KR101634940B1 - Polymer particles, process for producing same, and use thereof - Google Patents

Abstract

Polymer particles excellent in dispersibility and dispersion uniformity, a method for producing the same, and an optical film using the polymer particles. The polymer particles preferably have a coefficient of variation of particle diameter of 15.0% or less, a content of a surfactant having a polyoxyethylene chain per unit surface area of the polymer particles of 2.0 to 15.0 x 10 < ^-3 > The content of the other surfactant is 10.0 x 10 < ^-5 > g / m < 2 > or less.

Description

POLYMER PARTICLES, METHODS OF MANUFACTURING THEIR POLYMER PARTICLES, AND USES THEREOF

The present invention relates to a polymer particle preferably used as a raw material for an optical member such as a light diffusion film and an antiglare film, a method for producing the same, and a use (optical film) of the polymer particle. More specifically, the present invention relates to a polymer particle containing a surfactant having a predetermined amount of polyoxyethylene chain per unit surface area of the polymer particle, a process for producing the polymer particle, and a use of the polymer particle (optical film).

The polymer particles having a volume average particle diameter of 1 to 100 占 퐉 may be used as additives for coating agents such as paints (luster remover), additives for ink (luster remover), main components or additives for adhesives, A filler (filler for improving slidability) of an external preparation such as an additive (such as a low shrinkage agent), a paper treatment agent or a cosmetic, a column filler used for chromatography, an additive for toner used for electrostatic charge image development, And a light diffusing agent for optical members (optical films such as light diffusion films, antiglare films, light diffusers, etc.).

These polymer particles can be produced by polymerizing a polymerizable monomer. As polymerization methods for polymerizing a polymerizable monomer, there are known suspension polymerization, seed polymerization, emulsion polymerization and the like. In these polymerization methods, a surfactant is usually used so that polymerization reaction can be stably performed and generation of coarse particles can be suppressed.

For example, in Patent Document 1, a vinyl monomer is polymerized in a medium containing a surfactant (another surfactant having no polyoxyethylene chain in the embodiment) as the resin fine particles (polymer particles) used as a light diffusing agent And the amount of the surfactant remaining in the resin fine particles is 0.05 parts by weight or less (0.005 to 0.036 parts by weight in the examples) based on 100 parts by weight of the resin fine particles.

Further, Patent Document 2 discloses that organic particles (polymer particles) having a surface-active surface-active agent, which is obtained by emulsion polymerization or suspension polymerization, are washed as organic particles to be blended in the epoxy resin composition. Patent Document 2 does not disclose a surfactant having a polyoxyethylene chain and does not disclose the amount of the surfactant remaining in the organic particles subjected to the washing treatment.

Patent Document 3 discloses a colored resin particle used as a toner for developing electrostatic latent images, which is taken out from a dispersion of colored resin particles by washing. Patent Document 3 does not disclose a surfactant having a polyoxyethylene chain and does not disclose the amount of the surfactant remaining in the washed organic particles.

Patent Document 4 discloses an electrostatic latent image developing toner comprising a binder resin, a colorant and a charge control resin having a specific repeating unit, wherein the remaining surfactant (in the embodiment, another surfactant having no polyoxyethylene chain) 1000 ppm by weight of an electrostatic latent image developing toner.

Patent Document 5 discloses a coating composition containing organic particles and a surfactant, wherein the content of the surfactant is 500 to 2000 ppm based on the organic particles. Further, in Example 5 of Patent Document 5, a dispersion coefficient of 6.2% and a content of 520 to 1,550 ppm (0.1200%) of polyoxyethylene distyryl phenyl ether sulfuric acid ester ammonium salt (one kind of surfactant having polyoxyethylene chain) , And other surfactant-free organic particles are disclosed. In Examples 2 and 4 of Patent Document 5, the coefficient of variation is 35.5 to 37.1%, the content of polyoxyethylene distyryl phenyl ether sulfuric acid ester ammonium salt is 520 to 1,550 ppm (0.0520 to 0.1550%) and the content of other organic surfactant- Particles are disclosed. In Example 3 of Patent Document 5, a total of 1950 ppm (0.1950%) of polyoxyethylene distyryl phenyl ether sulfate ester ammonium salt and sodium lauryl sulfate (one kind of other surfactant having no polyoxyethylene chain) Particles are disclosed.

Patent Document 6 discloses a method in which a raw material for toner containing a binder resin, a colorant, a charge control agent, and a releasing agent is dissolved or dispersed in an organic solvent to prepare an oily raw material liquid, , Followed by granulation while spray-drying, to thereby form colored resin particles.

Japanese Laid-Open Patent Publication No. 2006-233055 Japanese Patent Application Laid-Open No. 2007-161830 Japanese Laid-Open Patent Publication No. 2011-158889 Japanese Laid-Open Patent Publication No. 2002-189317 Japanese Laid-Open Patent Publication No. 2009-203378 Japanese Laid-Open Patent Publication No. 2009-175632

[0005] Incidentally, as an optical film such as a light-diffusing film or an antiglare film, there is one obtained by coating a resin composition containing polymer particles and a binder on a film substrate.

In the case of producing such an optical film, before coating the resin composition on the film substrate so that uniform optical characteristics can be obtained by the coating film composed of the resin composition on the film substrate, (specifically, It is necessary to uniformly disperse the polymer particles.

However, even when the resin composition is produced by uniformly dispersing the polymer particles produced by using the surfactants disclosed in Patent Documents 1 to 5 in a mixture of a binder and an organic solvent, the resin composition thus prepared is applied onto the film substrate to form a coating film The dispersed state of the polymer particles in the resin composition may become uneven in some cases. For example, in the case of producing the optical film using the polymer particles disclosed in Patent Documents 1 to 5, the dispersion state of the polymer particles in the resin composition is not stable, and in the process of forming the coating film by the coating, The dispersed state of the polymer particles in the polymer particles became uneven, and the polymer particles sometimes aggregated locally excessively. As a result, the polymer particles are not uniformly diffused over the entire coating film formed on the base film, optical characteristics of the optical film are not uniform, and desired optical characteristics are not obtained in the entire optical film in some cases.

The reason why the dispersed state of the polymer particles in the resin composition is unstable and the dispersed state of the polymer particles in the resin composition in the process of forming the coating film by the coating is uneven is that the amount of the surface residual component on the surface of the polymer particles is varied, It is required that the amount of surface residual components on the surface of the polymer particles is made constant (same). In order to keep the amount of surface residual components on the surface of the polymer particles constant, it is preferable that a component that is strongly bonded to the surface of the polymer particles and contributes to the modification of the surface of the polymer particles (for example, a polyoxyethylene chain The amount of surface residual components on the surface of the polymer particles should be reduced as much as possible.

When polymer particles are used in an optical film such as a light diffusion film or an antiglare film, it is usually necessary to adjust the refractive index of the polymer particles to a desired refractive index. Therefore, the refractive index of the polymer particles is adjusted by adjusting the composition of the polymer particles. In the case of producing an optical film using a resin composition in which polymer particles are dispersed in a mixture of a binder and an organic solvent, the solubility parameter (hereinafter referred to as " SP value ") varies depending on the composition of the polymer particles, Dispersion may be difficult. For example, polymer particles composed of at least one of a (meth) acrylic polymer, a styrene polymer and a (meth) acrylic-styrene copolymer have an SP value of 14.3 to 19.4 (MPa) ^1/2 (7.0 to 9.0 / Cm < 3 >) ^1/2 , and an SP value of 20.5 (MPa) ^1/2 (10 (cal ^{/ 2} ) or an isopropyl alcohol having an SP value of 24.3 (MPa) ^1/2 (11.9 (cal / cm < 3 >) ^1/2 ), even if it is difficult to uniformly disperse .

As a method for improving the dispersibility of the polymer particles into the high SP value organic solvent, it is considered that the surface of the polymer particles is modified by adding a monomer having high hydrophilicity to the monomers used for producing the polymer particles. However, when a monomer having a high hydrophilicity is added to a monomer used for producing polymer particles and the dispersibility into the polymer particles in a high SP value organic solvent is tried to be imparted to the polymer particles, the composition of the polymer particles themselves changes, so that the control of the refractive index becomes difficult .

In addition, in the production method of Patent Document 6, since the colored resin particles are produced by spray-drying without carrying out the washing treatment, if the binder resin used in the production is an additive (other surfactant, dispersion stabilizer, Or the like), or when the binder resin used in the production is a resin particle containing a by-product (an emulsion polymerization product) generated during the polymerization reaction, additives such as other surfactants and by-products Emulsion polymerization product) is difficult to remove, and dispersion of the colored resin particles relative to the binder and the organic solvent becomes uneven.

Here, the term " emulsion polymerization product " refers to a product obtained by subjecting a polymer having a particle size of not smaller than a particle diameter of a desired polymer particle, which is produced by emulsion polymerization in a water phase in a side reaction in the seed polymerization for producing polymer particles having uniform particle diameters Means a polymer particle having a particle diameter (for example, a particle diameter of 300 nm or less). In the seed polymerization, the polymerization is sometimes carried out in the presence of a polymerization inhibitor in order to suppress the generation of by-products (emulsion polymerization products), but the generation of by-products (emulsion polymerization products) It is difficult to prevent. In addition, by increasing the addition amount of the polymerization inhibitor, the effect of suppressing the generation of the by-products (emulsion polymerization product) can be enhanced. On the other hand, the amount of the residual monomer in the polymer particles obtained increases, . ≪ / RTI >

As a result, the polymer particles do not uniformly spread over the entire coating film formed on the base film, the optical characteristics of the optical film become uneven, and desired optical characteristics can not be obtained throughout the optical film.

Thus, a uniform dispersion state can be obtained in the process of coating a resin composition obtained by dispersing polymer particles in a binder with good dispersibility in a high SP value organic solvent and forming a coating film on the film substrate, There has been a demand for development of polymer particles excellent in dispersion uniformity (uniformity of dispersed state) capable of imparting uniform optical characteristics.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polymer particle having excellent dispersibility and dispersion uniformity, a method for producing the same, and an optical film using the polymer particle.

The inventors of the present invention have conducted intensive studies in view of the above problems, and as a result, the surface state of the polymer particles affects the dispersibility and the dispersion uniformity, and in order to improve the dispersibility and the dispersion uniformity, It is important to adhere a suitable amount of a surfactant and to suppress the content of another surfactant to a predetermined amount or less, thereby completing the present invention.

The polymer particle of the present invention is a polymer particle containing a surfactant having a polyoxyethylene chain, wherein the coefficient of variation of the particle diameter is 15.0% or less, and the surface of the polymer particle having the polyoxyethylene chain and the content of the active agent 2.0~15.0 × 10 ^-3 g / ㎡, surfactants other than the surfactants having different surface active agent (polyoxyethylene chain in the unit surface area of said polymer particles, that have a polyoxyethylene chain Is not more than 10.0 x 10 < ^-5 > g / m < 2 >.

The polymer particles having the above-mentioned constitution are preferably such that the content of the surfactant having the polyoxyethylene chain per unit surface area of the polymer particles is not less than 2.0 x 10 < ^-3 > g / m < (The surface of the polymer particle is modified to the hydrophilic site), the hydrophilic region derived from the monomer having a high hydrophilicity is not included in the composition of the polymer constituting the polymer particle, so that the high SP value The dispersibility into the organic solvent can be improved.

Further, the polymer particles having the above-mentioned constitution have a coefficient of variation of particle diameter of 15.0% or less and a content of the polyoxyethylene chain-containing surfactant per unit surface area of the polymer particles is 15.0 x 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 x 10 < ^-5 > g / m < 2 > or less. Thus, the difference in surface state between the polymer particles is small, , The dispersion uniformity in the binder is excellent. Particularly, as described above, the polymer particles having the above-mentioned structure have a content of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles of 2.0 x 10 < ^-3 > g / m & It is possible to form a uniform dispersion state in a mixture of a high SP value organic solvent and a binder and to have excellent dispersion uniformity without deviation in dispersion into a high SP value organic solvent. When a resin composition obtained by dispersing the above polymer particles in a binder (particularly, in a mixture of a high SP value organic solvent and a binder) is coated on a film substrate, the polymer particles in the resin composition are uniformly dispersed Is kept substantially stable in the process of forming the coating film by the coating, and excessive aggregation of the polymer particles at the time of coating is suppressed. As a result, the polymer particles spread without deviating on the film substrate, so that optical properties such as uniform light diffusing property and anti-scattering property can be imparted to the entire coated film formed by the coating.

The polymer particles having the above-mentioned constitution have a coefficient of variation of particle diameter of 15.0% or less. Therefore, when polymer particles are used for optical members such as an antiglare film and a light diffusion film, optical properties The characteristics can be improved.

The optical film of the present invention is characterized in that the resin composition for coating comprising the polymer particles of the present invention and a binder is coated on a film substrate.

Since the optical film of the present invention is formed by coating a substrate with a resin composition for coating comprising the polymer particles of the present invention having excellent dispersibility and uniformity of dispersion, Optical properties such as diffusibility and flicker are obtained.

The production method of the polymer particles includes a polymerization step and, if necessary, includes a solid-liquid separation step, a washing step, a drying step and a classification step. The processes that can make a difference in the uniformity of the amount of the residual components on the surface of the polymer particles and the uniformity of the surface state caused thereby are the solid-liquid separation process and the cleaning process. When these processes become unstable, (Such as surfactants having surplus polyoxyethylene chains that do not contribute to the modification of the surface of the polymer particles and other surfactants to be used as needed) in the active agent and polymer dispersion stabilizers and the like which are used as needed are adversely affected And there is a deviation in the amount of residual components on the surface of the polymer particles. The present inventors have found that by adjusting the amount of the medium passing through the filter medium in the solid-liquid separation step and the cleaning step and the amount of the cleaning liquid in the cleaning step within a predetermined range, the dispersion uniformity is excellent, And that the polymer particles having improved dispersibility can be prepared by modifying the surface with a surfactant having an oxyethylene chain. The present invention has been accomplished on the basis of these findings.

The method for producing a polymer particle of the present invention is a method for polymerizing a vinyl monomer in the presence of a surfactant containing a surfactant having a polyoxyethylene chain in a liquid medium to obtain a polymer comprising the polyoxyethylene chain- A method for producing a crude product, comprising: a polymerization step of obtaining a crude product containing particles and the medium; feeding the crude product into a filter, passing the medium contained in the charged crude product through a filter medium of the filter, Liquid separating step of retaining the polymer particles contained in the filter medium on the filter medium; feeding the cleaning liquid into the filter holding the polymer particles on the filter medium, bringing the cleaning liquid into contact with the polymer particles, By passing the polymer particles washed with the cleaning liquid through the filter medium, In comprises a washing step of obtaining on the filter material, and the solid-liquid separation step, to the amount per unit time of the medium which has passed through the filter medium the condition (1);

X? 5.50 x A ... (One)

(In the formula (1), X represents the amount (kg / min) of the medium passing through the filter medium per unit time and A represents the area (m 2) of the interface between the filter medium and the object to be inspected) In the cleaning step, the amount of the cleaning liquid that has passed through the filter material per unit time satisfies the following conditional expression (2);

2.50 x A? Y? 8.50 x A ... (2)

(In the formula (2), Y represents the amount (kg / min) of the cleaning liquid passing through the filter medium per unit time and A represents the area (m 2) of the interface between the filter medium and the object to be inspected) In the washing step, a washing liquid having a weight of not less than 9 times and not more than 18 times the weight of the polymer particles held on the filter medium is used.

In the above production method, the amount of the medium passing through the filter medium in the solid-liquid separation step satisfies the conditional expression (1) and the amount per unit time of the cleaning liquid passing through the filter medium satisfies the conditional expression (2) And in that the cleaning process uses a cleaning liquid having a weight of not less than 9 times and not more than 18 times the weight of the polymer particles retained on the filter medium, it is preferable to use a cleaning liquid having a polyoxyethylene chain adhered to the polymer particles A surfactant containing no surfactant (which does not contribute to the modification of the surface of the polymer particles) is dissolved in an appropriate amount (amount of surfactant having excess polyoxyethylene chain which does not contribute to the modification of the surface of the polymer particles) Can be removed. In addition, when polymerization is carried out in the presence of a surfactant containing both a polyoxyethylene chain-containing surfactant and another surfactant, most of the other surfactant can be sufficiently removed together with the medium and the cleaning liquid. As a result, it was found that the content (residual amount) of the polyoxyethylene chain-containing surfactant per unit surface area of the polymer particles was an appropriate amount (2.0 to 15.0 × 10 ^-3 g / m 2) (10.0 x 10 < ^-5 > g / m < 2 > or less) of the other surfactant in the dispersion medium (residual amount).

Further, in the case of producing polymer particles composed of at least one of (meth) acrylic polymer, styrene polymer and (meth) acryl-styrene copolymer by the above-mentioned production method, the other surfactant is almost removed by washing (The content of other surfactant per unit surface area of the polymer particles is not more than 10.0 x 10 < ^-5 > g / m < 2 >). On the other hand, the surfactant having a polyoxyethylene chain is hardly removed by washing, (The surface of the polymer particles is covered) on the surface of the polymer particles at a level of 2.0 to 15.0 x 10 < ^-3 > g / m < 2 > This is because the polyoxyethylene chain of the surfactant having a polyoxyethylene chain has an SP value of about 14.3 to 19.4 (MPa) ^1/2 (7.0 to 9.0 (cal / cm3) ^1/2 ) (About 14.3 to 19.4 (MPa) ^1/2 (7.0 to 9.0 (cal / cm < 3 >) ^1/2 ) of the styrene-based polymer and the (meth) acryl- Is strong, and it is presumed that it is difficult to remove in water or hot water.

According to the present invention, it is possible to provide polymer particles having excellent dispersibility and dispersion uniformity, a method for producing the same, and an optical film using the polymer particles.

Fig. 1 is a schematic view showing a schematic configuration of a pressure filter usable in an embodiment of the present invention, wherein Fig. 1 (a) is a schematic sectional view of the pressure filter, Fig. 1 (b) is a schematic top view showing the inside of a pressure- to be.
Fig. 2 is a SEM (scanning electron microscope) image of the polymer particles obtained in Example 1. Fig.
3 is a view showing an SEM image of the polymer particles obtained after the solid-liquid separation step and the washing step of Example 1. Fig.

Hereinafter, the present invention will be described in detail.

[Polymer particle]

The polymer particle of the present invention is a polymer particle containing a surfactant having a polyoxyethylene chain, wherein the coefficient of variation of the particle diameter is 15.0% or less, and the surface of the polymer particle having the polyoxyethylene chain is the content of the active agent 2.0~15.0 × 10 ^-3 g / ㎡, and the content of other surfactants in the unit surface area of said polymer particles 10.0 × 10 ^-5 g / ㎡ below.

As described above, the polymer particles having the above-mentioned constitution can improve the dispersibility into a high SP value organic solvent without containing hydrophilic sites derived from monomers having a high hydrophilicity in the composition of the polymer constituting the polymer particles. Further, as described above, since the polymer particles having the above-mentioned constitution have a small difference in the surface state between the polymer particles, when the binder is used in combination with a binder (particularly, a mixture of a high SP value organic solvent and a binder) (In particular, in a mixture of a high SP value organic solvent and a binder). Further, the polymer particles having the above-mentioned constitution are excellent in quality stability because the difference in the surface state of the polymer particles with time or the difference in the surface state between the lot of the polymer particles is small. As a result, when the polymer particles having the above-described constitution are dispersed in a binder and used as a resin composition, the difference in dispersion state between the lot of the resin composition is small and the dispersion stability is excellent.

To the polymer particles having the above-mentioned composition, 15.0 g of water was added to 5.0 g of the polymer particles, and dispersion treatment was carried out for 60 minutes using an ultrasonic cleaner to disperse the polymer particles in water. The polymer particles were put into a centrifugal tube having an inner diameter of 24 mm and centrifuged (The emulsion polymerization product) when the polymer particles were prepared by seed polymerization, and the non-volatile components in the supernatant when the supernatant was recovered after centrifugation under the condition of K factor 6943 and the rotation time of 30 minutes using the above- Is preferably less than 1.0 wt%, more preferably less than 0.5 wt%, and even more preferably less than 0.3 wt%. This can reduce the difference in amounts of byproducts (emulsion polymerization products) present on the surface of the polymer particles, and therefore, polymer particles are mixed with a binder (particularly, a mixture of a high SP value organic solvent and a binder) , It is possible to further improve the dispersion uniformity of the polymer particles (particularly in the mixture of the high SP value organic solvent and the binder) in the binder.

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 x 10 < ^-3 > g / m < 2 >. This makes it possible to further improve the dispersibility of the polymer particles with respect to the high SP value organic solvent. The content of the polyoxyethylene chain-containing surfactant per unit surface area of the polymer particles is more preferably 4.0 to 15.0 x 10 < ^-3 > g / m < 2 >. As a result, 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 x ^10-5 g / m2 or less, still more preferably 5.0 x ^10-5 g / m2 or less, more preferably 3.0 x ^10-5 g / M < 2 > As a result, 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. As a result, the dispersion uniformity of the polymer particles can be further improved.

The content of the polyoxyethylene chain-containing surfactant and other surfactants in the polymer particles can be determined by measuring the content of the polyoxyalkylene group in the polymer particles measured by, for example, liquid chromatography mass spectrometry (LC-MS-MS) By dividing the content of the ethylene chain-containing surfactant and the other surfactant by the specific surface area of the polymer particles measured by the BET method (nitrogen adsorption method), respectively.

