be used, but in the polymerization step, the dispersion of the vinyl monomer in the liquid medium can be more stably ensured, Since polymer particles having a uniform particle diameter can be obtained, it is preferable to use at least one of an anionic surfactant having a polyoxyethylene chain and a nonionic surfactant having a polyoxyethylene chain.
  • At least an anionic surfactant having a polyoxyethylene chain is used as the surfactant having a polyoxyethylene chain.
  • the dispersion stability at the time of a polymerization reaction is securable.
  • the nonionic surfactant having a polyoxyethylene chain is used as the surfactant having a polyoxyethylene chain, significant aggregation may occur during the polymerization reaction.
  • anionic surfactant having a polyoxyethylene chain examples include known anionic surfactants such as fatty acid salt type, sulfate ester type, sulfonate salt type, phosphate ester salt type, and phosphate ester type.
  • polyoxyethylene alkyl phenyl ether sulfate ester salt polyoxyethylene alkyl ether sulfate salt such as sodium polyoxyethylene lauryl ether sulfate; polyoxyethylene alkyl sulfate ester; polyoxyethylene styrenated phenyl ether sulfate ester
  • polyoxyethylene such as polyoxyethylene nonylphenyl ether phosphate (for example, sodium polyoxyethylene nonylphenyl ether phosphate)
  • Emissions alkyl phenyl ether phosphates polyoxyethylene styrenated phenyl ether phosphate, polyoxyethylene alkyl ether phosphate and the like.
  • One kind of these anionic surfactants having a polyoxyethylene chain may be used alone, or two or more kinds may be used in combination.
  • nonionic surfactant having a polyoxyethylene chain any known nonionic surfactant such as an ester type, an ether type, and an ester / ether type can be used.
  • polyoxyethylene tridecyl ether Polyoxyethylene alkyl ethers such as polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene styrenated phenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acids such as polyoxyethylene sorbitan monolaurate Examples thereof include esters, polyoxyethylene alkylamines, and oxyethylene-oxypropylene block polymers.
  • One of these nonionic surfactants having a polyoxyethylene chain may be used alone, or two or more thereof may be used in combination.
  • the surfactant having a polyoxyethylene chain may be used alone or in combination of two or more.
  • the surfactant having a polyoxyethylene chain 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, preferably 0.5 g / 100 ml to 3.0 g / 100 ml. Are more preferred.
  • a surfactant having a polyoxyethylene chain having a solubility of less than 0.3 g / 100 ml is used, in the polymerization step, when the liquid medium is an aqueous medium, a vinyl monomer in the aqueous medium is used.
  • the surfactant having a polyoxyethylene chain 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.
  • the surfactant having the polyoxyethylene chain is used, in the polymerization step, when the liquid medium is an aqueous medium, the dispersion of the vinyl monomer in the aqueous medium is stabilized.
  • a surfactant having a large amount of polyoxyethylene chain is required, which is not preferable in terms of productivity.
  • the surfactant may contain another surfactant (a surfactant other than a surfactant having a polyoxyethylene chain, that is, a surfactant having no polyoxyethylene chain).
  • a surfactant other than a surfactant having a polyoxyethylene chain that is, a surfactant having no polyoxyethylene chain.
  • the other surfactants include an anionic surfactant having no polyoxyethylene chain, a cationic surfactant having no polyoxyethylene chain, a nonionic surfactant having no polyoxyethylene chain, and a polyoxyethylene chain.
  • any of the zwitterionic surfactants having no oxyethylene chain can be used, but in the polymerization step, the dispersion of the vinyl monomer in the liquid medium can be more stably ensured, Since polymer particles having a uniform particle size can be obtained, it is preferable to use at least one of an anionic surfactant having no polyoxyethylene chain and a nonionic surfactant having no polyoxyethylene chain. It is more preferable to use at least an anionic surfactant as the surfactant. Thereby, the dispersion stability at the time of a polymerization reaction is securable. On the other hand, when only a nonionic surfactant is used as the surfactant, significant aggregation may occur during the polymerization reaction.
  • any known anionic surfactant such as fatty acid salt type, sulfate ester type, sulfonate salt type, and phosphate ester salt type can be used.
  • Fatty acid soaps such as sodium oleate and castor oil potash soap; alkyl sulfate esters such as lauryl sulfate (eg sodium lauryl sulfate, ammonium lauryl sulfate); alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkyl Dialkylsulfosuccinates such as naphthalenesulfonate, alkanesulfonate, di (2-ethylhexyl) sulfosuccinate (sodium salt), dioctylsulfosuccinate (sodium salt); alkenyl succinate (dipotassium salt); Acid Este Salts;
  • nonionic surfactant having no polyoxyethylene chain any known nonionic surfactant such as an ester type, an ether type, an ester / ether type, and the like can be used.
  • the carbon number of an alkylene group And polyoxyalkylene alkyl ethers such as polyoxyalkylene tridecyl ether having 3 or more, sorbitan fatty acid ester, glycerin fatty acid ester and the like.
  • These nonionic surfactants having no polyoxyethylene chain may be used alone or in combination of two or more.
  • any known cationic surfactants such as amine salt type and quaternary ammonium salt type can be used.
  • An activator is advantageous for its handling.
  • Specific examples of the cationic surfactant having no polyoxyethylene chain include alkylamine salts such as laurylamine acetate and stearylamine acetate; lauryltrimethylammonium chloride, hexadecyltrimethylammonium chloride, cocoyltrimethylammonium chloride, dodecyltrimethyl.
  • alkyltrimethylammonium chlorides such as ammonium chloride
  • alkyldimethylbenzyl chlorides such as hexadecyldimethylbenzylammonium chloride and lauryldimethylbenzylammonium chloride.
  • alkyltrimethylammonium chlorides such as ammonium chloride
  • alkyldimethylbenzyl chlorides such as hexadecyldimethylbenzylammonium chloride and lauryldimethylbenzylammonium chloride.
  • One of these cationic surfactants having no polyoxyethylene chain may be used alone, or two or more thereof may be used in combination.
  • Examples of the zwitterionic surfactant having no polyoxyethylene chain include lauryl dimethylamine oxide, phosphate ester surfactants, phosphite ester surfactants, and the like. These amphoteric surfactants not having a polyoxyethylene chain may be used alone or in combination of two or more.
  • the surfactant having no polyoxyethylene chain may be used alone or in combination of two or more.
  • the surfactant having no polyoxyethylene chain preferably has a solubility in water at a liquid temperature of 25 ° C. of 0.3 g / 100 ml to 15.0 g / 100 ml, preferably 0.5 g / 100 ml to 5.0 g. / 100ml is more preferable.
  • a surfactant having no polyoxyethylene chain having a solubility of less than 0.3 g / 100 ml is used, when the liquid medium is an aqueous medium in the polymerization step, a vinyl monomer in the aqueous medium is used.
  • the body may not be stably dispersed, and it is difficult to elute the surfactant into water. Therefore, a large amount of washing liquid is required in the washing step described below for washing the polymer particles. It is not preferable in terms of surface.
  • the surfactant having a polyoxyethylene chain having a solubility exceeding 15.0 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. Therefore, when a surfactant having no polyoxyethylene chain is used, in the polymerization step, when the liquid medium is an aqueous medium, the dispersion of the vinyl monomer in the aqueous medium is stabilized. Therefore, a large amount of a surfactant having no polyoxyethylene chain is required, which is not preferable in terms of productivity.
  • Amount of surfactant used in the polymerization of the above vinyl monomer (when only an anionic surfactant having no polyoxyethylene chain is used as the surfactant, an anionic surfactant having no polyoxyethylene chain is used.
  • the amount of the agent used, and when using an anionic surfactant having no polyoxyethylene chain and another surfactant as the surfactant, the amount of the anionic surfactant having no polyoxyethylene chain is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the vinyl monomer used.
  • 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 includes an interface having seed particles and polyoxyethylene chains in a liquid medium.
  • a vinyl monomer is seed-polymerized in the presence of a surfactant containing an activator to obtain a crude product containing the polymer particles containing the surfactant having the polyoxyethylene chain and the medium. It is preferable to include.
  • seed particles are added to an emulsion (suspension) containing a vinyl monomer, an aqueous medium, and a surfactant containing a surfactant having a polyoxyethylene chain.
  • the emulsion can be prepared by a known method.
  • a vinyl monomer and a surfactant containing a surfactant having a polyoxyethylene chain are added to an aqueous medium and dispersed by a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer (registered trademark).
  • a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer (registered trademark).
  • the 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 within the range of 5 to 300 parts by weight of the vinyl monomer and 1 to 50 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 independently suspended and polymerized in an aqueous medium, resulting in abnormal particles that are not intended. Diameter 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 polymerization inhibitors such as water-soluble 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 polymerization reaction is included in the crude product together with the medium.
  • the surfactant having an excess polyoxyethylene chain that does not contribute to the modification of the polymer particle surface among the surfactant having a polyoxyethylene chain used as necessary Activators, other surfactants used as necessary, polymer dispersion stabilizers used as necessary, and unnecessary components such as polymerization additives (eg, polymerization inhibitors) used as necessary.
