JPWO2015029483A1 - Resin particle group and method for producing the same - Google Patents

Abstract

The resin particle group is a resin particle group having a volume average particle diameter of 0.5 to 10 μm made of a cross-linked vinyl resin, and the number of resin particles having a particle diameter more than twice the volume average particle diameter is 100,000. The proportion of resin particles having a circularity of 5 or less and 0.97 or less is 1% or less. In the method for producing a resin particle group having a volume average particle diameter of 0.5 to 10 μm made of a crosslinked vinyl-based resin, a classification step is performed without generating a crushing step after the generation of the resin particle group. The air from the guide vanes generates a swirling flow in the classification cavity, and classification is performed using an airflow classifier that injects air from the first and second injection nozzles above and below the classification cavity, respectively. .

Description

  The present invention relates to a resin particle group having a volume average particle diameter of 0.5 to 10.0 μm made of a crosslinked vinyl resin and a method for producing the same, and more specifically, such a resin particle group and a method for producing the resin particle group. The content of coarse resin particles is small, and the resin particle group having a small content of cracked resin particles or deformed resin particles, its production method and its use (resin composition and antiglare film). is there.

  In an image display device such as a liquid crystal display, when the surroundings are bright, external light is reflected like a mirror on the display surface, and there is a problem that images such as still images and videos displayed on the display surface are difficult to see. In order to solve such a problem, an anti-glare film is provided on the surface of the display surface of the image display device, and the light incident on the display surface is diffused to impart anti-glare properties to the surface of the display surface. A technology for reducing the reflection of external light due to reflection on the display surface is employed.

  A general anti-glare film has a structure in which a fine uneven shape is formed on the surface thereof, and the fine uneven shape provides anti-glare properties to the display surface of the image display device.

  As a method of forming a fine uneven shape on the antiglare film surface, from the viewpoint of easy adjustment of the uneven shape and production efficiency, a resin composition containing a resin particle group and a binder is applied on a base film. A method of forming a resin composition layer (coating film) having a fine uneven shape derived from the resin particle group formed on the surface by drying is the mainstream.

  The resin particle group used in the antiglare film is required to have a uniform particle diameter, and the aggregated particles (coarse resin particles formed by aggregating a plurality of resin particles) and the coarse resin particles are antiglare films. It causes a scratch on the surface or a bright spot defect on the antiglare film, which causes the display quality of the image display device to deteriorate.

  In recent years, the antiglare film has been made thinner for the purpose of high definition and cost reduction, and the required particle size has become smaller.

  The resin particle group having a smaller particle diameter has a stronger aggregating force between the resin particles, and easily forms agglomerated particles that are difficult to unaggregate. Therefore, in the conventional method, it is difficult to unaggregate the aggregated particles only by classification. Therefore, the conventional method requires a crushing (pulverization) step of crushing the agglomerated particles before the classification step in order to release the agglomerated particles and remove the coarse particles from the resin particle group. It was. For example, the method of Patent Document 1 requires a step of pulverizing powder fine particles before the step of dry classifying powder fine particles. Moreover, the method of patent document 2 requires the process of crushing with a jet mill before the process of classifying a fine powder polymer.

International Publication No. 2008/023648 Japanese Examined Patent Publication No. 4-71081 Japanese Patent Laid-Open No. 2002-40204

  However, in the crushing step, not only the aggregation of the resin particle group is crushed but also the resin particles may be broken (crushed) or deformed. Cracked (crushed) resin particles and deformed resin particles differ from spherical resin particles in properties such as light diffusivity. Therefore, if the resin particle group contains many cracked resin particles or deformed resin particles, for example, when the resin particle group is used in an antiglare film disposed on the display surface of the image display device, There is a problem that unevenness of transmitted light or light transmission (a defect in which a portion having a low diffusivity is locally generated) occurs in the glare film, thereby degrading the display quality of the image display device.

  In addition, in the resin particles contained in the antiglare and antireflection film, resin particles have been proposed in which the ratio of coarse particles that become the core of a rugged planar failure is reduced to less than a predetermined ratio (see Patent Document 3). . However, Patent Document 3 does not specifically describe any method for reducing the proportion of coarse particles, and only describes that the air-classified crosslinked polystyrene particles are used in the examples. . The above-mentioned air-classified product is also presumed to have been manufactured through a crushing process, and therefore cracking and deformation of resin particles may occur in the crushing process.

  The present invention has been made in view of the above-described conventional problems, and the object thereof is a resin particle group with a small content of coarse resin particles and a small content of cracked resin particles or deformed resin particles, and the production thereof. The present invention provides a method and a resin composition and an antiglare film using the resin particle group.

  In order to solve the above problems, the resin particle group of the present invention is a resin particle group having a volume average particle diameter of 0.5 to 10 μm made of a crosslinked vinyl resin, and is a particle having a volume average particle diameter of twice or more. The number of resin particles having a diameter is 5 or less out of 100,000, and the ratio of resin particles having a circularity of 0.97 or less is 1% or less.

  According to the said structure, the number of the resin particle which has a particle diameter 2 times or more of a volume average particle diameter is 5 or less out of 100,000, and there is little content rate of a coarse resin particle. Therefore, when the resin particle group is used for an optical component such as an antiglare film or a light diffusion film, it is possible to suppress the surface of the optical component from being scratched or the optical component from generating a bright spot defect.

  Further, according to the above configuration, since the ratio of the resin particles having a circularity of 0.97 or less is 1% or less, the content ratio of the broken resin particles or the deformed resin particles is small, and most of them are almost spherical. Consists of resin particles. Therefore, when the resin particle group is used for an optical component such as an antiglare film or a light diffusion film, it is possible to suppress the unevenness of transmitted light and the light transmission from occurring in the optical component.

  Accordingly, when the resin particle group is used for an optical component such as an antiglare film or a light diffusion film and the optical component is used for an image display device, an image display device with good display quality can be realized.

  In order to solve the above problems, the method for producing a resin particle group of the present invention includes a classification step of removing the coarse resin particle group from the resin particle group by classification using an airflow classifier after the resin particle group is generated. A method for producing a resin particle group having a volume average particle diameter of 0.5 to 10 μm made of a crosslinked vinyl resin, wherein the resin particle group classification step does not undergo a crushing step after the resin particle group is generated. The air classifier is disposed in the classification cavity to which the resin particle group is supplied and the outer periphery of the classification cavity, and the classifier is configured to generate a swirling flow in the classification cavity. A plurality of guide vanes for sending air into the cavity from each other, first and second injection nozzles for injecting air to the upper and lower parts of the classification cavity, and classification from the classification cavity Air flow containing resin particles And classifying the resin particles discharge port for discharging towards, it is characterized by comprising a coarse resin particles discharge port for discharging downwardly the coarse resin particles from the classification cavity portion.

  According to the above method, the air particle classifier having the above configuration is used to loosen the resin particle group in which the air injected from the first injection nozzle to the upper part of the classification cavity is loosened, so that the resin particle group is almost Classification can be carried out in a swirl flow in the form of a single resin particle. As a result, a resin particle group with a small content of coarse resin particles can be obtained without performing a crushing step. Further, by not performing the crushing step, it is possible to avoid the occurrence of cracking and deformation of the resin particles in the crushing step, and to obtain a resin particle group with a low content of cracked resin particles and deformed resin particles. it can. Therefore, when the resin particle group obtained by the above method is used for an optical component such as an antiglare film or a light diffusion film, the surface of the optical component may be scratched or a bright spot defect may be generated on the optical component. In addition, it is possible to suppress unevenness of transmitted light and light transmission in the optical component. Therefore, when the optical component is used in an image display device, an image display device with good display quality can be realized.

  In order to solve the above-mentioned problems, the resin composition of the present invention is characterized by including the resin particle group of the present invention and a binder.

  According to the above configuration, when an optical component such as an antiglare film or a light diffusion film is produced by applying the resin composition on a base film or molding the resin composition, the surface of the optical component It is possible to suppress the generation of scratches or the occurrence of bright spot defects in the optical component, and it is possible to suppress the unevenness of transmitted light and the transmission of light in the optical component. Therefore, when the optical component is used in an image display device, an image display device with good display quality can be realized.

  The antiglare film of the present invention is characterized in that the resin composition of the present invention is applied on a substrate film in order to solve the above-mentioned problems.

  According to the above configuration, generation of scratches on the surface of the antiglare film and generation of bright spot defects on the optical component can be suppressed, and unevenness of transmitted light and light transmission can occur in the antiglare film. Can be suppressed. Therefore, when the antiglare film is used in an image display device, an image display device with good display quality can be realized.

  According to the present invention, as described above, a resin particle group with a small content of coarse resin particles and a small content of cracked resin particles or deformed resin particles, a method for producing the same, and the resin particle group The used resin composition and antiglare film can be provided.

It is a schematic cross section which shows the swirl | vortex airflow classifier used for one Embodiment of the manufacturing method of this invention.

  Hereinafter, the present invention will be described in detail.

[Resin particle group]
The resin particle group of the present invention is a resin particle group having a volume average particle diameter of 0.5 to 10 μm made of a cross-linked vinyl resin, and the number of resin particles having a particle diameter that is twice or more the volume average particle diameter. The ratio of resin particles having a circularity of 0.97 or less is 5% or less out of 100,000, and 1% or less.

