WO2015029483A1 - 樹脂粒子群及びその製造方法 - Google Patents
樹脂粒子群及びその製造方法 Download PDFInfo
- Publication number
- WO2015029483A1 WO2015029483A1 PCT/JP2014/059310 JP2014059310W WO2015029483A1 WO 2015029483 A1 WO2015029483 A1 WO 2015029483A1 JP 2014059310 W JP2014059310 W JP 2014059310W WO 2015029483 A1 WO2015029483 A1 WO 2015029483A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- particle group
- resin particle
- classification
- particles
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B7/00—Selective separation of solid materials carried by, or dispersed in, gas currents
- B07B7/08—Selective separation of solid materials carried by, or dispersed in, gas currents using centrifugal force
- B07B7/086—Selective separation of solid materials carried by, or dispersed in, gas currents using centrifugal force generated by the winding course of the gas stream
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07B—SEPARATING SOLIDS FROM SOLIDS BY SIEVING, SCREENING, SIFTING OR BY USING GAS CURRENTS; SEPARATING BY OTHER DRY METHODS APPLICABLE TO BULK MATERIAL, e.g. LOOSE ARTICLES FIT TO BE HANDLED LIKE BULK MATERIAL
- B07B7/00—Selective separation of solid materials carried by, or dispersed in, gas currents
- B07B7/08—Selective separation of solid materials carried by, or dispersed in, gas currents using centrifugal force
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
Definitions
- the present invention relates to a resin particle group having a volume average particle diameter of 0.5 to 10.0 ⁇ m comprising a crosslinked vinyl resin and a method for producing the same, and more specifically, to such a resin particle group and a method for producing the same.
- 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.
- an image display device such as a liquid crystal display
- 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 imparts anti-glare properties to the display surface of the image display device.
- 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.
- the antiglare film has been made thinner for the purpose of high definition and cost reduction, and the required particle size is becoming smaller.
- the resin particle group having a smaller particle diameter has a stronger cohesive force between the resin particles, and tends to form aggregated 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.
- the method of Patent Document 1 requires a step of pulverizing powder fine particles before the step of dry classifying powder fine particles.
- the method of patent document 2 requires the process of crushing with a jet mill before the process of classifying a fine powder polymer.
- 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.
- Patent Document 3 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). .
- 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.
- the resin particle group of the present invention is a resin particle group having a volume average particle diameter of 0.5 to 10 ⁇ m made of a cross-linked 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.
- the number of resin particles having a particle diameter twice or more the volume average particle diameter is 5 or less out of 100,000, and the content of coarse resin particles is small. 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.
- 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.
- the resin particle group is used for an optical part such as an antiglare film or a light diffusion film, and the optical part is used for an image display device, an image display device with good display quality can be realized.
- 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.
- 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 Airflow containing resin particles And classifying the resin particles discharge port for discharging upward, it is characterized by comprising a coarse resin particles discharge port for discharging downwardly the coarse resin particles from the classification cavity portion.
- 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.
- a resin particle group with a small content of coarse resin particles can be obtained without performing a crushing step.
- 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.
- the resin composition of the present invention is characterized by including the resin particle group of the present invention and a binder in order to solve the above-mentioned problems.
- 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 base film in order to solve the above-mentioned problems.
- 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.
- the resin particle group of the present invention is a resin particle group having a volume average particle diameter of 0.5 to 10 ⁇ m 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.
- 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.
- 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.
- 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.
- 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.
- the volume average particle diameter of the resin particle group of the present invention is preferably 0.5 to 3.5 ⁇ m.
- 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 carboxylic acid such as ammonium salt or alkali metal salt of dialkyl monoalkyl ester Ethylenically
- Examples of the (meth) acrylate monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, acrylic acid Alkyl acrylate monomers such as lauryl and stearyl acrylate; alkyl methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and stearyl methacrylate; glycidyl acrylate (Meth) acrylic acid ester having an epoxy group (glycidyl group) such as glycidyl methacrylate; hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl acrylate; dimethyl Amino ethyl me
- the (meth) acrylic acid ester monomer preferably contains at least one of an alkyl acrylate monomer and an alkyl methacrylate monomer.
- (meth) acrylate means acrylate or methacrylate
- (meth) acryl means acryl or methacryl.
- styrenic monomer examples include styrene, ⁇ -methylstyrene, vinyl toluene, and ethyl vinyl benzene.
- polyfunctional polymerizable vinyl monomer examples 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 cross-linked vinyl resin is preferably any one of a cross-linked (meth) acrylic resin, a cross-linked styrene resin, and a cross-linked (meth) acryl-styrene copolymer resin.
- 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) acryl-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.
- a crosslinked (meth) acryl-styrene copolymer resin is more preferable from the viewpoint of easily adjusting the optical characteristics of the antiglare film obtained by applying the resin composition mixed with the binder to the base film.
- 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.
- 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.
- the resin particles 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.
- 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.
- kneading application a binder
- 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.
- 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 method for producing a resin particle group having a volume average particle diameter of 0.5 to 10 ⁇ m made of a crosslinked vinyl resin, and after the resin particle group is formed, 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.
- 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
- 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.
- methods such as seed polymerization, bulk polymerization, emulsion polymerization, soap-free emulsion polymerization, suspension polymerization, etc. Is mentioned.
- seed polymerization is most preferred because the resulting resin particle group has the least variation in particle diameter.
- a resin particle group having a desired particle diameter 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.
- 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.
- seed particles are added to an emulsion (suspension) containing a polymerizable vinyl monomer and an aqueous medium.
- the emulsion can be prepared by a known method.
- 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.
- 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. Further, the emulsion may be heated to about 30 to 50 ° C. in order to promote the absorption of the polymerizable vinyl monomer into the seed particle group.
- 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 within the range of ⁇ 250 parts by weight.
- 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.
- 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.
- the resin particle group is obtained by polymerizing the polymerizable vinyl monomer absorbed by the seed particle group.
- 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.
- the polymerization initiator and the polymerizable vinyl monomer may be dispersed. These may be mixed separately in an aqueous medium.
- the polymerization initiator is not particularly limited.
