KR101382369B1 - Microparticle, process for producing microparticle, and, loaded with the microparticle, resin composition and optical film - Google Patents

Abstract

The microparticles | fine-particles which content of coarse particle | grains out of an average particle diameter reduced to the low level, the manufacturing method of such microparticles | fine-particles, and the resin composition containing this microparticle are provided. The fine particles of the present invention are characterized in that the coarse particles having a particle diameter of twice or more the average particle diameter is 1000 particles / 0.5 g or less. In addition, the production method of the present invention is a step of wet classifying particulate dispersion having a solid content concentration of 0.5 to 50% by mass and a B-type viscosity of 0.5 to 20 mPa · s, and drying and pulverizing the fine particles after wet classification to obtain a water content of 0.05 to 2% by mass. The process of making powder fine particles, and the process of dry classification of the said powder fine particles are included.

Description

Microparticles | fine-particles, the manufacturing method of microparticles | fine-particles, the resin composition containing this microparticles | fine-particles, and an optical film {MICROPARTICLE, PROCESS FOR PRODUCING MICROPARTICLE, AND, LOADED WITH THE MICROPARTICLE, RESIN COMPOSITION AND OPTICAL FILM}

The present invention relates to fine particles having a highly controlled particle diameter, and a resin composition using the same.

Background Art Conventionally, there have been attempts to include fine particles in resins and resin compositions used for various uses, and to improve physical properties or usefulness of the resins and resin compositions. Such attempts have been made in the same way for optical resin materials used in optical applications such as liquid crystal displays (LCDs), plasma display panels (PDPs), electroluminescent displays (ELDs), transmissive screens and touch panels. For example, the optical resin composition containing microparticles | fine-particles which consists of an organic material or an inorganic material is used as a raw material for the optical resin film (sheet | sheet, board) which provides light diffusivity and anti-glare anti-glare property.

By the way, in the field of the image display apparatus as mentioned above in recent years, a big screen and a high definition tend to progress more and more, and the demand for peripheral technology is also increasing. Various studies have also been conducted on fine particles such as improvement of affinity with other materials (resin and other additives), improvement of mechanical properties and optical properties of the fine particles themselves. Moreover, about the microparticles | fine-particles used as these optical resin films and spacers for liquid crystal display elements, in addition to the said required characteristic, it is desired that particle diameter distribution is narrow and content of coarse particle | grains is small. This is because when the particle diameter distribution is wide, it is difficult to keep the film thickness of the liquid crystal uniformly and uniformly when used as a spacer of the liquid crystal display device. Therefore, coarse particles cause scratches on the film surface or the fine particles. This is because direct visual recognition causes a deterioration of the display quality of the image display apparatus.

For example, Patent Document 1 which discloses microparticles used for optical applications describes that the particle size distribution is obtained in a state where the particle size distribution is very sharp according to the production method of the microparticles. Further, in Patent Documents 2 to 4, a method for producing fine particles in which content of particles having a particle diameter exceeding a predetermined size with respect to the average particle diameter is reduced from the viewpoint that coarse particles cause deterioration of the display quality of the display device and defects of the optical film. (Patent Document 2) A method (Patent Documents 3 and 4) has been proposed to remove coarse particles by performing filtration on fine particles in an emulsion or dispersion state before use of fine particles.

Patent Document 1; Japanese Unexamined Patent Publication No. 2004-307644

Patent Document 2; Japanese Laid-Open Patent Publication No. 2002-166228, claims, etc.

Patent Document 3; Japanese Unexamined Patent Publication No. 2005-309399, patent claims, etc.

Patent Document 4; Japanese Laid-Open Patent Publication No. 2004-191956, claims, etc.

However, in the synthesis step of the fine particles as in Patent Document 1, it is practically difficult to control the particle diameter distribution highly. Moreover, as pointed out also in patent documents 2-4, even when the particle diameter distribution is managed in an appropriate range, when coarse particle | grains largely deviate from an average particle diameter exist, the fall of a display quality and an optical film generate | occur | produce a fault. do. Therefore, the demand for the reduction of the coarse particle amount tends to be even higher from the viewpoint of improving the visibility and productivity. Even as the technique of the said patent documents 2-4, it was difficult to obtain the microparticles | fine-particles which satisfy | fill these requirements sufficiently.

This invention is made | formed in view of the said situation, The objective is to provide the microparticles | fine-particles whose content of coarse particle | grains which fall out of an appropriate particle diameter was reduced to the low level, the manufacturing method of such microparticles, and the resin composition containing these microparticles | fine-particles. have.

The microparticles | fine-particles of this invention which solved the said subject have the summary that the coarse particle which has the particle diameter more than twice the average particle diameter is 1000 piece / 0.5g or less.

It is preferable that the said microparticles | fine-particles are organic inorganic composites containing an organic polymer skeleton and a polysiloxane skeleton.

In the method for producing the fine particles of the present invention, a step of wet classifying a fine particle dispersion having a solid content concentration of 0.5 to 50% by mass and a type B viscosity of 0.5 to 20 mPa · s, and drying and pulverizing the fine particles after the wet classification are carried out to a water content of 0.05 to 2 mass. It is characterized by including the process of making powder fine particles of%, and the process of dry classification of the said powder fine particles. Thus, by processing the raw material (fine particle dispersion liquid, powder) which has a specific physical property by the method which combined wet classification and dry classification, coarse particle and a microparticle which a particle diameter deviates from an appropriate range can be reduced more efficiently.

Also included are optical films (films having a concavo-convex shape on the surface, such as a light diffusing film and an antiglare film) obtained by applying the composition and the coating composition on a substrate.

In the fine particles of the present invention, the content of coarse particles having a particle diameter outside the appropriate range is reduced to a low level. Moreover, according to the method of the present invention, the content of the microparticles can also be reduced together with the coarse particles whose particle diameters deviate from the appropriate range. Therefore, the molded article obtained from the resin composition containing the particle | grains of this invention is considered to be hard to produce the fault which originates in a coarse particle. In addition, since the content of the fine particles is also reduced, it is considered that the transparency of the resin itself is also difficult to be impaired. The fine particles of the present invention are particularly preferable for the optical resin composition, and it is considered that the light diffusing film, the anti-glare film, and the light diffusing plate containing the fine particles of the present invention exhibit excellent optical properties.

Best Mode for Carrying Out the Invention

The fine particles of the present invention are characterized in that coarse particles having a particle diameter of twice or more the average particle diameter are 1000 particles / 0.5 g or less.

As described above, when the fine particles used in the optical field contain coarse particles having a particle diameter outside the appropriate range, there is a fear that the surface of the film may be scratched or the particles may be easily recognized. In particular, it has been confirmed by the present inventors that the above phenomenon becomes remarkable when the fine particles having a particle diameter of twice or more the average particle diameter of the fine particles to be used exist (increase). Preferably, the coarse particles having a particle diameter of 2 times or more of the average particle diameter is 500 / 0.5g or less, more preferably 200 / 0.5g or less, more preferably 100 / 0.5g or less, most Preferably it is 50 pieces / 0.5g or less.

Moreover, when the coarse particle amount is in the said range and the number of coarse particles which has a particle diameter of 2.5 times or more of the average particle diameter is 50 / 0.5g or less, when using for optical use, the defect originating in coarse particle further arises. It is preferable because it becomes difficult. More preferably, it is 30 pieces / 0.5g or less, More preferably, it is 10 pieces / 0.5g or less.

Moreover, it is preferable that the microparticles | fine-particles of this invention reduced the number of microparticles which have a particle diameter of 1/2 or less of an average particle diameter. If such fine particles are contained in a large amount, transparency or the like can be obtained when the particles are used for optical purposes (for example, a light diffusing film provided on an image display surface of various image display apparatuses, an antireflection anti-glare film, etc.). There is a risk of lowering the luminance. Therefore, it is preferable that the microparticles having a particle diameter of 1/2 or less of an average particle diameter are 10 volume% or less, More preferably, it is 7 volume% or less.

Moreover, although the average particle diameter of the microparticles | fine-particles of this invention is not specifically limited, It is preferable that it is 0.1-50 micrometers, More preferably, it is 1-30 micrometers, More preferably, it is 2-20 micrometers. In the case where the average particle diameter is in the above range, for example, when used for optical applications, it is possible to obtain advantageous effects such as excellent light diffusivity and surface luminescence (luminance). When the average particle diameter is too small, there is a fear that the dispersibility into a resin serving as a medium may decrease, and when too large, a sufficient light diffusion effect may not be obtained. In addition, particle size distribution measurement, average particle diameter, and content of the said microparticles are measured using the precision particle size distribution measuring apparatus (For example, "Multi Sizer II" of Beckman Coulter company) using the Coulter principle, Calculated.

Although the shape of the microparticles | fine-particles of this invention is not specifically limited, For example, spherical shape, needle shape, plate shape, scale shape, grinding | pulverization shape, flaky shape, cocoon shape, and corn candy form etc. are mentioned. . In particular, when used in optical applications (used in optical resin compositions, etc.), the shape of the spherical shape or almost the true spherical shape is 1.0 to 1.2. It is preferable that the coefficient of variation of the particle diameter is in the range of 10% or less.

The fine particles of the present invention are obtained by dry classification of powder fine particles having a predetermined moisture content, true specific gravity, volume specific gravity and particle diameter.

The powder particles provided to the dry classification have a water content of 0.05 to 2 mass%. If the moisture content is too large, such moisture acts as a binder during classification, and the particles aggregate with each other. On the other hand, when the moisture content is too small, the particles aggregate with each other due to static electricity, so that the classification accuracy is lowered in any case. Coarse particles tend to increase. If the water content is within the above range, the particles are hard to aggregate, and the classification operation can be smoothly performed. Moreover, it is preferable that true specific gravity is 1-1.25 g / ml, volume specific gravity is 0.1-1 g / ml, and average particle diameter is 1-50 micrometers. When the true specific gravity of powder microparticles | fine-particles is too small, the difference in centrifugal force and wind resistance by the magnitude | size of a particle diameter hardly arises, and classification classification may become low. If the weight ratio is too large, it is not preferable because large equipment and power are required. In addition, when the volume specific gravity is too large, large equipment and power are required, and when the volume specific gravity is too small, a difference according to the magnitude of the particle diameter is less likely to occur, so the classification accuracy may be lowered. When the particle diameter is too small, the agglomeration between the powders is strong, a good dispersion state may not be obtained, and the classification accuracy may be lowered. When too large, large equipment and power are required, which is not preferable.

It is preferable to make the content of the coarse particle | grains 2 times or more of the average particle diameter in the dispersion particle obtained by wet classification and the dispersion solution obtained by wet classification by wet classification into 200,000 or less per 0.5g. More preferably, it is 100,000 / 0.5g or less, More preferably, it is 50,000 / 0.5g or less. If the number of coarse particles of a specific size contained in the powder particles provided for dry classification and the dispersion solution obtained by wet classification is within the above range, coarse at high yield and / or high classification processing speed by performing dry classification. It is preferable because fine particles having a small content of particles are easily obtained.