  In the resin particle group of the present invention, it is preferable that the number of resin particles having a particle diameter of twice or more the volume average particle diameter is 4 or less out of 100,000. As a result, a resin particle group with a smaller content of coarse resin particles can be realized, so that when the resin particle group is used for an optical part such as an antiglare film or a light diffusion film, the surface of the optical part may be damaged. Generation of bright spot defects in the optical component can be further suppressed. Therefore, the display quality of the image display device can be further improved when the optical component is used in the image display device.

  In the resin particle group of the present invention, the ratio of resin particles having a circularity of 0.97 or less is preferably 0.7% or less, and the ratio of resin particles having a circularity of 0.97 or less is 0.5. The ratio of resin particles having a circularity of 0.97 or less is more preferably 0.3% or less. As a result, a resin particle group with a low content of cracked resin particles or deformed resin particles can be realized, so that when the resin particle group is used for an optical part such as an antiglare film or a light diffusion film, it is transmitted to the optical part. It is possible to further suppress the occurrence of light unevenness and light transparency. Therefore, the display quality of the image display device can be further improved when the optical component is used in the image display device.

  The volume average particle diameter of the resin particle group of the present invention is preferably 0.5 to 3.5 μm. Thereby, when a resin particle group is used for optical parts, such as an anti-glare film and a light-diffusion film, characteristics, such as anti-glare property and light diffusibility, of an optical part can be improved. Therefore, when the optical component is used in an image display device, the display quality of the image display device can be further improved.

  The vinyl resin is a polymer of a polymerizable vinyl monomer. The polymerizable vinyl monomer has an ethylenically unsaturated group (broadly defined vinyl group). The cross-linked vinyl resin is a copolymer of a monofunctional polymerizable vinyl monomer and a polyfunctional polymerizable vinyl monomer, and has a structure derived from the monofunctional polymerizable vinyl monomer. It contains a unit and a structural unit (crosslinked structure) derived from a polyfunctional polymerizable vinyl monomer. The monofunctional polymerizable vinyl monomer has one ethylenically unsaturated group, and the polyfunctional polymerizable vinyl monomer has two or more ethylenically unsaturated groups. Is.

  Examples of the monofunctional polymerizable vinyl monomer include, for example, (meth) acrylic acid ester monomers; styrene monomers (aromatic vinyl monomers); vinyl acetate, vinyl propionate, versatic Saturated fatty acid vinyl monomers such as vinyl acid; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; ethylene 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 monobutylmaleic acid; the above ethylenically unsaturated carboxylic acids and ethylenically unsaturated Ethylenically unsaturated carboxylates such as ammonium salts or alkali metal salts of dicarboxylic acid monoalkyl esters Ethylenically unsaturated carboxylic acid amides such as acrylamide, methacrylamide, and diacetone acrylamide; N-methylol acrylamide, N-methylol methacrylamide, methylolated diacetone acrylamide, and these monomers and those having 1 to 8 carbon atoms Examples thereof include methylolated products of ethylenically unsaturated carboxylic acid amides such as etherified products with alcohols (for example, N-isobutoxymethylacrylamide) and derivatives thereof.

  Examples of the (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, and acrylic acid. Alkyl acrylate monomers such as lauryl and stearyl acrylate; alkyl methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and stearyl methacrylate; glycidyl acrylate (Meth) acrylic acid ester having an epoxy group (glycidyl group) such as glycidyl methacrylate; hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl acrylate; Bruno methacrylate, having an amino group such as diethylaminoethyl methacrylate (meth) acrylic acid ester. The (meth) acrylic acid ester monomer preferably contains at least one of an alkyl acrylate monomer and an alkyl methacrylate monomer. In this application document, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acryl” means acryl or methacryl.

  Examples of the styrenic monomer include styrene, α-methylstyrene, vinyl toluene, and ethyl vinyl benzene.

  Examples of the polyfunctional polymerizable vinyl monomer include divinylbenzene, diallyl phthalate, triallyl cyanurate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Examples include triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like. These polymerizable vinyl monomers may be used alone or in combination of two or more.

  The crosslinked vinyl resin is preferably any one of a crosslinked (meth) acrylic resin, a crosslinked styrene resin, and a crosslinked (meth) acryl-styrene copolymer resin. Thereby, the resin particle with high light transmittance is realizable. The cross-linked (meth) acrylic resin is a copolymer of a monofunctional polymerizable vinyl monomer containing a monofunctional (meth) acrylic acid ester monomer and a polyfunctional polymerizable vinyl monomer. It is a coalescence. The cross-linked styrene resin is a copolymer of a monofunctional polymerizable vinyl monomer containing a monofunctional styrene monomer and a polyfunctional polymerizable vinyl monomer. The crosslinked (meth) acrylic-styrene copolymer resin includes a monofunctional polymerizable vinyl monomer including a monofunctional (meth) acrylic acid ester monomer and a monofunctional styrene monomer, and a polyfunctional monomer. It is a copolymer with a polymerizable vinyl monomer. Of these, a crosslinked (meth) acryl-styrene copolymer resin is more preferable from the viewpoint of easily adjusting the optical properties of the antiglare film obtained by applying the resin composition mixed with the binder to the base film. Among them, methyl methacrylate-styrene-ethylene glycol dimethacrylate copolymer is most preferable from the viewpoint of light resistance.

  The amount of the structural unit derived from the polyfunctional polymerizable vinyl monomer is preferably in the range of 5 to 50% by weight with respect to 100% by weight of the crosslinked vinyl resin. When the amount of the structural unit derived from the polyfunctional polymerizable vinyl monomer is less than the above range, the crosslinking degree of the crosslinked vinyl resin is lowered. As a result, when the resin particles are mixed with a binder and applied as a resin composition, the resin particles may swell to increase the viscosity of the resin composition, which may reduce the workability of the application. Furthermore, as a result of the low degree of crosslinking of the crosslinked vinyl resin, the resin particles are used when the resin particles are heated during mixing or molding in applications where the resin particles are mixed with a binder (so-called kneading application). Is easily dissolved or deformed. When the amount of the structural unit derived from the polyfunctional polymerizable vinyl monomer is more than the above range, the improvement in the effect commensurate with the amount of the polyfunctional polymerizable vinyl monomer used is not recognized, Production costs may increase.

[Production method of resin particle group]
The resin particle group of the present invention can be manufactured by any manufacturing method, but can be easily manufactured by the manufacturing method of the present invention. The production method of the present invention is a production method of a resin particle group having a volume average particle diameter of 0.5 to 10 μm made of a crosslinked vinyl-based resin, and after the formation of the resin particle group, the classification is performed using an air classifier. A classification step of removing the coarse resin particle group from the resin particle group is included. And the manufacturing method of the resin particle group of this invention performs the classification process of the said resin particle group, without passing through a crushing process after the production | generation of a resin particle group, and the said airflow classifier is the swirling airflow classifier mentioned later It is characterized by being.

[Production process of resin particles]
The step of generating the resin particle group can be performed by polymerizing the polymerizable vinyl monomer.

  The polymerization method of the polymerizable vinyl monomer is not particularly limited as long as it is a known polymerization method. For example, methods such as seed polymerization, bulk polymerization, emulsion polymerization, soap-free emulsion polymerization, suspension polymerization, etc. Is mentioned. Of these polymerization methods, seed polymerization is most preferred because the resulting resin particle group has the least variation in particle diameter.

  In the case of the above bulk polymerization, a resin particle group having a desired particle size can be generated by pulverizing and classifying after polymerization. The emulsion polymerization is a mixture of a medium such as water, a polymerizable vinyl monomer that is difficult to dissolve in the medium, and an emulsifier (surfactant), and a polymerization initiator that is soluble in the medium is added thereto. This is a polymerization method for carrying out polymerization. The emulsion polymerization is characterized in that there is little variation in the particle diameter of the resulting resin particle group. The soap-free emulsion polymerization is a polymerization method in which no emulsifier is used in the emulsion polymerization, and is characterized in that a group of resin particles having a relatively uniform particle diameter can be obtained. The above suspension polymerization is a polymerization method in which a polymerizable vinyl monomer and an aqueous medium such as water are mechanically stirred to suspend the polymerizable vinyl monomer in an aqueous medium for polymerization. is there. The suspension polymerization is characterized in that a resin particle group having a small particle diameter and a relatively uniform particle diameter can be obtained.

  In the seed polymerization, when polymerization of a polymerizable vinyl monomer is started, a seed (seed) particle group made of a polymer of a polymerizable vinyl monomer prepared separately is added to perform polymerization. It is. More specifically, the seed polymerization method uses a resin particle group made of a polymer of a polymerizable vinyl monomer as a seed particle group, and the polymerizable vinyl monomer is added to the seed particle group in an aqueous medium. In this method, the polymerizable vinyl monomer is polymerized within the seed particles. In this method, a resin particle group having a larger particle diameter than that of the original seed particle group can be obtained by growing the seed particle group.

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

  In seed polymerization, first, seed particle groups are added to an emulsion (suspension) containing a polymerizable vinyl monomer and an aqueous medium. The emulsion can be prepared by a known method. For example, an emulsion can be obtained by adding a polymerizable vinyl monomer to an aqueous medium and dispersing it with a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer. As the aqueous medium, water or a mixture of water and an organic solvent (for example, a lower alcohol (alcohol having 5 or less carbon atoms)) can be used.