- benzoyl peroxide lauroyl peroxide, benzoyl peroxide, o-methoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide
- Organic peroxides such as oxide, t-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (2,3-dimethylbutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,3,3) 3-trimethylbutyronitrile), 2,2′-azobis (2-isopropylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonite) ), 2,2′-azobis (4-methoxy-2,4-dimethylvaleron
- the polymerization temperature of the seed polymerization can be appropriately selected according to the type of 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.
- a polymer dispersion stabilizer may be added to the polymerization reaction system in order to improve the dispersion stability of the resin particle group.
- the polymer dispersion stabilizer include polyvinyl alcohol, polycarboxylic acid, celluloses (such as hydroxyethyl cellulose and carboxymethyl cellulose), and polyvinylpyrrolidone.
- the polymer dispersion stabilizer and an inorganic water-soluble polymer compound such as sodium tripolyphosphate may be used in combination.
- polyvinyl alcohol and polyvinyl pyrrolidone are preferred.
- the addition amount of the polymer dispersion stabilizer is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable vinyl monomer.
- a surfactant may be added to the emulsion.
- the surfactant any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a zwitterionic surfactant can be used.
- anionic surfactant examples 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 That.
- nonionic surfactant examples 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 include alkylamine, glycerin fatty acid ester, and oxyethylene-oxypropylene block polymer.
- cationic surfactant examples include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
- Examples of the zwitterionic surfactant include lauryl dimethylamine oxide, phosphate ester surfactants, phosphite ester surfactants, and the like. 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.
- the amount of the surfactant used is less than the above range, the polymerization stability may be lowered.
- there is more usage-amount of surfactant than the said range it is uneconomical in terms of cost.
- 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. .
- soap-free emulsion polymerization, dispersion polymerization, emulsion polymerization, suspension polymerization, etc. can be used.
- 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.
- a polymerization initiator is used as necessary.
- the polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate; benzoyl peroxide, lauroyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, 3, 5 , 5-trimethylhexanoyl peroxide, tert-butylperoxy-2-ethylhexanoate, organic peroxides such as di-tert-butyl peroxide; 2,2′-azobisisobutyronitrile, Examples thereof include azo compounds such as 1′-azobiscyclohexanecarbonitrile and 2,2′-azobis (2,4-dimethylvaleronitrile).
- the amount of the polymerization initiator used is preferably in the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the 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.
- a molecular weight modifier may be used in order to adjust the weight average molecular weight of the obtained seed particle group.
- the molecular weight modifier include mercaptans such as n-octyl mercaptan and tert-dodecyl mercaptan; ⁇ -methylstyrene dimer; terpenes such as ⁇ -terpinene and dipentene; halogenated hydrocarbons such as chloroform and carbon tetrachloride, etc. Can be used.
- the weight average molecular weight of the obtained seed particle group can be adjusted by adjusting the amount of the molecular weight modifier used.
- 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.
- the dry resin particle group is a fine resin particle group having a volume average particle diameter of 0.5 to 10 ⁇ m or close to it, and has a strong cohesive force between the resin particles, and tends to be an aggregated particle that is difficult to uncoagulate. 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.
- 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.
- 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.
- the ejection nozzles 22 are equally arranged on the circumference, but this is an example, and the arrangement of the ejection nozzles 22 is flexible.
- 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.
- 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.
- 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.
- the guide vanes 40 can be rotated by a predetermined angle to adjust the interval between the guide vanes 40 and change the flow velocity of the air passing therethrough.
- the classification performance specifically, the classification point
- 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.
- 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.
- positioned along the tangential direction is arrange
- 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).
- 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.
- 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.
- 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.
- donut-shaped raw material reclassification zones 28 are respectively formed at positions facing the air ejection holes.
- 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).
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- the coarse resin particle group exceeding the classification point may actually contain fine resin particles with a considerable probability.
- 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 swirling airflow classifier 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
- 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 resin particle groups having a volume average particle diameter of 0.5 to 10 ⁇ m can be realized.
- 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.
- 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.
- the binder include (meth) acrylic resins; (meth) acrylic-urethane resins; urethane resins; polyvinyl chloride resins; polyvinylidene chloride resins; melamine resins; styrene resins; alkyd resins.
- 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.
- thermosetting resin examples include thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin.
- the ionizing radiation curable resin synthesized from polyfunctional (meth) acrylate resin such as polyhydric alcohol polyfunctional (meth) acrylate; diisocyanate, polyhydric alcohol, and (meth) acrylic acid ester having a hydroxy group And polyfunctional urethane acrylate resins.
- the ionizing radiation curable resin is preferably a polyfunctional (meth) acrylate resin, and more preferably a polyhydric alcohol polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule.
- polyhydric alcohol polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexane tri (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate, etc. .
- Two or more kinds of the ionizing radiation curable resins may be used
- polyether resins having an acrylate functional group polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and the like can also be used.
- a photopolymerization initiator is added to the ultraviolet curable resin to form a binder.
- the said photoinitiator it is preferable to use what was suitable for the ultraviolet curable resin to be used.
- Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (Described in JP-A No. 2001-139663), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, active halogen compounds, ⁇ -acyloximes
- Examples include esters.
- acetophenones examples include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 1-hydroxydimethylphenyl ketone (also known as 2-hydroxy-2-methylpropiophenone), 1-hydroxycyclohexylphenyl.
- ketones 2-methyl-4′-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and the like.
- benzoins examples include benzoin, benzoin benzoate, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
- benzophenones examples include benzophenone, 2,4-dichlorobenzophenone, 4,4'-dichlorobenzophenone, p-chlorobenzophenone, and the like.
- phosphine oxides examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
- Examples of the ketals include benzylmethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one.
- Examples of the ⁇ -hydroxyalkylphenones include 1-hydroxycyclohexyl phenyl ketone.
- Examples of the ⁇ -aminoalkylphenones include 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone.
- radical photopolymerization initiators include trade names “Irgacure (registered trademark) 651” (2,2-dimethoxy-1,2-diphenylethane-1-one) manufactured by BASF Japan Ltd., manufactured by BASF Japan Ltd. Trade name “Irgacure (registered trademark) 184”, and trade name “Irgacure (registered trademark) 907” (2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) manufactured by BASF Japan Ltd. ) -1-propanone) and the like.
- the amount of the photopolymerization initiator used is usually in the range of 0.5 to 20% by weight, preferably in the range of 1 to 5% by weight with respect to 100% by weight of the binder.