Therefore, the water content, sesame seeds weight ratio, volume specific weight ratio and particle diameter are preferably in the above ranges, more preferably, the water content of the powder fine particles is preferably 0.1 to 0.5 mass%, and the sesame seeds weight is 1 to 1.5 g / ml. It is preferable that it is preferable that it is 0.3-0.8 g / ml, and it is preferable that an average particle diameter is 2-20 micrometers.

In addition, the said "water content" is a value measured by a Karl Fischer moisture meter (for example, Hiranuma Industrial Co., Ltd. product, a moisture measuring device). The "volume density" indicates the amount of powder that enters the container when the powder is placed in a container in a constant volume in mass per unit volume, and the value of the bulk density is determined by a powder tester (manufactured by Hosokawa Micron Co., Ltd.). It is measured. The "particulate weight" of the powder microparticles is a value in which the powder microparticles are filled into a container of a certain volume, the voids of the sample are completely replaced by a liquid, and the volume of the liquid required is reduced from the volume of the container. It is a value calculated from the relationship with the mass of the powder microparticles | fine-particles filled in the inside, and was measured by the true specific gravity meter (for example, the product of Seishin Corporation). The value of the said particle diameter is a value of the volume reference measured by the said precision particle size distribution measuring apparatus (for example, "Multi Sizer II" by Beckman Coulter).

It is preferable to use the airflow classification apparatus using wind power for the dry classification of the said powder fine particle. Air flow classifier is a device that separates the fine particles (powder layer) according to the particle size (particle diameter, mass of the granules) by using the air flow (that is, the flying distance is determined by the balance between the inertia of the particles and the drag received from the air stream). Classified). In general, in the classification apparatus using only a sieve or a filter, the physical properties of the recovered particles depend on the filtration efficiency of the sieve or filter of the sieve to be used, and therefore, in order to obtain only particles having a desired physical property, for example, a particle diameter, in a specific range. In this case, a plurality of classification operations need to be performed. On the other hand, if an airflow classifier is used, coarse particle | grains and microparticles can be removed simultaneously.

The classification mechanism of the air flow classifier is not particularly limited. Therefore, using only airflow, including a rotary rotor that provides propulsion to the airflow, or a guide vane for guiding the wind, and using airflow generated by the combined action of these, and also these and other classification means ( Sieve or mesh) may be combined.

Specific air flow classifiers include high-precision airflow classifiers such as DXF type (manufactured by Nippon Pneumatic Co., Ltd.); A rotary rotor airflow classifier having a classification rotor such as a turbo classifier (manufactured by Nisshin Engineering Co., Ltd.), a crack seal (manufactured by Seishin Corp.), and a turboflex (registered trademark, manufactured by Hosokawa Micronone Co., Ltd.); Air classifiers (elvojet type classifiers) using Koanda effects such as elbows (manufactured by Nitetsu Co., Ltd.); And an air flow classifier using a mesh body such as a dry body high bolter (manufactured by Toyo Hi-Tech Co., Ltd.) and a dry body blow shifter (manufactured by Yuglov Corporation). Among these, the highly accurate airflow classifier, the rotary rotor type airflow classifier, and the airflow classifier using the Coanda effect are preferred because they can efficiently remove coarse particles.

The high-precision airflow classifier is free of moving parts (movable members), generates high-speed swirling air by inflow air into the dispersion zone and the classification zone, and provides centrifugal force to the particles supplied into the apparatus. It is an apparatus which exhausts air from a classification zone by a suction blower so that it may become the drag of centrifugal force given to, and classifies coarse powder and fine powder from particle | grains by the balance of this centrifugal force and drag force. The rotary rotor type airflow classifier includes a cylinder (classifying rotor) that can be rotated freely, and an air inlet for inputting air into the apparatus from outside the apparatus, and generates particles in the apparatus by high-speed rotation of the rotor, and supplies the particles into the apparatus. The device provides a centrifugal force due to vortex flow, and sucks air from the intake port so as to become a drag force of the centrifugal force, and classifies coarse powder and fine powder from the particles by the balance between the centrifugal force and the drag force. The air flow classification device using the Coanda effect uses a Coanda effect that flows along this wall if the flow is placed on only one side thereof, and the device uses airflow (feed air). And ejector unit ejecting into the apparatus, a Coanda block leading to the classification (including particles) to the classification chamber, and a classification edge for isolating the particles according to their properties (powders, subdivisions (objects), fines, etc.) Equipped at the position. The fractionation (including particles) ejected from the ejector portion is allowed to flow along the Coanda block. At this time, the coarse particles and the microparticles are classified by the balance of the fluid resistance because the inertial force acting on the particles (the difference between the inertial forces acting on the microparticles and the coarse particles and the coarse particles try to fly farther).

Among the above airflow classifiers, airflow classifiers (elvojet type classifiers) using the Coanda effect are preferable. In the case of using this elbowjet classifier, it is preferable to raise the feed air to the maximum value of the recommended air pressure in order to increase the classification accuracy. Moreover, although feed air is normally operated at 0.1-10 kgf, it is recommended to set it as 1-5 kgf from a viewpoint of classification accuracy improvement. In general, if the feed air is excessively high, the fly distance of the coarse particles is long, and the coarse particles that protrude from the front wall are likely to enter the subdivision. However, the fine particles according to the present invention are obtained through a dry classification process after a wet classification process as described below, and since coarse particles are removed in the wet classification process, the coarse particles of the coarse particles are caused by springing. There is no mixing. Therefore, classifying precision can be improved by raising feed air.

It is also preferable to use a slim edge as the classification edge in order to improve the classification accuracy. As described above, the classification edge can be used to isolate particles according to their properties, and one end (particle entry side) is thin and has a wedge shape that becomes thick as it goes to the other end. The bottom end face (one end having a thickness in the wedge shape) is almost rectangular and has a specific width. In addition, the width of the classification edge is usually designed to be substantially equal to the width of the flow path through which the fraction containing particles flows. Here, the slim edge has a shorter distance between the wedge-shaped slope (inclined surface) than the standard edge used in general (particularly about half of the standard edge in the bottom end portion). Slim edges are usually used to prevent particles from depositing at the tip of the edges and lowering the classification accuracy when the particles are strongly charged. The reason why the classification accuracy is improved by using the slim edge is considered to be that the confusion of the airflow is less likely to occur in addition to the purpose of the slim edge (suppression of deterioration of the classification accuracy due to the deposition of particles).

The powder fine particles provided in the dry classification are preferably obtained by wet classifying a fine particle dispersion having a solid content concentration of 0.5 to 50% by mass and a B type viscosity of 0.5 to 20 mPa · s, followed by drying and grinding. It is preferable that solid content concentration of a microparticle dispersion is 0.5-20 mass%, and it is preferable that B-type viscosity is 0.5-10 mPa * s.

When the solid concentration of the particulate dispersion solution supplied to the wet classification apparatus is high or the viscosity is high, it is necessary for a long time to classify, or the load on the mesh is increased and the mesh body is enlarged and enlarged, resulting in a lower classification accuracy. There is a concern. Moreover, when solid content concentration is less than 0.5 mass%, it will require long time for classification.

Moreover, it is preferable that the particle | grains provided for wet classification have a content of the coarse particle larger than the particle diameter twice the average particle diameter. Specifically, the content of the coarse particles larger than the particle diameter twice the average particle diameter is preferably 1 million or less per 0.5 g. More preferably, it is 500,000 pieces / 0.5g, More preferably, it is 200,000 pieces / 0.5g or less.

The fine particle dispersion may be prepared by dispersing previously prepared fine particles in a dispersion medium (water, an organic solvent, etc.), or when the fine particles are composed of an organic polymer or an organic inorganic composite material described later, the reaction solution after the polymerization reaction may be used as it is. . Moreover, you may use the microparticle dispersion liquid obtained by the wet process as it is.

Although the apparatus which can be used for the wet classification of the said microparticle dispersion liquid is not specifically limited, The filtration apparatus using a filter and a sieve, the liquid cyclone apparatus using a centrifugal force, an inertial force, etc. are mentioned. As a specific wet classification apparatus, a cartridge filter (for example, the product made by Rocky Techno Co., Ltd., Japan Corporation) and the liquid cyclone (for example, the product made by LISA Corporation, Industria company) which classify using a centrifugal force are mentioned.

The cartridge filter can be used in combination of a plurality. For example, in order to reduce the running cost according to the long life, it is possible to use a combination of a final filter that satisfies the required filtration accuracy and a prefilter used for extending the final filter. However, it is preferable that the selection criteria of the final filter is a type capable of removing 50% by mass or more of particles twice the average particle diameter. For example, the SLP type cartridge filter manufactured by Rocky Techno Co., Ltd. is preferable as a final filter because it has a thickness of the filter medium which is a feature of the depth filter and a large filtration area which is characteristic of the pleated filter. As a selection criterion of a prefilter, it is preferable to set it as the type which can filter 50 mass% or more of particles 3 times or more of average particle diameter.

The liquid cyclone device is a device that classifies, by centrifugal force, particles dispersed in the liquid using a liquid as a medium. For example, in the case of a device having a cylindrical (or cone) portion, a fine particle dispersion is supplied in the tangential direction of the cylindrical portion of the device, and the coarse particles act as centrifugal force while the fine particle dispersion descends the cylindrical portion as a swirl flow. In the radial direction to collide with the inner wall of the cylinder, fall to the bottom of the device along the inner wall, and then recover from the bottom of the device. On the other hand, since the fine particles move upward in the apparatus by the upward swirl flow generated near the center, the fine particles are recovered from the upper portion of the apparatus.

It is preferable to dry and grind | pulverize the particle | grains after wet classification. The conditions for drying and pulverization can satisfy the above-described physical properties of the powder fine particles (water content of 0.05 to 2 mass%, 1 to 1.25 g / ml in true ratio, 0.1 to 1 g / ml in volume ratio, and 1 to 50 µm in particle size). It may be, and is not specifically limited.

The fine particles of the present invention are obtained by dry classification of powder fine particles having predetermined physical properties, but other classification means can be combined as necessary. In particular, the use of the above-described wet classification step for the adjustment of powder fine particles is recommended from the viewpoint of reducing the content of coarse particles and fine particles to a low level. That is, as a preferable process for obtaining the fine particles of the present invention, a process of wet classifying the fine particle dispersion having predetermined physical properties, drying and pulverizing the particles after the wet classification, and further dry classifying. By passing through such a process, the microparticles | fine-particles of this invention which are 1000 or more / 0.5g or less of coarse particles which have the particle diameter more than twice the average particle diameter can be obtained more efficiently.