The surfactant contained in the polymer particles of the present invention remains the surfactant used in the production of the polymer particles. Therefore, examples of the surfactant include all surfactants commonly used in the production of polymer particles, for example, anionic surfactants having a polyoxyethylene chain as described in the section [Process for the production of polymer particles] described later, A nonionic surfactant having a polyoxyethylene chain, a cationic surfactant having a polyoxyethylene chain, and a amphoteric surfactant having a polyoxyethylene chain. In addition, 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 an anionic surfactant. When the polymer particles of the present invention contain an anionic surfactant, dispersion stability during the polymerization reaction can be ensured. On the other hand, when the surfactant contained in the polymer particles of the present invention is only a nonionic surfactant, only a nonionic surfactant is present in the polymerization reaction, and significant aggregation may occur during the polymerization reaction.

The surfactant having a polyoxyethylene chain contained in the polymer particles of the present invention preferably contains at least one of an anionic surfactant having a polyoxyethylene chain and a nonionic surfactant having a polyoxyethylene chain, It is more preferable to include 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 secured. On the other hand, when the polyoxyethylene chain-containing surfactant contained in the polymer particles of the present invention is only a nonionic surfactant having a polyoxyethylene chain, the surfactant having a polyoxyethylene chain present in the polymerization reaction is preferably polyoxy Only a nonionic surfactant having an ethylene 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 polymer of a vinyl-based monomer. Examples of the vinyl monomer include a monofunctional vinyl monomer having one ethylenic unsaturated group and a polyfunctional vinyl monomer having two or more ethylenic unsaturated groups.

Examples of the monofunctional vinyl-based monomer include (meth) acrylic acid ester-based monomers; Styrene-based monomers (aromatic vinyl-based monomers); Saturated vinyl monomers such as vinyl acetate, vinyl propionate and vinyl versatate; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; Ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid and fumaric acid; Ethylenically unsaturated carboxylic acid anhydrides such as maleic anhydride; Ethylenically unsaturated dicarboxylic acid monoalkyl esters such as monobutyl maleic acid; Ethylenically unsaturated carboxylic acid salts such as an ammonium salt or an alkali metal salt of the ethylenically unsaturated carboxylic acid or the ethylenically unsaturated dicarboxylic acid monoalkyl ester; Ethylenically unsaturated carboxylic acid amides such as acrylamide, methacrylamide and diacetone acrylamide; Methylol acrylamide, N-methylol acrylamide, N-methylol methacrylamide, methylol diacetone acrylamide, and ether of these monomers and alcohols having 1 to 8 carbon atoms (for example, N-isobutoxymethyl acrylamide) And ethylenically unsaturated carboxylic acid amides such as methylol compounds and derivatives thereof.

Examples of the (meth) acrylate monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, stearyl acrylate An acrylic acid alkyl-based monomer; Methacrylic acid alkyl monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate; (Meth) acrylic acid esters having an epoxy group (glycidyl group) such as glycidyl acrylate and glycidyl methacrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl acrylate; (Meth) acrylic acid esters having an amino group such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate. The (meth) acrylic acid ester-based monomer preferably includes at least one of an acrylic acid alkyl-based monomer and an alkyl methacrylate-based monomer. In the present specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acryl" means acryl or methacryl.

Examples of the styrene-based monomer include styrene,? -Methylstyrene, vinyltoluene, and ethylvinylbenzene.

Examples of the polyfunctional vinyl monomer include allyl (meth) acrylate, divinylbenzene, diallyl phthalate, triallyl cyanurate, ethylene glycol di (meth) acrylate, diethylene glycol di Propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like.

These vinyl monomers may be used singly 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. As a result, polymer particles having high light transmittance can be realized. The (meth) acrylic polymer is a copolymer of a (meth) acrylic acid ester monomer or a (meth) acrylic acid ester monomer with a vinyl monomer other than a (meth) acrylic ester monomer and a styrene monomer. The styrene-based polymer is a copolymer of a styrene-based monomer, or a styrene-based monomer, a (meth) acrylate-based monomer, and a vinyl-based monomer other than a styrene-based monomer. The (meth) acrylic-styrenic copolymer may be a copolymer of a (meth) acrylic acid ester monomer and a styrene monomer, or a copolymer of a (meth) acrylic ester monomer, a styrene monomer, And a vinyl-based monomer other than the styrene-based monomer. Among these, the polymer particles are preferably composed of a (meth) acryl-styrene-based copolymer from the viewpoints of light diffusing property and dispersibility.

The polymer constituting the polymer particles is preferably a copolymer (cross-linked polymer) of the monofunctional vinyl-based monomer and the polyfunctional vinyl-based monomer. Therefore, the polymer constituting the polymer particles is particularly preferably a (meth) acryl-styrene crosslinking copolymer in view of light diffusing property and dispersibility. For example, the amount of the constituent unit derived from the polyfunctional vinyl monomer in the polymer is preferably in the range of 5 to 50% by weight based on 100% by weight of the polymer. When the amount of the structural unit derived from the polyfunctional vinyl monomer is less than the above range, the degree of crosslinking of the polymer is lowered. As a result, when the polymer particles are mixed with a binder to be coated as a resin composition, the polymer particles swell and the viscosity of the resin composition increases, which may lower the workability of the coating. In addition, as a result of lowering the degree of crosslinking of the polymer, polymer particles are liable to be dissolved or deformed when heat is applied to the polymer particles during mixing or molding in an application (so-called mixed use) in which polymer particles are mixed with a binder. When the amount of the structural unit derived from the polyfunctional vinyl monomer is larger than the above range, improvement in the effect corresponding to the usage amount of the polyfunctional vinyl monomer is not confirmed, and the production cost may increase.

The gel fraction of the polymer particles of the present invention is preferably 90% or more, more preferably 97% or more. When the gel fraction is less than 90%, sufficient solvent resistance can not be ensured. For example, polymer particles are mixed with an organic solvent together with a binder and coated on a film substrate to form an optical film such as an antiglare film or a light diffusion film There is a possibility that the polymer particles are dissolved in the organic solvent and optical properties such as light diffusibility and flicker resistance are not sufficiently obtained. In the present specification, the gel fraction refers to, for example, the gel fraction measured according to the method described in the embodiment.

The refractive index of the polymer particles of the present invention is preferably from 1.490 to 1.600. This makes it possible to realize an optical member having good optical properties (for example, light transmittance, scattering properties, light diffusibility, etc.) when the polymer particles are used in optical members such as an antiglare film and a light diffusion film have. Polymer particles prepared by adding a monomer having a high hydrophilicity to a monomer having a high refractive index of a homopolymer (for example, a styrenic monomer) are generally used in such a manner that a monomer having a high hydrophilicity generally has a low refractive index of the homopolymer (for example, Hereinafter), the refractive index is low as compared with the polymer particles prepared without adding the monomer having high hydrophilicity. For this reason, it is difficult to realize polymer particles having a refractive index of 1.570 to 1.600 in such a polymer particle. On the other hand, since the polymer particles of the present invention do not require the addition of a monomer having a high hydrophilicity, 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 占 퐉, more preferably 1 to 30 占 퐉. Therefore, when polymer particles are used for an optical member such as an antiglare film or a light diffusion film, it is possible to improve the optical characteristics such as the retardation and optical diffusibility of the optical member. Also, in this specification, the volume average particle diameter of the polymer particles indicates the arithmetic mean of the particle size distribution based on the volume, which is measured by the Coulter method, for example, the method described in the embodiment 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. The polymer particles are preferably obtained by absorbing a vinyl monomer into a seed particle, It is more preferable to be obtained by polymerizing (i. E., Subjecting to seed polymerization) in the presence of a surfactant containing a surfactant having a polyoxyethylene chain. Polymer particles obtained by the seed polymerization have a small variation in particle diameter. Therefore, when used in an optical member such as an antiglare film or a light diffusion film, the polymer particles can improve the optical characteristics such as the light- have.

[Method for producing polymer particles]

The polymer particles of the present invention can be produced by the production method of the present invention.

The method for producing a polymer particle of the present invention is a method for polymerizing a vinyl monomer in the presence of a surfactant containing a surfactant having a polyoxyethylene chain in a liquid medium and polymerizing the polymer containing the surfactant having the polyoxyethylene chain A method for producing a crude product, comprising: a polymerization step of obtaining a crude product containing particles and the medium; feeding the crude product into a filter, passing the medium contained in the crude product into a filter medium of the filter, Liquid separating step of retaining the polymer particles on the filter material, and a step of supplying the cleaning liquid to the filter holding the polymer particles on the filter material, bringing the cleaning liquid into contact with the polymer particles, By passing the cleaning liquid through the filter medium, the polymer particles washed with the cleaning liquid And a cleaning step obtained on the filter material. The production method of the present invention is preferable as a method for producing the above-mentioned polymer particles of the present invention.

Each step of the production method of the present invention will be described in detail below.

[Polymerization Process]

In the polymerization step, the vinyl monomer is polymerized in the presence of a surfactant containing a polyoxyethylene chain-containing surfactant in a liquid medium, and the polymer particles containing the polyoxyethylene chain-containing surfactant and the medium ≪ / RTI >

The liquid medium (the medium included in the crude product) is preferably an aqueous medium, for example, water; Lower alcohols (alcohols having 5 or less carbon atoms) such as methyl alcohol, ethyl alcohol and the like; A mixture of water and a lower alcohol, and the like.

Further, in the polymerization step, the surfactant stabilizes the dispersion of the vinyl monomer in the liquid medium. Examples of 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 a polyoxyethylene chain Can be used. In the polymerization step, however, it is possible to more stably ensure dispersion of the vinyl monomer in the liquid medium and to obtain polymer particles having uniform particle diameters It is preferable to use at least one of an anionic surfactant having a polyoxyethylene chain and a nonionic surfactant having a polyoxyethylene chain. As the surfactant having the polyoxyethylene chain, it is more preferable to use at least an anionic surfactant having a polyoxyethylene chain. As a result, the dispersion stability during the polymerization reaction can be secured. On the other hand, when only a nonionic surfactant having a polyoxyethylene chain is used as the surfactant having a polyoxyethylene chain, significant aggregation may occur during the polymerization reaction.

As the anionic surfactant having a polyoxyethylene chain, any of known anionic surfactants such as a fatty acid salt type, a sulfuric acid ester salt type, a sulfonic acid salt type, a phosphoric acid ester salt type and a phosphoric acid ester type can be used. Polyoxyethylene alkyl phenyl ether sulfuric acid ester salts; Polyoxyethylene alkyl ether sulfate such as polyoxyethylene lauryl ether sodium sulfate; Polyoxyethylene alkyl sulfate ester; Polyoxyethylene styrenated phenyl ether sulfuric acid ester salts such as polyoxyethylene styrenated phenyl ether sulfuric acid ester ammonium; Polyoxyethylene alkylphenyl ether phosphates such as polyoxyethylene nonylphenyl ether phosphate (for example, sodium polyoxyethylene nonylphenyl ether phosphate); Polyoxyethylene styrenated phenyl ether phosphate esters; And polyoxyethylene alkyl ether phosphate esters. These anionic surfactants having polyoxyethylene chains may be used singly or in combination of two or more.

As the nonionic surfactant having a polyoxyethylene chain, any of known nonionic surfactants such as ester type, ether type, ester and ether type can be used, and examples thereof include polyoxyethylene tridecyl ether Polyoxyethylene alkylphenyl ethers such as polyoxyethylene alkylphenyl ethers and polyoxyethylene octylphenyl ethers, polyoxyethylene styrenated phenyl ethers, polyoxyethylene fatty acid esters, and polyoxyethylene sorbitan monolaurate Sorbitan fatty acid esters, polyoxyethylene alkylamines, oxyethylene-oxypropylene block polymers, and the like. These nonionic surfactants having a polyoxyethylene chain may be used singly or in combination of two or more.

The polyoxyethylene chain surfactant may be used singly or in combination of two or more. The surfactant having a polyoxyethylene chain preferably has a solubility in water of 25 ° C at a liquid temperature of 0.3 g / 100 ml to 5.0 g / 100 ml, more preferably 0.5 g / 100 ml to 3.0 g / 100 ml Is more preferable. When the surfactant having a polyoxyethylene chain with a solubility of less than 0.3 g / 100 ml is used, in the polymerization process, when the liquid medium is an aqueous medium, the vinyl monomer is stably dispersed In addition, it is difficult to elute the surfactant with respect to water. Therefore, a large amount of cleaning liquid is required in the later-described cleaning step for cleaning the polymer particles, which is not preferable from the viewpoint of productivity. On the other hand, the surfactant having a polyoxyethylene chain having a solubility of more than 5.0 g / 100 ml has insufficient effect of a short period of time and lacks the effect of stabilizing the dispersion of the vinyl monomer in an aqueous medium. When a surfactant having an ethylene chain is used, in the case where the liquid medium is an aqueous medium in the polymerization step, since the dispersion of the vinyl monomer in the aqueous medium is stabilized, a large amount of polyoxyethylene chain- And this is not preferable from the viewpoint of productivity.

The surfactant may include another surfactant (a surfactant other than a surfactant having a polyoxyethylene chain, that is, a surfactant having no polyoxyethylene chain). Examples of the other surfactants include anionic surfactants having no polyoxyethylene chain, cationic surfactants having no polyoxyethylene chain, nonionic surfactants having no polyoxyethylene chain, and surfactants having no polyoxyethylene chain Both of the ionic surfactants can be used. However, in the polymerization step, it is possible to stably disperse the vinyl-based monomer in the liquid medium and to obtain polymer particles having uniform particle diameters 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. As a result, the dispersion stability during the polymerization reaction can be secured. On the other hand, when only the nonionic surfactant is used as the surfactant, significant aggregation may occur during the polymerization reaction.

As the anionic surfactant having no polyoxyethylene chain, any of known anionic surfactants such as a fatty acid salt type, a sulfuric acid ester salt type, a sulfonic acid salt type, and a phosphoric acid ester salt type can be used, and examples thereof include sodium oleate, Fatty acid soap such as castor oil potassium soap; Alkyl sulfuric acid ester salts such as lauryl sulfate (for example, sodium lauryl sulfate, ammonium lauryl sulfate and the like); Alkylbenzene sulfonic acid salts such as sodium dodecylbenzenesulfonate; Dialkylsulfosuccinates such as alkylnaphthalenesulfonate, alkanesulfonate, di (2-ethylhexyl) sulfosuccinate (sodium salt) and dioctylsulfosuccinate (sodium salt); Alkenylsuccinates (dipotassium salts); Alkyl phosphoric acid ester salts; Naphthalenesulfonic acid formalin condensate, and the like. These anionic surfactants having no polyoxyethylene chain may be used singly or in combination of two or more.

As the nonionic surfactant having no polyoxyethylene chain, any of known nonionic surfactants such as ester type, ether type, ester and ether type can be used. For example, when the number of carbon atoms of the alkylene group is 3 And polyoxyalkylene tridecyl ether, sorbitan fatty acid esters, and glycerin fatty acid esters. These nonionic surfactants having no polyoxyethylene chain may be used singly or in combination of two or more.

As the cationic surfactant having no polyoxyethylene chain, any of known cationic surfactants such as an amine salt type and a quaternary ammonium salt type can be used, but a water-soluble cationic surfactant can be used in view of its handling It is advantageous. Specific examples of the cationic surfactant having no polyoxyethylene chain include alkylamine salts such as laurylamine acetate and stearylamine acetate; Alkyl trimethyl ammonium chlorides such as lauryl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, cocoyl trimethyl ammonium chloride, and dodecyl trimethyl ammonium chloride; Hexyldimethylbenzylammonium chloride, hexadecyldimethylbenzylammonium chloride, and lauryldimethylbenzylammonium chloride; and the like. These cationic surfactants having no polyoxyethylene chain may be used singly or in combination of two or more.

Examples of the amphoteric surfactant having no polyoxyethylene chain include lauryldimethylamine oxide, phosphate ester surfactant, phosphorous ester surfactant, and the like. These amphoteric surfactants having no polyoxyethylene chain may be used singly or in combination of two or more.

The surfactant having no polyoxyethylene chain may be used singly or in combination of two or more. The surfactant having no polyoxyethylene chain preferably has a solubility of 0.3 g / 100 ml or more to 15.0 g / 100 ml, more preferably 0.5 g / 100 ml to 5.0 g / 100 ml, Ml. When a surfactant having no polyoxyethylene chain having a solubility of less than 0.3 g / 100 ml is used, in the case where the liquid medium is an aqueous medium in the polymerization step, the vinyl monomer is not stably dispersed in the aqueous medium In addition, it is difficult to elute the surfactant with respect to water. Therefore, a large amount of cleaning liquid is required in the later-described cleaning step for cleaning the polymer particles, which is not preferable from the viewpoint of productivity. On the other hand, a surfactant having no polyoxyethylene chain with a solubility of more than 15.0 g / 100 ml has insufficient effect of hydrophobic groups and lacks the effect of stabilizing the dispersion of vinyl monomers in an aqueous medium. When a surfactant having no polyoxyethylene chain is used, in the case where the liquid medium is an aqueous medium in the polymerization step, since the dispersion of the vinyl monomer in the aqueous medium is stabilized, a large amount of polyoxyethylene chain It is not preferable from the viewpoint of productivity.

The amount of the surfactant used in the polymerization of the vinyl monomer (in the case where only an anionic surfactant having no polyoxyethylene chain is used as the surfactant, the amount of the anionic surfactant having no polyoxyethylene chain, The sum of the amount of the anionic surfactant not having a polyoxyethylene chain and the amount of the other surfactant used when an anionic surfactant other than the polyoxyethylene chain is used) Is preferably in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the resin. If the amount of the surfactant used is less than the above range, the polymerization stability may be lowered. Further, when the amount of the surfactant used is larger than the above range, it is costly and uneconomical.

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, and examples thereof include seed polymerization, emulsion polymerization and suspension polymerization. Seed polymerization is most preferable in that the deviation of the particle diameters of the polymer particles obtained in these polymerization methods is the smallest.

The emulsion polymerization is a polymerization method in which a liquid phase medium, a vinyl monomer which is difficult to dissolve in the medium, and a surfactant (emulsifier) are mixed and a polymerization initiator soluble in the medium is added thereto to effect polymerization. The emulsion polymerization is characterized in that the deviation of the particle diameter of the obtained polymer particles is small. The suspension polymerization is a polymerization method in which a vinyl monomer is mechanically stirred with an aqueous medium such as water, and the vinyl monomer is suspended in an aqueous medium to polymerize. The suspension polymerization is characterized in that polymer particles having a small particle diameter and relatively uniform particle diameter can be obtained.

The seed polymerization is a method of introducing species (seed) particles made of a polymer of a vinyl-based monomer separately prepared to initiate polymerization of the vinyl-based monomer. More specifically, the seed polymerization is a method in which polymer particles composed of a polymer of a vinyl-based monomer are used as seed particles, a vinyl monomer is absorbed in the seed particles in an aqueous medium, and the vinyl monomer is polymerized in the seed particle to be. In this method, polymer particles having a particle diameter larger than that of the original seed particles can be obtained by growing the seed particles. As described above, the polymerization method of the vinyl monomer is most preferably the seed polymerization. Therefore, in the production method of the present invention, the polymerization step is preferably carried out in the presence of a surfactant having a seed particle and a polyoxyethylene chain In the presence of a surfactant containing a polyoxyethylene chain, thereby obtaining a polymer particle including the polyoxyethylene chain-containing surfactant and a crude product containing the medium.

The general method of seed polymerization is described below, but the polymerization method in the production method of the present invention is not limited to this method.

In the seed polymerization, the seed particles are first added to an emulsion (suspension) containing a surfactant containing a vinyl monomer and a surfactant having an aqueous medium and a polyoxyethylene chain. The emulsion can be prepared by a known method. For example, a surfactant containing a surfactant having a vinyl monomer and a polyoxyethylene chain is added to an aqueous medium and dispersed by a micro emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer (registered trademark) Can be obtained. As the aqueous medium, water or a mixture of water and an organic solvent (for example, a lower alcohol (an alcohol having 5 or less carbon atoms)) may 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 based on 100 parts by weight of the vinyl monomer. If the amount of the surfactant used is less than the above range, the polymerization stability may be lowered. Further, when the amount of the surfactant used is larger than the above range, it is costly and uneconomical.

The seed particles may be added to the emulsion as it is, or may be added to the emulsion in the form dispersed in an aqueous medium. After the seed particles are added to the emulsion, the vinyl monomer is absorbed into the seed particles. This absorption can be usually carried out by stirring the emulsion at room temperature (about 20 ° C) for 1 to 12 hours. Further, in order to accelerate the absorption of the vinyl monomer to the seed particles, the emulsion may be heated to about 30 to 50 캜.

The seed particles swell by absorbing the vinyl-based monomer. The mixing ratio of the vinyl monomer and the seed particle is preferably in the range of 5 to 300 parts by weight, more preferably in the range of 50 to 250 parts by weight, based on 1 part by weight of the seed particles. If the mixing ratio of the vinyl monomer is smaller than the above range, the increase of the particle diameter due to polymerization becomes small, and the production efficiency is lowered. On the other hand, if the mixing ratio of the vinyl monomer is larger than the above range, the vinyl monomer may not be completely absorbed by the seed particles, and suspension polymerization may be carried out independently in the aqueous medium to produce polymer particles having an abnormal particle size. The completion of the absorption of the vinyl monomer to the seed particles can be judged by confirming the enlargement of the particle diameter by observation of the optical microscope.