- thermoplastic resin As the binder resin, a thermoplastic resin can be used in addition to the curable resin.
- the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose; homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of vinyl chloride, and vinylidene chloride.
- Vinyl resins such as homopolymers and copolymers; acetal resins such as polyvinyl formal and polyvinyl butyral; homopolymers and copolymers of acrylate esters, homopolymers and copolymers of methacrylate esters, etc.
- Acrylic resin polystyrene resin; polyamide resin; linear polyester resin; polycarbonate resin.
- a rubber binder such as synthetic rubber or natural rubber, an inorganic binder, or the like can be used as the binder.
- the rubber binder 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.
- the inorganic binder examples include silica sol, alkali silicate, silicon alkoxide, and phosphate.
- an inorganic or organic-inorganic composite matrix obtained by hydrolysis and dehydration condensation of metal alkoxide or silicon alkoxide can also be used.
- a silicon oxide matrix obtained by hydrolysis and dehydration condensation of a silicon alkoxide such as tetraethoxysilane can be used.
- the resin composition may further contain an organic solvent.
- 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.
- organic solvent examples include aromatic solvents such as toluene and xylene; alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene Glycol ethers such as glycol diethyl ether, diethylene glycol dimethyl ether, and propylene glycol methyl ether; 2-methoxyethyl acetate Salts, glycol ether esters such as 2-ethoxyethyl acetate (cellosolve acetate),
- the 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.
- 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.
- 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.
- PET polyethylene terephthalate
- TAC triacetyl cellulose
- acrylic polymers such as polycarbonate polymers and polymethyl methacrylate.
- a film made of a polymer such as a polymer.
- a film made of a polymer such as a polymer or an amide polymer such as nylon or aromatic polyamide is also included.
- imide polymer sulfone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenyl sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral
- films made of polymers such as polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers and blends of the above polymers.
- a film having a particularly low birefringence is preferably used as the substrate film.
- 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 ⁇ m and within the range of 20 to 300 ⁇ m from the viewpoints of workability such as strength and handling, and thin layer properties. It is preferable that it is within a range of 30 to 200 ⁇ m.
- an additive may be added to the base film.
- 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.
- the binder contained in the resin composition is an ionizing radiation curable resin
- 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, ⁇ rays, ⁇ rays, ⁇ 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.
- a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp
- Electron beams, ⁇ rays, ⁇ rays, ⁇ rays and the like extracted from electron beam accelerators such as
- 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 ⁇ m, and more preferably in the range of 3 to 7 ⁇ m.
- the present invention is not limited to this.
- 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.
- LS 13 320 manufactured by Beckman Coulter, Inc.
- 0.1 g of a resin particle group in 10 ml of a 0.1% by weight nonionic surfactant aqueous solution was mixed with a touch mixer (manufactured by Yamato Kagaku Co., Ltd., “TOUCHMIXER MT-31”) and an ultrasonic cleaner (VEL Co., Ltd.). Dispersed using Vocrea's "ULTRASONIC CLEANER VS-150") and used as a dispersion.
- optical parameters required for evaluation based on the Mie theory are set in the software of the laser diffraction / scattering type particle size distribution measuring apparatus.
- the measurement is performed at room temperature, and 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.
- 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
- the polymer constituting the group was polystyrene
- a known refractive index of 1.595 of polystyrene was input.
- the variation coefficient (CV value) of the particle diameter of the resin particle group is determined by the standard deviation ( ⁇ ) 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 (%) ( ⁇ / 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 ⁇ m 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.
- 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” manufactured by Tosoh Corporation (inside diameter 4.6 mm ⁇ length 15 cm) ⁇ 2 Guard column: Trade name “TSK guard column Super HZ-H” (inside 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 ⁇ l Column temperature: 40 ° C System temperature: 40 ° C Eluent: Tetrahydrofuran (THF) ⁇ How to create a calibration curve> As standard polystyrene samples for calibration curve
- the method for 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 ⁇ l 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 ⁇ l 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 ⁇ l 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. .
- a surfactant solution as a dispersant preferably 0.05 g of alkylbenzene sulfonate, was added to 20 ml of ion exchange water to obtain a surfactant aqueous solution. Thereafter, 0.02 g of a resin particle group to be measured is added to the surfactant aqueous solution, and an ultrasonic cleaner (for example, “VS-150” manufactured by Velvo Crea Co., Ltd.) 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.
- an ultrasonic cleaner for example, “VS-150” manufactured by Velvo Crea Co., Ltd.
- the above-mentioned flow type particle image analyzer equipped with a standard objective lens (10 ⁇ ) is used.
- a particle sheath liquid used in the above 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
- Particle diameter measurement range 0.5 to 200 ⁇ m
- Measurement range of particle circularity 0.2 to 1.0
- Measurement number of particles 100,000
- suspension of standard polymer particles for example, “5200A” manufactured by Thermo Fisher Scientific (diluted standard polystyrene particles with ion-exchanged water)
- 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.
- the number of resin particles having a particle diameter more than twice 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.
- 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 ⁇ m 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.
- 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 ⁇ m 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.
- 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.
- the dispersion after polymerization was 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 consisting of a crosslinked (meth) acryl-styrene copolymer resin.
- a polymer particle group A dry resin particle group
- 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 carried out using a swirling airflow classifier with the name “Aero Fine Classifier AC-20”.
- 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.
- the discharge pressure from the upper and lower jet nozzles 20 and 22 was 0.5 MPa.
- 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. As a result, a resin particle group composed 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 3.15 ⁇ m and a coefficient of variation of the particle diameter 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 ⁇ m 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 diameter of 1.01 ⁇ m and a coefficient of variation of the particle diameter of 13.24%.
- 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%).
- the obtained resin particle group had a volume average particle diameter of 3.15 ⁇ m and a coefficient of variation of particle diameter of 11.18%.
- 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 ⁇ m and a coefficient of variation of the particle diameter of 9.54%.
- 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
- a photopolymerization initiator (2-methyl 1- (4-methylthiophenyl) -2-morpholinopropan-1-one, trade name “Irgacure (registered trademark) 907”, manufactured by BASF (registered trademark) Japan Co., Ltd.
- a resin composition for an antiglare film as a composition was prepared.