  The seed particle group may be added to the emulsion as it is, or may be added to the emulsion in a form dispersed in an aqueous medium. After the seed particle group is added to the emulsion, the polymerizable vinyl monomer is absorbed by the seed particle group. This absorption can usually be performed by stirring the emulsion at room temperature (about 20 ° C.) for 1 to 12 hours. Moreover, in order to accelerate | stimulate absorption of the polymerizable vinyl monomer to a seed particle group, you may heat an emulsion to about 30-50 degreeC.

  The seed particle group swells by absorbing the polymerizable vinyl monomer. The mixing ratio of the polymerizable vinyl monomer and the seed particle group is preferably within the range of 5 to 300 parts by weight of the polymerizable vinyl monomer with respect to 1 part by weight of the seed particle group. More preferably, it is in the range of ~ 250 parts by weight. When the mixing ratio of the polymerizable vinyl monomer is smaller than the above range, the increase in particle diameter due to polymerization is small, and thus the production efficiency is lowered. On the other hand, when the mixing ratio of the polymerizable vinyl monomer is larger than the above range, the polymerizable vinyl monomer is not completely absorbed by the seed particle group, and it is suspended and polymerized uniquely in an aqueous medium. In some cases, resin particles having a small particle diameter are produced. The end of absorption of the polymerizable vinyl monomer into the seed particle group can be determined by confirming the expansion of the particle diameter by observation with an optical microscope.

  Next, the resin particle group is obtained by polymerizing the polymerizable vinyl monomer absorbed by the seed particle group. In addition, you may obtain a resin particle group by repeating the process which makes a seed particle group absorb and polymerize a polymerizable vinyl-type monomer in multiple times.

  A polymerization initiator may be added to the polymerizable vinyl monomer as necessary. The polymerization initiator may be obtained by mixing the polymerization initiator with a polymerizable vinyl monomer, and then dispersing the obtained mixture in an aqueous medium. Alternatively, the polymerization initiator and the polymerizable vinyl monomer may be dispersed. These may be mixed separately in an aqueous medium. When the particle diameter of the polymerizable vinyl monomer droplets in the obtained emulsion is smaller than the particle diameter of the seed particle group, the polymerizable vinyl monomer is efficiently absorbed by the seed particle group. This is preferable.

  Although it does not specifically limit as said polymerization initiator, For example, benzoyl peroxide, lauroyl peroxide, o-chloro peroxide benzoyl, o-methoxy benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide Organic peroxides such as oxide, t-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (2,3-dimethylbutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,3,3) 3-trimethylbutyronitrile), 2,2′-azobis (2-isopropylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitri) ), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile, (2-carbamoylazo) isobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2 Examples include azo compounds such as' -azobisisobutyrate, etc. The polymerization initiator is used within a range of 0.1 to 1.0 part by weight with respect to 100 parts by weight of the polymerizable vinyl monomer. It is preferred that

  The polymerization temperature of the seed polymerization can be appropriately selected according to the type of polymerizable vinyl monomer and the type of polymerization initiator used as necessary. Specifically, the polymerization temperature of the seed polymerization is preferably 25 to 110 ° C, and more preferably 50 to 100 ° C. The polymerization time for the seed polymerization is preferably 1 to 12 hours. The polymerization reaction of the seed polymerization may be performed in an atmosphere of an inert gas (for example, nitrogen) that is inert to the polymerization. In addition, it is preferable that the polymerization reaction of the seed polymerization is performed by raising the temperature after the polymerizable vinyl monomer and the polymerization initiator used as necessary are completely absorbed by the seed particle group.

  In the seed polymerization, a polymer dispersion stabilizer may be added to the polymerization reaction system in order to improve the dispersion stability of the resin particle group. Examples of the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (such as hydroxyethyl cellulose and carboxymethyl cellulose), and polyvinylpyrrolidone. Moreover, the polymer dispersion stabilizer and an inorganic water-soluble polymer compound such as sodium tripolyphosphate may be used in combination. Of these polymer dispersion stabilizers, polyvinyl alcohol and polyvinyl pyrrolidone are preferred. The addition amount of the polymer dispersion stabilizer is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable vinyl monomer.

  A surfactant may be added to the emulsion. As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a zwitterionic surfactant can be used.

  Examples of the anionic surfactant include fatty acid soaps such as sodium oleate and castor oil potassium soap; alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkyl Dialkylsulfosuccinates such as naphthalenesulfonate, alkanesulfonate, sodium dioctylsulfosuccinate; alkenyl succinate (dipotassium salt); alkyl phosphate ester salt; naphthalenesulfonate formalin condensate; polyoxyethylene alkylphenyl ether sulfate Ester salts; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate; polyoxyethylene alkyl sulfates and the like .

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene tridecyl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene styrenated phenyl ether, and alkylene groups. Polyoxyalkylene alkyl ethers such as polyoxyalkylene tridecyl ether having 3 or more carbon atoms, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene Examples thereof include alkylamines, glycerin fatty acid esters, and oxyethylene-oxypropylene block polymers.

  Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.

  Examples of the zwitterionic surfactants include lauryl dimethylamine oxide, phosphate ester surfactants, and phosphite ester surfactants. 1 type may be used for the said surfactant and it may use it in combination of 2 or more type.

  The amount of the surfactant used in the seed polymerization is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the polymerizable vinyl monomer. When the amount of the surfactant used is less than the above range, the polymerization stability may be lowered. Moreover, when there is more usage-amount of surfactant than the said range, it is uneconomical in terms of cost.

  In addition, in order to suppress the generation of emulsified particles (resin particles having a too small particle diameter) in the aqueous medium in the polymerization reaction, nitrites such as sodium nitrite, sulfites, hydroquinones, ascorbic acids, water-soluble vitamins A water-soluble polymerization inhibitor such as B, citric acid, and polyphenols may be added to the aqueous medium. The addition amount of the polymerization inhibitor is preferably in the range of 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the polymerizable vinyl monomer.

  The polymerization method for polymerizing the polymerizable vinyl monomer to obtain the seed particle group is not particularly limited, but soap-free emulsion polymerization, dispersion polymerization, emulsion polymerization, suspension polymerization, etc. can be used. . In order to obtain a resin particle group having a substantially uniform particle diameter by seed polymerization, it is necessary to first use seed particle groups having a substantially uniform particle diameter and grow these seed particle groups substantially uniformly. . A seed particle group having a substantially uniform particle size as a raw material can be produced by polymerizing a polymerizable vinyl monomer by a polymerization method such as soap-free emulsion polymerization or dispersion polymerization. Accordingly, soap-free emulsion polymerization and dispersion polymerization are preferable as a polymerization method for polymerizing a polymerizable vinyl monomer to obtain a seed particle group.

  Also in the polymerization for obtaining the seed particle group, a polymerization initiator is used as necessary. Examples of the polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; benzoyl peroxide, lauroyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, 3, 5 , 5-trimethylhexanoyl peroxide, tert-butylperoxy-2-ethylhexanoate, organic peroxides such as di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, Examples thereof include azo compounds such as 1′-azobiscyclohexanecarbonitrile and 2,2′-azobis (2,4-dimethylvaleronitrile). The amount of the polymerization initiator used is preferably in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the polymerizable vinyl monomer used to obtain the seed particle group. By adjusting the amount of the polymerization initiator used, the weight average molecular weight of the seed particle group obtained can be adjusted.

  In the polymerization for obtaining the seed particle group, a molecular weight modifier may be used in order to adjust the weight average molecular weight of the obtained seed particle group. Examples of the molecular weight modifier include mercaptans such as n-octyl mercaptan and tert-dodecyl mercaptan; α-methylstyrene dimer; terpenes such as γ-terpinene and dipentene; halogenated hydrocarbons such as chloroform and carbon tetrachloride, etc. Can be used. The weight average molecular weight of the obtained seed particle group can be adjusted by adjusting the amount of the molecular weight modifier used.

  In the seed polymerization, after polymerization, the resin particle group is taken out from the aqueous medium to form a dry resin particle group, and then the dry resin particle group is subjected to a classification step to remove the coarse resin particle group. At that time, the dry resin particle group is a fine resin particle group having a volume average particle diameter of 0.5 to 10 μm or close to it, and has a strong cohesive force between the resin particles, and tends to be an aggregated particle that hardly aggregates. Therefore, if the classification step used in the conventional manufacturing method is carried out after the seed polymerization, it is necessary to carry out a crushing step before the classification step in order to unaggregate the resin particle groups. It becomes.

[Classification process]
The classification step in the production method of the present invention is carried out using a swirling airflow classifier described below without passing through the crushing step after the generation of the resin particle group. The swirling airflow classifier used in the production method of the present invention includes a classification cavity to which a resin particle group (hereinafter referred to as “raw material resin particle group”) obtained in the resin particle group generation step is supplied, and A plurality of guide vanes that are arranged on the outer periphery of the classification cavity, and that send air into the classification cavity from each other so that a swirling flow is generated in the classification cavity, and an upper part of the classification cavity And an air flow including first and second injection nozzles for injecting air to the lower part and a resin particle group (hereinafter referred to as “classified resin particle group”) classified from the classification cavity, respectively. A swirling airflow classifier including a classification resin particle group discharge port and a coarse resin particle group discharge port for discharging the coarse resin particle group downward from the classification cavity.