Subsequently, the vinyl monomer absorbed in the seed particles is polymerized to obtain polymer particles. Further, the polymer particles may be obtained by repeating the step of polymerizing the vinyl monomer by absorbing it into the seed particles several times.

If necessary, a polymerization initiator may be added to the vinyl monomer. The polymerization initiator may be prepared by mixing the polymerization initiator with the vinyl monomer, and then dispersing the resulting mixture in an aqueous medium. Alternatively, both of the polymerization initiator and the vinyl monomer may be separately dispersed in an aqueous medium. It is preferable that the particle diameter of the droplets of the vinyl monomer present in the obtained emulsion is smaller than the particle diameter of the seed particles because the vinyl monomer is efficiently absorbed to the seed particles.

Examples of the polymerization initiator include, but are not limited to, benzoyl peroxide, lauroyl peroxide, o-chloro benzoyl peroxide, o-methoxy benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t Organic peroxides such as butyl peroxy-2-ethylhexanoate and di-tert-butyl peroxide; (2,4-dimethylvaleronitrile), 2,2'-azobis (2,3-dimethylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'- Azobis (2-methylbutyronitrile), 2,2'-azobis (2,3,3-trimethylbutyronitrile), 2,2'-azobis (2-isopropylbutyronitrile) Azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), (2-carbamoyl azo) iso Azo compounds such as butyronitrile, 4,4'-azobis (4-cyanovaleric acid), and dimethyl-2,2'-azobisisobutylate. The polymerization initiator is preferably used in a range of 0.1 to 1.0 part by weight based on 100 parts by weight of the vinyl monomer.

The polymerization temperature of the seed polymerization can be appropriately selected depending on the kind of the vinyl-based monomer and the kind of the polymerization initiator to be used, if necessary. The polymerization temperature of the seed polymerization is preferably 25 to 110 캜, more preferably 50 to 100 캜. The polymerization time of the seed polymerization is preferably 1 to 12 hours. The polymerization reaction of the seed polymerization may be carried out in an atmosphere of an inert gas (for example, nitrogen) inert to polymerization. The polymerization reaction of the seed polymerization is preferably carried out after the vinyl monomer and, if necessary, the polymerization initiator to be used are completely absorbed by the seed particles.

In the seed polymerization, in order to improve the dispersion stability of the polymer particles, a polymer dispersion stabilizer may be added to the polymerization reaction system. Examples of the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, cellulose (hydroxyethylcellulose, carboxymethylcellulose, etc.), and polyvinylpyrrolidone. The polymer dispersion stabilizer may be used in combination with an inorganic water-soluble polymeric compound such as sodium tripolyphosphate. Of these polymer dispersion stabilizers, polyvinyl alcohol and polyvinyl pyrrolidone are preferable. The addition amount of the polymer dispersion stabilizer is preferably within a range of 1 to 10 parts by weight based on 100 parts by weight of the vinyl monomer.

In order to suppress the generation of emulsion polymerization products (polymer particles having excessively small particle diameters) in the aqueous medium in the polymerization reaction, nitrite salts such as sodium nitrite, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin B A water-soluble polymerization inhibitor such as citric acid, polyphenols or the like may be added to an aqueous medium. The addition amount of the polymerization inhibitor is preferably in the range of 0.02 to 0.2 parts by weight based on 100 parts by weight of the vinyl monomer.

The polymerization method for polymerizing the vinyl monomer to obtain the seed particles is not particularly limited, and examples thereof include dispersion polymerization, emulsion polymerization, soap-free emulsion polymerization (emulsion polymerization without using a surfactant as an emulsifier), seed polymerization, . In order to obtain polymer particles having an approximately uniform particle diameter by seed polymerization, it is first necessary to use the seed particles having substantially uniform particle diameters to grow these seed particles approximately constantly. The seed particles having a substantially uniform particle diameter serving as a raw material can be produced by polymerizing a vinyl-based monomer by a polymerization method such as soap-free emulsion polymerization (emulsion polymerization without using a surfactant) and dispersion polymerization. Therefore, emulsion polymerization, soap-free emulsion polymerization, seed polymerization and dispersion polymerization are preferable as the polymerization method for obtaining the seed particles by polymerizing the vinyl monomer.

Also in the polymerization for obtaining the seed particles, a polymerization initiator is used if necessary. Examples of the polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate; Benzoyl peroxide, lauroyl peroxide, o-chloro benzoyl peroxide, o-methoxy benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, di- Organic peroxides such as butyl peroxide; Azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, and 2,2'-azobis (2,4-dimethylvaleronitrile). have. The amount of the polymerization initiator used is preferably in the range of 0.1 to 3 parts by weight based on 100 parts by weight of the vinyl monomer used for obtaining the seed particles. By adjusting the amount of the polymerization initiator used, the weight average molecular weight of the obtained seed particles can be adjusted.

In the polymerization for obtaining the seed particles, a molecular weight adjuster may be used to adjust the weight average molecular weight of the obtained seed particles. Examples of the molecular weight adjusting agent include mercaptans such as n-octyl mercaptan and tert-dodecyl mercaptan; ? -methylstyrene dimer; terpenes such as? -terpinene and dipentene; And halogenated hydrocarbons such as chloroform and carbon tetrachloride. The weight average molecular weight of the obtained seed particles can be adjusted by adjusting the amount of the molecular weight adjuster used.

[Solid-liquid separation process]

In the solid-liquid separation step, the crude product is introduced into a filter, the medium contained in the crude product is passed through the filter medium of the filter, and the polymer particles contained in the crude product are retained on the filter medium.

In the solid-liquid separation step, the amount of the medium passing through the filter medium per unit time satisfies the following condition (1):

X? 5.50 x A ... (One)

(In the formula (1), X represents the amount (kg / min) of the medium that has passed through the filter medium per unit time, and A represents the area (m 2) of the interface between the filter medium and the object.

By controlling the amount of the medium per unit time passed through the filter medium to satisfy the conditional expression (1) in the solid-liquid separation step, by-products (emulsion polymerization product) generated during the polymerization reaction included in the crude product together with the medium, , Surfactants having surplus polyoxyethylene chains which do not contribute to the modification of the surface of the polymer particles among the surfactants having a polyoxyethylene chain which is used if necessary, other surfactants to be used if necessary, polymers It is possible to remove unnecessary components such as a dispersion stabilizer and a polymerization additive (for example, a polymerization inhibitor) which is used if necessary, and the amount of the above-mentioned unnecessary components remaining in the polymer particles remaining on the filter medium (specifically, The amount of deposition on the surface of the substrate can be reduced.

In the solid-liquid separation step, the filter is not particularly limited. For example, the filtration vessel 2 includes a pressure-resistant vessel 2 having a cylindrical inner space as shown in Fig. 1, And a pressurized filter 1 having a pressurized gas supply device (not shown) for supplying a pressurized gas (an inert gas such as nitrogen, air, etc.) into the pressure resistant container. 1 (b)) of the cylindrical inner space of the pressure-resistant vessel 2 is larger than the area of the bottom surface of the filtration material 3 and the inclusion (the crude product P) And becomes approximately equal to the area of the interface.

In the solid-liquid separation step using the pressure filter 1, for example, the crude product P is introduced into the pressure-resistant vessel 2 of the pressure filter 1 in the form of a slurry solution, The compressed gas is supplied to the upper space S of the filter material 3 in the pressure-resistant container 2 by the compressed gas supply device after the crude product P is charged on the inner wall 3 of the pressure- The upper space S of the filter medium 3 is pressed. As a result, the crude product P is strongly pressed on the filter medium 3 to cause the liquid medium contained in the crude product P to pass through the filter medium 3, And is discharged outside. Then, a cake of polymer particles is left on the filter material 3.

The pressure-resistant container 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 it can collect polymer particles reliably. Examples of the filter medium 3 include a woven fabric such as woven fabric and nonwoven fabric made of natural fibers and synthetic fibers; A wire net made of a sintered metal; A nonwoven fabric made of a sintered metal; A filter plate (perforated plate) made of natural fiber, glass fiber or the like; Mesh made of synthetic resin: filter paper; A glass fiber filter, and the like.

In the solid-liquid separation step, the pressurizing condition when pressurizing the upper space S of the filter material 3 in the pressure-resistant container 2 by using the pressure filter 1 is a pressure satisfying the condition (1) , It is preferable to pressurize the pressure-resistant container 2 so that the internal pressure thereof is in the range of 0.01 MPa to 0.50 MPa. In the solid separation step, it is preferable that the internal pressure of the pressure-resistant vessel 2 is kept substantially constant so as to satisfy the above-mentioned conditional expression (1) from the start of the pressurization to the termination of the solid- The pressure in the pressure-resistant container 2 gradually decreases as the medium contained in the crude product P passes through the filter material 3 after the pressurization. Concretely, when the medium passing through the filter medium 3 is less or substantially gone, the compressed air pressure in the pressure-resistant vessel 2 is released from the bottom, and it becomes difficult to maintain the internal pressure of the pressure-resistant vessel 2 at the pressure at the time of pressure- , The pressure at the time of pressing is lowered.

In the solid-liquid separation step, when the amount of the medium contained in the crude product (P) charged into the filter (pressure filter (1)) (the total crude product obtained in the polymerization step is put in the filter, The medium contained in the crude product P is desirably removed by passing the medium in an amount of 70 wt% or more to the filter medium 3 with respect to 100 wt%. In the solid-liquid separation step, a medium having an amount of 70% by weight or more is passed through the filter material 3 to 100% by weight of the medium contained in the crude product (P) charged into the filter (pressure filter (1) , A by-product (an emulsion polymerization product) generated during the polymerization reaction attached to the surface of the polymer particles remaining on the filter medium 3, and a surfactant having a polyoxyethylene chain, if necessary, A surfactant having a polyoxyethylene chain, another surfactant to be used if necessary, a polymer dispersion stabilizer to be used if necessary, and a polymerization additive (for example, a polymerization inhibitor) It is possible to sufficiently remove the unnecessary components, so that the amount of the unnecessary components remaining in the polymer particles can be reduced. When the amount (emission amount) of the medium to be passed through the filter medium 3 in the solid-liquid separation step is less than 70% by weight based on 100% by weight of the medium contained in the crude product P, by- A surfactant having an excess polyoxyethylene chain which does not contribute to the modification of the surface of the polymer particles among the surfactants having a polyoxyethylene chain which is used if necessary and other surfactants to be used if necessary, There is a possibility that unnecessary components such as a polymer dispersion stabilizer to be used and a polymerization additive (for example, a polymerization inhibitor) to be used as needed can not be sufficiently removed.

For example, in the case of using the pressurized filter 1 as the filter in the solid-liquid separation step, the solid-liquid separation step is carried out in such a manner that the amount of the medium contained in the crude product P fed into the pressure filter 1 When all of the obtained crude products P are fed to the pressure filter 1, a medium in an amount of not less than 70% by weight is passed through the filter material 3 to 100% by weight of the amount of the medium used in the polymerization step, It is preferable to terminate when the internal pressure of the pressure-resistant container 2 becomes 2/3 or less of the pressure at the time of pressurization. As a result, the polymer particles remaining on the filter material 3 do not contribute to the modification of the surface of the polymer particles in the surfactant having a by-product (an emulsion polymerization product) generated during the polymerization reaction and a polyoxyethylene chain, A surfactant having a polyoxyethylene chain in excess, another surfactant to be used if necessary, a polymer dispersion stabilizer to be used if necessary, and a polymerization additive (for example, a polymerization inhibitor) The residual amount can be reliably reduced.

[Cleaning process]

In the cleaning step, the cleaning liquid is introduced into the filter holding the polymer particles on the filter material, the cleaning liquid is brought into contact with the polymer particles, and the cleaning liquid in contact with the polymer particles is passed through the filter material, Polymer particles are obtained on the filter medium.

In the cleaning step, the amount of the cleaning liquid that has passed through the filter medium per unit time satisfies the following conditional expression (2);

2.50 x A? Y? 8.50 x A ... (2)

(In the formula (2), Y represents the amount per unit time (kg / min) of the cleaning liquid that has passed through the filter medium, and A represents the area (m 2) of the interface between the filter medium and the object to be inspected). When the amount (Y) per unit time of the cleaning liquid that has passed through the filter medium is less than 2.50 x A, it takes a long time to perform the cleaning process, which may lower the productivity. When the amount (Y) per unit time of the cleaning liquid that has passed through the filter medium is more than 8.50 x A, since the contact time between the polymer particles and the cleaning liquid is short, by- products generated during the polymerization reaction A surfactant having an excess polyoxyethylene chain which does not contribute to the modification of the surface of the polymer particles among the surfactants having a polyoxyethylene chain which is used if necessary and other surfactants to be used if necessary, Unnecessary components such as a polymer dispersion stabilizer to be used and a polymerization additive (for example, a polymerization inhibitor) to be used as needed can not be sufficiently removed, and there is a possibility that a large amount of the above-mentioned unnecessary components remain in the finally obtained polymer particles .

The amount of the cleaning liquid that has passed through the filter medium in the cleaning step is expressed by the following expression (3) on an average from the start to the end of cleaning of the polymer particles by passing the cleaning liquid through the filter medium:

2.50 x A? Y? 8.50 x A ... (3)

(In the formula (3), Y represents the amount (kg / min) of the cleaning liquid that has passed through the filter material per unit time and A represents the area (m 2) of the interface between the filter material and the object to be inspected) desirable. When the amount of the cleaning liquid that has passed through the filter medium in the cleaning step satisfies condition (3) on the average, the amount of the byproducts (emulsion polymerization A surfactant having an excess polyoxyethylene chain which does not contribute to the modification of the surface of the polymer particles among the surfactants having a polyoxyethylene chain which is used if necessary and other surfactants to be used if necessary, (For example, a polymerization inhibitor) and the like can be sufficiently removed to reduce the amount of the above-mentioned unnecessary components remaining in the polymer particles.

For example, when the pressure filter 1 as shown in Fig. 1 is used in the solid-liquid separation step, the cake of the polymer particles remaining on the filter material 3 is retained on the filter material 3 as it is, The cake is brought into contact with the rinsing liquid by supplying the rinsing liquid to the container 2 and the compressed gas is supplied to the upper space S of the filter material 3 in the pressure-resistant container 2 by the compressed gas supplying device, Thereby pressing the space S. As a result, the cake is cleaned in contact with the cleaning liquid, and the cleaning liquid after cleaning is discharged as a filtrate out of the pressure-resistant container 2. [ After the cleaning liquid is supplied, the cleaning liquid supplied into the pressure-resistant vessel 2 may be slurried by mixing with the cake before the pressure is applied, using an agitator. Before supplying the cleaning liquid for cleaning, the cake may be repaired by using a stirrer. As a result, the short path of the cleaning liquid is eliminated, and efficient cleaning can be performed.

In the cleaning step, when the upper space S of the filter medium 3 in the pressure-resistant vessel 2 is pressurized by using the pressure filter 1, the pressurizing condition when the pressure satisfies condition (2) It is preferable to pressurize the pressure-resistant container 2 so that the internal pressure of the pressure-resistant container 2 is in the range of 0.01 MPa to 0.50 MPa. The upper space S of the filter medium 3 is preferably pressed at a rate of 0.01 to 0.30 MPa / min. In the cleaning process, it is preferable that the internal pressure of the pressure-resistant container 2 is kept substantially constant so as to satisfy the conditional expression (2) from the start of the pressure application to the end of the cleaning process. However, The pressure in the pressure-resistant container 2 gradually decreases as the cleaning liquid that has been input into the pressure-resistant container 2 passes through the filter material 3. [ Specifically, when the amount of the cleaning liquid passing through the filter material 3 is reduced or substantially eliminated, the compressed air pressure in the pressure-resistant container 2 is released from the bottom, making it difficult to maintain the internal pressure of the pressure-resistant container 2 at the pressure at the time of pressure- , The pressure at the time of pressing is lowered.

The cleaning liquid used in the cleaning step is preferably an aqueous medium, for example, water; Lower alcohols (alcohols having 5 or less carbon atoms) such as methyl alcohol, ethyl alcohol and the like; And a mixture of water and a lower alcohol. However, it is preferable to use the same one as the medium used in the polymerization process.

The weight of the washing liquid used in the washing step is preferably such that the weight of the polymer particles held on the filter material 3 (whether or not the weight of the washing liquid obtained in the solid-liquid separation step The total amount of the vinyl-based monomers used in the polymerization step when all the crude products are put in the filter) is 9 times or more and 18 times or less. If the weight of the washing liquid used in the washing step is less than 9 times the weight of the polymer particles held on the filter material 3, the byproducts (emulsion polymerization products) generated during the polymerization reaction contained in the polymer particles, Surfactants having surplus polyoxyethylene chains which do not contribute to the modification of the surface of the polymer particles among the surfactants having an oxyethylene chain, other surfactants to be used if necessary, polymer dispersion stabilizers to be used as needed, (Particularly, the content of other surfactants per unit surface area of the polymer particles is 10.0 x 10 < ^-5 > g / M < 2 >) may not be obtained. The weight of the cleaning liquid used in the cleaning step is 18 times or less the weight of the polymer particles held on the filter material 3, and in the cleaning step, the amount of the non-surplus powder (contributing to the modification of the surface of the polymer particles) It is possible to securely obtain polymer particles having a content of the polyoxyethylene chain-containing surfactant of not less than 2.0 g / m 2 per unit surface area of the polymer particles, by preventing the surfactant having an ethylene chain from being eluted. Therefore, polymer particles having excellent dispersibility in a high SP value organic solvent can be reliably obtained.

When at least one other surfactant is used in the polymerization step, the weight (B) (kg) of the cleaning liquid used in the cleaning step is calculated by the following calculation formula (4) for each type of the other surfactant used in the polymerization step ) (ΣB _L ) of the lower limit value (B _L ) (kg) of the weight of the cleaning liquid calculated by the above formula (1) (equal to or higher than B _L when one type of another surfactant is used in the polymerization step) (ΣB _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 kind of the other surfactant used in the polymerization step It is preferably equal to or less than B _H when a surfactant is used). That is, the weight (B) (kg) of the cleaning liquid used in the cleaning process preferably satisfies the following inequality (6). When one kind of another surfactant is used in the polymerization step, the following inequality (6) becomes the following inequality (7).

B _{L =} (C / D) x 1.8 (4)

B _{H =} (C / D) x 2.3 ... (5)

ΣB _L ≤ _B ≤ ΣB _H ... (6)

B _L ? B? B _H ... (7)

(In the formulas (4) and (5), C represents the amount (g) of one kind of another surfactant used and D represents the solubility (g / 100 ml)

(ΣB _L ) (kg) of the lower limit value (B _L ) (kg) of the weight of the cleaning liquid calculated by the above-mentioned calculation formula (4) for each kind of the other surfactant used in the above- ), A by-product (an emulsion polymerization product) generated during the polymerization reaction attached to the surface of the polymer particles in the polymer particles and a surfactant having a polyoxyethylene chain which is used if necessary Such as a surfactant having an excess polyoxyethylene chain, another surfactant to be used if necessary, a polymer dispersion stabilizer to be used if necessary, and a polymerization additive (for example, a polymerization inhibitor) Can be further reduced. When the polymerization is carried out in the presence of a surfactant containing both a polyoxyethylene chain-containing surfactant and other surfactants, the weight of the cleaning liquid used in the cleaning step is different from the weight of the other surfactant used in the polymerization step (ΣB _H ) (kg) of the upper limit value (B _H ) (kg) of the weight of the cleaning liquid calculated by the equation (5), the poly The surfactant having an oxyethylene chain is also eluted slowly so that the amount of water retention by the surfactant having a polyoxyethylene chain on the surface of the polymer particle becomes uneven.

The temperature of the cleaning liquid used for cleaning is preferably a temperature at which the polyoxyethylene chain-containing surfactant and other surfactants are sufficiently eluted. For example, the temperature is preferably 40 to 80 ° C, more preferably 50 to 80 ° C More preferable. As a method of cleaning the cleaning liquid by heating to the above temperature, a method may be used in which the heated cleaning liquid is supplied to a filter (for example, the pressure resistant vessel 2 of the pressure filter 1) And then the cleaning liquid is heated by a heater jacket disposed around the filter.

The cleaning process is performed so that the conductivity of the cleaning liquid that has passed through the filter material 3 becomes 2.0 times or less the conductivity of the cleaning liquid before the cleaning liquid is introduced into the filter (pressure filter 1), and the internal pressure of the pressure- 3 < / RTI > The cleaning liquid is introduced into the pressure-resistant container 2 until the conductivity of the cleaning liquid that has passed through the filter material 3 becomes 2.0 times or less the conductivity of the cleaning liquid prior to the introduction into the filter (pressurizing filter 1) (Emulsion polymerization product) generated during the polymerization reaction contained in the polyoxyethylene chain, and a surfactant having an excess polyoxyethylene chain which does not contribute to the modification of the surface of the polymer particles among the surfactants having polyoxyethylene chains, The remaining amount of the unnecessary components such as other surfactant used in accordance with necessity, a polymer dispersion stabilizer to be used if necessary, and a polymerization additive (for example, polymerization inhibitor) to be used if necessary can be surely reduced. The amount of water that can be absorbed by the polymer particles is measured by passing the cleaning liquid introduced into the pressure-resistant container 2 through the filter material 3 until the internal pressure of the pressure-resistant container 2 becomes 2/3 or less of the pressure at the time of pressing So that the time required for drying the polymer particles after cleaning can be shortened.