- the coating film was formed by apply
- the said coating film was dried by heating at 80 degreeC for 1 minute (s).
- 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.
- 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.
- 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).
- the evaluation results of the antiglare property and surface property of the antiglare films prepared in Examples 4 to 6 and Comparative Examples 3 and 4 are the types and particles of the 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.
- 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.
- the antiglare film No. 6 had good surface properties with no unevenness of transmitted light and no light transmission.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Optical Elements Other Than Lenses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明の樹脂粒子群は、架橋ビニル系樹脂からなる体積平均粒子径が0.5~10μmの樹脂粒子群であって、体積平均粒子径の2倍以上の粒子径を有する樹脂粒子の個数が10万個中5個以下であり、0.97以下の円形度を有する樹脂粒子の割合が1%以下である。
本発明の樹脂粒子群は、任意の製造方法によって製造可能であるが、本発明の製造方法によって容易に製造できる。本発明の製造方法は、架橋ビニル系樹脂からなる体積平均粒子径が0.5~10μmの樹脂粒子群の製造方法であって、樹脂粒子群の生成後に、気流分級機を用いた分級により上記樹脂粒子群から粗大樹脂粒子群を除去する分級工程を含んでいる。そして、本発明の樹脂粒子群の製造方法は、樹脂粒子群の生成後に解砕工程を経ることなく上記樹脂粒子群の分級工程が実施され、上記気流分級機が、後述する旋回気流式分級機であることを特徴としている。
上記樹脂粒子群を生成する工程は、前記重合性ビニル系単量体を重合することにより行うことができる。
本発明の製造方法における分級工程は、樹脂粒子群の生成後に解砕工程を経ることなく、以下に説明する旋回気流式分級機を用いて実施される。本発明の製造方法に用いる旋回気流式分級機は、樹脂粒子群の生成工程で得られた樹脂粒子群(以下、「原料樹脂粒子群」と称する)が供給される分級用空洞部と、上記分級用空洞部の外周部に配置され、上記分級用空洞部に旋回流が発生するように上記分級用空洞部に互いの間から空気を送り込む複数のガイドベーンと、上記分級用空洞部の上部及び下部にそれぞれ空気を噴射する第1及び第2の噴射ノズルと、上記分級用空洞部から分級された樹脂粒子群(以下、「分級樹脂粒子群」と称する)を含む気流を上方へ排出する分級樹脂粒子群排出口と、上記分級用空洞部から粗大樹脂粒子群を下方へ排出する粗大樹脂粒子群排出口とを備える旋回気流式分級機である。
このように構成することで、本来は分級樹脂粒子群回収部方向に分離されるべき分級樹脂粒子群が、分級樹脂粒子群に混じって粗大樹脂粒子群回収部方向に分離されてしまうことを防止する上で大きな効果が得られる。
本発明の樹脂粒子群は、防眩フィルムや光拡散フィルム等の光学部品用として好適であり、また、バインダーと混合して樹脂組成物として使用するのに好適である。
本発明の樹脂組成物は、樹脂粒子群と、バインダーとを含んでいる。
本発明の防眩フィルムは、上記樹脂組成物を基材フィルム上に塗布してなる。
樹脂粒子群(種粒子群の製造例1・2で得られた種粒子群、及び実施例1~3及び比較例1・2で得られた樹脂粒子群)の体積平均粒子径の測定は、レーザー回折・散乱方式粒度分布測定装置(ベックマン・コールター株式会社製「LS 13 320」)及びユニバーサルリキッドサンプルモジュールによって行った。
液体(ノニオン性界面活性剤水溶液)の屈折率B.I.の実部=1.333(水の屈折率)
固体(測定対象の樹脂粒子群)の屈折率の実部=樹脂粒子群の屈折率
固体の屈折率の虚部=0
固体の形状因子=1
また、測定条件及び測定手順は、以下の通りとする。
測定時間:60秒
測定回数:1
ポンプ速度:50~60%
PIDS相対濃度:40~55%程度
超音波出力:8
<測定手順>
オフセット測定、光軸調整、バックグラウンド測定を行った後、上記した分散液を、スポイトを用いて、上記のレーザー回折・散乱方式粒度分布測定装置のユニバーサルリキッドサンプルモジュール内へ注入する。上記のユニバーサルリキッドサンプルモジュール内の濃度が上記のPIDS相対濃度に達し、上記のレーザー回折・散乱方式粒度分布測定装置のソフトウェアが「OK」と表示したら、測定を開始する。なお、測定は、ユニバーサルリキッドサンプルモジュール中でポンプ循環を行うことによって上記樹脂粒子群を分散させた状態、かつ、超音波ユニット(ULM ULTRASONIC MODULE)を起動させた状態で行う。
樹脂粒子群の粒子径の変動係数(CV値)は、前述の樹脂粒子群の体積平均粒子径の測定方法によって測定された体積基準の粒度分布の標準偏差(σ)及び体積平均粒子径(D)から、以下の式により算出した。
〔種粒子群の重量平均分子量の測定方法〕
種粒子群の製造例1・2で得られた種粒子群の重量平均分子量(Mw)の測定は、以下のようにして行った。
測定装置:高速GPC装置(東ソー株式会社製の商品名「HLC-8320GPC EcoSEC-WorkStation」、RI検出器(示差屈折率検出器)内蔵)
カラム:東ソー株式会社製の商品名「TSKgel Super HZM-H」(内径4.6mm×長さ15cm)×2本
ガードカラム:東ソー株式会社製の商品名「TSK guard column Super HZ-H」(内径4.6mm×長さ2cm)×1本
流量:試料側 0.175ml/min、リファレンス側 0.175ml/min
検出器:上記高速GPC装置に内蔵のRI検出器
濃度:0.3g/l
注入量:50μl
カラム温度:40℃
システム温度:40℃
溶離液:テトラヒドロフラン(THF)
<検量線の作成方法>
検量線用標準ポリスチレン試料としては、東ソー社株式会社製の商品名「TSK standard POLYSTYRENE」の重量平均分子量が、500、2630、9100、37900、102000、355000、3840000、及び5480000である標準ポリスチレン試料と、昭和電工株式会社製商品名「Shodex(登録商標) STANDARD」の重量平均分子量が1030000である標準ポリスチレン試料を用いる。