Next, the structure and manufacturing method of the fine particles according to the present invention will be described.

The form of the fine particles according to the present invention is not particularly limited and may be made of any of an organic polymer, an inorganic material, and an organic inorganic composite material. Examples of the organic polymer include linear polymers such as polystyrene, polymethyl methacrylate, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polysulfone, polycarbonate, and polyamide; Divinylbenzene, hexatriene, divinylether, divinylsulfone, diallylcarbinol, alkylenediacrylate, oligo or polyalkylene glycoldiacrylate, oligo or polyalkylene glycoldimethacrylate, alkylene tree Acrylates, alkylene tetraacrylates, alkylene trimethacrylates, alkylene tetramethacrylates, alkylenebisacrylamides, alkylenebismethacrylamides, both terminal acrylic modified polybutadiene oligomers, etc. Network polymers obtained by polymerization with monomers; The organic polymer which consists of an amino resin obtained by the polycondensation reaction of an amino compound (for example, benzoguanamine, melamine, urea, etc.) with formaldehyde is mentioned.

Examples of the organic inorganic composite material include (A) fine particles in which inorganic fine particles such as metal oxides such as silica, alumina and titania, metal nitrides, metal sulfides and metal carbides are dispersed and contained in the organic resin, and (B) (organo) Of fine particles obtained by complexing metal siloxane chains (molecular chains containing "metal-oxygen-metal" bonds) and organic molecules such as polysiloxane and polytitanoxane at the molecular level, and organoalkoxysilanes such as methyltrimethoxysilane Polysiloxane and a polymerizable group (for example, vinyl group, which uses as a raw material the silicone microparticles | fine-particles, such as polymethylsilsesquioxane obtained by the progress of a hydrolysis and a condensation reaction, and the silicone compound which has (C) hydrolyzable silyl group as a raw material) Organic inorganic composite material comprising an organic polymer skeleton obtained by reacting with a polymerizable monomer having a meta) acryloyl group or the like, and a polysiloxane skeleton .

As an inorganic material, glass, silica, alumina, etc. are mentioned, for example.

Among the above examples, the fine particles made of the organic polymer or the organic inorganic composite material are preferred because the design of the characteristics of the fine particles can be relatively freely performed and particles having a sharp particle diameter distribution are easily obtained. Moreover, in the microparticles | fine-particles which consist of organic polymers, the organic polymer which consists of amino resins, and the organic polymer particle obtained by the seed polymerization method (The ratio of the crosslinkable monomer with respect to polymeric monomer whole quantity is 20 mass% or more, More preferably, 30 Mass% or more, more preferably 50 mass% or more of particles) are preferable, and (C) is particularly preferable among the fine particles made of an organic inorganic composite material. In addition, these particles are cured or crosslinked in the synthesis process, and are difficult to dissolve and swell by an organic solvent. Therefore, when used in a coating resin composition for forming a light diffusing layer and an antiglare layer, which will be described later, even when used simultaneously with an organic solvent or the like, the particles are hardly deteriorated or a change in the particle diameter occurs, so that coarse particles are reduced within the above range. It is preferable because the effect obtained is sufficiently obtained.

These particles are preferably provided to the wet classification process in the state of the particle suspension obtained at the time of synthesis of each particle. That is, it is easy to obtain the suspension which is small in content of coarse particle | grains 2 times or more of average particle diameter (for example, less than 1 million pieces / 0.5 g). In particular, microparticles | fine-particles which consist of organic inorganic composite materials obtained by the preferable manufacturing method demonstrated below and organic polymer microparticles | fine-particles which consist of an amino resin are preferable.

In addition, the particles preferably have a coefficient of variation of particle diameter (based on particle size distribution calculated on a volume basis) of 20% or less. More preferably 10% or less. The smaller the value of the coefficient of variation of the particle diameter, the smaller the variation in the particle diameter. When the above range is satisfied, the coarse particle amount contained in the fine particles after the wet classification and dry classification process is easy to be reduced. In addition, the variation coefficient of a particle diameter is a value computed by the following formula here.

Coefficient of variation of particle diameter (%) =

Is the standard deviation of the particle diameter, and X represents the average particle diameter.

In the present invention, the standard deviation between the average particle diameter and the particle diameter was measured using the above-described precision particle size distribution measuring apparatus (for example, "Multi Sizer II" manufactured by Beckman Coulter, Inc.) and calculated on a volume basis.

Here, the structure and the manufacturing method of the microparticles | fine-particles (amino resin) which consist of the said organic polymer, and microparticles | fine-particles (the said (C)) which consist of organic inorganic composite materials are demonstrated.

<Amino resin Of crosslinked particles  Manufacturing method>

First, the manufacturing method of the amino resin (amino resin crosslinked particle) which is microparticles | fine-particles which consist of the said organic polymer is demonstrated.

As a manufacturing method of an amino resin crosslinked particle, the 1st manufacturing method and the 2nd manufacturing method demonstrated below are mentioned. According to these first and second production methods, the particle diameter can be controlled in the synthesis step of the fine particles, so that generation of coarse particles can be suppressed to some extent. Therefore, by adding the amino resin crosslinked particles obtained by the production method to the above-described process for obtaining the fine particles according to the present invention, since the reduction in the content of the particles whose particle diameter is outside the appropriate range can be performed more easily, it is preferable. Do. First, the first manufacturing method will be described.

-First Manufacturing Method-

The first production method of the amino resin crosslinked particles (hereinafter also referred to simply as "first production method") is a resination step of obtaining an amino resin precursor by reacting an amino compound with formaldehyde, and the resination An emulsification step of emulsifying the amino resin precursor obtained in the step in an aqueous medium to obtain an emulsion of the amino resin precursor, and a curing reaction of the amino resin precursor emulsified by adding a catalyst to the emulsion obtained in the emulsification step, And a curing step of obtaining amino resin crosslinked particles.

The resination step is a step of generating an amino resin precursor which is an initial condensation reaction product by reacting an amino compound with formaldehyde. Water can be used as a solvent at the time of making an amino compound and formaldehyde react. As a specific method for carrying out the resination step, an amino compound is added to react with formaldehyde in the form of an aqueous solution (formalin), or trioxane or paraformaldehyde is added to water to generate formaldehyde in water. The method etc. which add and react an amino compound to the adjusted aqueous solution are mentioned preferably. Especially, the former method is more preferable from an economic point of view because it does not require an adjustment tank of aqueous formaldehyde solution and the raw material is easily available. Moreover, even when employ | adopting any method, it is preferable to perform a resination process under stirring by a well-known stirring apparatus etc.

In the resination step, the amino compound used as the starting material is not particularly limited, but for example, benzoguanamine (2,4-diamino-6-phenyl-sym.-triazine), cyclohexanecarbo Guanamine, cyclohexenecarboguamine, melamine and the like. Among these, the amino compound which has a triazine ring is more preferable. In particular, since benzoguanamine has a benzene ring and two reactors, when benzoguanamine is included as an amino compound, the resulting amino resin crosslinked particles are flexible (hardness), fouling resistance, heat resistance and solvent resistance. It is especially preferable because of its excellent chemical resistance. The said amino type compound may be used independently and may use two or more types together.

In the whole amount of the amino compound to be used, it is preferable that the ratio which the said amino compound (benzoguanamine, cyclohexane carboguanamine, cyclohexene carboguanamine, and melamine) occupies is 40 mass% or more in total, More preferably, it is more preferable. Preferably it is 60 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 100 mass%. When content of the said amino type compound is 40 mass% or more, the amino resin crosslinked particle | grains produced will be excellent in heat resistance and solvent resistance.

It is preferable that the molar ratio (amino compound (mol) / formaldehyde (mol)) of the amino compound and formaldehyde made to react in a resination process is 1 / 3.5-1 / 1.5, and is 1 / 3.5-1 / 1.8 It is more preferable, and it is still more preferable that it is 1 / 3.2-1/2. If the molar ratio is less than 1 / 3.5, there may be a large amount of unreacted formaldehyde, and if it exceeds 1 / 1.5, there may be a large amount of unreacted amino-based compound.

In addition, the concentration of the amino compound and formaldehyde at the time of injection of the resination step is preferably higher concentration, as long as there is no problem in the reaction. Specifically, the viscosity in the 95-98 degreeC temperature range of the reaction liquid containing the amino resin precursor which is a reaction product is in the range of 2 * 10 <^-2> -5.5 * 10 <^-2> Pa * s (20-55 cP). It is desirable to have a concentration that can be controlled and controlled. More preferably, in the emulsifying step described later, the reaction solution is added to the aqueous solution of the emulsifier or the aqueous solution of the emulsifier or the emulsifier is added to the reaction solution so that the concentration of the amino resin precursor in the emulsion is in the range of 30 to 60 mass%. Can be concentration.

Therefore, the viscosity in the 95-98 degreeC temperature range of the reaction liquid containing the amino resin precursor obtained in the resination process is 2 * 10 <^-2> -5.5 * 10 <^-2> Pa * s (20-55 cP) It is preferable that it is, More preferably, it is 2.5 * 10 <^-2> -5.5 * 10 <^-2> Pa * s (25-55 cP), More preferably, it is 3.0 * 10 <^-2> -5.5 * 10 <^-2> Pa * s (30 55 cP). As said viscosity measuring method, the method of using a viscosity measuring instrument which can grasp | ascertain the progress of reaction immediately (in real time), and can confirm the end point of the reaction correctly is optimal. As such a viscosity measuring instrument, a vibratory viscometer (MIVIITS Japan, product name: MICI6001) can be used. The viscometer is provided with a vibrating part that is constantly vibrating. When the vibrating part is immersed in the reaction liquid, when the viscosity of the reaction liquid increases and a load is applied to the vibrating part, the load is immediately converted into a viscosity and displayed. It is supposed to be done.

By reacting an amino compound and formaldehyde in water (in an aqueous medium), an so-called initial condensate amino resin precursor is obtained. The reaction temperature is preferably within the temperature range of 95 to 98 ° C. so that the progress of the reaction can be grasped immediately and the end point of the reaction can be accurately identified. The reaction between the amino compound and formaldehyde is performed by performing an operation such as cooling the reaction solution when the viscosity of the reaction solution falls within the range of 2 × 10 ^{−2 to} 5.5 × 10 ⁻² Pa · s. You can exit. Thereby, the reaction liquid containing an amino resin precursor is obtained. The reaction time is not particularly limited.

The amino resin precursor obtained in the resination step has a molar ratio of the structural unit derived from the amino compound and the structural unit derived from formaldehyde constituting the amino resin precursor (structural unit (mol) derived from the amino compound / formaldehyde derived structure). It is preferable that a unit (mole) is 1 / 3.5-1 / 1.5, It is more preferable that it is 1 / 3.5-1 / 1.8, It is more preferable that it is 1 / 3.2-1 / 2. If the molar ratio is within the above range, particles having a narrow particle size distribution can be obtained.