The polymer particles obtained in the cleaning step can be made into polymer particles usable as a product by drying with a vacuum drier to substantially completely remove the cleaning liquid and classifying (if necessary, air stream classification) as necessary.

According to the production method of the polymer particles, the amount of the medium having passed through the filter medium per unit time in the solid-liquid separation step satisfies the conditional formula (1), and the amount of the cleaning liquid passing through the filter medium per unit time In the cleaning step, the cleaning liquid satisfying the condition (2) and having a weight of not less than 9 times and not more than 18 times the weight of the polymer particles held on the filter material is used, A surfactant containing a surfactant having an oxyethylene chain (which does not contribute to the modification of the surface of the polymer particles) is dissolved in an appropriate amount (an interface with excess polyoxyethylene chain which does not contribute to the modification of the surface of the polymer particles Amount of active agent). In addition, when polymerization is carried out in the presence of a surfactant containing both a polyoxyethylene chain-containing surfactant and another surfactant, most of the other surfactant can be sufficiently removed together with the medium and the cleaning liquid. As a result, a polyoxyethylene content of the surfactant having an ethylene chain (residual amount), the amount (in particular 2.0~15.0 × 10 ^-3 g / ㎡) in the unit surface area of the polymer particles, the unit surface area of the polymer particles (In particular, 10.0 x 10 < ^-5 > g / m < 2 > or less) of the other surfactant in the dispersion medium.

Further, according to the above production method, unnecessary components such as byproducts (emulsion polymerization products) generated during the polymerization reaction, polymer dispersion stabilizers to be used if necessary, and polymerization additives (if necessary, used as polymerization inhibitors) It is removed in a large amount in the process and the cleaning process. For this reason, the amount of these unnecessary components in the polymer particles obtained by the above production method may be small.

[Use of polymer particles]

The polymer particles of the present invention are preferable for an optical member such as an antiglare film or a light diffusion film, an optical member such as a light diffusion member, and particularly preferable for an antiglare member.

[Optical film]

The optical film of the present invention is formed by coating a film base material with a resin composition for coating comprising the polymer particles of the present invention and a binder. The optical film of the present invention can be obtained by, for example, dispersing the polymer particles in a binder to obtain a resin composition for coating, coating the obtained resin composition for coating on a film substrate, .

The binder is not particularly limited as long as it is used in the art depending on required properties such as transparency, polymer particle dispersibility, light resistance, moisture resistance and heat resistance. As the binder, for example, a (meth) acrylic resin; (Meth) acryl-urethane-based resin; Urethane resin; Polyvinyl chloride resins; Polyvinylidene chloride resins; Melamine resin; Styrene type resin; Alkyd resins; Phenolic resin; Epoxy resin; Polyester-based resin; Silicone resins such as alkylpolysiloxane resins; Modified silicone resins such as (meth) acrylic-silicone resins, silicone-alkyd resins, silicone-urethane resins and silicone-polyester resins; And fluorine-based resins such as polyvinylidene fluoride, fluoroolefin vinyl ether polymer and the like.

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 resin composition for coating. 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 ray curable resin and an electron ray curable resin, a thermosetting resin, and a heat curable resin depending on the curing type.

Examples of the thermosetting resin include thermosetting urethane resins, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins, each of which is composed of an acrylic polyol and an isocyanate-free polymer.

Examples of the ionizing radiation curable resin include polyfunctional (meth) acrylate resins such as polyhydric alcohol polyfunctional (meth) acrylates and the like; Polyfunctional urethane acrylate resins synthesized with diisocyanate, polyhydric alcohols and (meth) acrylic acid esters having a hydroxy group, and the like. The ionizing radiation curable resin is preferably a polyfunctional (meth) acrylate resin, more preferably a polyhydric alcohol polyfunctional (meth) acrylate having at least three (meth) acryloyl groups in one molecule. Specific examples of the multivalent alcohol polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule include trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol triacrylate, di Pentaerythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate, and the like. Two or more ionizing radiation curable resins may be used in combination.

As the ionizing radiation curable resin, a polyether resin, a polyester resin, an epoxy resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiol polyene resin and the like having an acrylate functional group may also be used.

When an ultraviolet ray curable resin is used as the ionizing radiation curable resin, a photopolymerization initiator is added to the ultraviolet ray curable resin to form a binder. Any of the above photopolymerization initiators may be used, but it is preferable to use those suitable for the ultraviolet curable resin to be used.

The photopolymerization initiator may be at least one compound selected from the group consisting of 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 ,? -acyloxime esters and the like.

Examples of the acetophenones include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenylketone, 1-hydroxycyclohexylphenylketone, 2- 4-methylthio-2-morpholinopropiophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of the benzoin include benzoin, benzoin benzoate, benzoin benzenesulfonic acid ester, benzoin toluenesulfonic acid ester, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like . Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4'-dichlorobenzophenone, and p-chlorobenzophenone. Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Examples of the kettle stream include benzylmethyl ketalization such as 2,2-dimethoxy-1,2-diphenylethane-1-one. Examples of the? -Hydroxyalkylphenols include 1-hydroxycyclohexyl phenyl ketone. Examples of the? -Aminoalkylphenols include 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone.

Commercially available photo radical polymerization initiators include trade names "Irgacure (registered trademark) 651" (2,2-dimethoxy-1,2-diphenylethane-1-one) manufactured by BASF Japan KK, Irgacure (registered trademark) 184 ", trade name" Irgacure (registered trademark) 907 "(trade name, manufactured by BASF Japan KK) Morpholinyl) -1-propanone), and the like.

The amount of the photopolymerization initiator used is usually in the range of 0.5 to 20 wt%, preferably in the range of 1 to 5 wt%, based on 100 wt% of the binder.

In addition to the curable resin, a thermoplastic resin can be used as the binder resin. Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetyl butylcellulose, ethylcellulose, and methylcellulose; Vinyl resins such as homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of vinyl chloride, homopolymers and copolymers of vinylidene chloride, and the like; Acetal resins such as polyvinyl formal, polyvinyl butyral and the like; (Meth) acrylic resins such as homopolymers and copolymers of acrylic acid esters, homopolymers and copolymers of methacrylic acid esters; Polystyrene resin; Polyamide resins; Linear polyester resins; Polycarbonate resin and the like.

In addition to the binder resin, a rubber binder such as synthetic rubber or natural rubber, or an inorganic binder may be used as the binder. Examples of the rubber-based binder resin include an ethylene-propylene copolymer rubber, a polybutadiene rubber, a styrene-butadiene rubber, and an acrylonitrile-butadiene rubber. These rubber-based binder resins may be used alone, or two or more of them may be used in combination.

Examples of the inorganic binders include silica sol, alkali silicate, silicon alkoxide, phosphate and the like. As the inorganic binder, an inorganic or organic-inorganic composite matrix obtained by hydrolysis and dehydration condensation of a metal alkoxide or a silicon alkoxide may be used. As the inorganic or organic-inorganic composite matrix, a silicon oxide-based matrix obtained by hydrolysis and dehydration condensation of a silicon alkoxide such as tetraethoxysilane can be used. These inorganic binders may be used alone or in combination of two or more.

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, and even more preferably 6 parts by weight or more, based on 100 parts by weight of the solid content of the binder. When the amount of the polymer particles is 2 parts by weight or more based on 100 parts by weight of the solid content of the binder, it is easy to make the coating film formed of the resin composition for coating sufficiently glossy. Therefore, it becomes easy to make the film formed by coating the resin composition for coating on the film substrate to have a sufficient optical property such as retardation and light diffusibility. 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 even more preferably 100 parts by weight or less, based on 100 parts by weight of the solid content of the binder. By setting the amount of the polymer particles to 300 parts by weight or less based on 100 parts by weight of the solid content of the binder, it becomes easy to make the linear permeability of the coated film formed by the resin composition for coating to be sufficient.

The resin composition for coating may further contain an organic solvent. There is no particular limitation so long as it is easy to coat the resin composition for coating on the substrate by incorporating the organic solvent into the resin composition for coating when the resin composition for coating is applied to a substrate such as a film substrate to be described later . Examples of the organic solvent 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; Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and propylene glycol methyl ether; Glycol ether esters such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate (cellosolve acetate), 2-butoxyethyl acetate and propylene glycol methyl ether acetate; Chlorinated solvents such as chloroform, dichloromethane, trichloromethane and methylene chloride; Ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, and 1,3-dioxolane; Amide solvents such as N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide and dimethylacetamide can be used. These organic solvents may be used singly or in combination of two or more kinds.

Since the polymer particles of the present invention are excellent in dispersibility with respect to a high SP value organic solvent, the resin composition for coating comprising the polymer particles of the present invention, the binder and the organic solvent is coated on the film substrate to produce the optical film of the present invention , The effect is remarkable. Specific examples of the high SP value organic solvent include isopropyl alcohol having an SP value calculated by the Fedors method of 24.3 (MPa) ^1/2 (11.9 (cal / cm3) ^1/2 ), an SP value of 28.2 ^{(MPa) 1/2 (13.8 (cal} / ㎤) 1/2) is methyl alcohol,, SP value, such as ethyl alcohol SP value of ^{26.2 (MPa) 1/2 (12.6 (} cal / ㎤) 1/2) Is not less than 20.5 (MPa) ^1/2 (10 (cal / cm < 3 >) ^1/2 ) or more. In this specification, " SP value " indicates the solubility parameter calculated by the Fedors method.

The film substrate is preferably transparent. Examples of the transparent film substrate include polyester polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate, cellulosic polymers such as diacetylcellulose and triacetylcellulose (TAC), polycarbonate polymers, polymethyl And (meth) acrylic polymers such as methacrylate. Examples of the transparent film substrate include styrene polymers such as polystyrene, acrylonitrile and styrene copolymers, olefin polymers such as polyethylene, polypropylene, polyolefins having a cyclic to norbornene structure, and ethylene / propylene copolymers, And amide polymers such as nylon, aromatic polyamide, and the like. Further, as the transparent film substrate, it is possible to use an imide polymer, a sulfon polymer, a polyether sulfone polymer, a polyether ether ketone polymer, a polyphenyl sulfide polymer, a vinyl alcohol polymer, a vinyl chloride polymer, a vinyl butyral polymer, A film composed of a polymer such as an aryl-based polymer, a polyoxymethylene-based polymer, an epoxy-based polymer, or a blend of the above-mentioned polymers. As the film base material, a material having a small birefringence is preferably used. Further, a film in which a (easy) adhesive layer such as a (meth) acrylic resin, a copolymerized polyester resin, a polyurethane resin, a styrene-maleic acid graft polyester resin, Can be used as a film substrate.

The thickness of the film base material can be appropriately determined, but it is generally in the range of 10 to 500 m, preferably in the range of 20 to 300 m, from the viewpoints of workability such as strength and handling, And more preferably in the range of about 200 mu m to about 200 mu m.

An additive may be added to the film substrate. Examples of the additive include an ultraviolet absorber, an infrared absorber, an antistatic agent, a refractive index adjuster, and an enhancer.

Examples of the method of applying the resin composition for coating on a film substrate include bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, microgravure coating, And a dipping method.

When the binder contained in the resin composition for coating is an ionizing radiation curable resin, the ionizing radiation curable resin may be cured by drying the solvent after the application of the resin composition for coating, if necessary, and further irradiating with an active energy ray .

Examples of the active energy ray include ultraviolet rays generated from a light source such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp or a tungsten lamp; Electron beams, alpha rays, beta rays, gamma rays, and gamma rays, which are extracted from electron beam accelerators such as Cockloff, Walton type, Bandegraph type, resonance type, resonance type, insulating core type, linear type, dynamictron type, Etc. may be used.

The thickness of the layer in which the polymer particles are dispersed in the binder formed by applying (and curing) the resin composition for coating is not particularly limited and is appropriately determined depending on the particle diameter of the polymer particles, but is preferably in the range of 1 to 10 탆 , And more preferably in the range of 3 to 7 mu m.

The optical film of the present invention can be preferably used for light diffusion or antiglare, that is, as a light diffusion film or an antiglare film.

[Molded resin]

The polymer particles of the present invention may be used in a resin molded article. The resin molded article is obtained by molding a resin composition for molding comprising the polymer particles of the present invention and a transparent resin. In the resin molded article, the polymer particles function as light diffusing particles. Therefore, the resin molded product functions as a light diffuser 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 article, and examples thereof include a (meth) acrylic resin, a polycarbonate resin, a polystyrene resin, a (meth) acryl-styrene resin (copolymer of (meth) acrylic acid ester and styrene) . Among them, a polystyrene resin or a (meth) acryl-styrene resin is preferable as the above-mentioned 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, more preferably in the range of 0.1 to 5 parts by weight, based on 100 parts by weight of the transparent resin. Additives such as an ultraviolet absorber, an antioxidant, a heat stabilizer, a light stabilizer, and a fluorescent whitening agent may be added to the resin composition.

The thickness and shape of the resin molded article can be appropriately selected depending on the use of the resin molded article.

The resin molded article can be obtained by melt-kneading the transparent resin and the polymer particles with a single screw extruder, a twin screw extruder, or the like. Further, the resin composition obtained by melt-kneading may be formed into a plate shape via a T-die and a roll unit to obtain a resin molded article. The resin composition obtained by melt kneading may be pelletized, and the pellets may be molded into a plate shape by injection molding, press molding or the like to obtain a resin molded article.

Since the resin molded article is obtained by molding the resin composition for molding containing the polymer particles of the present invention having excellent dispersion uniformity, it is possible to obtain optical properties such as uniform light diffusing property and anti- Loses.

Example

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. First, the method of measuring the coefficient of variation of the volume average particle diameter and the particle diameter of the polymer particles in the following Examples and Comparative Examples, the method of measuring the volume average particle diameter of the seed particles used in the production of the polymer particles, (Amount per unit time (kg / min) of the medium passed through the filter medium) in the solid-liquid separation process of the polymer particles, the Y value (the unit of the cleaning liquid passing through the filter medium A method for measuring the content of the surfactant in the polymer particles, a method for calculating the content of the surfactant per unit surface area of the polymer particles, a method for calculating the content of the surfactant in the polymer particles (the amount of the emulsion polymerization product ), A method of measuring the gel fraction of the polymer particles, a method of measuring the refractive index of the polymer particles, a method of dispersing the polymer particles in a high SP value organic solvent An evaluation method, and a method for measuring the solubility of one kind of other surfactant in a cleaning liquid having a liquid temperature of 25 ° C will be described.

[Method for measuring the variation coefficient of the volume average particle diameter and the particle diameter of the polymer particles]

The volume average particle diameter of the polymer particles is measured with a Coulter Multisizer ^TM 3 (measuring apparatus manufactured by Beckman Coulter, Inc.). The measurement shall be carried out using a calibrated aperture in accordance with the Multisizer ^TM 3 user manual published by Beckman Coulter, Inc.

Also, 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 set appropriately according to the size of the selected aperture. For example, when an aperture having a size of 50 μm is selected, the current (aperture current) is set to -800 and the gain (gain) is set to 4.

As a sample for measurement, 0.1 g of polymer particles were dissolved in 10 ml of a 0.1% by weight nonionic surfactant aqueous solution by using a touch mixer (TOUCHMIXER MT-31, manufactured by Yamato Scientific Co., Ltd.) and an ultrasonic cleaner (ULTRASONIC CLEANER VS -150 ") as a dispersion liquid. During the measurement, the inside of the beaker was slowly stirred so as not to contain bubbles, and the measurement was terminated at the time when 100,000 polymer particles were measured. The volume average particle diameter of the polymer particles is an arithmetic mean in the particle size distribution of 100,000 particles.

The coefficient of variation (CV value) of the particle diameter of the polymer particles is calculated by the following equation.

Coefficient of variation of particle diameter of polymer particles = (standard deviation of particle size distribution based on volume of polymer particles / volume average particle diameter of polymer particles) x 100

[Method for measuring volume average particle diameter of seed particles]

The volume average particle diameter of the seed particles used in the production of the polymer particles is measured by a laser diffraction / scattering type particle size distribution measuring apparatus (LS 13 320 manufactured by Beckman Coulter, Inc.) and a universal liquid sample module.

Specifically, 0.1 g of the slurry containing the seed particles was dispersed in 10 ml of a 0.1% by weight nonionic surfactant aqueous solution by using a touch mixer (TOUCHMIXER MT-31, manufactured by Yamato Scientific Co., Ltd.) and an ultrasonic cleaner CLEANER VS-150 ") as a dispersion liquid.

The measurement was carried out in a state in which the seed particles were dispersed by performing pump circulation in the universal liquid sample module and in a state in which the ultrasonic unit (ULM ULTRASONIC MODULE) was activated so that the volume average particle diameter of the seed particles The arithmetic mean diameter of the arithmetic mean of the arithmetic mean. Measurement conditions are shown below.

Medium = water

Refractive index of medium = 1.333

The refractive index of the solid = the refractive index of the seed particle

PIDS relative concentration: about 40 to 55%

[Method of measuring X value]

In the solid-liquid separation step, the time (T ₁ ) (min) from the start of passing the medium contained in the crude product through the filter medium to the completion of passage of the filter medium through the medium is measured. Further, the total weight (G ₁ ) (kg) of the filtrate (medium) obtained in the solid-liquid separation step is measured. Then, the quantity (X) (kg / min) per unit time of the medium having passed through the filter medium is obtained by the following calculation formula.

X (kg / min) = G ₁ (kg) / T ₁ (min)

[Measurement method of Y value]

The weight (G ₂ ) (kg) of the cleaning liquid used in the cleaning process is measured. In addition, in the cleaning process, the time required until the start of passing a cleaning liquid to the filter medium, and of 0.8 times the weight of the cleaning liquid of the weight of the cleaning liquid (G ₂₎ (g) used in the cleaning process through the filter medium after (T ₂ ) (min) is measured. Then, the amount (Y) (kg / min) per unit time of the cleaning liquid that has passed through the filter material is obtained by the following calculation formula.

Y (kg / min) = 0.8 x G ₂ (kg) / T ₂ (min)

[Method of measuring the content of the surfactant in the polymer particles]

The content of the surfactant in the polymer particles is measured using a liquid chromatograph mass spectrometer (LC / MS / MS apparatus) by extracting the polymer particles with a solvent.

In order to measure the content of the surfactant in the polymer particles of Examples and Comparative Examples described later, "UHPLC ACCELA" manufactured by Thermo Fisher Scientific and "Linear Ion Trap LC" manufactured by Thermo Fisher Scientific / MS ⁿ LXQ "

In addition, the polymer particles in Examples and Comparative Examples to be described later can be used as surfactants such as di (2-ethylhexyl) sulfosuccinate, polyoxyethylene nonylphenyl ether phosphate, lauryl sulfate, alkenyl succinate, polyoxyethylene styrene At least one of phenyl ether ether sulfate ester salt and polyoxyethylene styrenated phenyl ether phosphate ester was used. The content of the surfactant in the polymer particles of the examples and comparative examples was measured by the following method.

Approximately 0.10 g of polymer particles as a sample is precisely weighed in a centrifuge tube, and 5 ml of methanol as an extraction liquid is injected with a hole pipette to uniformly mix the polymer particles and the extract solution. After ultrasonic extraction is performed at room temperature for 15 minutes, centrifugation is carried out at 3500 rpm for 15 minutes, and the supernatant thus obtained is used as a test solution.

The surfactant concentration in this test solution is measured using an LC / MS / MS apparatus. From the measured concentration of the surfactant (占 퐂 / ml) in the measured test liquid, the weight of the polymer particles used as the sample (sample weight (g)) and the amount of the extracted liquid (extraction liquid amount (ml) The content (占 퐂 / g) of the surfactant in the particles is obtained. Here, the amount of the extract liquid is 5 ml.

Content of surfactant (占 퐂 / g)

= ({Surfactant concentration in test solution (占 퐂 / ml) x amount of extract solution (ml)} 占 sample weight (g)

Further, the surfactant concentration is calculated from the peak area value on the chromatogram obtained using the LC / MS / MS apparatus by the previously prepared calibration curve. When the polymer particles contain a plurality of surfactants, calibration curves are prepared for each of these surfactants, the concentration of the surfactant is calculated by the prepared calibration curve, and the sum of the surfactant concentrations of the respective surfactants Is the concentration of the surfactant in the test liquid (占 퐂 / ml) in the above calculation formula, and the content of the surfactant in the polymer particles is determined.

The method of preparing the calibration curve is as follows, depending on the kind of the surfactant used in Examples and Comparative Examples.

- Preparation method of di (2-ethylhexyl) sulfosuccinate -

About 1000 ppm of the intermediate standard solution (methanol solution) of di (2-ethylhexyl) sulfosuccinate was prepared and further diluted stepwise with methanol to prepare a standard solution for preparing a calibration curve of 0.1 ppm, 0.2 ppm, 0.5 ppm, 1.0 ppm and 2.0 ppm Prepare. The standard solution for the calibration of each concentration was measured under LC measurement conditions and MS measurement conditions to be described below and the peak area value on the chromatogram of monitor ion m / z = 421.3 (precursor ion)? 227.2 (product ion) . Plot each concentration and area value and calculate an approximate curve (quadratic curve) by the least squares method and use this as a calibration curve for quantification.