  • the amount of the unnecessary component remaining in the polymer particles remaining on the filter medium 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 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 surfactant having a polyoxyethylene chain used as necessary.
  • surfactants with excess polyoxyethylene chains that do not contribute to the modification of the polymer particle surface other surfactants used as necessary, polymer dispersion stabilizers used as necessary, necessary Accordingly, unnecessary components such as a polymerization additive (for example, a polymerization inhibitor) used depending on the temperature can be sufficiently removed together with the medium, and the residual amount of the unnecessary components in the polymer particles can be reduced.
  • a polymerization additive for example, a polymerization inhibitor
  • the solid-liquid separation step includes the amount of the medium contained in the crude product P introduced into the pressure filter 1 (When all the crude products P obtained in the polymerization step are put 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 the pressure vessel 2 is preferably terminated when the internal pressure of the pressure vessel 2 becomes 2/3 or less of the pressure at the time of pressurization.
  • 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): 2.50 ⁇ A ⁇ Y ⁇ 8.50 ⁇ A (2)
  • 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). If the amount Y of the cleaning liquid that has passed through the filter medium is less than 2.50 ⁇ A, the cleaning process takes too much time and the productivity may be lowered.
  • the time for which the polymer particles are in contact with the cleaning liquid is short, so that it adheres to the surface of the polymer particles.
  • surfactants having polyoxyethylene chains used as necessary by-products (emulsion polymerization products) generated during the polymerization reaction, surplus polyoxy which does not contribute to the modification of the polymer particle surface
  • surfactant having ethylene chain other surfactant used as necessary, polymer dispersion stabilizer used as necessary, polymerization additive used as necessary (for example, polymerization inhibitor)
  • Such unnecessary components may not be sufficiently removed, and a large amount of the unnecessary components may remain in the finally obtained polymer particles.
  • 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.
  • By-product emulsion polymerization product
  • a surfactant having an excess polyoxyethylene chain that does not contribute to the modification of the polymer particle surface among the surfactant having a polyoxyethylene chain used as necessary Other surfactants used as needed, polymer dispersion stabilizers used as needed, and unnecessary components such as polymerization additives (eg polymerization inhibitors) used as needed
  • polymerization additives eg polymerization inhibitors
  • 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 (solid-liquid separation step) regardless of whether or not at least one other surfactant is used in the polymerization step.
  • the total amount of vinyl monomers used in the polymerization step is 9 to 18 times.
  • the weight of the cleaning liquid used in the cleaning step is less than 9 times the weight of the polymer particles held on the filter medium 3, a by-product generated during the polymerization reaction (emulsion polymerization generation) contained in the polymer particles Product), a surfactant having an excess polyoxyethylene chain that does not contribute to the modification of the surface of the polymer particles among the surfactant having a polyoxyethylene chain, which is used as necessary, is used as necessary. Removal of unnecessary components such as other surfactants, polymer dispersion stabilizers used as necessary, polymerization additives used as necessary (for example, polymerization inhibitors) is insufficient, and the desired polymer There is a possibility that particles (particularly polymer particles in which the content of other surfactant per unit surface area of the polymer particles is 10.0 ⁇ 10 ⁇ 5 g / m 2 or less) cannot be obtained.
  • the weight of the washing liquid used in the washing step is 18 times or less of the weight of the polymer particles held on the filter medium 3, a portion that is not excessive in the washing step (a portion that contributes to the modification of the polymer particle surface)
  • the surfactant having the polyoxyethylene chain is prevented from eluting, and the content of the surfactant having the polyoxyethylene chain per unit surface area of the polymer particles is 2.0 g / m 2 or more.
  • cleaning process is the following for every kind of other surfactant used in the said superposition
  • the total amount .SIGMA.B L calculation expression (4) lower limit of the weight of the cleaning liquid is calculated by B L (kg) (equivalent to B L in the case of using one kind of other surfactants in the polymerization step) (kg ) And the total amount ⁇ B H of the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the following calculation formula (5) for each type of other surfactant used in the polymerization step (above the polymerization step)
  • it is preferably equal to or less than BH ). That is, the weight B (kg) of the cleaning liquid used in the cleaning process preferably satisfies the following inequality (6).
  • the following inequality (6) becomes the following inequality (7).
  • B L (C ⁇ D) ⁇ 1.8 (4)
  • B H (C ⁇ D) ⁇ 2.3 (5) ⁇ B L ⁇ B ⁇ ⁇ B H (6)
  • B L ⁇ B ⁇ B H (7) (In the formulas (4) and (5), C represents the amount (g) of one type of other surfactant used, and D represents the one type of other surfactant with respect to the cleaning liquid having a liquid temperature of 25 ° C.) Represents solubility (g / 100 ml)
  • the weight of the cleaning liquid used in the cleaning process is the total amount ⁇ B L (the lower limit value B L (kg) of the cleaning liquid weight calculated by the above calculation formula (4) for each type of other surfactant used in the polymerization process. kg) or more, a by-product (emulsion polymerization product) generated during the polymerization reaction adhered to the surface of the polymer particles in the polymer particles, and the polyoxyethylene chains used as necessary.
  • a by-product emulsion polymerization product generated during the polymerization reaction adhered to the surface of the polymer particles in the polymer particles, and the polyoxyethylene chains used as necessary.
  • surfactants possessed surfactants having excess polyoxyethylene chains that do not contribute to the modification of the polymer particle surface, other surfactants used as necessary, polymers used as needed
  • the content of unnecessary components such as dispersion stabilizers and polymerization additives (eg, polymerization inhibitors) used as necessary can be further reduced.
  • the weight of the cleaning liquid used in the cleaning step is the same as that of the other surfactant used in the polymerization step.
  • the total amount ⁇ B H (kg) of the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the above calculation formula (5) for each type of agent is exceeded, it contributes to the modification of the polymer particle surface.
  • the surfactant having a polyoxyethylene chain is also gradually eluted, and the amount of modification by the surfactant having a polyoxyethylene chain on the surface of the polymer particles becomes uneven.
  • the temperature of the cleaning liquid used for cleaning is preferably a temperature at which the surfactant having a polyoxyethylene chain and other surfactants are sufficiently eluted, for example, preferably 40 to 80 ° C., 50 More preferably, it is ⁇ 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 becomes 2/3 or less of the pressurizing pressure.
  • the amount of water that can be absorbed by the polymer particles is reduced 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 2/3 or less of the pressure at the time of pressurization.
  • 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.
  • the amount per hit satisfies the conditional expression (2), and in the washing step, a washing liquid having a weight of 9 to 18 times the weight of the polymer particles held on the filter medium is used.
  • a suitable amount of surfactant (which does not contribute to the modification of the polymer particle surface) containing a surfactant having a polyoxyethylene chain attached to the polymer particle (with no medium or cleaning solution) that does not contribute to the modification of the polymer particle surface can be removed. Furthermore, when polymerization is carried out in the presence of a surfactant containing both a surfactant having a polyoxyethylene chain and another surfactant, most of the other surfactant is sufficiently removed together with the medium and the cleaning liquid. can do.
  • the content (residual amount) of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles is an appropriate amount (particularly 2.0 to 15.0 ⁇ 10 ⁇ 3 g / m 2 ),
  • the content (remaining amount) of other surfactants per unit surface area of the polymer particles is extremely small (especially 10.0 ⁇ 10 ⁇ 5 g / m 2 or less), and the dispersibility and dispersion uniformity are excellent.
  • Polymer particles can be obtained.
  • a by-product (emulsion polymerization product) generated during the polymerization reaction, a polymer dispersion stabilizer used as necessary, and a polymerization additive used as necessary for example, Unnecessary components such as polymerization inhibitors are also removed in large amounts in the solid-liquid separation step and the washing step. For this reason, the polymer particle obtained by the said manufacturing method can also become a thing with few quantity of these unnecessary components.
  • 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-cyclohexane tri (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. .
  • 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 polymer particles of the present invention are excellent in dispersibility in an organic solvent having a high SP value
  • a coating resin composition containing the polymer particles of the present invention, a binder and an organic solvent is applied onto a film substrate.
  • the high SP value organic solvent include, for example, isopropyl having an SP value calculated by the Fedors method of 24.3 (MPa) 1/2 (11.9 (cal / cm 3 ) 1/2 ).
  • SP value refers to a solubility parameter calculated by the Fedors method.
  • 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 on the film substrate by bar coating, blade coating, spin coating, reverse coating, die coating, 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 rays include ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, etc .; 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.
  • light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, etc .
  • 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,
  • 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.
  • 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 polymer particles of the present invention can also be used for resin moldings.
  • the resin molded body is formed by molding a molding resin composition containing the polymer particles of the present invention and a transparent resin.