The amino resin precursor is usually organic such as acetone, dioxane, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, methyl ethyl ketone, toluene and xylene Soluble for solvents but substantially insoluble with water.

In a 1st manufacturing method, the particle diameter of the amino resin crosslinked particle finally obtained can be made small by making the viscosity of the reaction liquid in the resination process of preparing the reaction liquid containing the said amino resin precursor low. However, when the viscosity of the reaction solution is less than 2 x 10 ^-2 Pa.s or exceeds 5.5 x 10 ^-2 Pa.s, the amino resin crosslinked particles having a substantially uniform particle diameter (narrow in particle size distribution) are finally obtained. It may be difficult to obtain. That is, if the viscosity of the reaction solution is less than 2 x 10 ^-2 Pa.s (20 cP), the stability of the emulsion obtained in the emulsification step described later will be insufficient. For this reason, when hardening an amino resin precursor in a hardening process, there exists a possibility that the obtained amino resin crosslinked particle may enlarge or agglomerate mutually, and the particle diameter of an amino resin crosslinked particle cannot be controlled, and a particle size distribution There exists a possibility of becoming a wide amino resin crosslinked particle. Moreover, when the stability of an emulsion is inadequate, the particle diameter (average particle diameter) of amino resin crosslinked particle will change every time it manufactures (per batch), and there exists a possibility of causing a deviation to a product. On the other hand, if the viscosity of the reaction solution exceeds 5.5 x 10 ^-2 Pa.s (55 cP), the load applied to the high-speed stirrer used in the emulsification step to be described later becomes too large, and the shear force decreases, so that the reaction solution is sufficiently stirred ( There is a risk of becoming unsatisfactory). For this reason, it becomes difficult to control the particle diameter of the amino resin crosslinked particle finally obtained, and it may become an amino resin crosslinked particle with a wide particle size distribution. Therefore, it is preferable to adjust the reaction liquid to the said viscosity range in advance in a resination process.

The emulsification step is a step of emulsifying the amino resin precursor obtained by the resination step to prepare an emulsion of the amino resin precursor. In the emulsification of the amino resin precursor, for example, it is preferable to use an emulsifier capable of forming a protective colloid. In particular, it is preferable to use the emulsifier which consists of water-soluble polymers which can comprise a protective colloid.

As the emulsifier, for example, polyvinyl alcohol, carboxymethyl cellulose, sodium alginate, polyacrylic acid, water-soluble polyacrylate, polyvinylpyrrolidone and the like can be used. These emulsifiers may be used in the form of an aqueous solution by dissolving the whole amount in water, using a part of them in the form of an aqueous solution, and using the remainder in the same state (for example, in powder form, granule form, liquid form, etc.). . Among the emulsifiers exemplified above, polyvinyl alcohol is more preferable in consideration of stability of the emulsion, interaction with the catalyst and the like. The polyvinyl alcohol may be a complete saponified product or a partial saponified product. In addition, the polymerization degree of polyvinyl alcohol is not specifically limited.

It is preferable that it is 1-30 mass parts with respect to 100 mass parts of amino resin precursors obtained by the said resination process, and, as for the usage-amount of an emulsifier, it is more preferable that it is 1-5 mass parts. If the amount is out of the above range, there is a fear that the stability of the emulsion is insufficient. In addition, the larger the amount of the emulsifier used for the amino resin precursor, the smaller the particle diameter of the particles to be produced.

In the emulsification step, for example, the reaction solution obtained in the resination step is added to the aqueous solution of the emulsifier so that the concentration (that is, the solid content concentration) of the amino resin precursor is in the range of 30 to 60 mass%, and then 50 to 100. It is preferable to emulsify in the temperature range of ° C. More preferably, it is 60-100 degreeC, More preferably, it is 70-95 degreeC. The concentration of the aqueous solution of the emulsifier is not particularly limited, but may be a concentration capable of adjusting the concentration of the amino resin precursor within the above range. If the concentration of the amino resin precursor is less than 30% by mass, the productivity of the amino resin crosslinked particles may be lowered. If it exceeds 60% by mass, the resulting amino resin crosslinked particles may be enlarged or the particles may aggregate with each other. It becomes difficult to control the particle diameter of amino resin crosslinked particle, and there exists a possibility that the particle size distribution of the amino resin crosslinked particle obtained may become wide.

In the emulsifying step, it is preferable to use an apparatus (an apparatus having high shearing force) capable of stirring the amino resin precursor and the aqueous solution of the emulsifier more strongly as the stirring means. As a specific stirring device, for example, a so-called high speed stirrer, a homo mixer, a TK homo mixer (manufactured by Specialty Chemicals Co., Ltd.), a high speed disper, Ebara-Mizer (manufactured by Ebara Corporation), a high-pressure homogenizer ( Izumi Fudo Machinery Co., Ltd., static mixer (Noritake Co., Ltd. product), etc. are mentioned.

In the emulsification step, it is preferable to accelerate the emulsification until the amino resin precursor obtained in the resination step has a predetermined particle diameter. In addition, the predetermined particle diameter may be appropriately set so that amino resin crosslinked particles having a desired particle diameter are finally obtained. Specifically, emulsification is preferably performed so that the average particle diameter of the emulsified amino resin precursor is 0.1 to 20 µm by appropriately considering the type of vessel or stirring blade, stirring speed, stirring time, emulsification temperature, and the like. More preferably, it is 0.5-20 micrometers, More preferably, it is 1-5 micrometers. Thus, by emulsifying an amino resin precursor so that it may become the said particle diameter range, the particle diameter of an amino resin crosslinked particle can be controlled to a desired range.

In the first production method, in order to more reliably prevent the amino resin crosslinked particles finally obtained from agglomerating firmly, inorganic particles can be added to the emulsion obtained after the emulsification step as necessary. Specific examples of the inorganic particles include, for example, silica fine particles, zirconium oxide fine particles, aluminum powder, alumina sol, ceriezole, and the like, and among them, silica fine particles are more preferable. It is preferable that the specific surface area of an inorganic particle is 10-400 m <2> / g, More preferably, it is 20-350 m <2> / g, More preferably, it is 30-300 m <2> / g. The particle diameter of the inorganic particles is preferably 0.2 µm or less, more preferably 0.1 µm or less, and still more preferably 0.05 µm or less. If the specific surface area and the particle diameter are within the above ranges, an even more excellent effect can be exerted even when the resulting amino resin crosslinked particles are prevented from firmly agglomerated.

The method of adding the inorganic particles to the emulsion is not particularly limited. Specifically, for example, the inorganic particles are added in the state (particulate form) or in the form of a dispersion in which the inorganic particles are dispersed in water. And the like can be mentioned. The amount of the inorganic particles added to the emulsion is preferably 1 to 30 parts by mass, more preferably 2 to 28 parts by mass, still more preferably 3 to 25 parts by mass based on 100 parts by mass of the amino resin precursor contained in the emulsion. It is wealth. If it is less than 1 part by mass, there may be a possibility that the finally obtained amino resin crosslinked particles may not be sufficiently prevented from being agglomerated firmly, and if it is more than 30 parts by mass, aggregates of only inorganic particles may be generated. Moreover, as a stirring method at the time of adding an inorganic particle, the method of using the apparatus with the high shear force mentioned above is preferable at the point which fixes an inorganic particle firmly with amino resin particle.

In the curing step, an amino resin is added by adding a catalyst (in detail, a curing catalyst) to the emulsion adjusted in the emulsifying step and performing a curing reaction of the emulsified amino resin precursor (curing the amino resin precursor in an emulsion state). Crosslinked particles (in detail, suspensions of amino resin crosslinked particles) are produced.

As the catalyst (curing catalyst), an acid catalyst is suitable. As the acid catalyst, minerals such as hydrochloric acid, sulfuric acid, phosphoric acid (inorganic acid); Ammonium salts of these minerals (inorganic acid); Sulfamic acid; Sulfonic acids such as benzene sulfonic acid, paratoluene sulfonic acid and dodecylbenzene sulfonic acid; Organic acids such as phthalic acid, benzoic acid, acetic acid, propionic acid and salicylic acid; Among the acid catalysts of the above examples, in view of curing rate, photoacid (inorganic acid) is preferable, and sulfuric acid is more preferable in terms of corrosion to the apparatus, safety in use of photoacid (inorganic acid), and the like. When sulfuric acid is used as the catalyst, compared with the case where dodecylbenzenesulfonic acid is used, for example, the resulting amino resin crosslinked particles are less likely to be discolored and the solvent resistance is high. These acid catalysts may use only 1 type, or may use 2 or more types together.

It is preferable that the usage-amount of the said catalyst is 0.1-5 mass parts with respect to 100 mass parts of amino resin precursors in the emulsion obtained by the said emulsification process, More preferably, it is 0.3-4.5 mass parts, More preferably, it is 0.5-4.0 It is a mass part. If the amount of the catalyst used exceeds 5 parts by mass, the emulsion state may be broken, and the particles may aggregate with each other. If the amount is less than 0.1 parts by mass, the reaction may require a long time or insufficient curing. Similarly, the amount of the catalyst used is preferably 0.002 moles or more, more preferably 0.005 moles or more, and more preferably 0.01 to 0.1 moles with respect to 1 mole of the amino compound used as the starting compound. When the amount of the catalyst used is less than 0.002 moles with respect to 1 mole of the amino compound, there is a fear that the reaction requires a long time or the curing may be insufficient.

In the curing step in the curing step, the reaction solution (emulsion) is preferably kept at 15 (room temperature) to 80 ° C, more preferably at 20 to 70 ° C, more preferably at 30 to 60 ° C for at least 1 hour. Then, it is preferable to carry out at the temperature of the range of 60-150 degreeC, More preferably, 60-130 degreeC, More preferably, 60-100 degreeC under normal pressure or pressurization. When reaction temperature of hardening reaction is less than 60 degreeC, hardening does not advance sufficiently and there exists a possibility that the solvent resistance and heat resistance of the amino resin crosslinked particle obtained may fall. On the other hand, when reaction temperature exceeds 150 degreeC, a firm pressurization reactor is needed and it is not economical. The end point of the curing reaction may be determined by sampling or visual observation. In addition, the reaction time of hardening reaction is not specifically limited.

It is preferable to perform a hardening process under stirring, and a well-known stirring apparatus may be used as a stirring means. In the curing step, the average particle diameter of the amino resin crosslinked particles obtained by curing the emulsion of the amino resin precursor in an emulsion state is preferably 0.1 to 20 µm, more preferably 0.5 to 20 µm, still more preferably 1 to 5 micrometers.