- Calibration method of polyoxyethylene nonylphenyl ether phosphate -

About 1,000 ppm of the intermediate standard solution (methanol solution) of polyoxyethylene nonylphenyl ether phosphate was prepared and further diluted with methanol stepwise to prepare a standard solution for preparing a calibration curve of 0.1 ppm, 0.5 ppm, 1.0 ppm, 2.0 ppm and 10.0 ppm . The standard solution for the calibration of each concentration is measured under LC measurement conditions and MS measurement conditions to be described below to obtain a peak area value on the chromatogram of monitor ion m / z = 502.3 (precursor ion) to 485.2 (product ion). Plot each concentration and area value and calculate an approximate curve (quadratic curve) by the least squares method and use this as a calibration curve for quantification.

- Calibration method of lauryl sulfate -

About 1,000 ppm of the intermediate standard solution (methanol solution) of lauryl sulfate is prepared and further diluted stepwise with methanol to prepare a standard solution for calibration of 0.1 ppm, 0.2 ppm, 0.5 ppm, 1.0 ppm and 2.0 ppm. The standard solution for the calibration of each concentration is measured under LC measurement conditions and MS measurement conditions to be described later to obtain a peak area value on the chromatogram of monitor ion m / z = 421.3 (precursor ion)? 227.2 (product ion). Plot each concentration and area value and calculate an approximate curve (quadratic curve) by the least squares method and use this as a calibration curve for quantification.

- Calibration method of alkenyl succinate -

About 1000 ppm of the intermediate standard solution (methanol solution) of the alkenylsuccinate salt is prepared and further diluted with methanol stepwise to prepare a standard solution for preparing a calibration curve of 0.03 ppm, 0.15 ppm, 0.60 ppm, 1.5 ppm and 3.0 ppm. The standard solution for the calibration of each concentration is measured under LC measurement conditions and MS measurement conditions to be described later to obtain a peak area value on the chromatogram of monitor ion m / z = 339.3 (precursor ion) to 295.2 (product ion). Plot each concentration and area value and calculate an approximate curve (quadratic curve) by the least squares method and use this as a calibration curve for quantification.

- Calibration method of polyoxyethylene styrenated phenyl ether sulfuric acid ester salt -

About 1000 ppm of the intermediate solution (methanol solution) of polyoxyethylene styrenated phenyl ether sulfuric acid ester salt was prepared and further diluted stepwise with methanol to prepare a standard solution for the calibration curve of 0.1 ppm, 0.5 ppm, 1.0 ppm, 2.0 ppm and 10.0 ppm Prepare. The standard solution for the calibration of each concentration is measured under LC measurement conditions and MS measurement conditions to be described later to obtain a peak area value on the chromatogram of monitor ion m / z = 601.4 (precursor ion) to 301.2 (product ion). Plot each concentration and area value and calculate an approximate curve (quadratic curve) by the least squares method and use this as a calibration curve for quantification.

- Calibration method of polyoxyethylene styrenated phenyl ether phosphate ester -

About 1000 ppm of the intermediate solution (methanol solution) of polyoxyethylene styrenated phenyl ether phosphate ester was prepared and further diluted with methanol stepwise to prepare a standard solution for preparing a calibration curve of 0.1 ppm, 0.5 ppm, 1.0 ppm, 2.0 ppm and 10.0 ppm Prepare. The standard solution for the calibration of each concentration is measured under LC measurement conditions and MS measurement conditions to be described later to obtain a peak area value on the chromatogram of monitor ion m / z = 601.4 (precursor ion) to 301.2 (product ion). Plot each concentration and area value and calculate an approximate curve (quadratic curve) by the least squares method and use this as a calibration curve for quantification.

- LC measurement condition -

Measuring device: UHPLC ACCELA (manufactured by Thermo Fisher Scientific)

Column: Hypersil GOLD C18 manufactured by Thermo Fisher Scientific 1.9 mu m (inner diameter 2.1 mm, length 100 mm)

-MS measurement conditions -

Measurement apparatus: Linear Ion Trap LC / MS ⁿ LXQ (manufactured by Thermo Fisher Scientific)

Ionization: (ESI / negative)

Sheath Gas: 30arb

Aux Gas: 10 bar

Sweep Gas: 0arb

Spray Voltage (I Spray Voltage): 5.0 kV

Capillary Temp: 350 < 0 > C

Capillary Voltage: -20V

Tube Lens Voltage: -100V

Monitoring ion (m / Z):

Di (2-ethylhexyl) sulfosuccinate (n = 421.3 / n2 = 227.2)

Polyoxyethylene nonylphenyl ether phosphate (n = 502.3 / n2 = 485.2)

Lauryl sulfate (n = 421.3 / n2 = 227.2)

Alkenyl succinate (n = 339.3 / n2 = 295.2)

Polyoxyethylene styrenated phenyl ether sulfuric acid ester salt (n = 601.4 / n2 = 301.2)

Polyoxyethylene styrenated phenyl ether phosphate ester (n = 601.4 / n2 = 301.2)

[Method of measuring specific surface area of polymer particles]

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 by using an automatic specific surface area / pore distribution measuring instrument Tristar 3000 manufactured by Shimadzu Corporation, and the specific surface area was calculated from the nitrogen adsorption amount using the BET multi-point method. After the pretreatment by the heating gas purge, nitrogen was used as the adsorbent and the measurement was carried out by the constant capacity method under the condition of the adsorbate cross-sectional area of 0.162 nm ² . Specifically, the above-mentioned pretreatment is carried out in such a manner that while the vessel into which the polymer particles have been charged is heated to 65 DEG C while purging with nitrogen for 20 minutes and then allowed to cool to room temperature and the vessel is heated to 65 DEG C, By performing vacuum degassing.

[Method of calculating the content of the surfactant per unit surface area of the polymer particles]

From the content of the surfactant in the polymer particles measured by the measurement method described above and the specific surface area of the polymer particles measured by the measurement method described above, And the content thereof was calculated.

(Content of surfactant per unit surface area of polymer particles) (g / m 2) = (content of surfactant in polymer particles) (g / per 1 g of polymer particles)

÷ Specific surface area of polymer particles (m 2 / per 1 g of polymer particles)

[Method for measuring the content of by-products (emulsion polymerization product) in polymer particles (solvent dispersion method)] [

When the polymer particles are dispersed in water and centrifuged, the polymer particles having a desired particle diameter are precipitated, while the by-products (emulsion polymerization products) contained in the polymer particles float to form a supernatant together with a small amount of water. Therefore, here, the content of the by-product (emulsion polymerization product) of the seed polymerization in the polymer particles is measured as the content of the non-volatile component in the supernatant.

[Preparation of supernatant]

First, 5.0 g of the polymer particles obtained in each of the Examples and Comparative Examples was put into a sample bottle having an inner volume of 50 ml, and 15.0 g of water was added. Thereafter, dispersion treatment was carried out for 60 minutes using an ultrasonic cleaner ("ULTRASONIC CLEANER VS-150" manufactured by BELVO CORPORATION, Inc., oscillation frequency: 50 Hz, high frequency output: 150 W) to disperse the polymer particles in water to obtain a dispersion. When the polymer particles are difficult to be dispersed in water, the polymer particles may be dispersed in water after wetting with a small amount (0.8 g of the upper limit) of an alcohol (for example, ethanol).

Subsequently, 20.0 g of the above dispersion was charged into a centrifugal tube having an inner diameter of 24 mm, for example, a centrifugal tube having an inner volume of 50 ml and an inner diameter of 24 mm (trade name: Nalgen (registered trademark) 3119-0050, manufactured by Thermo Fisher Scientific) , And the centrifugal tube is set in a rotor, for example, an angle rotor (product number "RR24A", manufactured by Hitachi Kokusai K.K., a set of eight centrifugal tubes having an inner volume of 50 ml) and centrifugal, The rotor was set in a high-speed refrigerated centrifuge (product number " CR22GII ", manufactured by Hitachi, Ltd.), and the K factor 6943 (when the angle rotor was used, the rotation speed was 4800 rpm The K factor becomes 6943). After centrifugation under the condition of a rotation time of 30 minutes, the supernatant is recovered.

[Quantitative evaluation of by-products (emulsion polymerization product)] [

Then, the content of the by-product (emulsion polymerization product) contained in 5.0 g of the recovered supernatant is evaluated. That is, first, 5.0 g of the supernatant is weighed and taken in a sample bottle having an inner volume of 10 ml which is weighed in advance, and the mixture is put in a vacuum oven at 60 ° C for 5 hours to evaporate water. The weight (g) of the sample bottle containing the evaporated dry residue, i.e. the non-volatile component, is weighed.

From the weight g of the sample bottle containing the non-volatile component, the weight g of the sample bottle and the weight g of the supernatant (= 5.0 g) in the sample bottle, the supernatant (Weight%) of the nonvolatile component (corresponding to the by-product (emulsion polymerization product)) in the reaction mixture.

(Concentration of non-volatile component in the supernatant) (% by weight)

= {(Weight of sample bottle containing non-volatile component) (g) - (weight of sample bottle) (g)}

÷ (weight of supernatant in sample bottle) (g) × 100

[Method of measuring gel fraction of polymer particles]

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 vesicant are added to a 200 ml eggplant flask, 100 ml of toluene is further added thereto, and a cooling tube is attached to the eggplant flask and maintained at 130 캜 The branched flask is immersed in an oil bath and refluxed for 24 hours.

After refluxing, the content (solution) in the branched flask was weighed with a glass fiber filter "GB-140 (φ37 mm)" and "GA-200 (φ37 mm)" manufactured by ADVANTEC and weighed The filtration is performed using a funnel-shaped filter 3G (glass particle pore diameter 20 to 30 mu m, capacity 30 ml), and the solid content is recovered in the Buchner funnel-shaped filter 3G. The solids recovered in the Buchner funnel-shaped filter 3G were dried in a vacuum oven at 130 ° C for 1 hour under the Buchner funnel-type filter, and then dried at a gauge pressure of 0.06 MPa for 2 hours to remove toluene. And cooled.

After cooling, the total weight of the Buchner funnel-shaped filter 3G and the glass fiber filter and the solid content is measured with the solid content in the Buchner funnel-shaped filter 3G. Then, the weight (g) of the dried powder is obtained by subtracting the weight of the Buchner funnel-shaped filter 3G and the glass fiber filter and the weight of the booster from the measured gross weight.

Then, the weight (g) of the dry powder and the weight (g) of the sample put into the branch flask are used, and the gel fraction is calculated by the following calculation formula.

Gel fraction (% by weight) = {dry powder (g) / sample weight (g)} x 100

[Method of measuring refractive index of polymer particles]

The refractive index of the polymer particles was measured by the Becke method. First, polymer particles are placed on a slide glass, and a refraction liquid (Cargill standard refraction liquid manufactured by CARGILLE CO., LTD., Refraction liquid having a refractive index nD25 of 1.538 to 1.562 is prepared for plural refraction index differences of 0.002) is dropped. After the polymer particles and the refraction liquid were uniformly mixed, the outline of the polymer particles was observed with an optical microscope from the top while irradiating light of a high-pressure sodium lamp "NX35" (center wavelength: 589 nm) manufactured by Iwasaki Electric Co., Respectively. When the outline was not observed, it was judged that the refraction liquid and the refractive index of the polymer particles were the same.

In addition, observation with an optical microscope is not particularly problematic as long as observation at a magnification permitting the outline of polymer particles is observed, but observation magnification of about 500 times is suitable for polymer particles having a particle diameter of 5 mu m. The refractive index of the refraction liquid, which is difficult to confirm the outline of the polymer particles, is determined to be the same as the refractive index of the polymer particles because the outline of the polymer particles becomes less visible as the refractive indexes of the polymer particles and the refraction liquid become closer.

In the case where there is no difference in the way in which the polymer particles are seen between two kinds of refraction liquids having a refractive index difference of 0.002, the intermediate value of these two kinds of refraction liquids was judged as the refractive index of the polymer particles. For example, when the refractive indexes of 1.554 and 1.556 were tested with each of the refractive solutions, the refractive index of the polymer particles was determined to be 1.555, which is the intermediate value of these refractive solutions, when there is no difference in the way in which the polymer particles are observed in the two refractive solutions.

In the measurement, the measurement was carried out in an environment at a temperature of 23 ° C to 27 ° C in the laboratory.

[Evaluation method of dispersibility of polymer particles in a high SP value organic solvent (solvent dispersion method)] [

0.05 g of the polymer particles and 5.0 g of isopropyl alcohol as a high SP value organic solvent were weighed and placed in a dedicated plastic container and stirred with a stirring deaerator (product name: "Awatolirenotaro AR-100", manufactured by TINKISA CORPORATION) Followed by stirring for 5 minutes to obtain a polymer particle dispersion.

Thereafter, a drop of the polymer particle dispersion was dropped on the slide glass, and the cover glass was covered and observed with a digital microscope (product number " VHX-500 ", manufactured by KYOSEN Co., Ltd.) at a magnification of 1000 times and a field of 300 mu m x 300 mu m. The dispersibility into a high SP value organic solvent was evaluated by the following evaluation criteria.

<Evaluation Criteria>

⊚: Polymer particles are dispersed extremely uniformly without agglomeration (less than three aggregates in which more than five polymer particles are aggregated and aggregated, and dispersibility into a high SP value organic solvent is very good)

?: Polymer particles are uniformly dispersed without agglomeration (agglomerates in which five or more polymer particles are aggregated and agglomerated are dispersed in three or more and five or less points; good dispersibility into a high SP value organic solvent)

?: Part of the polymer particles were aggregated (aggregates in which 5 or more polymer particles were aggregated and aggregated at 6 points or more and 15 points or less; the dispersibility into the high SP value organic solvent was slightly poor)

X: The polymer particles are aggregated (aggregates having 5 or more polymer particles aggregated and aggregated at 16 points or more; poor dispersibility into a high SP value organic solvent)

[Method for measuring the solubility of one kind of other surfactant in a cleaning liquid having a liquid temperature of 25 캜]

Since the solubility of the liquid solute in the solvent is generally determined by the &quot; opacity &quot; or &quot; opacity &quot; of a solution formed by dissolving the liquid solute in a solvent, Was measured by measuring the &quot; transmittance &quot; of a solution having a liquid temperature of 25 DEG C which was obtained by dissolving one kind of another surfactant in a cleaning liquid. In addition, a part of the liquid solute does not dissolve in the solvent but precipitates, resulting in turbidity in the transparent liquid (solution), resulting in a decrease in the transmittance of the solution.

The procedure for measuring the solubility (D) of one kind of other surfactant relative to pure water as a cleaning liquid at a liquid temperature of 25 ° C is described below.

1) First, 4 ml of pure water is put into a dedicated cell, and the transmittance (T _water ) of pure _water at a wavelength of 380 nm is measured.

2) Subsequently, an adjustment liquid was prepared by dissolving Xg of one kind of other surfactant in 100 g of pure water in a room temperature atmosphere (25 ° C), and 4 ml of the adjustment liquid was injected into a dedicated cell to adjust the transmittance of the adjustment liquid at a wavelength of 380 nm _S ) is measured.

3) Then, the relative transmittance (T) of the adjusted liquid with respect to the transmittance of pure water is calculated by the following equation.

T = (T _s ) / (T _water )

Then, while changing X repeatedly, the relative transmittance T of the adjustment liquid is calculated,

T = (T _s ) / (T _water ) = 0.98

The solubility (S ₀ ) (g / 4 ml) of one kind of other surfactant is obtained as the value of X to be established. Then, the solubility (S ₀ ) (g / 4 ml)

D = S ₀ x 100/4

(D) (g / 100 ml) of one kind of other surfactant. Here, the transmittance (T _water ) and the transmittance (T _S ) are measured using an ultraviolet visible spectrophotometer (product number: UV-2450, manufactured by Shimadzu Corporation).

[Production Example 1 of seed particles]

1250 g of water as an aqueous medium, 64 g of methyl methacrylate as a (meth) acrylic acid ester-based monomer, and 0.64 g of n-octylmercaptan as a molecular weight regulator were introduced into a separable flask equipped with a stirrer, a thermometer and a reflux condenser, The interior of the separable flask was purged with nitrogen while stirring the contents of the flask, and the internal temperature of the separable flask was raised to 70 캜. An aqueous solution obtained by dissolving 0.32 g of potassium persulfate as a polymerization initiator in 50 g of water was added to the contents in the separable flask while keeping the inner temperature of the separable flask at 70 占 폚, followed by polymerization reaction for 5 hours.

Thereafter, 256 g of methyl methacrylate and 2.56 g of n-octylmercaptan as a molecular weight regulator were introduced, and the inside of the separable flask was again purged with nitrogen. Then, the internal temperature of the separable flask was elevated to 70 캜 Lt; / RTI &gt; An aqueous solution obtained by dissolving 1.2 g of potassium persulfate as a polymerization initiator in 50 g of water was added to the contents in the separable flask while maintaining the inner temperature of the separable flask at 70 占 폚, and polymerization was carried out for 12 hours.

The reaction liquid after the polymerization was filtered with a wire mesh of 400 mesh (interval of 32 占 퐉) to prepare a slurry containing 20% by weight of solid particles (referred to as seed particles (1)) made of polymethyl methacrylate as solid content. The seed particles (1) contained in this slurry were spherical particles having a volume average particle diameter of 0.54 占 퐉.

[Seed particle production example 2]

A separable flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 1450 g of water as an aqueous medium, 250 g of methyl methacrylate as a (meth) acrylate monomer and 2.5 g of n-octylmercaptan as a molecular weight regulator, The interior of the separable flask was purged with nitrogen while stirring the contents of the flask, and the internal temperature of the separable flask was raised to 70 캜. An aqueous solution obtained by dissolving 1.25 g of potassium persulfate as a polymerization initiator in 50 g of water was added to the contents in the separable flask while keeping the inner temperature of the separable flask at 70 占 폚, followed by polymerization for 12 hours.

The reaction liquid after the polymerization was filtered with a wire mesh of 400 mesh (interval of 32 占 퐉) to prepare a slurry containing 14% by weight of solid particles (referred to as seed particles (2)) made of polymethyl methacrylate as solid content. The seed particles (2) contained in this slurry were spherical particles having a volume average particle diameter of 0.42 占 퐉.

[Seed particle production example 3]

In a 5 L reactor equipped with a stirrer and a thermometer, 3300 g of water as an aqueous medium, 360 g of methyl methacrylate as a (meth) acrylate monomer and 3.6 g of n-octylmercaptan as a molecular weight regulator were charged, The slurry of the seed particles (2) prepared in Preparation Example 2 was added in an amount of 35.0 g as solid particles (seed particles), and the inside was replaced with nitrogen while stirring the contents, and the inner temperature of the reactor was raised to 70 캜. An aqueous solution obtained by dissolving 1.8 g of potassium persulfate as a polymerization initiator in 60 g of water was added to the contents in the reactor while maintaining the inner temperature of the reactor at 70 占 폚, followed by polymerization for 12 hours.

The reaction liquid after the polymerization was filtered through a wire mesh of 400 mesh (interval of 32 占 퐉) to prepare a slurry containing 10% by weight of solid particles of polymethyl methacrylate as a solid component (hereinafter referred to as seed particles (3)) Respectively. The seed particles (3) contained in this slurry were spherical particles having a volume average particle diameter of 1.02 占 퐉.

[Example 1: Production example of polymer particles]

(1) Polymerization process

400 g of methyl methacrylate (MMA) as a (meth) acrylic acid ester monomer, 300 g of styrene (St) as a styrene monomer and 300 g of ethylene glycol dimethacrylate (EGDMA) as a polyfunctional vinyl monomer were added, 6 g of benzoyl peroxide was dissolved in 1000 g of ion-exchanged water as an aqueous medium to prepare an aqueous solution of sodium di (2-ethylhexyl) sulfosuccinate (manufactured by Nichiyu K.K.) as an anionic surfactant having no polyoxyethylene chain (another surfactant) , 10 g of pure water as a raw material) and a homomixer (&quot; TK &quot; (trade name, manufactured by Freix Co., Ltd.) Homomixer MARKII 2.5 type &quot;), and treated at 10,000 rpm for 10 minutes to obtain an emulsion. To this emulsion was added a slurry of the seed particles (1) obtained in Production Example 1 as seed particles in an amount of 9.6 g as solid content (seed particles), followed by stirring at 30 캜 for 5 hours to obtain a dispersion.

10 g of sodium polyoxyethylene nonylphenyl ether phosphate (manufactured by Toho Chemical Co., Ltd., product name: &quot; FOSPHANOL (registered trademark) LO-529 &quot;) as an anionic surfactant having a polyoxyethylene chain and 10 g of a polymerization inhibitor , And then the mixture was stirred at 80 ° C for 5 hours and then at 105 ° C for 3 hours to carry out a polymerization reaction to obtain a slurry of polymer particles (hereinafter referred to as slurry (1)) As a crude product.

(2) Solid-liquid separation process

The slurry 1 of the polymer particles as the crude product P is introduced into the pressure-resistant vessel 2 of the pressure filter 1 having the constitution shown in Fig. 1 and the filter cloth 3 as the filter material 3 in the pressure- The compressed gas is supplied to the upper space S of the filter material 3 in the pressure-resistant container 2 by the compressed gas supplying device after the slurry 1 of the polymer particles is filled on the "T713" manufactured by Shikisima Canvas Co., The inside of the pressure-resistant vessel 2 (specifically, the space S on the upper side of the filter medium 3) was pressurized to 0.15 MPa. As a result, the slurry (1) of the polymer particles as the crude product (P) was subjected to pressure filtration and dehydration to remove water as an aqueous medium from the slurry (1) of the polymer particles as a filtrate. When the amount of the filtrate becomes 2.10 kg (70% of the weight of the water used in the polymerization process) or more, and the internal pressure of the pressure-resistant vessel 2 becomes 0.10 MPa (2/3 of the pressure at the time of pressurization) Lt; / RTI &gt; As a result, a cake of polymer particles was obtained on the filter material 3.