以下の実施例及び比較例の樹脂粒子群における、体積平均粒子径の2倍以上の粒子径を有する樹脂粒子の個数、及び0.97以下の円形度を有する樹脂粒子の割合は、フロー式粒子像分析装置(商品名「FPIA(登録商標)-3000S」、シスメックス株式会社製)を用いて測定した。
粒子径の測定範囲:0.5~200μm
粒子の円形度の測定範囲:0.2~1.0
粒子の測定個数:100000個
測定にあたっては、測定開始前に標準ポリマー粒子群の懸濁液(例えば、Thermo Fisher Scientific社製の「5200A」(標準ポリスチレン粒子群をイオン交換水で希釈したもの))を用いて上記フロー式粒子像分析装置の自動焦点調整を行った。なお、円形度は、樹脂粒子を撮像した画像と同じ投影面積を有する真円の直径から算出した周囲長を、樹脂粒子を撮像した画像の周囲長で除した値である。
攪拌機、温度計及び還流コンデンサーを備えたセパラブルフラスコに、水性媒体としての水3000gと、(メタ)アクリル酸エステル系単量体としてのメタクリル酸メチル500gと、分子量調整剤としてのn-オクチルメルカプタン5gとを仕込み、セパラブルフラスコの内容物を攪拌しながらセパラブルフラスコの内部を窒素置換しセパラブルフラスコの内温を70℃に昇温した。さらにセパラブルフラスコの内温を70℃に保ちながら、重合開始剤としての過硫酸カリウム2.5gをセパラブルフラスコの内容物に添加した後に12時間重合反応させ、エマルジョンを得た。得られたエマルジョンは、固形分(ポリメタクリル酸メチル粒子群)を14重量%含有し、その固形分は、体積平均粒子径が0.45μmであり、重量平均分子量が15000である真球状粒子群であった。この真球状粒子群を含むエマルジョンを種粒子群分散液として、後述する単分散粒子群の製造例1及び2に用いた。
攪拌機、温度計及び還流コンデンサーを備えたセパラブルフラスコに、水性媒体としての水3150gと、(メタ)アクリル酸エステル系単量体としてのメタクリル酸メチル350g、分子量調整剤としてのn-オクチルメルカプタン3gとを仕込み、セパラブルフラスコの内容物を攪拌しながらセパラブルフラスコの内部を窒素置換しセパラブルフラスコの内温を80℃に昇温した。さらにセパラブルフラスコの内温を80℃に保ちながら、重合開始剤としての過硫酸カリウム1.8gをセパラブルフラスコの内容物に添加した後に12時間重合反応させ、エマルジョンを得た。得られたエマルジョンは、固形分を10重量%含有し、その固形分は、体積平均粒子径が0.35μmであり、重量平均分子量が15000である真球状粒子群であった。この真球状粒子群を含むエマルジョンを種粒子群分散液として、後述する単分散粒子群の製造例3に用いた。
スチレン系単量体としてのスチレン300gと、(メタ)アクリル酸エステル系単量体としてのメタクリル酸メチル400gと、多官能の重合性ビニル系単量体としてのエチレングリコールジメタクリレート300gと、重合開始剤としての2,2’-アゾビスイソブチロニトリル8gとを互いに溶解させて単量体混合物を得た。得られた単量体混合物を、予めノニオン性界面活性剤としてのポリオキシエチレンオクチルフェニルエーテル10gをイオン交換水990gに溶解させることにより得られた界面活性剤水溶液1000gと混合し、高速乳化・分散機(商品名「ホモミクサーMARK II 2.5型」、プライミクス株式会社製)に入れて10000rpmで10分間処理して、乳化液を得た。
スチレン系単量体としてのスチレン510gと、(メタ)アクリル酸エステル系単量体としてのメタクリル酸n-ブチル370gと、多官能の重合性ビニル系単量体としてのジビニルベンゼン120gと、重合開始剤としての過酸化ベンゾイル8gとを互いに溶解させて単量体混合物を得た。この単量体混合物を実施例1の単量体混合物に代えて用いること以外は実施例1と同様にして、乳化液を得た。
(メタ)アクリル酸エステル系単量体としてのメタクリル酸メチル900gと、多官能の重合性ビニル系単量体としてのエチレングリコールジメタクリレート100gと、重合開始剤としての過酸化ベンゾイル8gとを互いに溶解させて単量体混合物を得た。この単量体混合物を実施例1の単量体混合物に代えて用いること以外は実施例1と同様にして、乳化液を得た。
この分散液を実施例1の分散液に代えて用い、ポリビニルアルコールの4重量%水溶液に代えてノニオン性界面活性剤としてのポリオキシエチレンオクチルフェニルエーテルの0.5重量%水溶液2000gを用いること以外は実施例1と同様にして、重合反応を行った。重合後の分散液をスプレードライによって乾燥し、架橋(メタ)アクリル系樹脂からなる樹脂粒子群である重合体粒子群C(乾燥樹脂粒子群)を得た。
単分散粒子群の製造例1で得られた重合体粒子群Aを、粉砕機を使用しない図1に示す旋回気流式分級機10であって、日清エンジニアリング株式会社製から市販されている商品名「エアロファインクラシファイアAC-20」の旋回気流式分級機を用いて、分級した。
単分散粒子群の製造例1で得られた重合体粒子群Aに代えて単分散粒子群の製造例2で得られた重合体粒子群Bを用いたこと以外は、実施例1と同様にして分級を行い、架橋ビニル系樹脂としての架橋(メタ)アクリル-スチレン共重合樹脂からなる樹脂粒子群を得た。
単分散粒子群の製造例1で得られた重合体粒子群Aに代えて単分散粒子群の製造例3で得られた重合体粒子群Cを用いたこと以外は、実施例1と同様にして分級を行い、架橋ビニル系樹脂としての架橋(メタ)アクリル系樹脂からなる樹脂粒子群を得た。
単分散粒子群の製造例1で得られた重合体粒子群Aをハンマーミル(型番「AIIW-5」、株式会社ダルトン製)にて解砕し、強制渦式分級機(商品名「ターボクラシファイアTC-15」、日清エンジニアリング株式会社製)にて分級を行い、樹脂粒子群を得た。
単分散粒子群の製造例1で得られた重合体粒子群Aに代えて単分散粒子群の製造例2で得られた重合体粒子群Bを用いたこと以外は、比較例1と同様にして、分級を行い、樹脂粒子群を得た。
紫外線硬化型樹脂としてのぺンタエリストールトリアクリレート及びペンタエリストールテトラアクリレートの混合物(商品名「アロニックス(登録商標)M-305」、東亞合成株式会社製)80重量部と、有機溶剤としてのトルエン及びシクロペンタノンの混合液(トルエンとシクロペンタノンとの体積比=7:3)120重量部と、実施例1にて製造した樹脂粒子群5重量部と、光重合開始剤(2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、商品名「イルガキュア(登録商標)907」、BASF(登録商標)ジャパン株式会社製)5重量部とを混合し、樹脂組成物としての防眩フィルム用樹脂組成物を調製した。
実施例1にて製造した樹脂粒子群に代えて実施例2にて製造した樹脂粒子群を用いること以外は、実施例4と同様にして、防眩フィルム用樹脂組成物を調製し、実施例2にて製造した樹脂粒子群を含有した防眩性ハードコートフィルムを作製した。
実施例1にて製造した樹脂粒子群に代えて実施例3にて製造した樹脂粒子群を用いること以外は、実施例4と同様にして、防眩フィルム用樹脂組成物を調製し、実施例3にて製造した樹脂粒子群を含有した防眩性ハードコートフィルムを作製した。
実施例1にて製造した樹脂粒子群に代えて比較例1にて製造した樹脂粒子群を用いること以外は、実施例4と同様にして、防眩フィルム用樹脂組成物を調製し、比較例1にて製造した樹脂粒子群を含有した防眩性ハードコートフィルムを作製した。