In a 1st manufacturing method, the coloring process of adding the aqueous solution which melt | dissolves dye in water in the emulsion of an amino resin precursor, and the suspension of amino resin crosslinked particle can be included.

In a 1st manufacturing method, the neutralization process which neutralizes the suspension containing the amino resin crosslinked particle obtained by the said hardening process can also be formed. The neutralization step is preferably performed when an acid catalyst such as sulfuric acid is used as the curing catalyst in the curing step. By performing the neutralization step, it is possible to remove the acid catalyst (specifically, to neutralize the acid catalyst). For example, the amino resin when the amino resin crosslinked particles are heated in a heating step or the like described later. Discoloration of the crosslinked particles (for example, discoloration to yellow) can be suppressed.

"Neutralization" as used in the neutralization process makes pH of suspension containing an amino resin crosslinked particle | grains 5 or more, More preferably, it is pH 5-9. When the pH of the suspension is less than 5, since the acid catalyst remains, the amino resin crosslinked particles may discolor in the heating step or the like described later. By adjusting the pH of the suspension within the above range by the neutralization, amino resin crosslinked particles having high hardness, excellent solvent resistance and heat resistance, and no discoloration are obtained. As the neutralizing agent that can be used in the neutralization step, for example, an alkaline substance is suitable. Examples of the alkaline substance include sodium carbonate, sodium hydroxide, potassium hydroxide and ammonia. Among them, sodium hydroxide is preferable, and sodium hydroxide aqueous solution can be suitably used. These may use only 1 type or may use 2 or more types together.

In the first production method, a separation step of extracting the amino resin crosslinked particles from the suspension of the amino resin crosslinked particles obtained after the curing step or after the neutralization step may be provided.

As a method of separating the amino resin crosslinked particles from the suspension (separation method), a method of filtration separation or a separator such as a centrifugal separator may be used as a convenient method, but is not particularly limited. Any can be used.

In addition, the amino resin crosslinked particles taken out from the suspension may be washed with water or the like as necessary.

In a 1st manufacturing method, it is preferable to perform the heating process of heating the amino resin crosslinked particle drawn out through the separation process at the temperature of 130-190 degreeC. By carrying out the heating process, water adhering to the amino resin crosslinked particles and remaining free (unreacted) formaldehyde can be removed, and further condensation (crosslinking) in the amino resin crosslinked particles is further promoted. You can. When the said heating temperature is lower than 130 degreeC, the condensation (crosslinking) in an amino resin crosslinked particle | grain can not be fully promoted, there exists a possibility that the hardness, solvent resistance, and heat resistance of an amino resin crosslinked particle may not be improved, and it is 190 degreeC. When exceeding, there exists a possibility that the obtained amino resin crosslinked particle may discolor. Even in the case where the above-described neutralization step is carried out, the effect when the heating temperature is outside the above temperature range is the same. From the viewpoint of improving various properties (hardness, solvent resistance, heat resistance, and discoloration resistance) of the obtained amino resin crosslinked particles, it is preferable to carry out the heating temperature of the amino resin crosslinked particles within the above range after the neutralization step.

The heating method in a heating process is not specifically limited, Usually, a well-known heating method may be used. The heating step may be completed, for example, at a stage where the water content of the amino resin crosslinked particles is 3% by mass or less (more preferably 2% by mass or less). In addition, a heating time is not specifically limited.

The amino resin crosslinked particles obtained in the first production method are separated from the aqueous medium in the emulsification, dried and pulverized, and then the obtained pulverized product is dispersed in a solvent to form a suspension. You can also supply. It is also a preferable aspect of the present invention method to provide a wet classification of the suspension after the curing step (including any suspension until the separation step, such as the suspension obtained through the neutralization step, until the separation step). It is preferable to obtain the fine powder of 0.05-2 mass% of water content, and to provide this to a dry classification process by drying and grinding | pulverizing the suspension after wet classification after the above-mentioned separation process and the heating process performed as needed.

Next, a second production method of amino resin crosslinked particles will be described.

-Second Manufacturing Method-

The second production method of the amino resin crosslinked particles (hereinafter, also simply referred to as "second production method") is used to prepare an amino resin precursor obtained by reacting an amino compound with formaldehyde with a surfactant in an aqueous medium. After mixing and adding a catalyst to this liquid mixture, the said amino resin precursor is made to granulate and precipitate in the said aqueous medium, the said amino resin crosslinked particle is isolate | separated from the said aqueous medium, and it is a method of grinding the obtained dried material.

In the second production method, a resination step is employed in the same manner as in the first production method, and in the resination step, the amino compound and formaldehyde are reacted to generate an amino resin precursor. The mixing process which mixes the amino resin precursor obtained by this with surfactant in an aqueous medium is employ | adopted, and a catalyst is added to the liquid mixture containing this amino resin precursor and surfactant, and the granulation and precipitation by hardening of an amino resin precursor are performed. It is different from the first manufacturing method in that a curing and granulating step of obtaining amino resin crosslinked particles is employed.

In a 2nd manufacturing method, preparation of the amino resin crosslinked particle with a small particle diameter becomes easy by starting hardening of an amino resin precursor in aqueous solution state (for example, an average particle diameter of 0.1-50 micrometers).

Moreover, as an amino compound used by a 2nd manufacturing method, it is preferable to set the kind and composition ratio suitably so that the grade of water miscibility mentioned later may be satisfy | filled. For example, it is more preferable to require an amino compound which can react with formalin to produce a water-soluble amino resin precursor.

Moreover, it is preferable that the amino resin precursor obtained at the resination process is water-soluble. The surfactant used in the second production method is used to impart water affinity to the aqueous medium of the amino resin precursor, and the surfactant does not include the emulsifier used in the first production method.

In the present invention, the water affinity is added to the amino resin precursor, which is the initial condensate, at 15 ° C., in mass% of the initial condensate of the dropwise amount of water until cloudiness occurs (hereinafter, referred to as 'water miscibility'). The larger the value, the higher the water affinity. Moreover, the water miscibility of the suitable amino resin precursor in a 2nd manufacturing method is 100% or more. In the amino resin precursor having a water miscibility of less than 100%, no matter how dispersed, it is formed only in a nonuniform suspension having a relatively large particle diameter, and the spherical fine particles finally obtained have a uniform particle diameter. It is hard to become (the particle size distribution is wide).

In the mixing step, the amino resin precursor obtained by the resination step is mixed with the surfactant by stirring or the like in an aqueous medium to prepare a mixed solution.

As the surfactant, for example, all surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants can be used. In particular, anionic surfactants or nonionic surfactants or mixtures thereof can be used. desirable.

As anionic surfactant, Alkali metal alkyl sulfates, such as sodium dodecyl sulfate and potassium dodecyl sulfate; Ammonium alkyl sulfates such as ammonium dodecyl sulfate and the like; Sodium dodecyl polyglycol ether sulfate; Sodium sulforicinolate; Alkylsulfonates such as alkali metal salts of sulfonated paraffins, ammonium salts of sulfonated paraffins, and the like; Fatty acid salts such as sodium laurate, triethanolamine oleate, triethanolamine abietate, and the like; Alkylarylsulfonates such as sodium dodecylbenzenesulfonate, alkali metal sulfates of alkali phenol hydroxyethylene and the like; High alkyl naphthalene sulfonates; Naphthalene sulfonic acid formalin condensate; Dialkyl sulfosuccinates; Polyoxyethylene alkylsulfate salts; Polyoxyethylene alkyl aryl sulfate salt etc. can be used, As a nonionic surfactant, Polyoxyethylene alkyl ether; Polyoxyethylene alkyl aryl ether; Sorbitan fatty acid esters; Polyethylene sorbitan fatty acid esters; Fatty acid monoglycerides such as monolaurate of glycerol; Polyoxyethyleneoxypropylene copolymer; Condensation products of ethylene oxide with fatty amines, amides, or acids.

As for the usage-amount of surfactant, the range of 0.01-10 mass parts is preferable with respect to 100 mass parts of amino resin precursors obtained by the said resination process. If it is less than 0.01 parts by mass, a stable suspension of the amino resin crosslinked particles may not be obtained, and if it exceeds 10 parts by mass, unnecessary foaming may occur in the suspension or adversely affect the physical properties of the finally obtained amino resin crosslinked particles. There is.

In the mixing step, for example, the reaction solution obtained in the above-mentioned resination step is added to the aqueous solution of the surfactant so that the concentration (that is, the solid content concentration) of the amino resin precursor is in the range of 3 to 25 mass%, and then mixed. It is desirable to. In this case, the concentration of the aqueous solution of the surfactant is not particularly limited, and may be a concentration capable of adjusting the concentration of the amino resin precursor within the above range. If the concentration of the amino resin precursor is less than 3% by mass, the productivity of the amino resin crosslinked particles may be lowered. If the concentration of the amino resin precursor is more than 25% by mass, the resulting amino resin crosslinked particles may be enlarged or particles may aggregate. Since the particle diameter of amino resin crosslinked particle | grains cannot be controlled, there exists a possibility that it may become amino resin crosslinked particle with a wide particle size distribution.

As the stirring method in the mixing step, a general stirring method can be adopted. For example, the method of stirring using stirring blades, such as a disk turbine, a pan turbine, a piddler type, a propeller type, and a multistage wing, is preferable.

In the second production method, in order to prevent the amino resin crosslinked particles finally obtained from agglomerating firmly, inorganic particles may be added to the mixed liquid obtained after the mixing step as necessary. The description in the above-described first manufacturing method can be similarly applied to the inorganic particles and the addition method thereof.

In the curing and granulating step, a catalyst (in detail, a curing catalyst) is added to the mixed liquid prepared in the above mixing step, and the curing reaction and granulation of the amino resin precursor are carried out and the amino resin crosslinked particles (in detail, the amino resin Suspension of crosslinked particles).

As the catalyst (curing catalyst), an acid catalyst is suitable. As an acid catalyst, the thing similar to what was illustrated by the 1st manufacturing method can be used preferably, but it is preferable to use the alkylbenzene sulfonic acid which has a C10-18 alkyl group especially in a 2nd manufacturing method. Alkylbenzene sulfonic acid having an alkyl group having 10 to 18 carbon atoms exhibits specific surfactant activity in an aqueous solution of the amino resin precursor which is the initial condensate, and produces a stable suspension of cured resin. Specifically, decyl benzene sulfonic acid, dodecyl benzene sulfonic acid, tetradecyl benzene sulfonic acid, hexadecyl benzene sulfonic acid, an octadecyl benzene sulfonic acid, etc. are mentioned, for example. These may use only 1 type or may use 2 or more types together.