  Hereinafter, based on FIG. 1, the swirl | vortex airflow classifier used for one Embodiment of the manufacturing method of this invention is demonstrated in detail. FIG. 1 is a schematic cross-sectional view showing a swirling air classifier used in an embodiment of the manufacturing method of the present invention.

  The swirling airflow classifier 10 shown in FIG. 1 is a centrifugal disc that is formed by disposing an upper disc-like member 12 and a lower disc-like member 14 so as to face each other at a predetermined interval, and also serves as a raw material dispersion zone. A raw material charging port 18 for supplying raw material resin particle groups into the centrifugal separation chamber 16 is disposed above the centrifugal separation chamber 16 at a position not intersecting with guide vanes 40 described later. Has been.

  A donut-shaped raw material reclassification zone 28 and a coarse resin particle group recovery port 30 are formed below the centrifugal separation chamber 16 along the outer peripheral wall of the lower disk-shaped member 14. A plurality of ejection nozzles 22 arranged along the tangential direction of the outer peripheral wall of the raw material reclassification zone 28 are arranged. The jet nozzle (first jet nozzle) 22 disperses the raw resin particles in the centrifuge chamber 16 and accelerates the centrifuge action in the centrifuge chamber 16 (accelerates the swirl flow). This is a nozzle that ejects air (compressed air) into the centrifuge chamber 16.

  Here, as an example, six of the ejection nozzles 22 are equally arranged on the circumference, but this is an example, and the arrangement of the ejection nozzles 22 has a degree of freedom.

  In the centrifugal separation chamber 16, a classification resin particle group collection port 32 connected to a suction blower (not shown) through an appropriate filter such as a bag filter, and a coarse resin directed downward from the raw material reclassification zone 28. Particle group collection ports 30 are formed respectively.

  In the central portion of the centrifuge chamber 16, ring-shaped edges 12 a and 14 a are formed on both the upper surface lower side and the lower surface upper side so as to fall (and rise) from these surfaces. ing.

  The ring-shaped edges 12a and 14a determine the classification performance in the swirling airflow classifier 10 according to the present embodiment, and sufficient determination is required for determining the mounting position and height thereof.

  In the outer peripheral portion of the centrifuge chamber 16, a plurality of (here, as an example) having a function of adjusting the swirl speed of the resin particle group that is centrifuge while moving downward while swirling inside the centrifuge chamber 16. 16 guide vanes 40 are arranged. The guide vane 40 is pivotally supported between the upper disk-shaped member 12 and the lower disk-shaped member 14 by a rotating shaft 40a, and is locked to a rotating plate (not shown) by a pin 40b. By rotating the rotating plate (rotating means), all the guide vanes 40 can be simultaneously rotated by a predetermined angle.

  As described above, the guide vanes 40 are rotated by a predetermined angle by rotating the rotating plate, thereby adjusting the interval between the guide vanes 40 and changing the flow velocity of the air passing therethrough. Thereby, the classification performance (specifically, the classification point) in the swirling airflow classifier 10 according to the present embodiment can be changed. Further, several types of guide vanes fixed in advance at a predetermined angle are prepared, and one type of guide vane is selected from these guide vanes according to the desired classification performance, and the guide vanes can be rotated. It can replace with the guide vane 40 and can also be used. Since the air in the centrifuge chamber 16 is sucked by the blower provided in the classified resin particle group collection unit and the inside of the centrifuge chamber 16 becomes negative pressure, the ambient air passes from between the guide vanes 40 to the centrifuge chamber 16. As a result, a swirling flow used for centrifugation is generated in the centrifugal separation chamber 16 along the direction of the guide vane 40.

  On the further outer peripheral portion of the guide vane 40 arranged on the outer peripheral portion of the centrifuge chamber 16, there are no components such as side walls. Here, it is preferable to install an air filter for preventing intrusion of dust and for reducing noise.

  From this air filter, since the inside of the centrifugal separation chamber 16 becomes negative pressure by being drawn by a blower provided in the classified resin particle group collection unit, the surrounding air is sucked into the centrifugal separation chamber 16 (whitened). As a result, the function of supplementing the amount of air used for centrifugation in the centrifuge chamber 16 is realized.

  Above the centrifuge chamber 16, a material dispersion zone 24, which is an annular cavity, is formed along the material inlet 18 and the outer peripheral wall of the upper disk-shaped member 12, and below the centrifuge chamber 16. A raw material reclassification zone 28 that is an annular cavity is formed along the outer peripheral wall of the lower disk-shaped member 14. The centrifugal separation chamber 16, the raw material dispersion zone 24, and the raw material reclassification zone 28 constitute the classification cavity.

  And in the said raw material dispersion | distribution zone 24, the jet nozzle (2nd jet nozzle) 20 of the high pressure air for the raw material resin particle group dispersion | distribution arrange | positioned along the tangential direction is arrange | positioned on the outer peripheral wall. . In the raw material reclassification zone 28, a high-pressure air jet nozzle 22 is arranged on the outer peripheral wall along the tangential direction for accelerating the centrifugal separation action. The ejection nozzle 20 is disposed above the guide vane 40 and injects compressed air into the raw material dispersion zone 24 (upper part of the classification cavity). The ejection nozzle 22 is disposed below the guide vane 40 and injects compressed air into the raw material reclassification zone 28 (lower part of the classification cavity).

  In the swirling airflow classifier 10 according to the present embodiment, the following consideration is given to the arrangement method of the two ejection nozzles 20 and the ejection nozzles 22 described above. That is, the ejection nozzle 20 is disposed along the tangential direction on the outer peripheral wall of the raw material dispersion zone 24, and the ejection nozzle 22 is disposed along the tangential direction on the outer peripheral wall of the raw material reclassification zone 28. In this case, the inclination angle from the tangential direction to the center of the ejection nozzle 20 and the ejection nozzle 22 is such that the inclination angle of the ejection nozzle 22 is slightly larger than the inclination angle of the ejection nozzle 20. Bring.

  That is, a doughnut-shaped raw material dispersion zone 24 is located above the centrifugal separation chamber 16 at a position facing the air ejection hole of the ejection nozzle 20, and the ejection nozzle 22 is disposed below the centrifugal separation chamber 16. Similarly, donut-shaped raw material reclassification zones 28 are respectively formed at positions facing the air ejection holes.

  Further, below the raw material reclassification zone 28, a coarse resin particle group collection port (coarse resin particle group discharge port) through a doughnut-shaped coarse resin particle group collection channel that leads to a coarse resin particle group collection unit (not shown). On the other hand, a classification resin particle group collection port (classification resin particle group discharge port) 32 that leads to a classification resin particle group collection unit (not shown) is formed above the centrifuge chamber 16. ing. The classified resin particle group collection port 32 is usually connected to an intake blower via an appropriate filter such as a bag filter.

  In the central portion of the centrifuge chamber 16, ring-shaped edges 12 a and 14 a are formed on both the upper surface lower side and the lower surface upper side so as to fall (and rise) from these surfaces. ing. The ring-shaped edges 12a and 14a determine the classification performance in the swirling airflow classifier 10 according to the present embodiment, and sufficient determination is required for determining the mounting position and height thereof.

  A guide vane 40 as described above is disposed on the outer periphery of the centrifugal separation chamber 16. The guide vane 40 is pivotally supported between the upper disk-shaped member 12 and the lower disk-shaped member 14 by a rotation shaft 40a, and is not illustrated by a pin 40b. The guide vanes 40 can be rotated by a predetermined angle by rotating the rotating plate.

Here, of the wall surface of the doughnut-shaped raw material dispersion zone 24 formed at the position facing the air ejection hole of the ejection nozzle 20 described above, the surface of the ejection nozzle 20 facing the air ejection hole is perpendicular to the vertical direction. The inclination angle is preferably in the range of 45 to 90 degrees.
By configuring in this way, the classified resin particle group that should be separated in the direction of the classified resin particle group collection unit is prevented from being mixed in the classified resin particle group and separated in the direction of the coarse resin particle group collection unit. A great effect can be obtained.

  The operation of the swirling airflow classifier 10 according to the second embodiment of the present invention configured as described above will be described below.

  When it is confirmed that the classified resin particle group collection port 32 and the coarse resin particle group collection port 30 of the swirling airflow classifier 10 are connected to the classified resin particle group collection port 30 and the coarse resin particle group collection port 30, respectively, The set angle of 40 is set to a predetermined angle, and the compressed air is ejected from the ejection nozzle 20 and the ejection nozzle 22 connected to the compressed air source under the predetermined condition.

  In this state, the raw material resin particle group to be classified is supplied from the raw material input port 18 at a predetermined input flow rate. The charged raw material resin particle group rides on the swirling flow rotating at high speed in the doughnut-shaped raw material dispersion zone 24 by the action of the compressed air ejected from the ejection nozzle 20 described above, and is centrifugally dispersed while being preliminarily dispersed therein. It falls into the separation chamber 16.