  • the polymer particles function as light diffusing particles. Therefore, the resin molded body functions as a light diffusing body such as a light diffusing plate and can be used as an LED illumination 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 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 is formed by molding a molding resin composition containing the polymer particles of the present invention having excellent dispersion uniformity, the resin molded body has uniform light diffusibility and Optical properties such as antiglare properties can be obtained.
  • the volume average particle diameter of the polymer particles and the measurement method of the coefficient of variation of the particle diameter the measurement method of the volume average particle diameter of the seed particles used for the production of the polymer particles, the polymer Method for measuring X value (amount of medium per unit time that passed through filter medium (kg / min)) in solid-liquid separation process of particle production, Y value (cleaning liquid that passed through filter medium) in washing process of polymer particle production Of the amount per unit time (kg / min)), the method for measuring the content of the surfactant in the polymer particles, the method for calculating the content of the surfactant per unit surface area of the polymer particles, Method for measuring content of by-product (emulsion polymerization product) in coalesced particles, method for measuring gel fraction of polymer particles, method for measuring refractive index of polymer particles, weight in high SP value organic solvent Evaluation method and dispers
  • the volume average particle diameter of the polymer particles is measured with a Coulter Multisizer TM 3 (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 aperture used for the measurement is appropriately selected depending on the size of the polymer particles to be measured.
  • Current (aperture current) and Gain (gain) are appropriately set according to the size of the selected aperture. For example, when an aperture having a size of 50 ⁇ m is selected, the current (aperture current) is set to ⁇ 800 and the gain (gain) is set to 4.
  • 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 based on volume / volume average particle diameter of polymer particles) ⁇ 100
  • the volume average particle size of the seed particles used for the production of the polymer particles is measured by a laser diffraction / scattering type 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 a slurry containing seed particles is placed in 10 ml of a 0.1 wt% nonionic surfactant aqueous solution, touch mixer (manufactured by Yamato Kagaku Co., Ltd., “TOUCHMIXER MT-31”) and ultrasonic cleaner. (Velvo Crea Co., Ltd., “ULTRASONIC CLEANER VS-150”) is used as a dispersion liquid.
  • the measurement is performed in a state where the seed particles are dispersed by performing pump circulation in the universal liquid sample module, and in a state where the ultrasonic unit (ULM ULTRASONIC MODULE) is activated, and the volume average particle diameter of the seed particles ( Calculate the arithmetic mean diameter in the volume-based particle size distribution.
  • the measurement conditions are shown below.
  • 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 to be described later include di (2-ethylhexyl) sulfosuccinate, polyoxyethylene nonylphenyl ether phosphate, lauryl sulfate, alkenyl succinate, At least one of oxyethylene styrenated phenyl ether sulfate salt and polyoxyethylene styrenated phenyl ether phosphate is used, and the surfactant content in the polymer particles of Examples and Comparative Examples is as follows: It measured by the method shown in.
  • 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 performing ultrasonic extraction at room temperature 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.
  • Surfactant content ( ⁇ g / g) ⁇ Surfactant concentration in test solution ( ⁇ g / ml) x Extraction liquid amount (ml) ⁇ ⁇ Sample weight (g)
  • 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.
  • the specific surface area of the polymer particles was measured by the BET method (nitrogen adsorption method) described in ISO 9277 1st edition JIS Z 8830: 2001.
  • the BET nitrogen adsorption isotherm was measured using an automatic specific surface area / pore distribution measuring device Tristar 3000 manufactured by Shimadzu Corporation, and the specific surface area was determined from the nitrogen adsorption amount using the BET multipoint method.
  • the measurement was performed using the constant volume method under the condition of the adsorbate cross section of 0.162 nm 2 using nitrogen as the adsorbate.
  • the pretreatment is performed by heating the container containing the polymer particles at 65 ° C., performing a nitrogen purge for 20 minutes, allowing to cool to room temperature, and then heating the container at 65 ° C. This was performed by performing vacuum deaeration until the pressure in the container was 0.05 mmHg or less.
  • a centrifuge tube having an inner diameter of 24 mm for example, a centrifuge tube having an internal volume of 50 mL and an inner diameter of 24 mm (manufactured by Thermo Fisher Scientific, trade name “Nalgen (registered trademark) 3119-0050”).
  • the centrifuge tube is set in a rotor, for example, an angle rotor (model number “RR24A”, manufactured by Hitachi Koki Co., Ltd., in which eight centrifuge tubes with an internal volume of 50 mL are set), and a centrifuge, for example, a high-speed cooling centrifuge (high -Speed refrigerated centrifuge (model number "CR22GII”, manufactured by Hitachi Koki Co., Ltd.) is set with the rotor described above, and using the high-speed cooling centrifuge, K-factor 6943 (when the angle rotor is used, the rotation speed is 4800 rpm) (K factor sometimes becomes 6943) After centrifugation at a rotational time 30 minutes, collecting the supernatant.
  • a centrifuge for example, an angle rotor (model number “RR24A”, manufactured by Hitachi Koki Co., Ltd., in which eight centrifuge tubes with an internal volume of 50 mL are set
  • a centrifuge for example,
  • the following calculation formula To calculate the concentration (% by weight) of a non-volatile component (corresponding to a by-product (emulsion polymerization product)) in the supernatant.
  • the gel fraction of the polymer particles indicates the degree of crosslinking of the polymer particles, and is measured by the following method. That is, first, 1.0 g of polymer particles as a sample and 0.03 g of boiling stone are precisely weighed and put into a 200 mL eggplant flask, and further 100 mL of toluene is added, and then a cooling tube is connected to the eggplant flask. The eggplant flask is immersed in an oil bath that is attached and maintained at 130 ° C. and refluxed for 24 hours.
  • 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 Buchner funnel type filter 3G, the glass fiber filter, and the total weight of the solid matter are measured in a state where the Buchner funnel type filter 3G contains the solid matter. Then, the weight (g) of the dry powder is obtained by subtracting the weight of the Buchner funnel type filter 3G and the glass fiber filter and the weight of the boiling stone from the measured total weight.
  • the refractive index of the polymer particles was measured by the Becke method. First, polymer particles are placed on a slide glass, and a plurality of refraction liquids (cargill standard: Cargill standard refraction liquid with a refractive index nD25 of 1.538 to 1.562 are prepared in increments of 0.002 in refractive index difference. ) Is dripped. After mixing the polymer particles and the refractive liquid well, the outline of the polymer particles is observed from above with an optical microscope while irradiating light from a high pressure sodium lamp “NX35” (center wavelength 589 nm) manufactured by Iwasaki Electric Co., Ltd. Observed. And when the outline was not visible, it was judged that the refractive index of a refractive liquid and a polymer particle was equal.
  • a high pressure sodium lamp “NX35” center wavelength 589 nm
  • observation with an optical microscope is not particularly problematic as long as it is an observation at a magnification at which the outline of the polymer particles can be confirmed, but an observation magnification of about 500 times is appropriate for polymer particles having a particle diameter of 5 ⁇ m.
  • the intermediate value between the two types of refractive liquid is set as the refractive index of the polymer particles. It was judged. For example, when a test is performed with refractive liquids having a refractive index of 1.554 and a refractive index of 1.556, if there is no difference in the appearance of polymer particles between the two refractive liquids, an intermediate value of 1.555 between these refractive liquids is overlapped. The refractive index of the coalesced particles was determined.
  • the measurement was performed in an environment with a test room temperature of 23 ° C. to 27 ° C.
  • the solubility of the liquid solute in the solvent is generally determined by the “cloudiness” or “white turbidity” of the solution obtained by dissolving the liquid solute in the solvent, here, the solubility of the liquid solute with respect to the cleaning liquid having a liquid temperature of 25 ° C.
  • the solubility (D) of one other surfactant was measured by measuring the “permeability” of a solution having a liquid temperature of 25 ° C. obtained by dissolving one other surfactant in a cleaning solution. .
  • the reaction liquid after polymerization was filtered through a 400 mesh (32 ⁇ m mesh) wire mesh to prepare a slurry containing 20% by weight of seed particles (referred to as seed particles (1)) made of polymethyl methacrylate as a solid content.
  • seed particles (1) made of polymethyl methacrylate as a solid content.
  • the seed particles (1) contained in this slurry were true spherical particles having a volume average particle diameter of 0.54 ⁇ m.
  • the reaction liquid after polymerization was filtered through a 400 mesh (mesh 32 ⁇ m) wire mesh to prepare a slurry containing 14% by weight of seed particles (referred to as seed particles (2)) made of polymethyl methacrylate as a solid content.
  • seed particles (2) contained in this slurry were true spherical particles having a volume average particle diameter of 0.42 ⁇ m.
  • the reaction liquid after polymerization was filtered through a 400 mesh (mesh 32 ⁇ m) wire mesh to prepare a slurry containing 10% by weight of seed particles (hereinafter referred to as seed particles (3)) made of polymethyl methacrylate as a solid content. .
  • seed particles (3) contained in this slurry were true spherical particles having a volume average particle diameter of 1.02 ⁇ m.