It is preferable that the usage-amount of the said catalyst is 0.1-20 mass parts with respect to 100 mass parts of amino resin precursors in the liquid mixture obtained by the said mixing process, More preferably, it is 0.5-10 mass parts, More preferably, it is 1-10 mass parts It is wealth. When the amount of the catalyst used is less than the above range, a long time is required for the condensation curing, and a stable suspension of the amino resin crosslinked particles is not obtained, so that the aggregate contains coarse coarse particles in a large amount. There is a fear that it will not be obtained only. In addition, in a large amount exceeding the above range, a catalyst such as alkylbenzene sulfonic acid or the like is distributed more than necessary in the amino resin crosslinked particles in the resulting suspension, and as a result, the amino resin crosslinked particles are plasticized, and the particles between particles during condensation curing. Aggregation and fusion tend to occur, and there exists a possibility that the amino resin crosslinked particle which finally has a uniform particle diameter may not be obtained.

Similarly, the amount of the catalyst used is preferably 0.0005 mol or more, more preferably 0.002 mol or more, and more preferably 0.005 to 0.05 mol, with respect to 1 mol of the amino compound used as the raw material compound. When the usage-amount of a catalyst is less than 0.0005 mol with respect to 1 mol of amino compounds, there exists a possibility that reaction may require a long time, or hardening may become inadequate.

The hardening reaction and granulation in a hardening and granulation process can add the said catalyst to the liquid mixture of an amino resin precursor, and can maintain it at a suitable temperature in the temperature from 0 degreeC low temperature to 100 degreeC or more under pressurization, stirring. There is no restriction | limiting in particular in the addition method of the said catalyst, It can select suitably. The end point of the curing reaction can be determined by sampling or visual observation. In addition, the reaction time of hardening reaction is not specifically limited. The curing reaction is generally completed by raising the temperature to 90 ° C. or higher and maintaining it for a certain time, but curing at high temperature is not necessarily required, and the amino resin crosslinked particles in the suspension obtained even at a low temperature for a short time may be reacted with methanol or acetone. It is enough if it is hardened to the extent that it does not swell.

It is preferable to perform a hardening and a granulation process under stirring with a well-known stirring apparatus etc. normally. The average particle diameter of a preferable amino resin crosslinked particle is the same as that of the average particle diameter of an amino resin crosslinked particle in the hardening process of a 1st manufacturing method.

In the second manufacturing method, a neutralization step of neutralizing the suspension containing the amino resin crosslinked particles obtained by the curing step may be included. For the details such as the range of pH in the neutralization step, the kind of neutralizing agent, and the like, the description in the first production method can be applied in the same manner.

In the second production method, a separation step of extracting the amino resin crosslinked particles may be formed from a suspension of the amino resin crosslinked particles obtained after the curing and granulation step or after the neutralization step. In the second production method, the amino resin crosslinked particles are separated from the suspension and taken out, and the amino resin crosslinked particles obtained by curing are separated from the aqueous medium in the mixing step and taken out. As to the method (separation method) for extracting the amino resin crosslinked particles from the suspension, the same method as in the first production method can be applied.

In a 2nd manufacturing method, it is preferable to perform the heating process which heats the amino resin crosslinked particle taken out through the separation process at the temperature of 130-190 degreeC. As conditions of a heating process, the conditions similar to the heating process of a 1st manufacturing method are applicable.

The amino resin crosslinked particles obtained in the second production method are separated from the aqueous medium in the mixing step or the curing and granulation step, dried and pulverized, and the obtained pulverized product is mixed with a solvent to obtain a suspension. It is preferable to perform wet classification, separation and drying, followed by dry classification. It is preferable to supply the suspension after the said hardening and granulation process or the suspension which passed through the neutralization process / the water washing process to wet and dry classification. After wet classification, it is preferable to separate particle | grains, to dry it, to grind | pulverize, if necessary, to make powder fine particles of 0.05-2 mass% of water content, and to dry classify.

Next, the structure and manufacturing method of the microparticles | fine-particles (the said (C)) which consist of an organic-inorganic composite material are demonstrated. The polymerization method of the fine particles of the organic inorganic composite material is not particularly limited, and known polymerization methods such as emulsion polymerization, suspension polymerization, seed polymerization and sol gel polymerization can be applied.

As mentioned above, the microparticles | fine-particles (henceforth "composite particle") which consist of organic-inorganic composite materials are particle | grains which contain the organic polymer skeleton as an organic part, and the polysiloxane skeleton as an inorganic part. The composite particles are preferably in a form (chemical bond type) in which at least one carbon atom in the organic polymer skeleton has an organic silicon atom in which a silicon atom in the polysiloxane skeleton is directly chemically bonded. As a specific form, the silicon atom in a polysiloxane skeleton and the carbon atom in an organic polymer skeleton couple | bond, and the aspect which the polysiloxane skeleton and the organic polymer skeleton comprise the three-dimensional network structure is preferable.

The organic polymer skeleton may have a side chain, a branched structure, or a crosslinked structure. The molecular weight, composition, structure, presence or absence of a functional group, and the like of the organic polymer forming the skeleton are not particularly limited. Examples of the organic polymer include (meth) acrylic resins, vinyl polymers such as polystyrene and polyolefins, polyamides such as nylon, polyimides, polyesters, polyethers, polyurethanes, polyureas, polycarbonates, phenol resins, and melamines. At least one selected from the group consisting of resin and urea resin is preferable.

The form of the organic polymer skeleton is preferably a polymer (so-called vinyl polymer) having a main chain composed of a repeating unit represented by the following formula (1) because of the fact that the hardness of the composite particles can be appropriately controlled.

Polysiloxane frame | skeleton is defined as the compound which the siloxane unit represented by following formula (2) chemically bonds continuously, and comprised the network of network structure.

Preferably the amount of SiO ₂ constituting the polysiloxane framework is the 0.1 to 25 mass% based on the weight of the composite particle, more preferably from 1 to 10 parts by mass. If the amount of SiO _{2 in} the polysiloxane skeleton is in the above range, the hardness of the composite particles can be easily controlled. Moreover, when it is less than 0.1 mass%, the softness | flexibility and elasticity of particle | grains fall, and when a external stress increases in a resin composition, defects, such as destruction of an internal part of a particle, may arise, and when it exceeds the said range, There exists a possibility that the adhesiveness of resin may fall and the particle | grains in a resin composition may fall easily. In addition, a percentage of mass required by the amount of the particles of SiO ₂ constituting the polysiloxane framework measuring the weight before and after firing at a temperature of more than 800 ℃ oxidizing atmosphere such as air.

When the composite particles are used in combination with a resin having a ratio of the number of carbon atoms and the number of silicon atoms (surface atom number ratio (C / Si)) of 1.0 to 1.0 × 10 ⁴ obtained by photoelectron spectroscopy It is preferable at the point which is excellent in adhesiveness with the resin of the. If the surface atomic number ratio (C / Si) is less than 1.0, the adhesiveness to the resin may be deteriorated. If the surface atomic number ratio (C / Si) is more than 1.0 × 10 ⁴ , the flexibility and elasticity of the particles may be deteriorated, and the external stress may be reduced in the resin composition. If it is increased, there is a possibility that a defect such as destruction of the inside of the particle occurs.

The composite particles can be arbitrarily adjusted by appropriately changing the ratio of the polysiloxane skeleton portion or the organic polymer skeleton portion with respect to each of mechanical properties such as hardness and fracture strength.

The polysiloxane skeleton in the composite particles is preferably obtained by hydrolysis condensation reaction of a silicone compound having a hydrolyzable group.

Although it does not specifically limit as a hydrolyzable silicone compound, For example, the silicone compound represented by following General formula (3), its derivative (s), etc. are mentioned:

In the formula (3), R 'may have a substituent, and represents at least one group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group and an unsaturated aliphatic group, and X represents a hydroxyl group, an alkoxy group and an acyloxy group At least 1 group chosen from the group which consists of, and m is an integer of 0-3.

Although it does not specifically limit as a silicone compound represented by the said General formula (3), For example, as thing of m = 0, 4, such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, etc. Functional silanes; As m = 1, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane and benzyl tree Methoxysilane, naphthyltrimethoxysilane, methyltriacetoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, Trifunctional silanes such as 3- (meth) acrylooxypropyltrimethoxysilane and 3,3,3-trifluoropropyltrimethoxysilane; Examples of m = 2 include bifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diacetoxydimethylsilane and diphenylsilanediol; Examples of m = 3 include monofunctional silanes such as trimethylmethoxysilane, trimethylethoxysilane, and trimethylsilanol.

Among these, silane compounds having a structure of 1 in formula (3), wherein X is a methoxy group or an ethoxy group and a refractive index of 1.30 to 1.60 can obtain organic inorganic composite particles having a refractive index suitable for optical applications. It is preferable because of that. Specifically, methyltrimethoxysilane, phenyltrimethoxysilane, 3- (meth) acrylooxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3,3, 3-trifluoropropyl trimethoxysilane etc. are mentioned.

Although it does not specifically limit as a derivative | guide_body of the silicone compound represented by the said General formula (3), For example, the compound in which a part of X substituted with the group which can form chelate compounds, such as a carboxyl group and (beta) -dicarbonyl group, or the said silane And low condensates obtained by partially hydrolyzing the compound.

Only 1 type may be used for a silicone compound which has hydrolyzability, and may be used for it combining two or more types suitably. In the formula (3), when only the silane compound having m = 3 and its derivatives are used as raw materials, composite particles are not obtained.

When the composite particle has a form in which a polysiloxane skeleton has an organic silicon atom in which a silicon atom is directly bonded to at least one carbon atom in an organic polymer skeleton in a molecule, the silicone compound having hydrolyzability can form an organic polymer skeleton. It is necessary to use what has an organic group containing a polymerizable reactor, and a radical polymerizable group, an epoxy group, a hydroxyl group, an amino group, etc. are mentioned as the reactor, for example.

Examples of the organic group containing the radical polymerizable group include radical polymerizable groups represented by the following formulas (4), (5) and (6):

In the above formula, R ^a represents a hydrogen atom or a methyl group, R ^b represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent, R ^c represents a hydrogen atom or a methyl group, and R ^d represents a hydrogen atom or a methyl group R ^e represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent.

As a radical polymerizable group containing organic group of the said General formula (4), an acryloxy group, a methacryloxy group, etc. are mentioned, for example, As a silicone compound of the said General formula (3) which has this organic group, for example, (gamma)- Methacryloxypropyl trimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyl triace Oxysilane, γ-methacryloxyethoxypropyltrimethoxysilane (or also referred to as 'γ-trimethoxysilylpropyl-β-methacryloxyethyl ether'), γ-methacryloxypropylmethyldimethoxysilane, (gamma) -methacryloxypropyl methyl diethoxysilane, (gamma) -acrylooxypropyl methyl dimethoxysilane, etc. are mentioned. These may use only 1 type or may use 2 or more types together.