  In this process, external air is sucked from the respective gaps of the plurality of guide vanes 40 arranged on the outer peripheral portion of the centrifugal chamber 16 described above (see the white arrow), so that the centrifugal separation in the centrifugal chamber 16 is performed. The action is promoted.

  As a result of the centrifuge action in the centrifuge chamber 16, basically, classified resin particle groups having a size smaller than the classification point are mixed by the ring-shaped edges 12 a and 14 a at the center of the centrifuge chamber 16. The coarse resin particle group in the resin particle group is left and collected from the classified resin particle group collection port 32 to the classified resin particle group collection unit outside the system. In this classified resin particle group, there are very few coarse resin particles exceeding the classification point.

  On the other hand, as a result of the centrifugal separation in the centrifugal separation chamber 16, the coarse resin particle group exceeding the classification point may actually contain fine resin particles with a considerable probability. This should be called the fate of the centrifugal separation method, but in the swirling air flow classifier, in order to improve this, it is ejected to the inlet of the raw material reclassification zone 28 below the centrifugal separation chamber 16. A nozzle 22 is provided, and the fine resin particles flowing into the raw material reclassification zone 28 are returned into the centrifugal separation chamber 16 by an air flow ejected from the nozzle 22.

  The coarse resin particle group from which the fine resin particles have been efficiently removed through the reclassification operation by the ejection nozzle 22 as described above is collected in the coarse resin particle group collection unit through the raw material reclassification zone 28. The

  The above is the outline of the operation of the swirling airflow classifier used in one embodiment of the manufacturing method of the present invention.

  According to the swirling airflow classifier, external air is sucked from the respective gaps of the plurality of guide vanes 40 arranged on the outer periphery of the centrifuge chamber 16 (see the white arrow), so that the centrifuge chamber 16 In addition to the action of promoting the centrifugal separation in the inside, the auxiliary classification function unit 50 formed by the inclined portion below the jet nozzle 22 of the raw material reclassification zone 28 allows the fine resin particles to be fed to the coarse resin particle group side. Mixing is effectively prevented, and a swirling airflow classifier that is advantageous for producing a resin particle group having a volume average particle diameter of 0.5 to 10 μm can be realized.

[Uses of resin particles]
The resin particle group of the present invention is suitable for optical parts such as an antiglare film and a light diffusion film, and is suitable for use as a resin composition by mixing with a binder.

(Resin composition)
The resin composition of the present invention contains a resin particle group and a binder.

  The binder is not particularly limited as long as it is used in the field according to required properties such as transparency, resin particle dispersibility, light resistance, moisture resistance and heat resistance. Examples of the binder include (meth) acrylic resins; (meth) acrylic-urethane resins; urethane resins; polyvinyl chloride resins; polyvinylidene chloride resins; melamine resins; styrene resins; alkyd resins. Phenol resin; epoxy resin; polyester resin; silicone resin such as alkylpolysiloxane resin; (meth) acrylic-silicone resin, silicone-alkyd resin, silicone-urethane resin, silicone-polyester resin, etc. Modified silicone resins; binder resins such as fluororesins such as polyvinylidene fluoride and fluoroolefin vinyl ether polymers.

  The binder resin is preferably a curable resin capable of forming a crosslinked structure by a crosslinking reaction from the viewpoint of improving the durability of the resin composition. The curable resin can be cured under various curing conditions. The curable resin is classified into an ionizing radiation curable resin such as an ultraviolet curable resin and an electron beam curable resin, a thermosetting resin, a hot air curable resin, and the like depending on the type of curing.

  Examples of the thermosetting resin include thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin.

  As the ionizing radiation curable resin, synthesized from polyfunctional (meth) acrylate resin such as polyhydric alcohol polyfunctional (meth) acrylate; diisocyanate, polyhydric alcohol, and (meth) acrylic acid ester having a hydroxy group And polyfunctional urethane acrylate resins. The ionizing radiation curable resin is preferably a polyfunctional (meth) acrylate resin, and more preferably a polyhydric alcohol polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule. As polyhydric alcohol polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule, specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexane tri (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate, etc. . Two or more kinds of the ionizing radiation curable resins may be used in combination.

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

  When using an ultraviolet curable resin among the ionizing radiation curable resins, a photopolymerization initiator is added to the ultraviolet curable resin to form a binder. Although what kind of thing may be used for the said photoinitiator, it is preferable to use what was suitable for the ultraviolet curable resin to be used.

  Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, α-hydroxyalkylphenones, α-aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (Described in JP 2001-139663 A), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, active halogen compounds, α-acyloximes Examples include esters.

  Examples of the acetophenones include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 1-hydroxydimethylphenyl ketone (also known as 2-hydroxy-2-methylpropiophenone), 1-hydroxycyclohexyl phenyl. Examples include ketones, 2-methyl-4′-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and the like. Examples of the benzoins include benzoin, benzoin benzoate, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4'-dichlorobenzophenone, p-chlorobenzophenone, and the like. Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Examples of the ketals include benzylmethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one. Examples of the α-hydroxyalkylphenones include 1-hydroxycyclohexyl phenyl ketone. Examples of the α-aminoalkylphenones include 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone.

  Commercially available radical photopolymerization initiators include trade names “Irgacure (registered trademark) 651” (2,2-dimethoxy-1,2-diphenylethane-1-one) manufactured by BASF Japan Ltd., manufactured by BASF Japan Ltd. Trade name “Irgacure (registered trademark) 184”, trade name “Irgacure (registered trademark) 907” manufactured by BASF Japan Ltd. (2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) ) -1-propanone) and the like.

  The usage-amount of the said photoinitiator is in the range of 0.5-20 weight% normally with respect to 100 weight% of binders, Preferably it exists in the range of 1-5 weight%.

  As the binder resin, a thermoplastic resin can be used in addition to the curable resin. Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose; homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of vinyl chloride, and vinylidene chloride. Vinyl resins such as homopolymers and copolymers; acetal resins such as polyvinyl formal and polyvinyl butyral; homopolymers and copolymers of acrylate esters, homopolymers and copolymers of methacrylate esters, etc. ) Acrylic resin; polystyrene resin; polyamide resin; linear polyester resin; polycarbonate resin.

  In addition to the binder resin, rubber binders such as synthetic rubber and natural rubber, inorganic binders, and the like can be used as the binder. Examples of the rubber-based binder include ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, and acrylonitrile-butadiene rubber. These rubber-type binders may be used independently and 2 or more types may be used together.

  Examples of the inorganic binder include silica sol, alkali silicate, silicon alkoxide, and phosphate. As the inorganic binder, an inorganic or organic-inorganic composite matrix obtained by hydrolysis and dehydration condensation of metal alkoxide or silicon alkoxide can also be used. As the inorganic or organic-inorganic composite matrix, a silicon oxide 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 resin composition may further contain an organic solvent. When the resin composition is applied to a substrate such as a substrate film to be described later, the organic solvent can be easily applied to the substrate by including the organic solvent in the resin composition. If it is a thing, it will not specifically limit. 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; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene Glycol ethers such as glycol diethyl ether, diethylene glycol dimethyl ether, and propylene glycol methyl ether; 2-methoxyethyl acetate Salts, glycol ether esters such as 2-ethoxyethyl acetate (cellosolve acetate), 2-butoxyethyl acetate, 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, 1,3-dioxolane; amide solvents such as N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, and dimethylacetamide can be used. These organic solvents may be used alone or in combination of two or more.

  The resin composition can be used not only for producing an antiglare film, which will be described later, but also for producing a product such as a light diffusion film by molding the resin composition into a predetermined shape (for example, a film shape). You can also

[Anti-glare film]
The antiglare film of the present invention is formed by applying the above resin composition on a base film.

  The base film is preferably transparent. Examples of the transparent base film include polyester polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose (TAC), acrylic polymers such as polycarbonate polymers and polymethyl methacrylate. Examples thereof include a film made of a polymer such as a polymer. In addition, as transparent base film, polystyrene, styrene polymer such as acrylonitrile / styrene copolymer, polyethylene, polypropylene, polyolefin having cyclic or norbornene structure, olefin polymer such as ethylene / propylene copolymer, vinyl chloride A film made of a polymer such as a polymer or an amide polymer such as nylon or aromatic polyamide is also included. Furthermore, as transparent base film, imide polymer, sulfone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenyl sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral Examples thereof include films made of polymers such as polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers and blends of the above polymers. As the substrate film, a film having a particularly low birefringence is preferably used. In addition, a film in which an easy adhesion layer such as an acrylic resin, a copolymerized polyester resin, a polyurethane resin, a styrene-maleic acid graft polyester resin, or an acrylic graft polyester resin is further provided on these films may be used as the base film. it can.

  The thickness of the base film can be determined as appropriate, but is generally within the range of 10 to 500 μm and within the range of 20 to 300 μm from the viewpoint of workability such as strength and handling, and thin layer properties. It is preferable that it is within a range of 30 to 200 μm.

  Moreover, you may add an additive to a base film. Examples of the additive include an ultraviolet absorber, an infrared absorber, an antistatic agent, a refractive index adjuster, and an enhancer.

  The above resin composition can be applied on a base film by bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, air knife coating. And known coating methods such as a dipping method.