実施例1にて製造した樹脂粒子群に代えて比較例2にて製造した樹脂粒子群を用いること以外は、実施例4と同様にして、防眩フィルム用樹脂組成物を調製し、比較例2にて製造した樹脂粒子群を含有した防眩性ハードコートフィルムを作製した。
実施例4~6及び比較例3・4で作製した防眩フィルムの各々の塗工面ではない面をABS樹脂(アクリロニトリル-ブタジエン-スチレン共重合樹脂)板に張り付け、当該防眩フィルムの2m離れた場所から、輝度10000cd/cm2の蛍光灯を塗工面に映し、目視にて防眩フィルムの防眩性を評価した。防眩性の評価基準は、蛍光灯の反射像の輪郭がはっきり見えない場合には防眩性が「○」(良好)、蛍光灯の反射像の輪郭がはっきりと見える場合には防眩性が「×」(不良)と評価した。
実施例4~6及び比較例3・4で作製した防眩フィルムの各々を蛍光灯の真上に配置し、目視にて防眩フィルムの表面性を評価した。表面性の評価基準は、透過光のムラ及び光の透け(欠点)が何れもない場合を表面性が「○」(良好)、透過光のムラ及び光の透け(欠点)の少なくとも一方がある場合を表面性が「×」(不良)、と評価した。
12 上部円盤状部材
12a及び14a リング状のエッジ
14 下部円盤状部材
16 遠心分離室(分級用空洞部)
18 原料投入口
20 噴出ノズル(第1の噴出ノズル)
22 噴出ノズル(第2の噴出ノズル)
24 原料分散ゾーン(分級用空洞部、分級用空洞部の上部)
28 原料再分級ゾーン(分級用空洞部、分級用空洞部の下部)
30 粗大樹脂粒子群回収口(粗大樹脂粒子群排出口)
32 分級樹脂粒子群回収口(分級樹脂粒子群排出口)
40 ガイドベーン
40a 回動軸
40b ピン
50 補助分級機能部
Claims (6)
- 架橋ビニル系樹脂からなる体積平均粒子径が0.5~10μmの樹脂粒子群であって、
体積平均粒子径の2倍以上の粒子径を有する樹脂粒子の個数が10万個中5個以下であり、
0.97以下の円形度を有する樹脂粒子の割合が1%以下であることを特徴とする樹脂粒子群。 - 上記架橋ビニル系樹脂が、架橋(メタ)アクリル系樹脂、架橋スチレン系樹脂、架橋(メタ)アクリル-スチレン共重合樹脂の何れかであることを特徴とする請求項1に記載の樹脂粒子群。
- 光学部品用であることを特徴とする請求項1又は2に記載の樹脂粒子群。
- 樹脂粒子群の生成後に、気流分級機を用いた分級により前記樹脂粒子群から粗大樹脂粒子群を除去する分級工程を含む、架橋ビニル系樹脂からなる体積平均粒子径が0.5~10μmの樹脂粒子群の製造方法であって、
前記樹脂粒子群の分級工程は、樹脂粒子群の生成後に解砕工程を経ることなく実施され、
前記気流分級機は、
樹脂粒子群が供給される分級用空洞部と、
前記分級用空洞部の外周部に配置され、前記分級用空洞部に旋回流が発生するように前記分級用空洞部に互いの間から空気を送り込む複数のガイドベーンと、
前記分級用空洞部の上部及び下部にそれぞれ空気を噴射する第1及び第2の噴射ノズルと、
前記分級用空洞部から分級された樹脂粒子群を含む気流を上方へ排出する分級樹脂粒子群排出口と、
前記分級用空洞部から粗大樹脂粒子群を下方へ排出する粗大樹脂粒子群排出口とを備えていることを特徴とする樹脂粒子群の製造方法。 - 請求項1~3の何れか一つに記載の樹脂粒子群と、バインダーとを含むことを特徴とする樹脂組成物。
- 請求項5に記載の樹脂組成物を、基材フィルム上に塗布してなることを特徴とする防眩フィルム。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020187023837A KR102091410B1 (ko) | 2013-08-30 | 2014-03-28 | 수지 입자군 및 그 제조 방법 |
KR1020167006507A KR20160043036A (ko) | 2013-08-30 | 2014-03-28 | 수지 입자군 및 그 제조 방법 |
JP2015534017A JP6363607B2 (ja) | 2013-08-30 | 2014-03-28 | 樹脂粒子群及びその製造方法 |
KR1020207007600A KR102224659B1 (ko) | 2013-08-30 | 2014-03-28 | 수지 입자군 |
CN201480048093.3A CN105555840B (zh) | 2013-08-30 | 2014-03-28 | 树脂颗粒群及其制造方法 |
KR1020217006333A KR102293994B1 (ko) | 2013-08-30 | 2014-03-28 | 수지 입자군 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-180231 | 2013-08-30 | ||
JP2013180231 | 2013-08-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015029483A1 true WO2015029483A1 (ja) | 2015-03-05 |
Family
ID=52586066
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/059310 WO2015029483A1 (ja) | 2013-08-30 | 2014-03-28 | 樹脂粒子群及びその製造方法 |
Country Status (4)
Country | Link |
---|---|
JP (2) | JP6363607B2 (ja) |
KR (4) | KR102091410B1 (ja) |
CN (1) | CN105555840B (ja) |
WO (1) | WO2015029483A1 (ja) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107022220A (zh) * | 2016-02-01 | 2017-08-08 | 日本爱克兰工业株式会社 | 复合聚集树脂颗粒群、以及该颗粒群的制造方法和含有该颗粒群的组合物 |
KR20170113010A (ko) * | 2016-03-29 | 2017-10-12 | 세키스이가세이힝코교가부시키가이샤 | 중합체 입자 및 그 제조 방법 및 용도 |
CN108137719A (zh) * | 2015-09-30 | 2018-06-08 | 积水化成品工业株式会社 | 聚合物颗粒和其用途 |
JP2018172691A (ja) * | 2013-08-30 | 2018-11-08 | 積水化成品工業株式会社 | 樹脂粒子群及びその製造方法 |
WO2019182113A1 (ja) * | 2018-03-23 | 2019-09-26 | 積水化成品工業株式会社 | ビニル系樹脂粒子及びその製造方法 |
JP2020015853A (ja) * | 2018-07-26 | 2020-01-30 | デクセリアルズ株式会社 | 樹脂粒子、及び樹脂粒子の製造方法 |
JP2020023631A (ja) * | 2018-08-08 | 2020-02-13 | 東京インキ株式会社 | ポリメタクリル酸メチル粒子の製造方法、コロイド結晶の製造方法、および水懸濁液 |