  • Example 1 Production example of polymer particles
  • MMA methyl methacrylate
  • St styrene
  • ethylene a polyfunctional vinyl monomer
  • polyoxyethylene nonylphenyl ether sodium phosphate product name “Phosphanol (registered trademark) LO-529” manufactured by Toho Chemical Co., Ltd.
  • anionic surfactant having a polyoxyethylene chain 2000 g of an aqueous solution in which 10 g as a pure component and 0.60 g of sodium nitrite as a polymerization inhibitor are dissolved is added, and then a polymerization reaction is performed by stirring at 80 ° C. for 5 hours and then at 105 ° C. for 3 hours.
  • a slurry of particles hereinafter referred to as slurry (1) was obtained as a crude product.
  • 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 becomes 2.10 kg (70% of the weight of water used in the polymerization step) or more and the internal pressure of the pressure vessel 2 becomes 0.10 MPa (2/3 of the pressure at the time of pressurization) or less.
  • the pressurization was finished.
  • 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 2.24 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 45.0 minutes. Therefore, the amount X per unit time of the medium that passed through the filter medium in the solid-liquid separation step was 0.0498 kg / min.
  • the washing is performed using a washing liquid having a weight 10 times or more of the weight of the polymer particles obtained in the polymerization process (total amount of vinyl monomers used in the polymerization process 1000 g).
  • the test was performed until the electric conductivity of water became 2.0 times or less (specifically, 15 ⁇ S or less) and the internal pressure of the pressure vessel 2 became 0.066 MPa (2/3 of the pressure during pressurization) or less.
  • Weight G 2 of water as a cleaning solution used in the washing step of the present embodiment is 13.0 kg (13.0 times the weight of the resulting polymer particles in the polymerization step), the lower limit value B L or more, the The weight was within the range of the upper limit BH or less.
  • the cleaning step of this embodiment from the start of passing a cleaning liquid to the filter medium 3, 10.4 kg of (0.8 times the weight of the weight G 2 of water as the cleaning liquid used in the washing step)
  • the time T 2 (min) spent for the cleaning liquid to pass through the filter medium 3 was 140.5 minutes. Therefore, the amount Y of the medium that passed through the filter medium in the washing step per unit time was 0.0740 kg / min.
  • the polymer particles were extracted by immersing them in methanol, and the change over time in the amount of the surfactant having a polyoxyethylene chain contained in the extraction component was observed.
  • the extraction time is short (15 to 30 minutes)
  • the extracted component is generally composed of only components extracted from the surface of the polymer particles, and from the inside of the polymer particles contained in the extracted component as the extraction time increases. It is thought that the ratio of the extracted component increases.
  • FIG. 2 shows an SEM image of the polymer particles immediately after the polymerization reaction obtained in Example 1
  • FIG. 3 shows an SEM image of the polymer particles obtained after the solid-liquid separation step and the washing step in Example 1.
  • FIG. 2 it was confirmed that particles having a particle size of about 100 to 200 nm, which is a by-product (emulsion polymerization product), adhere to the surface of the polymer particles.
  • FIG. 3 it was confirmed that the by-product (emulsion polymerization product) hardly adhered to the surface of the polymer particles (very slightly adhered).
  • Example 2 Production example of polymer particles
  • sodium lauryl sulfate manufactured by Kao Corporation, product name “Di (2-ethylhexyl) sodium sulfosuccinate”
  • Emal (R) 2FG liquid solubility temperature 25 ° C. water; 10 g / 100 ml) was 50g used as pure content, the total weight G 1 is 2.30kg next filtrate obtained by solid-liquid separation step (medium)
  • the solid liquid is adjusted so that the time T 1 from the start of passing the medium (water) contained in the crude product P through the filter medium 3 to the end of the passage of the medium through the filter medium 3 is 50.0 minutes.
  • the washing liquid Time T 2 spent from the start of passing the timber 3 until the wash of 8.4 kg (0.8 times the weight of the weight G 2 of water as a cleaning solution used in the washing step) to pass through the filter medium 3
  • the target polymer particles were obtained in the same manner as in Example 1 except that the washing process conditions were changed so that (min) was 150.2 minutes.
  • the amount X per unit time of the medium that passed through the filter medium in the solid-liquid separation process was 0.0460 kg / min, and the amount Y of the medium that passed through the filter medium in the washing process was 0.0559 kg / min. .
  • Weight G 2 of water as the cleaning liquid used in the washing step of the present embodiment is 10.5 kg (10.5 times the weight of the resulting polymer particles in the polymerization step), the lower limit value B L or more, the The weight was within the range of the upper limit BH or less.
  • Example 3 Production Example of Polymer Particles
  • dipotassium alkenyl succinate manufactured by Kao Corporation, instead of pure di- (2-ethylhexyl) sulfosuccinate sodium as a pure component of 10 g
  • the target polymer particles were obtained in the same manner as in Example 1 except that 10 g of the product name “Latemul (registered trademark) ASK”, solubility in water at a liquid temperature of 25 ° C .; 1.7 g / 100 ml) was used as a pure component.
  • the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.30 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 40.9 minutes. Therefore, the quantity X per unit time of the medium that passed through the filter medium in the solid-liquid separation step was 0.0562 kg / min.
  • Weight G 2 of water as a cleaning solution used in the washing step of the present embodiment is 13.0 kg (13.0 times the weight of the resulting polymer particles in the polymerization step), the lower limit value B L or more, the The weight was within the range of the upper limit BH or less.
  • the cleaning step of this embodiment from the start of passing a cleaning liquid to the filter medium 3, 10.4 kg of (0.8 times the weight of the weight G 2 of water as the cleaning liquid used in the washing step)
  • the time T 2 (min) spent for the cleaning liquid to pass through the filter medium 3 was 132.0 minutes. Therefore, the amount Y of the medium that passed through the filter medium in the washing step per unit time was 0.0788 kg / min.
  • Example 4 Production Example of Polymer Particles
  • polyoxyethylene nonylphenyl ether sodium phosphate is replaced with 10 g of pure polyoxyethylene styrenated phenyl ether ammonium sulfate (Daiichi Kogyo Seiyaku Co., Ltd., product 10 g of pure “Haitenol (registered trademark) NF-08”) was used, and 10.4 kg (the weight G of water as the cleaning liquid used in the cleaning step) after starting to pass the cleaning liquid through the filter medium 3 Except that the conditions of the cleaning process were changed so that the time T 2 (min) taken until the cleaning liquid of 0.8 times the weight of 2 ) passed through the filter medium 3 was 129.0 minutes. Similarly, target polymer particles were obtained.
  • the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.28 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 41.0 minutes. Therefore, the amount X per unit time of the medium that passed through the filter medium in the solid-liquid separation step was 0.0556 kg / min. Moreover, the amount Y per unit time of the medium that passed through the filter medium in the washing step was 0.0806 kg / min.
  • the lower limit value B L (kg) and the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the above calculation formulas (4) and (5) for one type of other surfactant used in the polymerization step are the same as in Example 1.
  • Example 5 Production example of polymer particles
  • an anionic surfactant having a polyoxyethylene chain polyoxyethylene nonylphenyl ether sodium phosphate is replaced with 10 g of pure polyoxyethylene styrenated phenyl ether phosphate (Daiichi Kogyo Seiyaku Co., Ltd., product 10 g of pure “Plysurf (registered trademark) AL”) was used as a pure component, and the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step was 2.25 kg, and the medium contained in the crude product P ( The condition of the solid-liquid separation step is changed so that the time T 1 from the start of passing the water) through the filter medium 3 to the end of the passage of the medium through the filter medium 3 is 40.8 minutes.
  • passing cleaning liquid started from 10.4 kg (0.8 times the weight of the weight G 2 of water as the cleaning liquid used in the washing step) is the filter medium 3 that is passed through a filter medium 3 Time T 2 (min) spent until the are except for changing the conditions of the washing process so as to 133.5 minutes, in the same manner as in Example 1 to obtain a polymer particle of interest.
  • the amount X of the medium per unit time that passed through the filter medium in the solid-liquid separation step was 0.0551 kg / min.
  • the amount Y of the medium that passed through the filter medium in the washing step per unit time was 0.0779 kg / min.
  • the lower limit value B L (kg) and the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the above calculation formulas (4) and (5) for one type of other surfactant used in the polymerization step are the same as in Example 1.
  • Example 6 Production example of polymer particles
  • sodium di (2-ethylhexyl) sulfosuccinate is used as a pure component in place of a pure component of 10 g, and a polyoxyethylene chain-containing anionic surfactant.
  • 20 g of pure oxyethylene nonylphenyl ether phosphate manufactured by Toho Chemical Co., Ltd., product name “Phosphanol (registered trademark) LO-529” was used as a pure component, and polyoxyethylene was used for the dispersion in the polymerization process.
  • the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation process of this example is 2.29 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 43.0 minutes. Therefore, the quantity X per unit time of the medium that passed through the filter medium in the solid-liquid separation step was 0.0533 kg / min. Further, the amount Y of the medium that passed through the filter medium in the washing step per unit time was 0.0795 kg / min.