Here, the interface between the filter medium 3 (filter cloth) of the pressure filter 1 used in this embodiment and the object (i.e., the crude product P) is circular and its diameter is larger than the diameter of the inside of the pressure- Which is the same as the diameter of the bottom surface of the space (indicated by R in Fig. 1). Therefore, the area A of the interface between the filter material 3 (filter cloth) of the pressure filter 1 used in this embodiment and the object (i.e., 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 the present embodiment is 2.24 kg and the medium (water) contained in the crude product P is started to pass through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 45.0 minutes. Therefore, the amount (X) per unit time of the medium having passed through the filter medium in the solid-liquid separation step was 0.0498 kg / min.

(3) Cleaning process

Water of 60 deg. C serving as a cleaning liquid (60 deg. C water was also used in the washing step in the other examples and the comparative example) as the cleaning liquid while the cake of the polymer particles was held on the filter material 3, The compressed gas is supplied to the space S in the upper space S of the filter material 3 in the pressure-resistant container 2 by the compressed gas supply device so that the inside of the pressure-resistant container 2 (specifically, (The upper space S in the upper space 3) was pressurized to 0.10 MPa. As a result, the pressure filtration and dehydration were performed, the cake of the polymer particles was washed, and the water after washing was removed as a filtrate to obtain polymer particles after washing on the filter material 3. The cleaning is carried out by using a cleaning liquid having a weight of 10 times or more the weight of the polymer particles obtained in the polymerization step (the total amount of the vinyl monomers used in the polymerization step: 1000 g), and the conductivity of the filtrate is 2.0 times or less , 15 μS or less), and the inner pressure of the pressure-resistant container 2 was 0.066 MPa (2/3 of the pressure at the time of pressurization).

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 equations (4) and (5) for one kind of other surfactant used in the above- Were as follows.

B _{L =} (10 (g) / 1.5 (g / 100 ml)) x 1.8 = 12.0 (kg)

B _H = (10 (g) / 1.5 (g / 100 ml)) x 2.3 = 15.3 (kg)

This embodiment of water as washing liquid weight used in the example the washing step (G ₂₎ is a 13.0㎏ (13.0 times the weight of the polymer particles obtained in the polymerization step), the lower limit value (B _L) over the range of less than or equal to the upper limit value (B _H) Lt; / RTI &gt;

In the cleaning process of this embodiment, after the cleaning liquid is passed through the filter material 3, a cleaning liquid of 10.4 kg (0.8 times the weight of water (G ₂ ) as the cleaning liquid used in the cleaning process) ) Was 140.5 minutes (T ₂ ) (min). Therefore, the amount (Y) per unit time of the medium having passed through the filter medium in the cleaning step was 0.0740 kg / min.

(4) Post-treatment process

[Drying process]

The washed polymer particles obtained by the washing step were dried using a vacuum drier (shredding drier) until the moisture value of the polymer particles measured by the Karl Fischer method was less than 1.0% by weight under the following drying conditions.

(Drying condition)

Vacuum degree: -0.1 to -0.3 MPa

Temperature: 50 ~ 60 ℃

[Classification Process (Coarse Particle Removal)]

The polymer particles after drying obtained by the drying process are dispersed in an air stream classifier (&quot; Turbo classifier (registered trademark) TC-15 &quot; manufactured by Nissei Engineering Co., Ltd.) And classified so as to remove particles having a particle diameter, thereby obtaining desired polymer particles.

(Confirmation of Formula for Polymer Particle Surfaces of Surfactants Having Polyoxyethylene Chains)

For the polymer particles of Example 1, the content of sodium polyoxyethylene nonylphenyl ether phosphate as anionic surfactant having a polyoxyethylene chain was measured by a method for measuring the content of the surfactant described above (ultrasonic extraction time of 15 minutes) As a result, it was 0.79% by weight.

It is impossible to deny the possibility that a surfactant having a polyoxyethylene chain is introduced into the polymer particles only by these measurement results. Here, the polymer particles were extracted by immersing in methanol, and the change in the amount of the surfactant having the polyoxyethylene chain contained in the extracted component was observed over time. When the extraction time is short (from 15 minutes to 30 minutes), the extraction component generally consists only of components extracted from the surface of the polymer particles, and as the extraction time becomes longer, the proportion of components extracted from the polymer particles contained in the extraction component .

Except that the polymer particles of Example 1 were changed to ultrasound extraction time of 30 minutes, 12 hours, and 24 hours, respectively, in the same manner as in the above-mentioned method for measuring the content of the surfactant, the polyoxyethylene nonylphenyl ether sodium phosphate (Amount of surfactant having polyoxyethylene chain contained in the extracted component) were measured, and found to be 0.79 wt%, 0.80 wt%, and 0.80 wt%, respectively.

Further, the polymer particles of Example 1 were measured in the same manner as the above-mentioned method for measuring the content of the surfactant, except that water was used instead of methanol as an extraction liquid and the ultrasonic extraction time was changed to 30 minutes, 12 hours, and 24 hours, respectively The content of sodium polyoxyethylene nonylphenyl ether phosphate (amount of surfactant having a polyoxyethylene chain contained in the extraction component) was measured to be 0.003% by weight, 0.004% by weight and 0.004% by weight, respectively. The results of these measurements are summarized in Table 1.

As can be seen from the results of Table 1, even in the case of using either methanol or water as the extraction liquid, even if the extraction time is observed from 30 minutes to 12 hours to 24 hours, the polyoxyethylene nonylphenyl No significant increase in the amount of sodium ether phosphate was observed. From this point of view, it was judged that there was no (very small amount) extraction of polyoxyethylene nonylphenyl ether sodium phosphate from the inside of the polymer particles, that is, there was no introduction of the surfactant having a polyoxyethylene chain into the polymer particles.

(Identification of by-product (emulsion polymerization product)

An SEM image of the polymer particles immediately after the polymerization reaction obtained in Example 1 is shown in Fig. 2, and an SEM image of the polymer particles obtained after the solid-liquid separation process and the cleaning process of Example 1 are shown in Fig. From Fig. 2, it was confirmed that particles having a particle diameter of about 100 to 200 nm as a by-product (emulsion polymerization product) adhered to the surface of the polymer particles. From Fig. 3, it was confirmed that the by-product (emulsion polymerization product) was hardly adhered to the surface of the polymer particles (a very small amount was adhered).

[Example 2: Production example of polymer particles]

Sodium di (2-ethylhexyl) sulfosuccinate was used as an anionic surfactant having no polyoxyethylene chain (another surfactant) in place of 10 g of sodium laurylsulfate (product name: (Solubility in water having a liquid temperature of 25 ° C of 10 g / 100 ml) as the pure water was used to obtain a total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step of 2.30 kg, Liquid separation process so that the time (T ₁ ) from the start of passage of the medium (water) contained in the filter medium 3 to the filter medium 3 through the filter medium 3 and the completion of the passage of the filter medium 3 of the medium is 50.0 minutes (G ₂ ) as a cleaning liquid used in the cleaning process was changed to 10.5 kg (10.5 times the weight of the polymer particles obtained in the polymerization process), and the cleaning liquid was passed through the filter material 3 8.4 kg (cleaning Was the time of the cleaning liquid of 0.8 times by weight) of water by weight as the cleaning liquid (G ₂₎ used in the process is consumed by passing through the filter medium _{(3) (T 2) (} min) changing the conditions of the washing step so that the minute 150.2 The target polymer particles were obtained in the same manner as in Example 1 except for the above.

The amount X of the medium passed through the filter medium in the solid-liquid separation step was 0.0460 kg / min per unit time, and the amount (Y) per unit time of the medium passed through the filter medium in the washing step was 0.0559 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 equations (4) and (5) for one kind of other surfactant used in the above- Were as follows.

B _{L =} (50 (g) / 10 (g / 100 ml) x 1.8 = 9.0 (kg)

B _H = (50 (g) / 10 (g / 100 ml)) x 2.3 = 11.5 (kg)

By weight of water as the cleaning liquid used in this embodiment, the washing step (G ₂₎ is a 10.5㎏ (10.5 times the weight of the polymer particles obtained in the polymerization step), the lower limit value (B _L) over the range of less than or equal to the upper limit value (B _H) Lt; / RTI &gt;

[Example 3: Production example of polymer particles]

Sodium di (2-ethylhexyl) sulfosuccinate as an anionic surfactant having no polyoxyethylene chain (another surfactant) was used instead of 10 g of purified water as a pure component, and potassium potassium alkenylsuccinate (manufactured by Kao Corporation, (Registered trademark) ASK ", solubility in water at 25 ° C of water: 1.7 g / 100 ml) were used in the same manner as in Example 1, to obtain the desired polymer particles.

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step of this embodiment is 2.30 kg and the medium (water) contained in the crude product P is started to pass through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 40.9 minutes. Therefore, the amount (X) per unit time of the medium having passed through the filter medium in the solid-liquid separation step was 0.0562 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 equations (4) and (5) for one kind of other surfactant used in the above- Were as follows.

B _{L =} (10 (g) / 1.7 (g / 100 ml) x 1.8 = 10.6 (kg)

B _H = (10 (g) / 1.7 (g / 100 ml)) x 2.3 = 13.5 (kg)

This embodiment of water as washing liquid weight used in the example the washing step (G ₂₎ is a 13.0㎏ (13.0 times the weight of the polymer particles obtained in the polymerization step), the lower limit value (B _L) over the range of less than or equal to the upper limit value (B _H) Lt; / RTI &gt;

In the cleaning process of this embodiment, after the cleaning liquid is passed through the filter material 3, a cleaning liquid of 10.4 kg (0.8 times the weight of water (G ₂ ) as the cleaning liquid used in the cleaning process) ) (T ₂ ) (min) before passing through the tube was 132.0 minutes. Therefore, the amount (Y) per unit time of the medium having passed through the filter medium in the washing step was 0.0788 kg / min.

[Example 4: Production example of polymer particles]

As an anionic surfactant having a polyoxyethylene chain, 10 g of sodium polyoxyethylene nonylphenyl ether phosphate was used instead of 10 g of polyoxyethylene styrenated phenyl ether sulfuric acid ester ammonium (manufactured by Daiichi Kogyo Seiyaku Co., trademark) NF-08 ") of the cleaning liquid used as sunbun 10g and, after the start passing the cleaning liquid to the filter medium (3) 10.4㎏ (0.8 times by weight) the weight of water as a cleaning liquid (G ₂₎ used in the cleaning process The target polymer particles were obtained in the same manner as in Example 1, except that the conditions for the washing step were changed so that the time (T ₂ ) (min) consumed until passing through the filter material 3 was 129.0 minutes.

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step of the present embodiment is 2.28 kg, and after starting to pass the medium (water) contained in the crude product P through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 41.0 minutes. Therefore, the amount (X) per unit time of the medium having passed through the filter medium in the solid-liquid separation step was 0.0556 kg / min. The amount (Y) per unit time of the medium having passed through the filter medium in the cleaning 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 equations (4) and (5) for one kind of other surfactant used in the above- Is the same as that of the first embodiment. The weight (G ₂ ) of water as the cleaning liquid used in the cleaning step of this embodiment is 13.0 kg (13.0 times the weight of the polymer particles obtained in the polymerization step), and is not less than the lower limit value B _L (= 12.0 (B _H ) (= 15.3 (kg)) or less.

[Example 5: Production example of polymer particles]

As an anionic surfactant having a polyoxyethylene chain, 10 g of polyoxyethylene nonylphenyl ether phosphate sodium as a pure fraction was substituted for 10 g of polyoxyethylene styrenated phenyl ether phosphate ester (manufactured by Daiichi Kogyo Seiyaku Co., Ltd. under the trade name &quot; (Water) contained in the crude product P is added to the filtration media 3 in the same manner as in Example ₁ , , The conditions of the solid-liquid separation step were changed so that the time (T ₁ ) from the start of the passage of the filtration media 3 through the medium ₁ to the completion of the passage of the medium 3 of the medium was 40.8 minutes, and after the time of the cleaning liquid 10.4㎏ (0.8 times the weight of the weight of water as a cleaning liquid (G ₂₎ used in the washing step) is consumed up to pass through the filter medium _{(3) (T 2) (} min) is 133.5 minutes Except for changing the conditions of the washing process to the same manner as in Example 1, to obtain the polymer particles for the purpose.

The amount (X) per unit time of the medium passed through the filter medium in the solid-liquid separation step was 0.0551 kg / min. The amount (Y) per unit time of the medium having passed through the filter medium in the washing step 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 equations (4) and (5) for one kind of other surfactant used in the above- Is the same as that of the first embodiment. The weight (G ₂ ) of water as the cleaning liquid used in the cleaning step of this embodiment is 13.0 kg (13.0 times the weight of the polymer particles obtained in the polymerization step), and is not less than the lower limit value B _L (= 12.0 (B _H ) (= 15.3 (kg)) or less.

[Example 6: Production example of polymer particles]

As a surfactant used for obtaining an emulsion in the polymerization process, 10 g of sodium di (2-ethylhexyl) sulfosuccinate as a pure substance was used instead of 10 g of polyoxyethylene nonylphenyl ether phosphate as an anionic surfactant having a polyoxyethylene chain 20 g of sodium (manufactured by TOHO Chemical Industry Co., Ltd., product name: "FOSPANOL (registered trademark) LO-529") "was used as a pure substance. In the polymerization step, the polyoxyethylene nonylphenyl ether sodium phosphate was added Using 2000 g of an aqueous solution obtained by dissolving 0.60 g of sodium nitrite in place of 2000 g of an aqueous solution obtained by dissolving 10 g of pure polyoxyethylene nonylphenyl ether phosphate as an aqueous solution and 0.60 g of sodium nitrite as an aqueous solution to be used in the cleaning step (G ₂ ) as the cleaning liquid used in Example ₁ was changed to 10.0 kg (the weight of the polymer particles obtained in the polymerization step 10.0 times the weight of the filtration material 3), the cleaning liquid is passed through the filter material 3 and then a cleaning liquid of 8.0 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 for the washing step were changed so that the time (T ₂ ) (min) consumed until passing was 100.6 minutes.

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment is 2.29 kg. After starting to pass the medium (water) contained in the crude product P through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 43.0 minutes. Therefore, the amount (X) per unit time of the medium having passed through the filter medium in the solid-liquid separation step was 0.0533 kg / min. The amount (Y) per unit time of the medium having passed through the filter medium in the cleaning step was 0.0795 kg / min.

[Example 7: Production example of polymer particles]

The use amount of methyl methacrylate (MMA) was changed to 700 g without using styrene and the washing liquid was passed through the filter material 3 at 10.4 kg (the weight of water used as a cleaning liquid in the cleaning step (G ₂₎ time the cleaning liquid of 0.8 times by weight) consumed by passing through the filter medium (3) (T ₂₎ (except that the min) to change the condition of the cleaning process such that minutes 143.8 in the same manner as in example 1, To obtain the intended polymer particles.

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step of the present embodiment is 2.31 kg and the medium (water) contained in the crude product P is started to pass through the filter medium 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 43.2 minutes. Therefore, the amount (X) per unit time of the medium having passed through the filter medium in the solid-liquid separation step was 0.0535 kg / min. The amount (Y) per unit time of the medium having passed through the filter medium in the cleaning 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 equations (4) and (5) for one kind of other surfactant used in the above- Is the same as that of the first embodiment. The weight (G ₂ ) of water as the cleaning liquid used in the cleaning step of this embodiment is 13.0 kg (13.0 times the weight of the polymer particles obtained in the polymerization step), and is not less than the lower limit value B _L (= 12.0 (B _H ) (= 15.3 (kg)) or less.

[Example 8: Production example of polymer particles]

The amount of styrene (St) was changed to 900 g, the amount of ethylene glycol dimethacrylate (EGDMA) was changed to 100 g, and the cleaning liquid was passed through the filter material 3 without using methyl methacrylate (MMA) (T ₂ ) (min) of consumption of 10.4 kg (0.8 times the weight of water (G ₂ ) as the cleaning liquid used in the cleaning process) until the cleaning liquid passes through the filter material 3 is 137.5 minutes The intended polymer particles were obtained in the same manner as in Example 1 except that the conditions of the washing step were changed.

Further, the total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step of this embodiment is 2.30 kg, and the medium (water) contained in the crude product P is started to pass through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 44.0 minutes. Therefore, the amount (X) per unit time of the medium having passed through the filter medium in the solid-liquid separation step was 0.0523 kg / min. The amount (Y) per unit time of the medium having passed through the filter medium in the cleaning step 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 equations (4) and (5) for one kind of other surfactant used in the above- Is the same as that of the first embodiment. The weight (G ₂ ) of water as the cleaning liquid used in the cleaning step of this embodiment is 13.0 kg (13.0 times the weight of the polymer particles obtained in the polymerization step), and is not less than the lower limit value B _L (= 12.0 (B _H ) (= 15.3 (kg)) or less.

[Example 9: Production example of polymer particles]

The slurry of the seed particles (3) obtained in Production Example 3 of the seed particles was replaced with 4.7 g of solid particles (seed particles) in place of 9.6 g of the slurry of the seed particles (1) And 10.4 kg (0.8 times the weight of water (G ₂ ) as the cleaning liquid used in the cleaning process) is started to be passed through the filter material 3 until the cleaning liquid is passed through the filter material 3 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 130.0 minutes.

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step of the present embodiment is 2.45 kg and the medium (water) contained in the crude product P is started to pass through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 45.0 minutes. Therefore, the amount (X) per unit time of the medium having passed through the filter medium in the solid-liquid separation step was 0.0544 kg / min. The amount (Y) per unit time of the medium having passed through the filter medium in the cleaning step 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 equations (4) and (5) for one kind of other surfactant used in the above- Is the same as that of the first embodiment. The weight (G ₂ ) of water as the cleaning liquid used in the cleaning step of this embodiment is 13.0 kg (13.0 times the weight of the polymer particles obtained in the polymerization step), and is not less than the lower limit value B _L (= 12.0 (B _H ) (= 15.3 (kg)) or less.

[Comparative Example 1: Production example of polymer particles]

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step becomes 2.33 kg and the medium (water) contained in the crude product P is started to pass through the filter material 3, The condition of the solid-liquid separation step was changed so that the time (T ₁ ) until the completion of the passage of the cleaning liquid 3 was 47.5 minutes, and the weight of the cleaning liquid (G ₂ ) ), The objective polymer particles were obtained in the same manner as in Example 1. The amount (X) per unit time of the medium passed through the filter medium in the solid-liquid separation step was 0.0491 kg / min.

[Comparative Example 2: Production example of polymer particles]

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step becomes 2.41 kg and the medium (water) contained in the crude product P is started to pass through the filter material 3, Liquid separation process so that the time (T ₁ ) until the completion of the passage of the cleaning liquid 3 is 45.0 minutes is changed, and the weight (G ₂ ) of water as the cleaning liquid used in the cleaning process is 5.0 kg (5.0 times the weight of the polymer particles), the cleaning liquid is passed through the filter material 3, and then a cleaning liquid of 4.0 kg (0.8 times the weight of water (G ₂ ) used as the cleaning liquid in the cleaning process) The intended polymer particles were obtained in the same manner as in Example 1, except that the conditions for the washing step were changed so that the time (T ₂ ) (min) consumed until passing through the filter material 3 was 48.6 minutes.

The amount X of the medium passing through the filter medium in the solid-liquid separation step was 0.0536 kg / min per unit time, and the amount Y of the medium passed through the filter medium in the cleaning step per unit time was 0.0823 kg / min.

[Comparative Example 3: Production example of polymer particles]

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step becomes 2.39 kg and the medium (water) contained in the crude product P is started to pass through the filter material 3, Liquid separation process so that the time (T ₁ ) until the completion of the passage of the cleaning liquid 3 was 47.7 minutes, and the weight (G ₂ ) of water as the cleaning liquid used in the cleaning process was 5.0 kg (5.0 times the weight of the polymer particles), the cleaning liquid is passed through the filter material 3, and then a cleaning liquid of 4.0 kg (0.8 times the weight of water (G ₂ ) used as the cleaning liquid in the cleaning process) The target polymer particles were obtained in the same manner as in Example 4, except that the conditions of the washing step were changed so that the time (T ₂ ) (min) consumed until passing through the filter material 3 was 55.2 minutes.

The amount (X) per unit time of the medium passed through the filter medium in the solid-liquid separation step was 0.0501 kg / min, and the amount (Y) per unit time of the medium passed through the filter medium in the washing step was 0.0725 kg / min.

[Comparative Example 4: Production example of polymer particles]

Except that 10 g of polyoxyethylene nonylphenyl ether sodium phosphate as a pure fraction was replaced with 50 g of pure polyvinyl alcohol (PVA) (Gosenol GM-14L, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as a polymer dispersion stabilizer, The total weight (G ₁ ) of the filtrate (medium) obtained in the separation step becomes 2.35 kg and the medium (water) contained in the crude product P is started to pass through the filter material 3, Liquid separation process was changed so that the time (T ₁ ) until the completion of the passage of the cleaning liquid 3 was 44.8 minutes and the cleaning liquid was passed through the filter material 3, 10.4 kg Except that the condition of the cleaning step was changed so that the time (T ₂ ) (min) during which the cleaning liquid, which was 0.8 times the weight of water (G ₂ ) as water as the water The same as To obtain the polymer particles for the purpose.