As a radical polymerizable group containing organic group of the said General formula (5), a vinyl group, an isopropenyl group, etc. are mentioned, for example, As a silicone compound of the said General formula (3) which has this organic group, For example, vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldiacetoxysilane and the like. These may use only 1 type or may use 2 or more types together. As a radical polymerizable group containing organic group of the said General formula (6), a 1-alkenyl group or a vinylphenyl group, an isoalkenyl group, an isopropenyl phenyl group, etc. are mentioned, for example, The silicone of the said General formula (3) which has this organic group As the compound, for example, 1-hexenyltrimethoxysilane, 1-hexenyltriethoxysilane, 1-octenyltrimethoxysilane, 1-decenyltrimethoxysilane, γ-trimethoxysilylpropylvinyl Ether, ω-trimethoxysilyl undecanoic acid vinyl ester, p-trimethoxysilyl styrene (p-styryl trimethoxysilane), 1-hexenylmethyldimethoxysilane, 1-hexenyldimethoxysilane, etc. are mentioned. Can be. These may use only 1 type or may use 2 or more types together.

As a silicone compound which has an organic group containing an epoxy group, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propylmethyl diethoxysilane, 3-glycidoxy propyl triethoxysilane, (beta)-(3 And 4-epoxycyclohexyl) ethyltrimethoxysilane. These may use only 1 type or may use 2 or more types together. As a silicone compound which has an organic group containing a hydroxyl group, 3-hydroxypropyl trimethoxysilane etc. are mentioned, for example. These may use only 1 type or may use 2 or more types together.

Examples of the silicone compound having an organic group containing an amino group include N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β ( Amino ethyl) (gamma)-aminopropyl triethoxysilane, (gamma) -aminopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, N-phenyl- (gamma)-aminopropyl trimethoxysilane, etc. are mentioned. These may use only 1 type or may use 2 or more types together.

In addition, the organic polymer skeleton contained in the composite particles may include, for example, 1) an organic group containing a polymerizable reactor capable of forming an organic polymer skeleton such as a radical polymerizable group or an epoxy group together with a hydrolyzable group. In the case of having a radical, a radically polymerizable monomer and an epoxy group are added to particles having a polysiloxane skeleton obtained by 1-1) a method of polymerization after the hydrolytic condensation reaction of the silicone compound or 1-2) a hydrolysis condensation reaction of the silicone compound. The polymerizable monomer having a polymerizable reactor such as a monomer having a monomer, a monomer having a hydroxyl group, and a monomer having an amino group is absorbed and then obtained by a method of polymerization. 2) When the silicone compound does not have an organic group containing a polymerizable reactor capable of forming an organic polymer skeleton such as a radical polymerizable group, an epoxy group, a hydroxyl group, or an amino group, it is obtained by hydrolysis condensation reaction of the silicone compound. A polymerizable reactor, such as a radical polymerizable monomer, a monomer having an epoxy group, a monomer having a hydroxyl group, a monomer having an amino group, or the like, to particles having a polysiloxane skeleton (seed particles composed of polysiloxane particles, hereinafter also referred to as 'polysiloxane particles') The branch is also obtained by absorbing the polymerizable monomer and then polymerizing.

As described above, the composite particles may be a form in which a) the polysiloxane skeleton has an organosilicon atom in which a silicon atom is directly chemically bonded to at least one carbon atom in the organic polymer skeleton (chemical bond type), b) such organic It may be a form having no silicon atom in the molecule (IPN type), and is not particularly limited. For example, when an organic polymer skeleton is obtained together with a polysiloxane skeleton in the same manner as in 1-1) above, a) A composite particle having the form of can be obtained, and in the case of 2) above, a composite particle having the form of b) can be obtained. In the case of obtaining an organic polymer skeleton together with a polysiloxane skeleton as in the above 1-2), a composite particle having a form having the form of a) to b) is obtained.

In the method of 1-2) or 2) above, it is preferable that the radical polymerizable monomer which can be absorbed by the particles having a polysiloxane skeleton is a monomer component which is essentially a radical polymerizable vinyl monomer. As said radically polymerizable vinyl monomer, if the compound contains at least 1 or more ethylenically unsaturated group in a molecule | numerator, the kind etc. are not specifically limited, For example, it can select suitably according to the physical property of desired composite particle. These may use only 1 type or may use 2 or more types together.

For example, a hydrophobic radically polymerizable vinyl monomer is preferable because it can produce a stable emulsion obtained by emulsifying and dispersing the monomer component when the monomer component is absorbed into particles having a polysiloxane skeleton. Moreover, a crosslinkable monomer can also be used as a radical polymerizable vinyl monomer. By using a crosslinkable monomer, it is possible to easily control the mechanical properties of the obtained composite particles and to improve the solvent resistance of the composite fine particles. Specifically, ethylene glycol dimethacrylate, trimethylol propane trimethyl acrylate, 1,6-hexanediol diacrylate, divinylbenzene, etc. are mentioned. These may be used independently and may use two or more types together.

As a method of manufacturing the said composite particle, the manufacturing method containing the hydrolysis, condensation process, and superposition | polymerization process which are mentioned later is mentioned preferably. If necessary, a water absorption step of absorbing the polymerizable monomer after the hydrolysis and condensation step and before the polymerization step may be included (in the case of 1-2 and 2). If the silicone compound used in the hydrolysis and condensation process does not have an element which can constitute a polysiloxane skeleton structure and an element which constitutes an organic polymer skeleton (in the case of 2), the absorption step is performed. Essentially, the organic polymer skeleton is formed in the polymerization step following the absorption step.

The said hydrolysis and condensation process is a process of carrying out the reaction which hydrolyzes and condenses a silicon compound mentioned above in the solvent containing water. By this process, particles (polysiloxane particles) having a polysiloxane skeleton can be obtained. Hydrolysis and axial synthesis can employ | adopt arbitrary methods, such as batch, division | segmentation, and continuous. In the case of hydrolysis and axial synthesis, basic catalysts such as ammonia, urea, ethanolamine, tetramethylammonium hydroxide, alkali metal hydroxide and alkaline earth metal hydroxide can be preferably used as the catalyst.

In the solvent containing water, an organic solvent can be contained in addition to water and a catalyst. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol and 1,4-butanediol; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate; (Cyclo) paraffins such as isooctane, cyclohexane and the like; Aromatic hydrocarbons, such as benzene and toluene, are mentioned. These may be used alone or in combination of two or more.

In the hydrolysis and condensation step, anionic, cationic or nonionic surfactants and polymer dispersants such as polyvinyl alcohol and polyvinylpyrrolidone may also be used in combination. These may be used alone or in combination of two or more.

Hydrolysis and condensation are carried out for 30 minutes to 100 hours at a temperature of 0 to 100 ° C, preferably 0 to 70 ° C after mixing the silicon compound as a raw material with a solvent containing a catalyst, water and an organic solvent. It can carry out by doing. In addition, after hydrolysis and condensation reaction are carried out to a desired degree to produce particles, these may be seed (species) particles, and a silicon compound may be added to the reaction system to grow the seed particles.

It is preferable that the weight average molecular weights of polysiloxane particle | grains are 250-10000, More preferably, it is 250-5000. If the weight average molecular weight is in the above range, the absorption rate of the polymerizable monomer in the absorption step is high, and generation of coarse particles derived from the polymerizable monomer remaining without being absorbed in the system can be suppressed, and as a result, Coarse particle content of 2 times or more of average particle diameters in a composite particle (to provide to dry classification), or a composite particle with a low microparticle content is obtained. Further, by providing the composite particles in a wet classification and dry classification process, particles with a very low coarse particle content can be obtained in high yield.

As described above, the absorption step may be an essential step depending on the silicon compound to be used, or may be an optional step. The absorption step is not particularly limited as long as the absorption step proceeds in the presence of the polymerizable monomer in the presence of the polysiloxane particles. Therefore, a polymerizable monomer may be added to the solvent which disperse | distributed polysiloxane particle | grains, and polysiloxane particle | grains may be added to the solvent containing a polymerizable monomer. Especially, it is preferable to add a polymerizable monomer in the solvent which disperse | distributed polysiloxane particle previously like the former, and also, without taking out the polysiloxane particle obtained by the hydrolysis and condensation process from the reaction liquid (polysiloxane particle dispersion liquid). The method of adding a polymerizable monomer to the reaction liquid is preferable because the process is not complicated and excellent in productivity.

In the absorption step, the polymerizable monomer is absorbed in the structure of the polysiloxane particles, but the concentration of each of the polysiloxane particles and the polymerizable monomer, or the mixing ratio of the polysiloxane and the polymerizable monomer so that the absorption of the polymerizable monomer proceeds quickly. It is preferable to set the processing method, means for mixing, the temperature and time at the time of mixing, the processing method after mixing, and the means, and to carry out under the conditions. These conditions may be appropriately considered depending on the kind of polysiloxane particles, polymerizable monomers used, and the like. In addition, these conditions may apply only 1 type or may apply it in combination of 2 or more type.

It is preferable to make the addition amount of a polymerizable monomer in the said absorption process into 0.01 times-100 times by mass with respect to the mass of the silicone compound used as a raw material of a polysiloxane particle. More preferably, it is 0.5-50 times, More preferably, it is 0.5-30 times, Especially preferably, it is 1-15 times. When the addition amount is less than the above range, the amount of absorption of the polymerizable monomer of the polysiloxane particles decreases, and it may be difficult to obtain the mechanical properties of the composite particles to be produced. It tends to be difficult to completely absorb the polysiloxane particles, so that unabsorbed polymerizable monomer remains, so that agglomeration between particles occurs in a subsequent polymerization step, or coarse particles derived from unabsorbed polymerizable monomer are generated. There is a possibility that it will be easy to do.

In the absorption step, the timing for adding the polymerizable monomer is not particularly limited, and the polymerizable monomer may be added in a batch, may be added in several portions, or may be fed at an arbitrary speed. have. In addition, when adding a polymerizable monomer, even if it adds only with a polymerizable monomer or the solution of a polymerizable monomer may be added, it is polysiloxane particle which adds to a polysiloxane particle in the state previously emulsified-dispersed with an emulsifier. It is preferable because the absorption of the erosion is made more efficient.

The emulsifier is not particularly limited, for example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polymeric surfactants, polymerization having at least one polymerizable carbon-carbon unsaturated bond in the molecule And surfactants. Among them, anionic surfactants and nonionic surfactants are preferable because they can stabilize the dispersion state of the polysiloxane particles, the polysiloxane particles absorbing the polymerizable monomer, and the polymer fine particles. Even if these emulsifiers use only 1 type, they can also use 2 or more types together.