  • Example 7 Production example of polymer particles
  • Styrene (St) is not used, the amount of methyl methacrylate (MMA) used is changed to 700 g, and 10.4 kg (water as the cleaning liquid used in the cleaning process) is started after passing the cleaning liquid through the filter medium 3. Except that the cleaning process conditions were changed so that the time T 2 (min) required for the cleaning liquid of 0.8 times the weight G 2 ) to pass through the filter medium 3 was 143.8 minutes.
  • target polymer particles were obtained.
  • the total weight G 1 of the solid-liquid filtrate obtained in the separation step of the present example (medium) is 2.31 kg, start to pass the medium (water) to the filter medium 3 contained in the crude product P Then, the time T 1 until the passage of the medium through the filter medium 3 was 43.2 minutes. Therefore, the amount X per unit time of the medium that passed through the filter medium in the solid-liquid separation step was 0.0535 kg / min. In addition, the amount Y per unit time of the medium that passed through the filter medium in the washing step was 0.0723 kg / min.
  • the lower limit value B L (kg) and the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the above calculation formulas (4) and (5) for one type of other surfactant used in the polymerization step are the same as in Example 1.
  • Example 8 Production example of polymer particles
  • MMA methyl methacrylate
  • St styrene
  • EGDMA ethylene glycol dimethacrylate
  • T 2 (min) spent until 10.4 kg (0.8 times the weight G 2 of the weight of water used as the cleaning liquid used in the cleaning process) of the cleaning liquid passes through the filter medium 3 is 137.5 minutes.
  • the target polymer particles were obtained in the same manner as in Example 1 except that the conditions of the washing step were changed so that
  • the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.30 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 44.0 minutes. Therefore, the amount X per unit time of the medium that passed through the filter medium in the solid-liquid separation step was 0.0523 kg / min. In addition, the amount Y of the medium that passed through the filter medium in the washing step per unit time was 0.0756 kg / min.
  • the lower limit value B L (kg) and the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the above calculation formulas (4) and (5) for one type of other surfactant used in the polymerization step are the same as in Example 1.
  • Example 9 Production example of polymer particles
  • the slurry of seed particles (3) obtained in Production Example 3 of seed particles is replaced with the solid content (seed 10.4 kg from the start of passing the cleaning liquid through the filter medium 3 (0.8 times the weight of water G 2 as the cleaning liquid used in the cleaning step)
  • the target polymer particles were obtained in the same manner as in Example 1 except that the washing process conditions were changed so that the time T 2 (min) required for the washing liquid to pass through the filter medium 3 was 130.0 minutes.
  • 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 filter medium 3. Then, the time T 1 until the passage of the medium through the filter medium 3 was 45.0 minutes. Therefore, the quantity X per unit time of the medium that passed through the filter medium in the solid-liquid separation process was 0.0544 kg / min. Further, the amount Y of the medium that passed through the filter medium in the washing step per unit time was 0.0800 kg / min.
  • the lower limit value B L (kg) and the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the above calculation formulas (4) and (5) for one type of other surfactant used in the polymerization step are the same as in Example 1.
  • the total weight G 1 is 2.41kg next filtrate obtained by solid-liquid separation step (medium), the filter medium 3 of the medium a medium contained in the crude product P (water) from the start of passing the filter medium 3
  • the condition of the solid-liquid separation process was changed so that the time T 1 until the passage of water was 45.0 minutes, and the weight G 2 of water as a cleaning liquid used in the cleaning process was 5.0 kg (obtained in the polymerization process).
  • the weight of water as the cleaning liquid used in the cleaning step is 0.
  • the weight of water G 2 as the cleaning liquid used in the cleaning step is 0. .Times.8 times the weight) of the washing liquid passed through the filter medium 3, except that the washing process conditions were changed so that the time T 2 (min) was 48.6 minutes.
  • the target polymer particles were obtained.
  • the amount X of medium passing through the filter medium in the solid-liquid separation process was 0.0536 kg / min, and the amount Y of medium passing through the filter medium in the washing process was 0.0823 kg / min. .
  • the total weight G 1 is 2.39kg next filtrate obtained by solid-liquid separation step (medium), the filter medium 3 of the medium a medium contained in the crude product P (water) from the start of passing the filter medium 3
  • the solid-liquid separation process conditions were changed so that the time T 1 until the end of the passage of water was 47.7 minutes, and the weight G 2 of water as the cleaning liquid used in the cleaning process was 5.0 kg (obtained in the polymerization process).
  • the weight of water as the cleaning liquid used in the cleaning step is 0.
  • the weight of water G 2 as the cleaning liquid used in the cleaning step is 0. .Times.8 times the weight) of the washing liquid passing through the filter medium 3 except that the washing process conditions were changed so that the time T 2 (min) was 55.2 minutes.
  • the target polymer particles were obtained.
  • the amount X of medium passing through the filter medium in the solid-liquid separation step was 0.0501 kg / min, and the amount Y of medium passing through the filter medium in the washing process was 0.0725 kg / min. .
  • the amount X of medium passing through the filter medium in the solid-liquid separation step was 0.0525 kg / min, and the amount Y of medium passing through the filter medium in the washing step was 0.0728 kg / min. .
  • Example 10 Production example of polymer particles
  • the amount X of the medium per unit time that passed through the filter medium in the solid-liquid separation step was 0.0499 kg / min.
  • the cleaning step of this embodiment from the start of passing a cleaning liquid to the filter medium 3, 10.4 kg of (0.8 times the weight of the weight G 2 of water as the cleaning liquid used in the washing step)
  • the time T 2 (min) spent for the cleaning liquid to pass through the filter medium 3 was 170.0 minutes. Therefore, the amount Y of the medium that passed through the filter medium in the washing step per unit time was 0.0612 kg / min.
  • Example 11 Production example of polymer particles
  • Addition of pure polyoxyethylene nonylphenyl ether sodium phosphate product name “Phosphanol (registered trademark) LO-529” manufactured by Toho Chemical Co., Ltd.
  • the amount is changed from 10 g to 25 g, the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step becomes 2.35 kg, and the medium (water) contained in the crude product P is allowed to pass through the filter medium 3.
  • the condition of the solid-liquid separation step is changed so that the time T 1 from the start to the end of the passage of the medium through the filter medium 3 is 43.3 minutes, and the cleaning liquid is started to pass through the filter medium 3.
  • the amount X of medium passing through the filter medium in the solid-liquid separation step was 0.0543 kg / min, and the amount Y of medium passing through the filter medium in the washing step was 0.0820 kg / min. .
  • the lower limit value B L (kg) and the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the above calculation formulas (4) and (5) for one type of other surfactant used in the polymerization step are the same as in Example 1.
  • Example 12 Production example of polymer particles
  • Addition of pure polyoxyethylene nonylphenyl ether sodium phosphate product name “Phosphanol (registered trademark) LO-529” manufactured by Toho Chemical Co., Ltd.
  • an anionic surfactant having a polyoxyethylene chain After changing the amount from 10 g to 5 g and starting to pass the cleaning liquid through the filter medium 3, 10.4 kg (0.8 times the weight of water G 2 as the cleaning liquid used in the cleaning process)
  • the target polymer particles were obtained in the same manner as in Example 1 except that the conditions of the washing step were changed so that the time T 2 (min) spent before passing through the filter medium 3 was 135.5 minutes. .
  • the total weight G 1 of the solid-liquid filtrate obtained in the separation step of the present example is 2.32 kg, 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 45.5 minutes. Therefore, the amount X per unit time of the medium that passed through the filter medium in the solid-liquid separation step was 0.0510 kg / min. In addition, the amount Y of the medium that passed through the filter medium in the washing step per unit time was 0.0768 kg / min.
  • the lower limit value B L (kg) and the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the above calculation formulas (4) and (5) for one type of other surfactant used in the polymerization step are the same as in Example 1.
  • Example 13 Production example of polymer particles
  • Change the weight G 2 of water as a cleaning liquid used in the washing step 12.1 kg (12.1 times the weight of the resulting polymer particles in the polymerization step), the start of passing a cleaning liquid to the filter medium 3 From the above, the time T 2 (min) spent until 9.68 kg (0.8 times the weight G 2 of the weight of water as the cleaning liquid used in the cleaning process) passes through the filter medium 3 is 110.0 minutes.
  • the target polymer particles were obtained in the same manner as in Example 1 except that the conditions of the washing process were changed.
  • the amount Y of the medium that has passed through the filter medium per unit time is 0.0880 kg / min.
  • the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.37 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 43.2 minutes. Therefore, the quantity X per unit time of the medium that passed through the filter medium in the solid-liquid separation step was 0.0549 kg / min.
  • the lower limit value B L (kg) and the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the above calculation formulas (4) and (5) for one type of other surfactant used in the polymerization step are the same as in Example 1.