  When the binder contained in the resin composition is an ionizing radiation curable resin, after application of the resin composition, if necessary, the solvent is dried and further irradiated with active energy rays to cure the ionizing radiation curable resin. You can do it.

  Examples of the active energy ray include ultraviolet rays emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp; Electron beams, α rays, β rays, γ rays and the like extracted from electron beam accelerators such as a bandegraph type, a resonant transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used.

  The thickness of the layer in which the resin particle group is dispersed in the binder (antiglare layer) formed by application (and curing) of the resin composition is not particularly limited, and is appropriately determined depending on the particle diameter of the resin particle group. Is preferably in the range of 1 to 10 μm, and more preferably in the range of 3 to 7 μm.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this. First, in the following Examples and Comparative Examples, the volume average particle diameter of the resin particle group and the method of measuring the coefficient of variation of the particle diameter, the method of measuring the weight average molecular weight of the seed particle group, and more than twice the volume average particle diameter A method for measuring the number of resin particles having a particle diameter and the ratio of resin particles having a circularity of 0.97 or less will be described.

[Method for measuring volume average particle diameter of resin particle group]
Measurement of the volume average particle diameter of the resin particle group (the seed particle group obtained in Production Examples 1 and 2 of the seed particle group, and the resin particle group obtained in Examples 1 to 3 and Comparative Examples 1 and 2) The measurement was performed using a laser diffraction / scattering particle size distribution measuring apparatus (“LS 13 320” manufactured by Beckman Coulter, Inc.) and a universal liquid sample module.

  For measurement, 0.1 g of a resin particle group was added to 10 ml of a 0.1% by weight nonionic surfactant aqueous solution with a touch mixer (manufactured by Yamato Kagaku Co., Ltd., “TOUCHMIXER MT-31”) and an ultrasonic cleaner (VEL Co., Ltd.). Dispersed by using “ULTRASONIC CLEANER VS-150” manufactured by Vocrea Co., Ltd., and used as a dispersion.

  In addition, in the laser diffraction / scattering type particle size distribution measuring device software described above, the following optical parameters required for evaluation based on the Mie theory are set.

<Parameter>
Refractive index of liquid (nonionic surfactant aqueous solution) I. Real part = 1.333 (refractive index of water)
Real part of refractive index of solid (resin particle group to be measured) = refractive index of resin particle group Imaginary part of refractive index of solid = 0
Solid form factor = 1
Measurement conditions and measurement procedures are as follows.

<Measurement conditions>
Measurement time: 60 seconds Number of measurements: 1
Pump speed: 50-60%
PIDS relative concentration: about 40-55% Ultrasonic output: 8
<Measurement procedure>
After performing offset measurement, optical axis adjustment, and background measurement, the above-described dispersion liquid is injected into the universal liquid sample module of the laser diffraction / scattering particle size distribution measuring apparatus using a dropper. When the concentration in the universal liquid sample module reaches the PIDS relative concentration and the software of the laser diffraction / scattering particle size distribution measuring apparatus displays “OK”, the measurement is started. The measurement is performed in a state in which the resin particle group is dispersed by performing pump circulation in the universal liquid sample module and an ultrasonic unit (ULM ULTRASONIC MODULE) is activated.

  In addition, the measurement is performed at room temperature, and from the obtained data, the software of the laser diffraction / scattering type particle size distribution measuring apparatus is used to set the volume average particle size of the resin particle group using the preset optical parameters. The diameter (arithmetic mean diameter in the volume-based particle size distribution) is calculated.

  The refractive index of the resin particle group was measured by inputting the refractive index of the polymer constituting the resin particle group. For example, when the polymer constituting the resin particle group is polymethyl methacrylate or polyethyl methacrylate, the known refractive index 1.495 of polymethyl methacrylate and polyethyl methacrylate is input, and the resin particles When the polymer constituting the group was polystyrene, a known refractive index of 1.595 of polystyrene was input.

[Measurement method of coefficient of variation of particle diameter of resin particle group]
The variation coefficient (CV value) of the particle diameter of the resin particle group is determined by the standard deviation (σ) of the volume-based particle size distribution measured by the above-described method for measuring the volume average particle diameter of the resin particle group and the volume average particle diameter (D ) From the following formula.

Variation coefficient of particle diameter of resin particle group (%) = (σ / D) × 100
[Method for measuring weight average molecular weight of seed particle group]
The weight average molecular weight (Mw) of the seed particle group obtained in Production Examples 1 and 2 of the seed particle group was measured as follows.

  The weight average molecular weight (Mw) of the seed particle group is measured using GPC (gel permeation chromatography). The weight average molecular weight (Mw) to be measured is a polystyrene (PS) equivalent weight average molecular weight.

  A sample (seed particle group) of 0.003 g is completely dissolved in 10 ml of tetrahydrofuran (THF) by standing at 23 ° C. for 24 hours. If it is not completely dissolved at this point, it is confirmed whether or not it is completely dissolved every 24 hours (up to 72 hours in total). If the sample cannot be completely dissolved after 72 hours, it is determined that the sample contains a crosslinking component. The resulting solution is filtered using a 0.45 μm non-aqueous chromatographic disk. The obtained filtrate is analyzed by GPC, and the PS-converted weight average molecular weight is measured (if it cannot be completely dissolved, the dissolved component is filtered, and the PS-converted weight average molecular weight is measured using the filtrate). The PS-converted weight average molecular weight of the sample is determined from a calibration curve created in advance by the calibration curve creation method shown below. The measurement conditions are as follows.

<Measurement conditions>
Measuring device: High-speed GPC device (trade name “HLC-8320GPC EcoSEC-WorkStation” manufactured by Tosoh Corporation, built-in RI detector (differential refractive index detector))
Column: Trade name “TSKgel Super HZM-H” (inner diameter 4.6 mm × length 15 cm) × 2 from Tosoh Corporation Guard column: Trade name “TSK guard column Super HZ-H” (inner diameter, manufactured by Tosoh Corporation) 4.6 mm × length 2 cm) × 1 flow rate: sample side 0.175 ml / min, reference side 0.175 ml / min
Detector: RI detector built in the high-speed GPC device Concentration: 0.3 g / l
Injection volume: 50 μl
Column temperature: 40 ° C
System temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
<How to create a calibration curve>
As standard polystyrene samples for calibration curves, standard polystyrene samples having a weight average molecular weight of 500, 2630, 9100, 37900, 102000, 355000, 3840000, and 5480000 are trade names “TSK standard POLYSYRENE” manufactured by Tosoh Corporation. The standard polystyrene sample whose weight average molecular weight of Showa Denko Co., Ltd. brand name "Shodex (trademark) STANDARD" is 1030000 is used.

  The method of creating a calibration curve is as follows. First, the standard polystyrene samples for calibration curves are group A (with a weight average molecular weight of 1030000), group B (with a weight average molecular weight of 500, 9100, 102000, and 3480000) and group C (with a weight average molecular weight of 2630, 37900). 355,000 and 5480000). A standard polystyrene sample belonging to group A having a weight average molecular weight of 1030000 is weighed in 5 mg, dissolved in 20 ml of THF, and 50 μl of the resulting solution is injected into the sample side column. Standard polystyrene samples belonging to group B having weight average molecular weights of 500, 9100, 102000, and 3480000 are weighed 10 mg, 5 mg, 5 mg, and 5 mg, respectively, dissolved in 50 ml of THF, and 50 μl of the resulting solution is injected into the sample side column. . Standard polystyrene samples having a weight average molecular weight of 2630, 37900, 355000, and 5480000 belonging to group C were weighed 5 mg, 5 mg, 5 mg, and 1 mg, respectively, dissolved in 40 ml of THF, and 50 μl of the obtained solution was injected into the sample side column. . A calibration curve (third-order equation) is created from the retention time of these standard polystyrene samples by the data analysis program GPC workstation (EcoSEC-WS) dedicated to the high-speed GPC device, and this is used as a calibration curve for PS-converted weight average molecular weight measurement. .

[Method for measuring the number of resin particles having a particle size of twice or more the volume average particle size and the proportion of resin particles having a circularity of 0.97 or less]
In the resin particle groups of the following examples and comparative examples, the number of resin particles having a particle diameter of twice or more the volume average particle diameter, and the ratio of resin particles having a circularity of 0.97 or less are flow type particles. Measurement was performed using an image analyzer (trade name “FPIA (registered trademark) -3000S”, manufactured by Sysmex Corporation).

  As a specific measuring method, a surfactant solution as a dispersant, preferably 0.05 g of an alkylbenzene sulfonate, was added to 20 ml of ion-exchanged water to obtain a surfactant aqueous solution. Thereafter, 0.02 g of a resin particle group to be measured is added to the aqueous surfactant solution, and an ultrasonic cleaner (for example, “VS-150” manufactured by VervoCrea Inc.) is used as a disperser. A dispersion treatment for dispersing the resin particle group in the aqueous surfactant solution was performed over a period of minutes to obtain a dispersion for measurement.

  For the measurement, the flow type particle image analyzer equipped with a standard objective lens (10 times) is used. As the sheath liquid used in the flow type particle image analyzer, a particle sheath (trade name “PSE-900A”, Sysmex Corporation) was used. The measurement dispersion prepared according to the above procedure was introduced into the flow type particle image analyzer and measured under the following measurement conditions.