WO2021261506A1 (ja) * | 2020-06-27 | 2021-12-30 | 松永正文 | 粒子の製造方法、粒子またはスラリーの塗布方法、2次電池または2次電池の製造方法、全固体電池または全固体電池の製造方法、ledまたはledの製造方法、蛍光体シートまたは蛍光体シートの製造方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008023648A1 (fr) * | 2006-08-21 | 2008-02-28 | Nippon Shokubai Co., Ltd. | Microparticules, procédé servant à produire des microparticules et composition de résine et film optique comprenant les microparticules en tant que matière de charge |
JP2009034560A (ja) * | 2007-07-31 | 2009-02-19 | Nisshin Seifun Group Inc | 粉体分級装置 |
WO2013047687A1 (ja) * | 2011-09-29 | 2013-04-04 | 株式会社日本触媒 | ビニル重合体微粒子、その製造方法、樹脂組成物および光学用材料 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0471081A (ja) | 1990-07-11 | 1992-03-05 | Yasutomo Oguchi | パターン識別機能を持つニューラルネットワークの構成法 |
JP2002040204A (ja) | 2000-07-19 | 2002-02-06 | Fuji Photo Film Co Ltd | 防眩性反射防止フィルム、偏光板及び液晶表示装置 |
JP4247147B2 (ja) * | 2004-03-26 | 2009-04-02 | 積水化成品工業株式会社 | 単分散樹脂粒子の製造方法 |
JP2012193244A (ja) * | 2011-03-15 | 2012-10-11 | Sekisui Plastics Co Ltd | 光拡散剤用樹脂粒子、その製造方法およびそれを含む光拡散フィルム |
JP5785261B2 (ja) * | 2011-08-31 | 2015-09-24 | 積水化成品工業株式会社 | 樹脂粒子集合体、その製造方法、およびその用途 |
WO2015029483A1 (ja) * | 2013-08-30 | 2015-03-05 | 積水化成品工業株式会社 | 樹脂粒子群及びその製造方法 |
-
2014
- 2014-03-28 WO PCT/JP2014/059310 patent/WO2015029483A1/ja active Application Filing
- 2014-03-28 KR KR1020187023837A patent/KR102091410B1/ko active IP Right Grant
- 2014-03-28 KR KR1020207007600A patent/KR102224659B1/ko active IP Right Grant
- 2014-03-28 KR KR1020167006507A patent/KR20160043036A/ko active Application Filing
- 2014-03-28 CN CN201480048093.3A patent/CN105555840B/zh active Active
- 2014-03-28 KR KR1020217006333A patent/KR102293994B1/ko active IP Right Grant
- 2014-03-28 JP JP2015534017A patent/JP6363607B2/ja active Active
-
2018
- 2018-06-28 JP JP2018122563A patent/JP2018172691A/ja active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008023648A1 (fr) * | 2006-08-21 | 2008-02-28 | Nippon Shokubai Co., Ltd. | Microparticules, procédé servant à produire des microparticules et composition de résine et film optique comprenant les microparticules en tant que matière de charge |
JP2009034560A (ja) * | 2007-07-31 | 2009-02-19 | Nisshin Seifun Group Inc | 粉体分級装置 |
WO2013047687A1 (ja) * | 2011-09-29 | 2013-04-04 | 株式会社日本触媒 | ビニル重合体微粒子、その製造方法、樹脂組成物および光学用材料 |
Non-Patent Citations (3)
Title |
---|
AKIHIKO EMA: "Koseido Bunkyu Sochi Aerofine Classifier Series", FUNTAI GIJUTSU, vol. 3, no. 5, 2011, pages 88 - 89 * |
NISSHIN ENGINEERING CO., LTD., AEROFINE CLASSIFIER CATALOG, 2012 * |
NISSHIN ENGINEERING CO., LTD.: "Bifun Ryoiki de Koremade ni Nai Bunkyu Seino o Hakki suru Kadobu no Nai Hanjiyuka o Mochiita Bunkyuki 'Aerofine Classifier", SEIHIN & GIJUTSU TOPICS, June 2013 (2013-06-01), Retrieved from the Internet <URL:http://www.nisshineng.co.jp/knowledge/topics/aero/index.html> * |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018172691A (ja) * | 2013-08-30 | 2018-11-08 | 積水化成品工業株式会社 | 樹脂粒子群及びその製造方法 |
CN113336976A (zh) * | 2015-09-30 | 2021-09-03 | 积水化成品工业株式会社 | 聚合物颗粒和其用途 |
US11098167B2 (en) | 2015-09-30 | 2021-08-24 | Sekisui Plastics Co., Ltd. | Polymer particles and use thereof |