  • Example 14 Production example of polymer particles
  • the target polymer particles were obtained in the same manner as in Example 1 except that the conditions of the washing step were changed so that the time T 2 (min) was 357.4 minutes.
  • the amount Y of the medium that has passed through the filter medium in the cleaning process per unit time is 0.0291 kg / min.
  • the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.34 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 50.2 minutes. Therefore, the quantity X per unit time of the medium that passed through the filter medium in the solid-liquid separation step was 0.0466 kg / min.
  • the lower limit value B L (kg) and the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the above calculation formulas (4) and (5) for one type of other surfactant used in the polymerization step are the same as in Example 1.
  • Example 15 Production example of polymer particles
  • the time T 2 (min) required for 9.60 kg (0.8 times the weight G 2 of the water used as the cleaning liquid used in the cleaning process) to pass through the filter medium 3 is 109.0 minutes.
  • the target polymer particles were obtained in the same manner as in Example 1 except that the conditions of the washing process were changed.
  • the amount Y of the medium that has passed through the filter medium in the washing step per unit time is 0.0881 kg / min.
  • the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step of this example is 2.30 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 41.5 minutes. Accordingly, the amount X of the medium per unit time that passed through the filter medium in the solid-liquid separation step was 0.0554 kg / min.
  • the lower limit value B L (kg) and the upper limit value B H (kg) of the weight of the cleaning liquid calculated by the above calculation formulas (4) and (5) for one type of other surfactant used in the polymerization step are the same as in Example 1.
  • the weight is within the following range.
  • the amount X of medium passing through the filter medium in the solid-liquid separation step was 0.0537 kg / min, and the amount Y of medium passing through the filter medium in the washing step was 0.0805 kg / min. .
  • the amount X per unit time of the medium that passed through the filter medium in the solid-liquid separation process was 0.0426 kg / min, and the amount Y of the medium that passed through the filter medium in the washing process was 0.0800 kg / min. .
  • the amount X of medium passing through the filter medium in the solid-liquid separation step was 0.1032 kg / min, and the amount Y of medium passing through the filter medium in the washing step was 0.1115 kg / min. .
  • the amount X of medium passing through the filter medium in the solid-liquid separation step is 0.1271 kg / min, and the amount Y of medium passing through the filter medium in the washing step is 0.0879 kg / min. there were.
  • the total weight G 1 of the solid-liquid filtrate obtained in the separation step of this comparative example (medium) is 2.33 kg, 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 55.2 minutes. Therefore, the quantity X per unit time of the medium that passed through the filter medium in the solid-liquid separation step was 0.0422 kg / min.
  • the total weight G 1 of the solid-liquid filtrate obtained in the separation step of this comparative example (medium) is 2.25 kg, start to pass the medium (water) to the filter medium 3 contained in the crude product P Then, the time T 1 until the passage of the medium through the filter medium 3 was 40.2 minutes. Therefore, the amount X per unit time of the medium that passed through the filter medium in the solid-liquid separation step was 0.0560 kg / min. The amount Y of the medium passed through the filter medium in the washing step per unit time was 0.0880 kg / min.
  • polyoxyethylene styrenated phenyl ether sulfate ammonium salt which is an anionic surfactant having a polyoxyethylene chain
  • product name “Hitenol (registered trademark) NF-08” In a solution obtained by dissolving 20.0 g (about 19 g as a pure component) with 1750 g of ion-exchanged water, 600 g of styrene (St), 400 g of 1,6-hexanediol dimethacrylate (HDDMA), 2,2′-azobis (2, 4-Dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd., V-65) in a solution of 20 g was added, and TK homomixer (Primics Co., Ltd.
  • reaction solution was heated to 65 ° C. under a nitrogen atmosphere and held at 65 ° C. for 2 hours to perform radical polymerization of the monomer.
  • the reaction solution was cooled and then filtered, and the polymerization product was collected by filtration. At this time, the solid content concentration of the recovered product (the polymerization product collected by filtration) was 67% by weight.
  • the recovered material was dried with a dryer at 100 ° C. for 6 hours to obtain organic-inorganic composite particles.
  • the volume average particle diameter and the coefficient of variation of the particle diameter were measured by the measurement method described above.
  • the volume average particle diameter was 3.82 ⁇ m, and the coefficient of variation of the particle diameter was 7.22%. It was.
  • the obtained organic / inorganic composite particles were measured for the content of the surfactant by the above-described measurement method, and found to be 1940 ppm by weight (0.19% by weight).
  • the first filtration uses a quantitative filter paper (quantitative filter paper No. 5C, manufactured by Advantech Toyo Co., Ltd.) instead of the filter cloth as the filter medium 3, and the total weight G 1 of the filtrate (medium) obtained in the solid-liquid separation step. Is 0.80 kg, and the time T 1 from the start of passing the medium (water) contained in the crude product P through the filter medium 3 to the end of the passage of the medium through the filter medium 3 is 18.5 minutes. This was performed in the same manner as the solid-liquid separation step of Example 1 except that the conditions of the solid-liquid separation step were changed.
  • Second filtration 1.0 times the weight of the resulting polymer particles the weight G 2 of water as a cleaning liquid used in the washing step to a solid concentration of 40 wt% with 1.0 kg (polymerization step ) And starting to pass the cleaning liquid through the filter medium 3, 0.8 kg (0.8 times the weight of water G 2 as the cleaning liquid used in the cleaning process) of the cleaning liquid passes through the filter medium 3.
  • the condition of the washing process was changed so that the time T 2 (min) spent before passing was 28.9 minutes, and instead of the filter cloth as the filter medium 3, a quantitative filter paper (quantitative filter paper No. 5C manufactured by Advantech Toyo Co., Ltd.) ) was used in the same manner as in the cleaning process of Example 1.
  • the amount X per unit time of the medium that has passed through the filter medium in the solid-liquid separation step is 0.0432 / min, and the amount Y of the medium that has passed through the filter medium in the washing step is 0.0277 kg / min. there were.
  • Example 16 Production example of optical film
  • an ultrasonic cleaner (“Velvo Crea Co., Ltd.“ ULTRASONIC CLEANER VS-150 ”) and stirred for 1 minute to disperse the polymer particles in butyl acetate as an organic solvent to obtain a dispersion.
  • This dispersion further contains 1 acrylic resin (“Acridic® A-817” manufactured by DIC Corporation, 49.0 to 51.0 wt% of toluene and butyl acetate as organic solvents).
  • a coater with a 75 ⁇ m slit on a 100 ⁇ m thick PET film (trade name “FUJIX (registered trademark) OHP film for copying machine” manufactured by Fuji Film Co., Ltd.) having a thickness of 100 ⁇ m. Coated. After coating, the film was placed in a drier maintained at 70 ° C. and left for 1 hour to obtain an optical film.
  • Example 17 Production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Example 2 was used instead of 0.20 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 16 except that 0.20 g of the polymer particles obtained in Example 3 was used instead of 0.20 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 16 except that 0.20 g of the polymer particles obtained in Example 4 was used instead of 0.20 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 16 except that 0.20 g of the polymer particles obtained in Example 5 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Example 21 Production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Example 6 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Example 22 Production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Example 7 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Example 23 Production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Example 8 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Example 24 Production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Example 9 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Comparative Example 12 Comparative production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Comparative Example 1 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Comparative Example 14 Comparative production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Comparative Example 3 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Example 25 Production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Example 10 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Example 26 Production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Example 11 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Example 27 Production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Example 12 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Example 28 Production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Example 13 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Example 29 Production example of optical film
  • An optical film was obtained in the same manner as in Example 16, except that 0.20 g of the polymer particles obtained in Example 14 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Example 30 Production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Example 15 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Comparative Example 16 Comparative production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Comparative Example 5 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Comparative Example 18 Comparative production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Comparative Example 7 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Comparative Example 20 Comparative production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Comparative Example 9 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Comparative Example 21 Comparative production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Comparative Example 10 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • Comparative Example 22 Comparative production example of optical film
  • An optical film was obtained in the same manner as in Example 16 except that 0.20 g of the polymer particles obtained in Comparative Example 11 was used instead of 0.20 g of the polymer particles obtained in Example 1.
  • optical characteristics of the optical films of Examples 16 to 30 and Comparative Examples 12 to 22 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 five locations) manufactured by Nippon Denshoku Industries Co., Ltd. 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.
  • 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
  • the number of seed particles used in the polymerization process (seed particle number), the composition of the monomers used in the polymerization process (monomer composition), and used in the polymerization process
  • Types of other surfactants and surfactants having polyoxyethylene chains types of polymer dispersion stabilizers used in the polymerization process
  • X values in the solid-liquid separation process (amount of medium passed through the filter medium per unit time) (Kg / min)) measurement result
  • Y value in the washing step (amount of washing liquid that passed through the filter medium per unit time (kg / min)), amount of washing liquid (water) used in the washing step (kg )
  • Measurement results of volume average particle diameter ( ⁇ m) and coefficient of variation (CV value (%)) of the obtained polymer particles measurement results of refractive index of the obtained polymer particles, and obtained Measurement result of gel fraction (%) of polymer particles Table 2 and Table 4.