The amount (X) per unit time of the medium passed through the filter medium in the solid-liquid separation step was 0.0525 kg / min, and the amount (Y) per unit time of the medium passed through the filter medium in the washing step was 0.0728 kg / min.

[Example 10: Production example of polymer particles]

10 g of sodium polyoxyethylene nonylphenyl ether as an anionic surfactant having a polyoxyethylene chain was used instead of 10 g of pure sodium polyoxyethylene styrenated phenyl ether as a nonionic surfactant having a polyoxyethylene chain (G) of the filtrate (medium) obtained in the solid-liquid separation step was 2.29 kg, and the crude product (P) was obtained in the same manner as in Example ₁ , except that 10 g of pure product (product name: "NOIGEN (registered trademark) EA- (T ₁ ) from the start of passage of the medium (water) contained in the filter medium 3 through the filter medium 3 to the passage of the filter medium 3 of the medium is 51.0 minutes , The objective polymer particles were obtained in the same manner as in Example 1.

The amount (X) per unit time of the medium passed through the filter medium in the solid-liquid separation step was 0.0499 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 equations (4) and (5) for one kind of other surfactant used in the above- Is the same as that of the first embodiment. The weight (G ₂ ) of water as the cleaning liquid used in the cleaning step of this embodiment was 13.0 kg (weight of the polymer particles obtained in the polymerization step was 13.0 times).

In the cleaning process of this embodiment, after the cleaning liquid is passed through the filter material 3, a cleaning liquid of 10.4 kg (0.8 times the weight of water (G ₂ ) as the cleaning liquid used in the cleaning process) (T ₂ ) (min) before passing through the tube was 170.0 minutes. Therefore, the amount (Y) per unit time of the medium having passed through the filter medium in the washing step was 0.0612 kg / min.

[Example 11: Production example of polymer particles]

The addition amount of sodium polyoxyethylene nonylphenyl ether phosphate (manufactured by Toho Chemical Co., Ltd., product name: &quot; Phosphanol (registered trademark) LO-529 &quot;) as an anionic surfactant having a polyoxyethylene chain was 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 started to pass through the filter material 3, The condition of the solid-liquid separation step was changed so that the time (T ₁ ) until the completion of the passage of the washing liquid 3 was 43.3 minutes, and the washing liquid was passed through the filter material 3 and then 10.4 kg (as the washing liquid used in the washing step Except that the conditions of the washing step were changed such that the time (T ₂ ) (min) during which the washing liquid of the washing liquid, which was 0.8 times the weight of water (G ₂ ), was passed through the filter material 3 was 126.8 minutes. copper To to give the polymer particles for the purpose.

The amount X of the medium passed through the filter medium in the solid-liquid separation step was 0.0543 kg / min, and the amount Y of the medium passed 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 equations (4) and (5) for one kind of other surfactant used in the above- Is the same as that of the first embodiment. The weight (G ₂ ) of water as the cleaning liquid used in the cleaning step of this embodiment is 13.0 kg (13.0 times the weight of the polymer particles obtained in the polymerization step), and is not less than the lower limit value B _L (= 12.0 (B _H ) (= 15.3 (kg)) or less.

[Example 12: Production example of polymer particles]

The addition amount of sodium polyoxyethylene nonylphenyl ether phosphate (manufactured by Toho Chemical Co., Ltd., product name: "Phospholone (registered trademark) LO-529") as a pure anionic surfactant having a polyoxyethylene chain was changed from 10 g to 5 g, after the start passing the cleaning liquid to the filter medium (3) the time of the cleaning liquid 10.4㎏ (0.8 times the weight of the weight of water as a cleaning liquid (G ₂₎ used in the washing step) is consumed up to pass through the filter medium (3) (T ₂ ) (min) was changed to 135.5 minutes, the target polymer particles were obtained in the same manner as in Example 1.

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step of the present embodiment is 2.32 kg. After starting to pass the medium (water) contained in the crude product P through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 45.5 minutes. Therefore, the amount (X) per unit time of the medium having passed through the filter medium in the solid-liquid separation step was 0.0510 kg / min. The amount (Y) per unit time of the medium having passed through the filter medium in the cleaning step 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 equations (4) and (5) for one kind of other surfactant used in the above- Is the same as that of the first embodiment. The weight (G ₂ ) of water as the cleaning liquid used in the cleaning step of this embodiment is 13.0 kg (13.0 times the weight of the polymer particles obtained in the polymerization step), and is not less than the lower limit value B _L (= 12.0 (B _H ) (= 15.3 (kg)) or less.

[Example 13: Production example of polymer particles]

The weight (G ₂ ) of water as a cleaning liquid used in the cleaning step was changed to 12.1 kg (12.1 times the weight of the polymer particles obtained in the polymerization step), and the cleaning liquid was passed through the filter material 3 and then 9.68 kg (T ₂ ) (min) consumed until the cleaning liquid, which is 0.8 times the weight of water (G ₂ ) as the cleaning liquid used in the cleaning process, passed through the filter material 3 was 110.0 minutes , The objective polymer particles were obtained in the same manner as in Example 1. In the washing step of this embodiment, the amount (Y) per unit time of the medium having passed through the filter medium is 0.0880 kg / min.

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step of the present embodiment is 2.37 kg. After starting to pass the medium (water) contained in the crude product P through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 43.2 minutes. Therefore, the amount (X) per unit time of the medium having 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 equations (4) and (5) for one kind of other surfactant used in the above- Is the same as that of the first embodiment. The weight (G ₂ ) (= 12.1 kg) of water as the cleaning liquid used in the cleaning step of this embodiment is preferably not less than the lower limit value B _L (= 12.0 (kg)) and the upper limit value B _H (= 15.3 The weight is within the following range.

[Example 14: Production example of polymer particles]

After the start passing the cleaning liquid to the filter medium (3), the time of the cleaning liquid 10.4㎏ (0.8 times the weight of the weight of water as a cleaning liquid (G ₂₎ used in the washing step) is consumed up to pass through the filter medium (3) ( T ₂ ) (min) was changed to 357.4 minutes, the target polymer particles were obtained in the same manner as in Example 1. In the cleaning step of this embodiment, the amount (Y) per unit time of the medium having passed through the filter medium in the cleaning step is 0.0291 kg / min.

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation process of the present embodiment is 2.34 kg. After starting to pass the medium (water) contained in the crude product P through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 50.2 minutes. Therefore, the amount (X) per unit time of the medium 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 equations (4) and (5) for one kind of other surfactant used in the above- Is the same as that of the first embodiment. The weight (G ₂ ) of water as the cleaning liquid used in the cleaning step of this embodiment is 13.0 kg (13.0 times the weight of the polymer particles obtained in the polymerization step), and is not less than the lower limit value B _L (= 12.0 (B _H ) (= 15.3 (kg)) or less.

[Example 15: Production example of polymer particles]

The weight (G ₂ ) of the water as the cleaning liquid used in the cleaning step was changed to 12.0 kg (weight of the polymer particles obtained in the polymerization step 12.0 times), and the cleaning liquid was passed through the filter material 3, (T ₂ ) (min) consumed until the cleaning liquid, which is 0.8 times the weight of the water (G ₂ ) as the cleaning liquid used in the cleaning process, passed through the filter material 3 was 109.0 minutes , The objective polymer particles were obtained in the same manner as in Example 1. The amount (Y) per unit time of the medium passed through the filter medium in the cleaning process is 0.0881 kg / min.

Further, the total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step of this embodiment is 2.30 kg, and the medium (water) contained in the crude product P is started to pass through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 41.5 minutes. Therefore, the amount (X) per unit time of the medium having 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 equations (4) and (5) for one kind of other surfactant used in the above- Is the same as that of the first embodiment. The weight (G ₂ ) (= 12.0 kg) of water used as the cleaning liquid used in the cleaning process of this embodiment is not more than the lower limit value B _L (= 12.0 (kg)) and not more than the upper limit value B _H (= 15.3 Lt; / RTI &gt;

[Comparative Example 5: Production example of polymer particles]

The addition amount of sodium polyoxyethylene nonylphenyl ether phosphate (manufactured by TOHO Chemical Industry Co., Ltd., product name: "FOSPANOL (registered trademark) LO-529") as a pure anionic surfactant having a polyoxyethylene chain was changed from 10 g to 40 g, the total weight (G ₁₎ of the filtrate (medium) obtained by changing the weight of water as a cleaning liquid (G ₂₎ used in the washing step to 5.0㎏ (5.0 times the weight of the polymer particles obtained in the polymerization step), and, in the solid-liquid separation process (T ₁ ) from the start of passage of the medium (water) contained in the crude product P into the filter medium 3 until the passage of the filter medium 3 of the medium is terminated changing the conditions of the solid-liquid separation step to be 42.8 minutes, washed in the washing liquid the filter material (3) and then 4.0㎏ (0.8 times the weight of the weight of water as a cleaning liquid (G ₂₎ used in the washing step) discloses passing the The objective 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) consumed until the liquid passed through the filter medium 3 was 49.7 minutes.

The amount (X) of the medium passing through the filter medium in the solid-liquid separation step per unit time was 0.0537 kg / min, and the amount (Y) per unit time of the medium passed through the filter medium in the washing step was 0.0805 kg / min.

[Comparative Example 6: Production example of polymer particles]

The total weight (G ₁₎ of the filtrate (medium) obtained by changing the cleaning liquid as the weight of water (G ₂₎ used in the washing step to 25.0㎏ (weight of 25.0 times of the polymer particles obtained in the polymerization step), and in the solid-liquid separation process (T ₁ ) from the start of passage of the medium (water) contained in the crude product P into the filter medium 3 until the passage of the filter medium 3 of the medium is terminated changing the conditions of the solid-liquid separation step to be 54.2 minutes, after the start passing the cleaning liquid to the filter medium (3) in the cleaning liquid 20.0㎏ (0.8 times the weight of the weight of water as a cleaning liquid (G ₂₎ used in the cleaning process), the filter material ( 3), 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)

The amount (X) per unit time of the medium passed through the filter medium in the solid-liquid separation step was 0.0426 kg / min, and the amount (Y) per unit time of the medium passed through the filter medium in the washing step was 0.0800 kg / min.

[Comparative Example 7: Production example of polymer particles]

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step becomes 2.25 kg and the medium (water) contained in the crude product P is started to pass through the filter material 3, The condition of the solid-liquid separation step was changed so that the time (T ₁ ) until the completion of the passage of the cleaning liquid 3 was 21.8 minutes, and the cleaning liquid was passed through the filter material 3. Then, 10.4 kg Except that the conditions of the cleaning step were changed so that the time (T ₂ ) (min) during which the cleaning liquid, which was 0.8 times the weight of water (G ₂ ) as water as the water , The objective polymer particles were obtained.

The amount (X) per unit time of the medium passed through the filter medium in the solid-liquid separation step was 0.1032 kg / min, and the amount (Y) per unit time of the medium passed through the filter medium in the washing step was 0.1115 kg / min.

[Comparative Example 8: Production example of polymer particles]

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step becomes 2.25 kg and the medium (water) contained in the crude product P is started to pass through the filter material 3, The condition of the solid-liquid separation step was changed so that the time (T ₁ ) until the completion of the passage of the cleaning liquid 3 was 17.7 minutes, and the cleaning liquid was passed through the filter material 3 and then 10.4 kg (as the cleaning liquid used in the cleaning step Except that the conditions of the cleaning step were changed so that the time (T ₂ ) (min) during which the cleaning liquid of the cleaning liquid, which was 0.8 times the weight of the water weight (G ₂ ), passed through the filter material 3 was 118.3 minutes. In the same manner, the aimed polymer particles were obtained.

The amount (X) per unit time of the medium passed through the filter medium in the solid-liquid separation step was 0.1271 kg / min, and the amount (Y) per unit time of the medium having passed through the filter medium in the washing step was 0.0879 kg / min.

[Comparative Example 9: Production example of polymer particles]

After the start passing the cleaning liquid to the filter medium (3) the time of the cleaning liquid 10.4㎏ (0.8 times the weight of the weight of water as a cleaning liquid (G ₂₎ used in the washing step) is consumed up to pass through the filter medium (3) (T ₂ ) (min) was changed to 90.0 minutes in the same manner as in Example 1, except that the conditions of the washing step were changed. The amount (Y) per unit time of the medium having passed through the filter medium in the washing step was 0.1156 kg / min.

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step of this comparative example is 2.33 kg. After starting to pass the medium (water) contained in the crude product P through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 55.2 minutes. Therefore, the amount (X) per unit time of the medium passed through the filter medium in the solid-liquid separation step was 0.0422 kg / min.

[Comparative Example 10: Production example of polymer particles]

(G ₂ ) as a cleaning liquid to be used in the cleaning process was changed to 3.0 kg (3.0 times the weight of the polymer particles obtained in the polymerization process), and the cleaning liquid was passed through the filter material 3 and then 2.4 kg time the cleaning liquid of 0.8 parts by weight of times) of water as the cleaning liquid by weight of (G ₂₎ used in the process is consumed by passing through the filter medium _{(3) (T 2) (} min) is for changing the condition of the cleaning process to be 27.3 minutes , The objective polymer particles were obtained in the same manner as in Example 6.

The total weight (G ₁ ) of the filtrate (medium) obtained in the solid-liquid separation step of this comparative example is 2.25 kg. After starting to pass the medium (water) contained in the crude product P through the filter material 3 , And the time (T ₁ ) until the passage of the filter medium 3 of the medium was terminated was 40.2 minutes. Therefore, the amount (X) per unit time of the medium passed through the filter medium in the solid-liquid separation step was 0.0560 kg / min. The amount (Y) per unit time of the medium passed through the filter medium in the washing step was 0.0880 kg / min.

[Comparative Example 11: Production example of polymer particles]

Polymer particles were prepared in accordance with Example 5 of Patent Document 5 (JP-A-2009-203378). Namely, first, 529 g of ion-exchanged water, 1.6 g of a 25 mol% ammonia solution and 118 g of methanol were fed into a four-necked flask equipped with a cooling tube, a thermometer and a dropping funnel. While stirring, 3-methacryloxypropyl trimethyl (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added thereto from the dropping funnel to carry out hydrolysis and condensation of 3-methacryloxypropyltrimethoxysilane to prepare organopolysiloxane particles. After 2 hours from the initiation of the reaction, the emulsion of the obtained organopolysiloxane particles was sampled, and the volume average particle diameter was measured by the measurement method described in [Measurement method of variation coefficient of volume average particle diameter and particle diameter of polymer particles] , And the volume average particle diameter was 1.9 mu m.

Subsequently, 20.0 g of a polyoxyethylene styrenated phenyl ether sulfuric acid ester ammonium salt (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name "HITENOL (registered trademark) NF-08"), which is an anionic surfactant having a polyoxyethylene chain 600 g of styrene (St), 400 g of 1,6-hexanediol dimethacrylate (HDDMA), 2,2'-azobis (2,4-dimethylvalerate (Manufactured by Wako Pure Chemical Industries, Ltd., V-65) was added and dispersed by emulsification at 6000 rpm for 5 minutes in a TK homomixer (manufactured by PRIMIX Co., Ltd.) And the obtained monomer emulsion was added to the emulsion of the organopolysiloxane particles, and further stirring was carried out. After 2 hours from the addition of the monomer emulsion, the reaction solution was sampled and observed with a microscope. As a result, it was confirmed that the organopolysiloxane particles absorbed the monomer and became non-enlarged.

Subsequently, the reaction solution was heated to 65 DEG C under a nitrogen atmosphere, and maintained at 65 DEG C for 2 hours to perform radical polymerization of the monomer. The reaction solution was cooled, filtered and the polymerized product was filtered. At this time, the solid content concentration of the recovered product (filtration polymerized product) was 67% by weight.

1 kg of ion-exchanged water was added to the recovered water to adjust the solid content concentration to 40 wt%, and the mixture was stirred for 30 minutes and then filtered to recover the washed polymerized product. At this time, the solid concentration of the recovered product after washing was 60% by weight.

After the washing, the recovered material was dried in a drier at 100 DEG C for 6 hours to obtain an organic-inorganic composite particle. The obtained organic-inorganic composite particles were measured for the coefficient of variation of the volume-average particle diameter and the particle diameter by the measurement method described above. As a result, the volume average particle diameter was 3.82 μm and the coefficient of variation of the particle diameter was 7.22%. The content of the surfactant was measured by the above-described measurement method on the obtained organic-inorganic composite particles, and found to be 1940 ppm by weight (0.19% by weight).

The first filtration was performed by using a quantitative filter paper (Quantitative Filter Paper No. 5C, manufactured by Advantech Co., Ltd.) in place of the filter cloth as the filter material 3 and measuring the total weight (G ₁ ) of the filtrate (medium) (T ₁ ) from the start of passage of the medium (water) contained in the crude product P through the filter medium 3 to the completion of the passage of the medium 3 of the filter medium 3, Liquid separation process of Example 1 was changed so that the temperature of the solid-liquid separation process was changed to 18.5 minutes. In the second filtration, the weight (G ₂ ) of water as the cleaning liquid used in the cleaning step was changed to 1.0 kg (1.0 times the weight of the polymer particles obtained in the polymerization step) so that the solid content concentration became 40% by weight, 3), the time (T ₂ ) during which the cleaning liquid of 0.8 kg (0.8 times the weight of the water (G ₂ ) as the cleaning liquid used in the cleaning process) is consumed until the cleaning liquid passes through the filter material 3 min) was changed to 28.9 minutes, and the filtration material 3 was used as a filtration material (quantitative filter paper No. 5C, manufactured by Advantech Co., Ltd.) instead of the filter cloth, .

The amount (X) per unit time of the medium passed through the filter medium in the solid-liquid separation step was 0.0432 kg / min, and the amount (Y) per unit time of the medium passed through the filter medium in the washing step was 0.0277 kg / min.

[Example 16: Production example of optical film]

0.20 g of the polymer particles obtained in Example 1 and 1.00 g of high SP value organic solvent as an organic solvent were added to a 10 ml sample tube and then ultrasonically cleaned using an ultrasonic cleaner (ULTRASONIC CLEANER VS-150, manufactured by Belvo Clear Co., Ltd.) The mixture was stirred for one minute, and polymer particles were dispersed in butyl acetate as an organic solvent to obtain a dispersion. To this dispersion was further added 1.50 g of an acrylic resin ("ACRYDIC (registered trademark) A-817" manufactured by DIC Co., Ltd., containing 49.0 to 51.0% by weight of toluene and butyl acetate as organic solvents) Followed by stirring for about 2 minutes to obtain a resin composition for coating. After the resin composition for coating was allowed to stand for 4 hours, 5.50 g of butyl acetate as an organic solvent was added to the resin composition for coating, and the mixture was stirred with the ultrasonic cleaner for 1 minute to obtain a diluted solution of the resin composition for coating.

The diluted solution of the obtained resin composition for coating was coated on a PET film having a thickness of 100 占 퐉 (FUJIX (registered trademark) OHP film for copying machine manufactured by Fuji Film Co., Ltd.) using a 75 탆 slit coater. After coating, the film was placed in a drier maintained at a temperature of 70 캜 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 1 was used instead of 0.20 g of the polymer particles obtained in Example 2. [

[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 1 was used instead of 0.20 g of the polymer particles obtained in Example 3. [

[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 1 was used instead of 0.20 g of the polymer particles obtained in Example 4. [

[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 1 was used instead of 0.20 g of the polymer particles obtained in Example 6.

[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 8.

[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 9. [

[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 13: 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 Example 1 was used instead of 0.20 g of the polymer particles obtained in Comparative Example 2. [

[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.

[Comparative Example 15: 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 Example 1 was used instead of 0.20 g of the polymer particles obtained in Comparative Example 4. [

[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 1 was used instead of 0.20 g of the polymer particles obtained in Example 10.

[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 1 was used instead of 0.20 g of the polymer particles obtained in Example 11.

[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 1 was used instead of 0.20 g of the polymer particles obtained in Example 13.

[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 14.

[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 1 was used instead of 0.20 g of the polymer particles obtained in Example 15.

[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 Example 1 was used instead of 0.20 g of the polymer particles obtained in Comparative Example 5.

[Comparative Example 17: 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 Example 1 was used instead of 0.20 g of the polymer particles obtained in Comparative Example 6.

[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 Example 1 was used instead of 0.20 g of the polymer particles obtained in Comparative Example 7.

[Comparative Example 19: 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 Example 1 was used instead of 0.20 g of the polymer particles obtained in Comparative Example 8.

[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 Example 1 was used instead of 0.20 g of the polymer particles obtained in Comparative Example 9.

[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 Example 1 was used instead of 0.20 g of the polymer particles obtained in Comparative Example 10.

[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 properties of the optical films of Examples 16 to 30 and Comparative Examples 12 to 22 were evaluated by the following methods.

[Evaluation method of optical characteristics (less haze deviation)] [

The optical film was cut into a square of 6 cm x 6 cm and used as a test piece. The haze of each of the four end portions and the central portion (the total of five points) of the top, bottom, left and right sides of the coated surface of the resin composition for coating of the test piece was measured according to JIS K 7136 using "NDH-4000" . The haze difference (%) is calculated by the following calculation formula using the maximum value, the minimum value and the average value of the haze (%) of the measured five points and the haze difference Respectively.