CN108137719A (zh) * | 2015-09-30 | 2018-06-08 | 积水化成品工业株式会社 | 聚合物颗粒和其用途 |
JP2020128536A (ja) * | 2015-09-30 | 2020-08-27 | 積水化成品工業株式会社 | 重合体粒子及びその用途 |
EP3357934A4 (en) * | 2015-09-30 | 2019-05-01 | Sekisui Plastics Co., Ltd. | POLYMER PARTICLES AND USE THEREOF |
CN108137719B (zh) * | 2015-09-30 | 2021-05-14 | 积水化成品工业株式会社 | 聚合物颗粒和其用途 |
CN113336976B (zh) * | 2015-09-30 | 2023-10-31 | 积水化成品工业株式会社 | 聚合物颗粒和其用途 |
JPWO2017056529A1 (ja) * | 2015-09-30 | 2018-07-26 | 積水化成品工業株式会社 | 重合体粒子及びその用途 |
CN107022220B (zh) * | 2016-02-01 | 2021-07-16 | 日本爱克兰工业株式会社 | 复合聚集树脂颗粒群、以及该颗粒群的制造方法和含有该颗粒群的组合物 |
CN107022220A (zh) * | 2016-02-01 | 2017-08-08 | 日本爱克兰工业株式会社 | 复合聚集树脂颗粒群、以及该颗粒群的制造方法和含有该颗粒群的组合物 |
KR102001826B1 (ko) * | 2016-03-29 | 2019-07-19 | 세키스이가세이힝코교가부시키가이샤 | 중합체 입자 및 그 제조 방법 및 용도 |
KR20170113010A (ko) * | 2016-03-29 | 2017-10-12 | 세키스이가세이힝코교가부시키가이샤 | 중합체 입자 및 그 제조 방법 및 용도 |
WO2019182113A1 (ja) * | 2018-03-23 | 2019-09-26 | 積水化成品工業株式会社 | ビニル系樹脂粒子及びその製造方法 |
JP2020015853A (ja) * | 2018-07-26 | 2020-01-30 | デクセリアルズ株式会社 | 樹脂粒子、及び樹脂粒子の製造方法 |
WO2020022234A1 (ja) * | 2018-07-26 | 2020-01-30 | デクセリアルズ株式会社 | 樹脂粒子、及び樹脂粒子の製造方法 |
JP7101070B2 (ja) | 2018-07-26 | 2022-07-14 | デクセリアルズ株式会社 | 樹脂粒子の製造方法 |
JP7244233B2 (ja) | 2018-08-08 | 2023-03-22 | 東京インキ株式会社 | ポリメタクリル酸メチル粒子の製造方法、コロイド結晶の製造方法、および水懸濁液 |
JP2020023631A (ja) * | 2018-08-08 | 2020-02-13 | 東京インキ株式会社 | ポリメタクリル酸メチル粒子の製造方法、コロイド結晶の製造方法、および水懸濁液 |
WO2021261506A1 (ja) * | 2020-06-27 | 2021-12-30 | 松永正文 | 粒子の製造方法、粒子またはスラリーの塗布方法、2次電池または2次電池の製造方法、全固体電池または全固体電池の製造方法、ledまたはledの製造方法、蛍光体シートまたは蛍光体シートの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2018172691A (ja) | 2018-11-08 |
JP6363607B2 (ja) | 2018-07-25 |
JPWO2015029483A1 (ja) | 2017-03-02 |
KR20160043036A (ko) | 2016-04-20 |
CN105555840B (zh) | 2020-10-30 |
CN105555840A (zh) | 2016-05-04 |
KR102293994B1 (ko) | 2021-08-25 |
KR20200031710A (ko) | 2020-03-24 |
KR102224659B1 (ko) | 2021-03-05 |
KR102091410B1 (ko) | 2020-03-20 |
KR20180095142A (ko) | 2018-08-24 |
KR20210025731A (ko) | 2021-03-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6363607B2 (ja) | 樹脂粒子群及びその製造方法 | |
TWI411619B (zh) | 含有中空粒子之液狀組成物、其製法、及光學物件 | |
JP6612417B2 (ja) | 重合体粒子及びその用途 | |
TWI531585B (zh) | 樹脂粒子集合體、其製造方法以及其用途 | |
JP6685316B2 (ja) | 重合体粒子及びその用途 | |
JP2004026974A (ja) | 低屈折率ポリマー球状粒子及びその製造方法、その粒子を用いる光特性フィルム及びそのフィルムを設ける画像表示装置 | |
JP2020125477A (ja) | 架橋アクリル系樹脂粒子及びその製造方法、樹脂組成物並びに包装物品 | |
WO2018055786A1 (ja) | 重合体粒子分散液及びそれに用いる重合体粒子、分散剤及び分散媒体、並びにそれらの用途 | |
JP6550456B2 (ja) | 重合体粒子、重合体粒子の製造方法、及びその用途 | |
JP6087189B2 (ja) | 多孔質樹脂粒子及びその製造方法、並びに、その用途 | |
JP5603726B2 (ja) | 着色樹脂粒子及びその用途 | |
JP2019052306A (ja) | 重合体粒子及びその用途 | |
JP6650857B2 (ja) | 重合体粒子並びにその製造方法及び用途 | |
CN105778008B (zh) | 聚合物粒子、聚合物粒子的制造方法及其用途 | |
TW202132355A (zh) | 聚合物粒子及其用途 | |
JPWO2021171669A5 (ja) | ||
KR20160113564A (ko) | 중합체 입자, 중합체 입자의 제조 방법 및 그 용도 | |
KR20160079391A (ko) | 중합체 입자, 중합체 입자의 제조 방법 및 그 용도 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480048093.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14839579 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015534017 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20167006507 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14839579 Country of ref document: EP Kind code of ref document: A1 |