Measurement mode: HPF measurement mode Measurement range of particle diameter: 0.5 to 200 μm
Measurement range of particle circularity: 0.2 to 1.0
Measurement number of particles: 100,000 In measurement, suspension of standard polymer particles (for example, “5200A” manufactured by Thermo Fisher Scientific (diluted standard polystyrene particles with ion-exchanged water)) before the start of measurement. Was used to perform automatic focus adjustment of the flow type particle image analyzer. The circularity is a value obtained by dividing the perimeter calculated from the diameter of a perfect circle having the same projected area as the image obtained by imaging the resin particles by the perimeter of the image obtained by imaging the resin particles.

  From the particle diameter of the resin particle group measured by the above method, the number of resin particles having a particle diameter twice or more the volume average particle diameter was counted. Further, by counting the number of resin particles having a circularity of 0.97 or less from the circularity of the resin particle group measured by the above method, and dividing this number by the measured number, a circularity of 0.97 or less The ratio of resin particles having a degree was calculated.

[Production Example 1 of seed particle group]
In a separable flask equipped with a stirrer, a thermometer and a reflux condenser, 3000 g of water as an aqueous medium, 500 g of methyl methacrylate as a (meth) acrylate monomer, and n-octyl mercaptan as a molecular weight regulator 5 g was charged and the inside of the separable flask was replaced with nitrogen while stirring the contents of the separable flask, and the internal temperature of the separable flask was raised to 70 ° C. Furthermore, while maintaining the internal temperature of the separable flask at 70 ° C., 2.5 g of potassium persulfate as a polymerization initiator was added to the contents of the separable flask and then subjected to a polymerization reaction for 12 hours to obtain an emulsion. The obtained emulsion contains 14% by weight of a solid content (polymethyl methacrylate particle group), and the solid content has a volume average particle diameter of 0.45 μm and a weight average molecular weight of 15,000. Met. The emulsion containing this true spherical particle group was used as a seed particle group dispersion in Production Examples 1 and 2 of monodisperse particle groups described later.

[Production Example 2 of seed particle group]
In a separable flask equipped with a stirrer, a thermometer and a reflux condenser, 3150 g of water as an aqueous medium, 350 g of methyl methacrylate as a (meth) acrylic acid ester monomer, 3 g of n-octyl mercaptan as a molecular weight regulator And the inside of the separable flask was replaced with nitrogen while stirring the contents of the separable flask, and the internal temperature of the separable flask was raised to 80 ° C. Furthermore, while maintaining the internal temperature of the separable flask at 80 ° C., 1.8 g of potassium persulfate as a polymerization initiator was added to the contents of the separable flask and then subjected to a polymerization reaction for 12 hours to obtain an emulsion. The obtained emulsion contained 10% by weight of a solid content, and the solid content was a group of spherical particles having a volume average particle diameter of 0.35 μm and a weight average molecular weight of 15,000. The emulsion containing the true spherical particle group was used as a seed particle group dispersion in Production Example 3 of a monodisperse particle group described later.

[Production Example 1 of Monodispersed Particle Group]
300 g of styrene as a styrene monomer, 400 g of methyl methacrylate as a (meth) acrylic acid ester monomer, 300 g of ethylene glycol dimethacrylate as a polyfunctional polymerizable vinyl monomer, and initiation of polymerization A monomer mixture was obtained by dissolving 8 g of 2,2′-azobisisobutyronitrile as an agent. The obtained monomer mixture was mixed with 1000 g of a surfactant aqueous solution obtained by dissolving 10 g of polyoxyethylene octylphenyl ether as a nonionic surfactant in 990 g of ion-exchanged water in advance, and high-speed emulsification / dispersion It was put into a machine (trade name “Homomixer MARK II 2.5 type”, manufactured by Primix Co., Ltd.) and treated at 10,000 rpm for 10 minutes to obtain an emulsion.

  To this emulsion, 23 g of seed particle group dispersion (volume 3 g) having a volume average particle diameter of 0.45 μm obtained in Seed Particle Group Production Example 1 was added, and the mixture was stirred at 30 ° C. for 3 hours. Obtained. To this dispersion, 2000 g of a 4% by weight aqueous solution of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “GOHSENOL (registered trademark) GH-17”) as a polymer dispersion stabilizer, and 0.6 g of sodium nitrate was added, and then the polymerization reaction was carried out by stirring at 70 ° C. for 5 hours and then stirring at 105 ° C. for 2.5 hours.

  The dispersion liquid after polymerization is dehydrated with a pressure filter, washed with warm water, and then vacuum-dried at 70 ° C. for 24 hours to obtain a resin particle group composed of a crosslinked (meth) acryl-styrene copolymer resin. A polymer particle group A (dry resin particle group) was obtained.

[Production Example 2 of monodisperse particles]
Polymerization started with 510 g of styrene as a styrene monomer, 370 g of n-butyl methacrylate as a (meth) acrylic acid ester monomer, and 120 g of divinylbenzene as a polyfunctional polymerizable vinyl monomer A monomer mixture was obtained by dissolving 8 g of benzoyl peroxide as an agent. An emulsion was obtained in the same manner as in Example 1 except that this monomer mixture was used instead of the monomer mixture in Example 1.

  To this emulsion, 70 g of seed particle group dispersion (solid content: 9.8 g) having a volume average particle size of 0.45 μm obtained in Production Example 1 of the seed particle group was added, and the mixture was stirred at 30 ° C. for 3 hours. A dispersion was obtained. A crosslinked (meth) acryl-styrene copolymer resin is obtained by performing a polymerization reaction, dehydration, washing, and vacuum drying in the same manner as in Example 1 except that this dispersion is used instead of the dispersion of Example 1. The polymer particle group B (dry resin particle group) which is the resin particle group which consists of was obtained.

[Production Example 3 of Monodispersed Particle Group]
900 g of methyl methacrylate as a (meth) acrylic acid ester monomer, 100 g of ethylene glycol dimethacrylate as a polyfunctional polymerizable vinyl monomer, and 8 g of benzoyl peroxide as a polymerization initiator are mutually dissolved. To obtain a monomer mixture. An emulsion was obtained in the same manner as in Example 1 except that this monomer mixture was used instead of the monomer mixture in Example 1.

To this emulsion was added 500 g of seed particle group dispersion (volume content: 50 g) having a volume average particle size of 0.35 μm obtained in Production Example 2 of the seed particle group, and the mixture was stirred at 30 ° C. for 3 hours. Got.
This dispersion was used in place of the dispersion of Example 1, except that 2000 g of a 0.5% by weight aqueous solution of polyoxyethylene octylphenyl ether as a nonionic surfactant was used instead of the 4% by weight aqueous solution of polyvinyl alcohol. Was carried out in the same manner as in Example 1 to carry out the polymerization reaction. The dispersion after polymerization was dried by spray drying to obtain a polymer particle group C (dry resin particle group) which is a resin particle group made of a crosslinked (meth) acrylic resin.

[Example 1]
The polymer particle group A obtained in Production Example 1 of the monodispersed particle group is a swirling air flow classifier 10 shown in FIG. 1 that does not use a pulverizer, and is a product that is commercially available from Nissin Engineering Co., Ltd. Classification was performed using a swirling airflow classifier having the name “Aero Fine Classifier AC-20”.

In the present embodiment, the angle of the guide vane 40 is 80 degrees from the tangential direction of the outer peripheral surface of the centrifuge chamber 16 toward the center. Moreover, the discharge pressure from the upper and lower jet nozzles 20 and 22 was 0.5 MPa. Further, classification was performed while sucking air from the classification resin particle group collection port 32 using a blower having a suction air volume of 3.5 m ³ / min. Thereby, the resin particle group which consists of crosslinked (meth) acryl-styrene copolymer resin as crosslinked vinyl-type resin was obtained.

  The obtained resin particle group had a volume average particle diameter of 3.15 μm and a particle diameter variation coefficient of 11.55%. Further, in the obtained resin particle group, the number of resin particles having a particle diameter of twice or more of the volume average particle diameter is 2 in 100,000, and the number of resin particles having a circularity of 0.97 or less. The number was 200 out of 100,000 (the ratio of resin particles having a circularity of 0.97 or less was 0.2%).

[Example 2]
In the same manner as in Example 1, except that the polymer particle group B obtained in Production Example 2 of the monodisperse particle group was used instead of the polymer particle group A obtained in Production Example 1 of the monodisperse particle group. Thus, a resin particle group made of a crosslinked (meth) acryl-styrene copolymer resin as a crosslinked vinyl resin was obtained.

  The obtained resin particle group had a volume average particle diameter of 2.27 μm and a coefficient of variation of the particle diameter of 9.54%. Further, in the obtained resin particle group, the number of resin particles having a particle diameter of twice or more of the volume average particle diameter is 2 in 100,000, and the number of resin particles having a circularity of 0.97 or less. The number was 100 out of 100,000 (the ratio of resin particles having a circularity of 0.97 or less was 0.1%).

Example 3
In the same manner as in Example 1, except that the polymer particle group C obtained in Production Example 3 of the monodisperse particle group was used instead of the polymer particle group A obtained in Production Example 1 of the monodisperse particle group. Thus, a resin particle group made of a crosslinked (meth) acrylic resin as a crosslinked vinyl resin was obtained.