  • DSS represents sodium di (2-ethylhexyl) sulfosuccinate
  • LS represents sodium lauryl sulfate
  • ASK represents dipotassium alkenyl succinate
  • POEPS represents polyoxyethylene nonylphenyl ether phosphorus. It represents sodium acid
  • ASPSE represents polyoxyethylene styrenated phenyl ether ammonium sulfate
  • POESE represents polyoxyethylene styrenated phenyl ether phosphate ester
  • PVA represents polyvinyl alcohol
  • PSE represents polyoxyethylene styrenated phenyl Represents ether.
  • the area A of the interface is 0.0104 (m 2 ). Therefore, in Examples 1 to 15 and Comparative Examples 1 to 11, the upper limit value of the X value satisfying 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 lower limit value of the Y value satisfying the above conditional expression (2) (the amount per unit time of the cleaning liquid that has passed through the filter medium (kg / min)) is 0.0260 kg / min, and the upper limit value is 0.0884 kg / min. .
  • the cleaning liquid (water ) Is 9 times or more (9 kg or more) of the weight of the polymer particles, specifically 10.0 to 13.0 times, and the polymer particles obtained in Examples 1 to 15 are units of polymer particles.
  • While the content of other surfactants per surface area is less than 10.0 ⁇ 10 ⁇ 5 g / m 2 , specifically 0.88 to 8.38 ⁇ 10 ⁇ 5 g / m 2 ,
  • the washing step was omitted (corresponding to the case where the amount of washing liquid (water) used for washing is 0), and the amount of washing liquid (water) used for washing was less than 9 times the weight of the polymer particles (9 kg) Less), specifically, the polymer particles obtained in Comparative Examples 2, 3, and 5 which are 5.0 times the polymer
  • the content of other surfactants per unit surface area of the particles was higher than 10.0 ⁇ 10 ⁇ 5 g / m 2 , specifically 131.76 to 413.62 ⁇ 10 ⁇ 5 g / m 2 .
  • the other surfactant used in the polymerization step is applied to the polymer particle surfaces. It was observed that the amount of adhesion per unit surface area can be reduced.
  • the amount of the cleaning liquid (water) used for cleaning was 18 times or less (18 kg or less), specifically 10.0 to 13.0 times the weight of the polymer particles.
  • the content of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles is 2.0 ⁇ 10 ⁇ 3 g / m 2 to 15.0 ⁇ 10 ⁇ .
  • the amount of the cleaning liquid (water) used for cleaning is 9 to 18 times the weight of the polymer particles
  • the surfactant having polyoxyethylene chains used in the polymerization step It was confirmed that the adhesion amount per unit surface area to the surface of the polymer particles can be within an appropriate range of 2.0 ⁇ 10 ⁇ 3 g / m 2 to 15.0 ⁇ 10 ⁇ 3 g / m 2 .
  • the coalesced particles had a measured content of by-products (emulsion polymerization products) of less than 1.0% by weight, specifically 0.05 to 0.82% by weight.
  • Comparative Example 1 Omitted (corresponding to the case where the amount of cleaning liquid (water) used for cleaning is 0) Comparative Example 1, and the amount of cleaning liquid (water) used for cleaning is less than 9 times the weight of the polymer particles (less than 9 kg), Specifically, the polymer particles obtained in Comparative Examples 2, 3, 5, 10, and 11 that are 1.0 to 5.0 times have a measured value of the content of by-products (emulsion polymerization products) of 1. More than 0.0% by weight, specifically 1.99 to 4.33% by weight. Therefore, according to the production method of the present invention in which the amount of the cleaning liquid (water) used for the cleaning is 9 times or more the weight of the polymer particles, the content of by-products (emulsion polymerization products) in the polymer particles is reduced. It was found that it can be reduced.
  • the X value (the amount per unit time of the medium passing through the filter medium) ) Is obtained in Examples 1 to 15 having an upper limit value 0.0572 (kg / min) or less (specifically 0.0460 to 0.0566 (kg / min)) satisfying the conditional expression (1).
  • the polymer particles have a content of other surfactants per unit surface area of the polymer particles of 10.0 ⁇ 10 ⁇ 5 g / m 2 or less, specifically 0.88 to 8.38 ⁇ 10 ⁇ 5.
  • the X value is larger than the upper limit value 0.0572 (kg / min) that satisfies the conditional expression (1) (specifically, 0.1032 to 0.1271 (kg / min)
  • the polymer particles obtained in Comparative Examples 7 and 8 are polymers.
  • the content of other surfactants per unit surface area of the particles is as large as 10.0 ⁇ 10 ⁇ 5 g / m 2 (specifically, 12.33 to 29.79 ⁇ 10 ⁇ 5 g / m 2 ). It was. Therefore, according to the production method of the present invention in which the X value satisfies the conditional expression (1), it is possible to reduce the amount of other surfactants used in the polymerization step per unit surface area on the polymer particle surface. Admitted.
  • the measured content of the by-product (emulsion polymerization product) was less than 1.0% by weight, specifically 0.05 to 0.82% by weight.
  • X value is larger than upper limit value 0.0572 (kg / min) satisfying conditional expression (1) (specifically, 0.0762 to 0.1271 (kg / min))
  • the Y value (the amount per unit time of the cleaning liquid that has passed through the filter medium) ) within the range of 0.0260 (kg / min) to 0.0884 (kg / min) satisfying the conditional expression (2) (specifically, 0.0291 to 0.0881 (kg / min)).
  • the content of the other surfactant per unit surface area of the polymer particles is 10.0 ⁇ 10 ⁇ 5 g / m 2 or less, specifically 0.8.
  • the Y value is larger than the upper limit value 0.0884 kg / min that satisfies the conditional expression (2) (specifically, 0.1115 to 0). 1156 (kg / min)) obtained in Comparative Examples 7 and 9
  • the obtained polymer particles have a content of other surfactant per unit surface area of the polymer particles of more than 10.0 ⁇ 10 ⁇ 5 g / m 2 (specifically, 11.95 to 29.79 ⁇ 10 ⁇ 5 g / m 2 ).
  • the polymer particles obtained in Examples 1 to 15 satisfying the conditional expression (2) are used as by-products.
  • the measured value of the content of (emulsion polymerization product) was less than 1.0% by weight, specifically 0.05 to 0.82% by weight, whereas the Y value was the above conditional expression (2)
  • the polymer particles obtained in Comparative Examples 7 and 9 are larger than 0.0884 kg / min (specifically, 0.1115 to 0.1156 (kg / min)) satisfying the above-mentioned by-product (emulsion polymerization).
  • the measured value of the content of the product was as high as 1.0% by weight or more (specifically, 1.89 to 2.33% by weight). Therefore, according to the production method of the present invention in which the Y value satisfies the conditional expression (2), it was confirmed that the content of by-products (emulsion polymerization products) in the polymer particles can be reduced.
  • the content of the other surfactant per unit surface area of the polymer particles is 10.0 ⁇ 10 ⁇ 5 g / m 2 or less (specifically, 0.88 to 8.38 ⁇ 10 ⁇ 5 g / m 2). 2 )
  • the content of the other surfactant per unit surface area of the polymer particles is more than 10.0 ⁇ 10 ⁇ 5 g / m 2 (specifically 11 .95 to 413.62 ⁇ 10 ⁇ 5 g / m 2 ), it is recognized that the polymer particles of Comparative Examples 1 to 3, 5, and 7 to 9 are excellent in dispersibility in high SP organic solvents. It was.
  • a coating resin composition comprising the polymer particles of Examples 1 to 15 in which the content of other surfactant per unit surface area of the polymer particles is 10.0 ⁇ 10 ⁇ 5 g / m 2 or less.
  • the contents of other surfactants per unit surface area of the polymer particles are more than 10.0 ⁇ 10 ⁇ 5 g / m 2 in Comparative Examples 1 to Compared with the optical films of Comparative Examples 12-14, 16, and 18-20, which are coated with a coating resin composition containing polymer particles of 3, 5, 7-9, there is little haze difference and light diffusibility It was confirmed that there was little unevenness.
  • the content of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles is 2.0 to 15.0 ⁇ 10 ⁇ 3 g / m 2 (specifically, 2.15 to 12.32).
  • the content of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles of Comparative Example 4 and the polymer particles is 2.0 ⁇ 10 ⁇ Compared with the polymer particles of Comparative Examples 6 and 11 which are less than 3 g / m 2 (specifically 0.80 to 1.46 ⁇ 10 ⁇ 3 g / m 2 ), the dispersibility in organic solvents with high SP value It was recognized that it was excellent.
  • the polymer particles of Examples 1 to 15 in which the content of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles is 2.0 to 15.0 ⁇ 10 ⁇ 3 g / m 2 are used.