<Formula for calculating the haze value (%)>

R = {(Hz _MAX- Hz _MIN ) / Hz _AVE )} 100

R: Hayes tea (%)

Hz _MAX : Maximum value of haze (%) at 5 points

Hz _MIN : Minimum value of haze (%) at 5 points

Hz _AVE : Mean value of haze (%) at 5 points

<Evaluation Criteria>

◎: Less than 0.5% in haze

○: The haze difference is 0.5% or more and less than 1.0%

?: Haze difference of 1.0% or more and less than 3.0%

X: 3.0% or more in haze difference

For each of Examples 1 to 15 and Comparative Examples 1 to 11, the number of the seed particles (seed particle number) used in the polymerization step, the composition of the monomers used in the polymerization step (monomer composition), the other surfactants used in the polymerization process, As a result of measurement of the kind of the surfactant having an ethylene chain, the type of the polymer dispersion stabilizer used in the polymerization process, and the X value (amount per unit time (unit / kg) of the medium passed through the filter medium) in the solid- (Water) in the cleaning step, the volume average particle diameter (占 퐉) of the obtained polymer particles (占 퐉), the Y value (the amount of the cleaning liquid passing through the filter medium (kg / ) And the coefficient of variation (CV value (%)) of the particle diameter are shown in Tables 2 and 4, and the measurement results of the refractive index of the obtained polymer particles and the gel fraction (%) of the obtained polymer particles are shown in Tables 2 and 4.

As a result of measurement of the specific surface area (m 2 / g) of the polymer particles and the content (ppm by weight) of the other surfactants in the polymer particles to the polymer particles obtained in Examples 1 to 15 and Comparative Examples 1 to 11, As a result of measurement of the content (ppm by weight) of the polyoxyethylene chain-containing surfactant in the polymer particles, the measurement result of the content (10 ^-3 g / m 2) of the other surfactant in the polymer particles per unit surface area of the polymer particles , The content of the surfactant having a polyoxyethylene chain in the polymer particles per unit surface area of the polymer particles (x 10 ^-5 g / m 2), the evaluation result of the dispersibility of the polymer particles in the high SP value organic solvent And the content of by-products (emulsion polymerization product) in the polymer particles are shown in Tables 3 and 5. The results of measurement of the haze difference (%) of the optical film and the evaluation results of the optical characteristics of the optical film are shown in Table 3 and Table 5 for the optical films of Examples 16 to 30 and Comparative Examples 12 to 22, respectively.

In Table 2 and Table 4, DSS denotes sodium di (2-ethylhexyl) sulfosuccinate, LS denotes sodium lauryl sulfate, ASK denotes dipotassium alkenyl succinate, POEPS denotes polyoxyethylene nonylphenyl ether Sodium phosphate, ASPSE represents polyoxyethylene styrenated phenyl ether sulfuric acid ester ammonium, POESE represents polyoxyethylene styrenated phenyl ether phosphate ester, PVA represents polyvinyl alcohol, PSE represents polyoxyethylene styrenated phenyl Ether.

(Filter cloth 3) (filter cloth) and filtrate (that is, crude product P) of the pressure filter 1 (see Fig. 1) used in the solid-liquid separation and cleaning processes of Examples 1 to 15 and Comparative Examples 1 to 11, ) Is 0.0104 (m &lt; 2 &gt;). Therefore, in Examples 1 to 15 and Comparative Examples 1 to 11, the upper limit value of the X value (amount per unit time (kg / min) of the medium having passed through the filter medium) satisfying the conditional expression (1) min. The lower limit value of 0.0260 kg / min and the upper limit value of 0.0884 kg / min of the Y value satisfying condition (2) (the amount per kg of the cleaning liquid passing through the filter medium (kg / min)

From the results shown in Tables 2 to 5, it is found that the amount of the cleaning liquid (water) used for cleaning among the polymer particles obtained in the Examples and Comparative Examples in which the surfactant having polyoxyethylene chains was used in combination with another surfactant, Polymer particles obtained in Examples 1 to 15, which are 9 times or more (9 kg or more), specifically 10.0 to 13.0 times, have a content of other surfactant per unit surface area of polymer particles of 10.0 x 10 &lt; ^-5 &gt; (Corresponding to the case where the amount of the cleaning liquid (water) used for cleaning is 0), which is omitting the cleaning process, compared with the case where the amount of the cleaning liquid used is less than 0.88 to 8.38 × 10 ^-5 g / The polymer particles obtained in Comparative Examples 2, 3, and 5 in which the amount of water (water) is less than 9 times (9 kg or less), specifically 5.0 times the weight of the polymer particles, When the content is 10.0 × 10 ^-5 g / m &lt; 2 &gt;, specifically, 131.76 to 413.62 x 10 &lt; ^-5 &gt; g / m & Therefore, according to the production method of the present invention, in which the amount of the cleaning liquid (water) used for washing is 9 times or more the weight of the polymer particles, the amount of the surface surfactant added to the surface of the polymer particles used in the polymerization step can be reduced .

From the results shown in Tables 2 to 5, the polymer particles obtained in Examples 1 to 15, in which the amount of 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 in the unit surface area of the polymer particles, ^{2.0 × 10 -3 g / ㎡~15.0 ×} 10 -3 g / ㎡, specifically, 2.15~12.32 × 10 ^-3 g / The polymer particles obtained in Comparative Example 6 in which the amount of the cleaning liquid (water) used for cleaning exceeds 18 times the weight of the polymer particles (more than 18 kg), specifically, 25.0 times (25.0 kg) The content of the polyoxyethylene chain-containing surfactant per unit surface area was less than 2.0 x ^10-3 g / m2, specifically, 1.46 x ^10-3 g / m2. Therefore, according to the manufacturing method of the present invention, in which the amount of the cleaning liquid (water) used for cleaning is 9 times or more and 18 times or less the weight of the polymer particles, the unit of the surface of the polymer particles of the polyoxyethylene chain- the adhesion amount of surface area was confirmed that a suitable range of 2.0 × 10 ^-3 g / ㎡~15.0 to a × 10 ^-3 g / ㎡.

The polymer particles obtained in Examples 1 to 15, in which the amount of the cleaning liquid (water) used for washing was 9 times or more (9 kg or more), specifically 10.0 to 13.0 times the weight of the polymer particles, Comparative Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 1, Comparative Example 1, And polymer particles obtained in Comparative Examples 2, 3, 5, 10, and 11 in which the amount of the cleaning liquid (water) used for cleaning was less than 9 times (9 kg or less), specifically 1.0 to 5.0 times the weight of the polymer particles, (Emulsion polymerization product) was found to be 1.0% by weight or more, specifically, 1.99 to 4.33% by weight. Therefore, it has been confirmed that the production method of the present invention, in which the amount of the cleaning liquid (water) used for washing is 9 times or more the weight of the polymer particles, can reduce the content of by-products (emulsion polymerization products) in the polymer particles .

Among the polymer particles obtained in Examples and Comparative Examples in which a surfactant having a polyoxyethylene chain was used in combination with another surfactant, the X value (the amount of the medium passing through the filter medium per unit time) satisfies the conditional expression (1) The polymer particles obtained in Examples 1 to 15 having an upper limit value of 0.0572 (kg / min) or less (specifically 0.0460 to 0.0566 kg / min) to be contained in the polymer particles had a content of other surfactants per unit surface area of the polymer particles of 10.0 x (X) is larger than the upper limit value of 0.0572 (kg / min) satisfying the above conditional formula (1) (specifically, X is 10 ^-5 g / m 2 or less, specifically 0.88 to 8.38 x 10 ^-5 g / The polymer particles obtained in Comparative Examples 7 and 8 (in which the content of the other surfactant per unit surface area of the polymer particles is 10.0 x 10 &lt; ^-5 &gt; g / m &lt; 2 & 29.79 × 10 ^-5 g / ㎡). Therefore, it was confirmed that the production method of the present invention in which the X value satisfies the conditional formula (1) can reduce the amount of the surface layer per unit surface area of the other surface active agent used in the polymerization step.

The polymer particles obtained in Examples 1 to 15 having an X value of 0.0572 (kg / min) or less (specifically 0.0460 to 0.0566 kg / min) satisfying the above conditional formula (1) The X value is larger than the upper limit value of 0.0572 (kg / min) satisfying the above conditional formula (1) (specifically, the X value is less than 1.0% The polymer particles obtained in Comparative Examples 7, 8 and 11 (in which 0.0762-0.1271 kg / min) had a measured value of the content of by-products (emulsion polymerization product) of 1.0% by weight or more (specifically 1.98 to 2.33% by weight) There were many. Therefore, it was confirmed that the production method of the present invention in which the X value satisfies the conditional formula (1) can reduce the content of by-products (emulsion polymerization product) in the polymer particles.

Among the polymer particles obtained in Examples and Comparative Examples in which a surfactant having a polyoxyethylene chain was used in combination with another surfactant, the Y value (the amount per unit time of the cleaning liquid which passed through the filter material) satisfied the conditional formula (2) The polymer particles obtained in Examples 1 to 15 which are in the range of 0.0260 (kg / min) to 0.0884 (kg / min) (specifically 0.0291 to 0.0881 (kg / min)) of the polymer particles the content of other surfactant 10.0 × 10 ^-5 g / ㎡ or less, specifically, 0.88~8.38 × 10 ^-5 to less than a g / ㎡, Y value of the upper limit value 0.0884㎏ / min satisfying the condition (2) The polymer particles obtained in Comparative Examples 7 and 9 having a larger (more specifically, 0.1115 to 0.1156 (kg / min)) of the polymer particles had a content of the other surfactant per unit surface area of the polymer particles exceeding 10.0 × 10 ^-5 g / (Specifically, 11.95 to 29.79 × 10 ^-5 g / m 2). Thus, according to the production method of the present invention in which the Y value satisfies the above-mentioned conditional formula (2), it was confirmed that the amount of adhesion of the other surface active agent to the surface of the polymer particles used in the polymerization step per unit surface area can be reduced.

The polymer particles obtained in Examples 1 to 15 in which the Y value satisfies the conditional formula (2) (specifically, 0.0291 to 0.0881 (kg / min)) show that the measured value of the content of the by- (Specifically 0.1115 to 0.1156 (kg / min)), which is lower than 1.0% by weight, specifically 0.05 to 0.82% by weight, In the polymer particles obtained in Comparative Examples 7 and 9, the measured value of the content of the by-product (emulsion polymerization product) was 1.0% by weight or more (specifically, 1.89 to 2.33% by weight). Therefore, it has been confirmed that the production method of the present invention in which the Y value satisfies the conditional formula (2) can reduce the content of by-products (emulsion polymerization products) in the polymer particles.

The polymer particles of Examples 1 to 15 in which the content of the other surfactant per unit surface area of the polymer particles is not more than 10.0 x 10 ^-5 g / m 2 (specifically, 0.88 to 8.38 x 10 ^-5 g / m 2) is the content of other surfactants in the unit surface area of the polymer particles 10.0 × 10 ^-5 g / ㎡ than (specifically, 11.95~413.62 × 10 ^-5 g / ㎡) of Comparative examples 1 to 3, 5, 7 It was confirmed that the polymer particles were excellent in dispersibility with respect to the high SP value organic solvent.

Examples 16 to 30, which were obtained by coating a resin composition for coating comprising polymer particles of Examples 1 to 15 having a content of other surfactant per unit surface area of polymer particles of 10.0 x 10 &lt; ^-5 &gt; g / of the optical film is coated with a resin composition comprising polymer particles of Comparative examples 1 to 3, 5 and 7 to 9 the content is more than 10.0 × 10 ^-5 g / ㎡ of different surfactants in a unit surface area of the polymer particles It was confirmed that the haze difference was small and the deviation of the light diffusivity was small as compared with the optical films of Comparative Examples 12 to 14, 16 and 18 to 20, That is, in the optical film comprising the polymer particles having the content of the other surfactant per unit surface area of the polymer particles of 10.0 x ^10-5 g / m &lt; 2 &gt; or less, more uniform optical characteristics (scattering property and light diffusibility) . This indicates that the polymer particles having a content of other surfactants per unit surface area of the polymer particles of 10.0 x 10 &lt; ^-5 &gt; g / m &lt; 2 &gt; or less have excellent dispersion uniformity.

Further, in Examples where 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 × 10 ^-3 g / m 2) The polymer particles 1 to 15 had no polyoxyethylene chain-containing surfactant (equivalent to a case where the content of the polyoxyethylene chain-containing surfactant per unit surface area of the polymer particles was 0) Polymer particles and the content of the surfactant having a polyoxyethylene chain per unit surface area of the polymer particles is less than 2.0 x ^10-3 g / m2 (specifically, 0.80 to 1.46 x ^10-3 g / m2) It was confirmed that the polymer particles of Examples 6 and 11 were superior in dispersibility to the high SP value organic solvent.

The resin composition for coating comprising 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 was 2.0 to 15.0 x 10 &lt; ^-3 &gt; g / m & (Corresponding to the case where the content of the surfactant having a polyoxyethylene chain is 0 per unit surface area of the polymer particles) is not used, the optical film of Examples 16 to 30, When the content of the optical film of Comparative Example 15 prepared by coating the resin composition for coating comprising the polymer particles of Comparative Example 4 and the surfactant having polyoxyethylene chain per unit surface area of the polymer particles was 2.0 x 10 ^-3 Compared with the optical films of Comparative Examples 17 and 22 obtained by coating the resin composition for coating comprising the polymer particles of Comparative Examples 6 and 11 having a weight average molecular weight , It was confirmed that the haze difference was small and the deviation of light diffusibility was small. That is, in an optical film comprising polymer particles having a polyoxyethylene chain-containing surfactant content of 2.0 to 15.0 x 10 &lt; ^-3 &gt; g / m &lt; 2 &gt; per unit surface area of polymer particles, And light diffusibility) were obtained. This indicates that the polymer particles having a polyoxyethylene chain-containing surfactant content of 2.0 to 15.0 x 10 ^-3 g / m 2 per unit surface area of the polymer particles are excellent in dispersion uniformity.

Further, in Examples where 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 × 10 ^-3 g / m 2) The polymer particles 1 to 15 preferably have a content of the polyoxyethylene chain-containing surfactant per unit surface area of the polymer particles of not less than 15.0 x 10 &lt; ^-3 &gt; g / m2 (specifically, 15.16 to 17.41 x ^10-3 g / ), As compared with the polymer particles of Comparative Examples 5 and 10, it was confirmed that the dispersibility to the high SP value organic solvent was excellent.

The resin composition for coating comprising 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 was 2.0 to 15.0 x 10 &lt; ^-3 &gt; g / m & , Polymer particles of Comparative Examples 5 and 10 having a content of a surfactant having a polyoxyethylene chain per unit surface area of the polymer particles exceeding 15.0 x 10 &lt; ^-3 &gt; g / m &lt; It was confirmed that the haze difference was small and the deviation of light diffusivity was small as compared with the optical films of Comparative Examples 16 and 21 prepared by coating the resin composition for coating including That is, in an optical film comprising polymer particles having a polyoxyethylene chain-containing surfactant content of 2.0 to 15.0 x 10 &lt; ^-3 &gt; g / m &lt; 2 &gt; per unit surface area of polymer particles, And light diffusibility) were obtained. This indicates that the polymer particles having a polyoxyethylene chain-containing surfactant content of 2.0 to 15.0 x 10 ^-3 g / m 2 per unit surface area of the polymer particles are excellent in dispersion uniformity.

The polymer particles of Examples 1 to 15, in which the content of the by-product (emulsion polymerization product) is less than 1.0% by weight (specifically, 0.05 to 0.82% by weight), are used to measure the content of the by- It was confirmed that the polymer particles of Comparative Examples 1 to 3, 5, and 7 to 11 having a value of 1.0 wt% or more were superior in dispersibility to a high SP value organic solvent.

Further, the optical films of Examples 16 to 30, in which the resin composition for coating comprising the polymer particles of Examples 1 to 15, in which the content of the by-product (emulsion polymerization product) is less than 1.0% by weight, Comparative Examples 12 to 14, 16 and 18 to 22 (Comparative Examples 12 to 14) obtained by coating a resin composition for coating comprising the polymer particles of Comparative Examples 1 to 3, 5 and 7 to 11 in which the content of the emulsion polymerization product It was confirmed that the haze difference was small and the deviation of light diffusibility was small. That is, it was confirmed that more uniform optical characteristics (light-diffusing property and light diffusing property) were obtained in an optical film comprising polymer particles having a measured value of the content of by-products (emulsion polymerization product) of less than 1.0 wt%. This indicates that the polymer particles having a measured value of the content of by-products (emulsion polymerization product) of less than 1.0% by weight are excellent in dispersion uniformity.

The present invention may be embodied in other forms without departing from the spirit or essential characteristics thereof. For that reason, the above-described embodiments are merely illustrative in all respects and should not be construed as limiting. The scope of the present invention is defined by the appended claims, and is not to be construed as being limited thereto at all. Modifications and variations that fall within the equivalents of the claims are all within the scope of the present invention.

This application also claims priority to Patent Application No. 2014-201702, filed on September 30, 2014, in Japan. By way of example, the entire contents of which are incorporated herein by reference.

1 pressure filter
2 Pressure vessel
3 filter media
R Diameter of interface (desorption surface) between filter medium and feed pipe
P-product
S upper space of the filter medium

Claims (12)

As the polymer particles containing a surfactant having a polyoxyethylene chain,
The variation coefficient of the particle diameter is 15.0% or less,
Wherein the content of the polyoxyethylene chain-containing surfactant per unit surface area of the polymer particles is 2.0 to 15.0 x 10 &lt; ^-3 &gt; g / m2,
The content of the other surfactant per unit surface area of the polymer particles is 10.0 x 10 &lt; ^-5 &gt; g / m &lt;
Wherein the surfactant having the polyoxyethylene chain is selected from the group consisting of polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester and polyoxyethylene alkylamine At least one nonionic surfactant selected from the group consisting of anionic surfactants having a polyoxyethylene chain,
Wherein the polymer particles are obtained by absorbing the vinyl monomer into the seed particle and polymerizing in the presence of a surfactant containing a polyoxyethylene chain-containing surfactant. 9. The polymer particle of claim 1,
15.0 g of water was added to 5.0 g of the polymer particles and dispersion treatment was carried out for 60 minutes using an ultrasonic cleaner to disperse the polymer particles in water. The polymer particles were put into a centrifugal tube having an inner diameter of 24 mm and centrifuged at a K factor of 6943, Wherein the concentration of the non-volatile component in the supernatant is less than 1.0% by weight when the supernatant is recovered after centrifugation under the condition of 30 minutes. delete 9. The polymer particle of claim 1,
Wherein the polymer particles are composed of at least one of a (meth) acrylic polymer, a styrene polymer and a (meth) acryl-styrene copolymer. 9. The polymer particle of claim 1,
A polymer particle characterized in that the gel fraction is 90% or more. As the polymer particles containing a surfactant having a polyoxyethylene chain,
The variation coefficient of the particle diameter is 15.0% or less,
Wherein the content of the polyoxyethylene chain-containing surfactant per unit surface area of the polymer particles is 2.0 to 15.0 x 10 &lt; ^-3 &gt; g / m2,
The content of the other surfactant per unit surface area of the polymer particles is 10.0 x 10 &lt; ^-5 &gt; g / m &lt;
Wherein the refractive index is 1.490 to 1.600. delete 7. A polymer particle as claimed in any one of claims 1, 2 and 4 to 6,
Polymer particles for optical members. As the polymer particles containing a surfactant having a polyoxyethylene chain,
The variation coefficient of the particle diameter is 15.0% or less,
Wherein the content of the polyoxyethylene chain-containing surfactant per unit surface area of the polymer particles is 2.0 to 15.0 x 10 &lt; ^-3 &gt; g / m2,
The content of the other surfactant per unit surface area of the polymer particles is 10.0 x 10 &lt; ^-5 &gt; g / m &lt;
Wherein the polymer particle is an antiglare member. An optical film comprising a film base material coated with a resin composition for coating comprising the polymer particles of any one of claims 1, 2, and 4 to 6 and a binder. 11. The optical film of claim 10,
Wherein the optical film is an antiglare film. As a method for producing polymer particles,
Polymerizing a vinyl monomer in the presence of a surfactant comprising a polyoxyethylene chain-containing surfactant in a liquid medium to obtain a polymer particle comprising a surfactant having the polyoxyethylene chain and a crude product A polymerization step for obtaining a polymer,
A solid-liquid separation step in which the crude product is fed into a filter, the medium contained in the crude product is passed through a filter medium of the filter, and the polymer particles contained in the crude product are held on the filter medium;
The cleaning liquid is introduced into the filter holding the polymer particles on the filter material, the cleaning liquid is brought into contact with the polymer particles, and the cleaning liquid contacted with the polymer particles is passed through the filter material, And a cleaning step obtained on the filter material,
In the solid-liquid separation step, the amount of the medium that has passed through the filter medium per unit time satisfies the following condition (1):
X? 5.50 x A ... (One)
(In the formula (1), X represents the amount (kg / min) of the medium passing through the filter medium per unit time and A represents the area (m 2) of the interface between the filter medium and the object to be inspected)
In the cleaning step, the amount of the cleaning liquid that has passed through the filter material per unit time satisfies the following conditional expression (2);
2.50 x A? Y? 8.50 x A ... (2)
(In the formula (2), Y represents the amount (kg / min) of the cleaning liquid passing through the filter medium per unit time and A represents the area (m 2) of the interface between the filter medium and the object to be inspected)
Wherein the cleaning step uses a cleaning liquid having a weight of not less than 9 times and not more than 18 times the weight of the polymer particles held on the filter material.

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