  The obtained resin particle group had a volume average particle size of 1.01 μm and a coefficient of variation of the particle size of 13.24%. In addition, in the obtained resin particle group, the number of resin particles having a particle diameter that is twice or more the volume average particle diameter is 4 out of 100,000, and the number of resin particles having a circularity of 0.97 or less. The number was 300 out of 100,000 (the ratio of resin particles having a circularity of 0.97 or less was 0.3%).

[Comparative Example 1]
The polymer particle group A obtained in Production Example 1 of monodispersed particle group was crushed with a hammer mill (model number “AIIW-5”, manufactured by Dalton Co., Ltd.), and a forced vortex classifier (trade name “Turbo Classifier”). Classification was performed with “TC-15” (manufactured by Nisshin Engineering Co., Ltd.) to obtain a resin particle group.

  The obtained resin particle group had a volume average particle diameter of 3.15 μm and a coefficient of variation of the particle diameter of 11.18%. In addition, in the obtained resin particle group, the number of resin particles having a particle diameter that is twice or more the volume average particle diameter is 4 out of 100,000, and the number of resin particles having a circularity of 0.97 or less. The number was 1300 out of 100,000 (the ratio of resin particles having a circularity of 0.97 or less is 1.3%).

[Comparative Example 2]
As in Comparative Example 1, except that the polymer particle group B obtained in Production Example 2 of the monodisperse particle group was used instead of the polymer particle group A obtained in Production Example 1 of the monodisperse particle group. Then, classification was performed to obtain a resin particle group.

  The obtained resin particle group had a volume average particle diameter of 2.27 μm and a coefficient of variation of the particle diameter of 9.54%. In addition, in the obtained resin particle group, the number of resin particles having a particle diameter that is twice or more the volume average particle diameter is 4 out of 100,000, and the number of resin particles having a circularity of 0.97 or less. The number was 2000 out of 100,000 (the ratio of resin particles having a circularity of 0.97 or less is 2.0%).

[Example 4] (Preparation of resin composition for antiglare film and production of antiglare film)
80 parts by weight of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name “Aronix (registered trademark) M-305”, manufactured by Toagosei Co., Ltd.) as an ultraviolet curable resin, and toluene as an organic solvent And 120 parts by weight of a mixed liquid of cyclopentanone (volume ratio of toluene and cyclopentanone = 7: 3), 5 parts by weight of the resin particle group produced in Example 1, and a photopolymerization initiator (2-methyl -1- (4-Methylthiophenyl) -2-morpholinopropan-1-one, trade name “Irgacure (registered trademark) 907”, 5 parts by weight of BASF (registered trademark) Japan Co., Ltd.), and resin A resin composition for an antiglare film as a composition was prepared.

A polyethylene terephthalate (PET) film having a thickness of 0.2 mm, which is a transparent plastic film, was prepared as a base film. The coating film was formed by apply | coating the said resin composition for glare-proof films to the single side | surface of the said polyethylene-terephthalate film using a bar coater. Next, the said coating film was dried by heating at 80 degreeC for 1 minute (s). Thereafter, the coating film was cured by irradiating the coating film with ultraviolet light with an integrated light quantity of 300 mJ / cm ^{2 using} a high-pressure mercury lamp, thereby forming an antiglare hard coat layer. This produced the anti-glare hard coat film containing the resin particle group manufactured in Example 1 as an anti-glare film (molded article).

Example 5
An antiglare film resin composition was prepared in the same manner as in Example 4 except that the resin particle group produced in Example 2 was used instead of the resin particle group produced in Example 1. An antiglare hard coat film containing the resin particle group produced in 2 was prepared.

Example 6
An antiglare film resin composition was prepared in the same manner as in Example 4 except that the resin particle group produced in Example 3 was used instead of the resin particle group produced in Example 1. An antiglare hard coat film containing the resin particle group produced in 3 was produced.

[Comparative Example 3]
A resin composition for an antiglare film was prepared in the same manner as in Example 4 except that the resin particle group produced in Comparative Example 1 was used instead of the resin particle group produced in Example 1, and a comparative example was prepared. An antiglare hard coat film containing the resin particle group produced in 1 was produced.

[Comparative Example 4]
A resin composition for an antiglare film was prepared in the same manner as in Example 4 except that the resin particle group produced in Comparative Example 2 was used instead of the resin particle group produced in Example 1, and a comparative example was prepared. An antiglare hard coat film containing the resin particle group produced in 2 was prepared.

[Evaluation of antiglare property of antiglare film]
The surface of each of the antiglare films prepared in Examples 4 to 6 and Comparative Examples 3 and 4 that was not the coated surface was attached to an ABS resin (acrylonitrile-butadiene-styrene copolymer resin) plate, and the antiglare film was separated by 2 m. From the place, a fluorescent lamp having a luminance of 10000 cd / cm ² was projected on the coated surface, and the antiglare property of the antiglare film was visually evaluated. The evaluation criteria for anti-glare are anti-glare when the outline of the reflected image of the fluorescent lamp is not clearly visible (“Good”), and when the outline of the reflected image of the fluorescent lamp is clearly visible, anti-glare Evaluated as “x” (bad).

[Evaluation of surface properties of antiglare film]
Each of the anti-glare films prepared in Examples 4 to 6 and Comparative Examples 3 and 4 was placed immediately above a fluorescent lamp, and the surface properties of the anti-glare film were visually evaluated. The evaluation criteria for the surface property include at least one of “O” (good), non-uniformity of transmitted light, and translucency of light (defect) when there is no unevenness of transmitted light and no light transmission (defect). The case was evaluated as having a surface property of “x” (defect).

  Evaluation results of antiglare properties and surface properties of antiglare films prepared in Examples 4 to 6 and Comparative Examples 3 and 4 are the types and particles of resin particle groups used in Examples 4 to 6 and Comparative Examples 3 and 4 It is shown in Table 1 together with the diameter distribution.

  As can be seen from the results in Table 1, the antiglare films of Comparative Examples 3 and 4 including a resin particle group in which the ratio of the resin particles having a circularity of 0.97 or less according to the present invention is greater than 1% are transmitted light. Examples 4 to 5 including resin particle groups in which the ratio of resin particles having a circularity of 0.97 or less according to the present invention is 1% or less, while unevenness and light transmission occur and surface properties are poor. The antiglare film No. 6 had good surface properties with no unevenness of transmitted light and no light transmission.

  The present invention can be implemented in various other forms without departing from the spirit or main features thereof. For this reason, the above-described embodiment is merely an example in all respects and should not be interpreted in a limited manner. The scope of the present invention is indicated by the claims, and is not restricted by the text of the specification. Further, all modifications and changes belonging to the equivalent scope of the claims are within the scope of the present invention.

  This application claims priority based on Japanese Patent Application No. 2013-180231 filed in Japan on August 30, 2013. By this reference, the entire contents thereof are incorporated into the present application.

10 Swirling airflow classifier (airflow classifier)
12 Upper disk-shaped members 12a and 14a Ring-shaped edges 14 Lower disk-shaped members 16 Centrifugal separation chamber (classification cavity)
18 Raw material inlet 20 Ejection nozzle (first ejection nozzle)
22 ejection nozzle (second ejection nozzle)
24 Raw material dispersion zone (classification cavity, upper part of classification cavity)
28 Raw material reclassification zone (classification cavity, lower part of classification cavity)
30 Coarse resin particle group recovery port (coarse resin particle group discharge port)
32 Classification resin particle group collection port (Classification resin particle group discharge port)
40 Guide vane 40a Rotating shaft 40b Pin 50 Auxiliary classification function unit

Claims (6)

A resin particle group having a volume average particle diameter of 0.5 to 10 μm made of a crosslinked vinyl resin,
The number of resin particles having a particle size of 2 or more times the volume average particle size is 5 or less out of 100,000,
A resin particle group, wherein the ratio of resin particles having a circularity of 0.97 or less is 1% or less.   The resin particle group according to claim 1, wherein the crosslinked vinyl resin is any one of a crosslinked (meth) acrylic resin, a crosslinked styrene resin, and a crosslinked (meth) acryl-styrene copolymer resin.   The resin particle group according to claim 1, wherein the resin particle group is for an optical component. A resin having a volume average particle diameter of 0.5 to 10 μm made of a crosslinked vinyl resin, including a classification step of removing the coarse resin particle group from the resin particle group by classification using an airflow classifier after the resin particle group is generated. A method for producing a particle group,
The classification step of the resin particle group is performed without passing through the crushing step after the generation of the resin particle group,
The air classifier
A classification cavity to which resin particles are supplied;
A plurality of guide vanes that are arranged on the outer periphery of the classification cavity, and that feed air into the classification cavity from between each other so that a swirling flow is generated in the classification cavity;
First and second injection nozzles for injecting air into the upper and lower portions of the classification cavity,
A classification resin particle group discharge port for discharging an air flow including the resin particle group classified from the classification cavity, upward;
A method for producing a resin particle group, comprising: a coarse resin particle group outlet for discharging the coarse resin particle group downward from the classification cavity.   A resin composition comprising the resin particle group according to claim 1 and a binder.   An antiglare film obtained by coating the resin composition according to claim 5 on a base film.

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