  • the optical film of Comparative Example 15 obtained by coating the resin composition for coating containing the polymer particles of Comparative Example 4 and the unit surface area of the polymer particles Coating a coating resin composition containing the polymer particles of Comparative Examples 6 and 11 in which the content of the surfactant having a polyoxyethylene chain is less than 2.0 ⁇ 10 ⁇ 3 g / m 2 As compared with the optical films of Comparative Examples 17 and 22, the haze difference was small and the light diffusivity was found to be less uneven.
  • the content of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles is 2.0 to 15.0 ⁇ 10 ⁇ 3 g / m 2 (specifically, 2.15 to 12.32).
  • the polymer particles of Examples 1 to 15 that are ⁇ 10 ⁇ 3 g / m 2 ) have a content of surfactant having a polyoxyethylene chain per unit surface area of the polymer particles of 15.0 ⁇ 10 ⁇ 3.
  • the dispersibility in organic solvents having a high SP value is improved. It was recognized that it was excellent.
  • the polymer particles of Examples 1 to 15 in which the content of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles is 2.0 to 15.0 ⁇ 10 ⁇ 3 g / m 2 are used.
  • the content of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles is 15.0 ⁇ 10 ⁇ 3.
  • the optical films of Comparative Examples 16 and 21 obtained by coating the coating resin compositions containing the polymer particles of Comparative Examples 5 and 10 that are greater than g / m 2 the haze difference is small and the light diffusibility is uneven. Was found to be small.
  • the organic solvent has a high SP value. It was recognized that the dispersibility with respect to was excellent.
  • the optical film of 16 to 30 is a coating containing the polymer particles of Comparative Examples 1 to 3, 5, and 7 to 11 in which the measured value of the by-product (emulsion polymerization product) content is 1.0% by weight or more Compared to the optical films of Comparative Examples 12 to 14, 16, and 18 to 22 obtained by coating the resin composition for coating, it was confirmed that the difference in haze was small and the unevenness of light diffusibility was small.

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CN107988669A (zh) * 2018-01-15 2018-05-04 苏州耐德新材料科技有限公司 一种改性聚苯硫醚缝纫线制备方法及其复合的滤袋缝纫线
CN111712463A (zh) * 2018-05-01 2020-09-25 宇部兴产株式会社 碳酸锶颗粒、光学膜和图像显示装置
WO2021171669A1 (ja) * 2020-02-28 2021-09-02 積水化成品工業株式会社 重合体粒子及びその用途

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10545420B2 (en) * 2017-07-04 2020-01-28 Canon Kabushiki Kaisha Magnetic toner and image-forming method
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CN113227858B (zh) * 2018-12-28 2023-03-14 株式会社可乐丽 聚乙烯醇膜和使用其的偏振膜的制造方法
JP2020190686A (ja) * 2019-05-23 2020-11-26 コニカミノルタ株式会社 光学フィルム及び光学フィルムの製造方法
CN115248172A (zh) * 2021-04-25 2022-10-28 南通第六元素材料科技有限公司 一种氧化石墨烯产品均匀度的检测方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03162405A (ja) * 1989-11-20 1991-07-12 Nippon Zeon Co Ltd ペースト用塩化ビニル系重合体の製造方法
JPH08217809A (ja) * 1995-02-10 1996-08-27 Kuraray Co Ltd 樹脂の製造方法
JP2003040915A (ja) * 2001-05-24 2003-02-13 Mitsubishi Rayon Co Ltd ラテックス、重合体、および、重合体の凝固、回収方法
JP2006233055A (ja) * 2005-02-25 2006-09-07 Jsp Corp 光拡散剤及び光拡散剤の製造方法並びに光拡散性シート
JP2009203378A (ja) * 2008-02-28 2009-09-10 Nippon Shokubai Co Ltd 塗料組成物およびこれを用いた光学フィルム
WO2011046186A1 (ja) * 2009-10-16 2011-04-21 旭硝子株式会社 凝析加工用ポリテトラフルオロエチレン水性分散液の製造方法及び凝析加工用ポリテトラフルオロエチレン水性分散液

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2725031B2 (ja) * 1988-09-30 1998-03-09 ナトコペイント株式会社 架橋重合体微粒子の製造方法
JP3157141B2 (ja) * 1993-11-09 2001-04-16 株式会社日本触媒 有機ポリマー複合無機微粒子、この微粒子を含有する分散体および成膜用組成物
JP2002189317A (ja) 2000-12-21 2002-07-05 Konica Corp 静電荷像現像用トナー及び、その製造方法
DE102004012576A1 (de) * 2004-03-12 2005-09-29 Basf Ag Effektstoffe enthaltende wässrige Polymerdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
KR101190990B1 (ko) * 2004-09-28 2012-10-12 세키스이가가쿠 고교가부시키가이샤 구형 수지 미립자, 구형 수지 미립자의 제조 방법, 및 액정표시 소자용 스페이서
JP2006307207A (ja) * 2005-03-31 2006-11-09 Sanyo Chem Ind Ltd 樹脂粒子
JP2006330519A (ja) * 2005-05-27 2006-12-07 Nippon Zeon Co Ltd 重合トナーの製造方法
JP2007161830A (ja) 2005-12-13 2007-06-28 Sekisui Chem Co Ltd エポキシ系樹脂組成物
KR20090033251A (ko) * 2006-08-21 2009-04-01 니폰 쇼쿠바이 컴파니 리미티드 미립자, 미립자의 제조방법, 이 미립자를 포함하는 수지 조성물 및 광학 필름
JP2008239734A (ja) * 2007-03-27 2008-10-09 Sekisui Plastics Co Ltd 合成樹脂粒子、並びに、この合成樹脂粒子を用いた光学材料、塗料、化粧料及び合成樹脂シート
JP2009175632A (ja) 2008-01-28 2009-08-06 Nippon Zeon Co Ltd トナーの製造方法
JP5000613B2 (ja) * 2008-09-30 2012-08-15 株式会社日本触媒 有機粒子含有組成物
JP5578080B2 (ja) * 2008-10-22 2014-08-27 東亞合成株式会社 重合体微粒子の製造方法
JP5634031B2 (ja) * 2009-03-27 2014-12-03 株式会社日本触媒 重合体粒子およびそれを用いた重合体粒子含有組成物
US8440380B2 (en) 2010-01-06 2013-05-14 Ricoh Company, Ltd. Toner and method for producing the same
JP5492613B2 (ja) * 2010-03-16 2014-05-14 積水化成品工業株式会社 光学シート
JP5613431B2 (ja) * 2010-03-29 2014-10-22 積水化成品工業株式会社 表面に凸部を有する樹脂粒子及びその製造方法、それを用いた塗布用組成物、塗布物及び外用剤
WO2011142482A1 (en) * 2010-05-12 2011-11-17 Canon Kabushiki Kaisha Toner
JP5433536B2 (ja) 2010-09-15 2014-03-05 積水化成品工業株式会社 重合体粒子の製造方法
JP5592735B2 (ja) * 2010-09-15 2014-09-17 積水化成品工業株式会社 親水性重合体粒子の製造方法及び親水性重合体粒子
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
JP2012201844A (ja) * 2011-03-28 2012-10-22 Sekisui Plastics Co Ltd （メタ）アクリル酸エステル系樹脂粒子の製造方法
JP5581276B2 (ja) * 2011-07-29 2014-08-27 株式会社日本触媒 導電性微粒子

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03162405A (ja) * 1989-11-20 1991-07-12 Nippon Zeon Co Ltd ペースト用塩化ビニル系重合体の製造方法
JPH08217809A (ja) * 1995-02-10 1996-08-27 Kuraray Co Ltd 樹脂の製造方法
JP2003040915A (ja) * 2001-05-24 2003-02-13 Mitsubishi Rayon Co Ltd ラテックス、重合体、および、重合体の凝固、回収方法
JP2006233055A (ja) * 2005-02-25 2006-09-07 Jsp Corp 光拡散剤及び光拡散剤の製造方法並びに光拡散性シート
JP2009203378A (ja) * 2008-02-28 2009-09-10 Nippon Shokubai Co Ltd 塗料組成物およびこれを用いた光学フィルム
WO2011046186A1 (ja) * 2009-10-16 2011-04-21 旭硝子株式会社 凝析加工用ポリテトラフルオロエチレン水性分散液の製造方法及び凝析加工用ポリテトラフルオロエチレン水性分散液

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107988669A (zh) * 2018-01-15 2018-05-04 苏州耐德新材料科技有限公司 一种改性聚苯硫醚缝纫线制备方法及其复合的滤袋缝纫线
CN111712463A (zh) * 2018-05-01 2020-09-25 宇部兴产株式会社 碳酸锶颗粒、光学膜和图像显示装置
WO2021171669A1 (ja) * 2020-02-28 2021-09-02 積水化成品工業株式会社 重合体粒子及びその用途
KR20220119097A (ko) 2020-02-28 2022-08-26 세키스이가세이힝코교가부시키가이샤 중합체 입자 및 그 용도
JP7652352B2 (ja) 2020-02-28 2025-03-27 積水化成品工業株式会社 重合体粒子及びその用途

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