The usage-amount of the said emulsifier is not specifically limited. Specifically, it is preferable that it is 0.01-10 mass% with respect to the gross mass of the said polymerizable monomer, More preferably, it is 0.05-8 mass%, More preferably, it is 1-5 mass%. When the amount of the emulsifier used is less than 0.01% by mass, a stable emulsion dispersion of the polymerizable monomer may not be obtained, and when it exceeds 10% by mass, emulsion polymerization or the like may occur as a side reaction. Regarding the said emulsion dispersion, it is preferable to make the said polymerizable monomer into emulsion state in water normally using a homomixer, an ultrasonic homogenizer, etc. with an emulsifier.

Moreover, when emulsion-dispersing a polymerizable monomer with an emulsifier, it is preferable to use 0.3-10 times of water or a water-soluble organic solvent with respect to the mass of a polymerizable monomer. As said water-soluble organic solvent, Alcohol, such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, 1, 4- butanediol; Ketones such as acetone and methyl ethyl ketone; Ester, such as ethyl acetate, etc. are mentioned.

It is preferable to perform the said absorption process, stirring, for 5 to 720 minutes in the temperature range of 0-60 degreeC. What is necessary is just to set these conditions suitably according to the kind of polysiloxane particle | grains, polymerizable monomers, etc. which are used, and these conditions can also employ | adopt only 1 type or in combination of 2 or more types.

In the absorption step, the determination of whether or not the monomer component is absorbed into the polysiloxane particles is carried out by observing the particles under a microscope, for example, before adding the monomer component and after completion of the absorption step. It can be judged easily by confirming that diameter is large.

The polymerization step is a step of polymerizing the polymerizable reactor to obtain particles having an organic polymer backbone. Specifically, in the case where a silicon compound having a polymerizable reactor-containing organic group is used, the polymerizable reactor of the organic group is polymerized to form an organic polymer skeleton. Although it is a process of polymerizing the polymerizable monomer which has a, and forming an organic polymer skeleton, in either case, it can be a process of forming an organic polymer skeleton by either reaction.

The polymerization reaction may be carried out during the hydrolysis condensation step or the absorption step, or may be carried out after either or both steps. Although it does not specifically limit, Usually, it starts after a hydrolysis condensation process (after an absorption process, when an absorption process is performed).

Although polymerization reaction is not specifically limited, For example, the method of using a radical polymerization initiator, the method of irradiating an ultraviolet-ray or a radiation, the method of adding heat, etc. are all employable. Although it does not specifically limit as said radical polymerization initiator, For example, persulfates, such as potassium persulfate, hydrogen peroxide, peracetic acid, benzoyl peroxide, lauroyl peroxide, orthochloro benzoyl peroxide, ortho methoxy benzoyl peroxide, 3,5, 5-trimethylhexanoylperoxide, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxide, benzoylperoxide, 1,1-bis (t-butylperoxy) -3,3, Peroxide initiators such as 5-trimethylcyclohexane and t-butylhydroperoxide; Azobisisobutyronitrile, azobiscyclohexacarbonitrile, azobis (2,4-dimethylvaleronitrile), 2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane ), Dihydrochloride, 4,4'- azobis (4-cyanopentanoic acid), 2,2'- azobis- (2-methylbutyronitrile), 2,2'- azobisisobutyronitrile, Azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile); And the like. These radical polymerization initiators may be used independently or may use 2 or more types together.

It is preferable that the usage-amount of the said radical polymerization initiator is 0.001 mass%-20 mass% with respect to the gross mass of the said polymerizable monomer, More preferably, it is 0.01 mass%-10 mass%, More preferably, 0.1 mass%-5 It is mass%. When the usage-amount of the said radical polymerization initiator is less than 0.001 mass%, the polymerization degree of a polymerizable monomer may not increase. The method of injecting the radical polymerization initiator into the solvent is not particularly limited, and a method of injecting the radical polymerization initiator in its entirety at the first time (before the start of the reaction) (a form in which the radical polymerization initiator is emulsified and dispersed together with the polymerizable monomer and the polymerizable monomer is Injecting a radical polymerization initiator after absorption); The conventionally well-known methods, such as the method of injecting a part initially and adding the remainder continuously, the method of pulse-adding intermittently, or the combination of these, can be employ | adopted.

It is preferable that it is 40-100 degreeC, and, as for the reaction temperature at the time of said radical polymerization, 50-80 degreeC is more preferable. When the reaction temperature is too low, the degree of polymerization does not sufficiently increase, and the mechanical properties of the polymer fine particles tend to be difficult to be obtained. On the other hand, when reaction temperature is too high, there exists a tendency for aggregation between particle | grains to occur easily during superposition | polymerization. In addition, although the reaction time at the time of radical polymerization can be suitably changed with the kind of polymerization initiator to be used, 5-600 minutes are preferable normally, and 10-300 minutes are more preferable. If the reaction time is too short, the degree of polymerization may not sufficiently increase. If the reaction time is too long, aggregation tends to occur easily between the particles.

In the present invention, after the polymerization step, the prepared liquid containing the polymer fine particles can be supplied as it is, or after distilling the organic solvent into a dispersion medium containing water and / or alcohol, and then supplying the above-described wet classification step. Furthermore, the produced polymer microparticles | fine-particles may be isolate | separated, dried, and may disperse | distribute in water and / or an organic solvent, and may supply to a wet classification process.

Since the fine particles of the present invention have reduced content of coarse particles and fine particles and have a narrow particle size distribution, they are used for optical applications such as light diffusion sheets, light guide plates used in LCDs, or PDPs, EL displays, and touch panels. It is useful as additives, such as a light-diffusion agent and an antiblocking agent, which are contained in the optical resin to be used. Of course, it can use suitably also as anti-blocking agent for various films other than these optical uses.

The resin composition according to the present invention is a resin composition comprising the fine particles of the present invention and a transparent binder resin. As mentioned above, since the content of microparticles as well as coarse particles is suppressed at a very low level, the fine particles of the present invention can be suitably used for optical applications.

Although content of the microparticles | fine-particles in the said resin composition can be suitably determined according to a use and desired optical characteristic, when using for an optical use, it is good to set it as 1 mass part or more and 300 mass parts or less with respect to 100 mass parts of binder resin compositions. desirable. More preferably, it is 2 mass parts or more, More preferably, it is 5 mass parts or more, More preferably, it is 200 mass parts or less, More preferably, it is 150 mass parts or less. When there is too much content of microparticles | fine-particles, there exists a possibility that the intensity | strength of an optical member may fall, and when too small, it may be difficult to obtain the effect (light diffusivity etc.) anticipated by addition of microparticles | fine-particles.

The transparent binder resin contained in the resin composition of this invention is not specifically limited, Any thing used as binder resin in the said field | area can be used. For example, (I) When the member formed using the resin composition of this invention is shape | molded by the resin composition of this invention just in desired shape, such as plate shape and a sheet form (that is, binder resin is plate shape, As the base resin of the sheet-shaped molded body), as the transparent resin, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acrylic resins, polystyrene resins, polycarbonate resins, polyethersulfone resins, polyurethane resins, polysulfone resins, Polyolefin resins such as polyether resins, polymethylpentene resins, polyether ketone resins, (meth) acrylonitrile resins, polypropylene resins, norbornene resins, amorphous polyolefin resins, polyamide resins, polyimide resins and triacetyl cellulose Resin and the like.

In the case where the (II) member is formed by integrating the resin composition of the present invention on a substrate surface such as a plate or sheet prepared in advance by laminating (coating, laminating or the like), the binder resin may be a transparent binder resin. Although the same thing can be used, For example, an acrylic resin, polypropylene resin, polyvinyl alcohol resin, polyvinyl acetate resin, polystyrene resin, polyvinyl chloride resin, a silicone resin, a polyurethane resin, a polyester resin, etc. are mentioned. .

The resin composition of this invention can contain other components as needed if it is a range which does not impair the effect of this invention other than the said microparticles | fine-particles and transparent binder resin. As other components, in order to improve physical properties, such as light resistance and UV resistance, a hardening | curing agent, a crosslinking agent, various additives, a stabilizer, a flame retardant, antioxidant, and a ultraviolet absorber are mentioned, for example. These may use only 1 type or may use 2 or more types together.

Since the molded article obtained from the resin composition of the present invention is a molded article in which the fine particles of the binder present invention are dispersed and fixed, the molded article has excellent optical properties such as light diffusing property and light transmittance. Therefore, the resin composition of this invention can be used suitably as a raw material of the structural member of various optical products. In addition, from the viewpoint of effectively utilizing the excellent light diffusing property and the light transmittance derived from the fine particles of the present invention described above, it is provided on the front of various image display apparatuses, and the image display is prevented by preventing external light or indoor lighting equipment from being reflected. It can be used suitably for optical members, such as an anti-reflective anti-glare film which makes it clear, and an optical-diffusion film and a light-diffusion plate which spread | diffuse light light from a light source uniformly on an image display surface in an image display apparatus.

The shape of the optical member is not limited to a film (sheet) or a plate, but may be molded into a desired shape such as a main body, a vertebral body, a sphere, and the like. In addition, from the viewpoint of securing excellent light diffusing effect and antiglare effect (antiglare effect by suppressing and reflecting light specular reflection of light), irregularities derived from the fine particles of the present invention described above are formed on the surface of the optical member. It is preferable.

For example, when the said optical member is a molded object of the film form (henceforth an "optical film"), such as a light-diffusion film and an anti-reflective anti-glare film, it has a planar part as the form, The form which has the structure (optical functional layer) by which light-diffusion particle is fixed by at least one part is mentioned. For example, (i) the form of the transparent binder resin immediately constituting the resin composition as a base resin such as a plate or sheet, (formed as a light diffusion plate), (ii) a plate or sheet form prepared in advance. The form (surface uneven film, such as a light-diffusion film and an anti-glare film, a light-diffusion plate, etc.) etc. which laminated | stacked (coated and laminated) the layer which consists of said resin composition on one part or whole of the base material surface, etc. are mentioned. . Also in the case of any of said (i) and (ii), since particle | grains are disperse | distributed and fixed in transparent binder resin, the outstanding optical characteristic can be exhibited.

In addition, the said "having a planar part" generally means that the shape of the optical member is substantially flat surface part having a certain area enlargement (width), such as plate, sheet or film. (A case where it is formed) is a main component of the shape, but the present invention is not limited to this form, and may have a substantially flat surface portion on at least a part of the shape, even if it is not the main component. have.

As a method of manufacturing the optical member of the form of said (i), the resin composition of this invention is extruded while melt-kneading with a well-known extruder, and the method of shape | molding into a sheet form, a plate form, and a film form is mentioned. At this time, if necessary, additives such as various additives, stabilizers, and flame retardants may be added to the resin composition in order to enhance physical properties such as light resistance and UV resistance. In order to obtain a molded article with uniform optical characteristics, it is preferable that the above-mentioned resin composition mixes and disperse | distributes the microparticles of this invention in transparent binder resin beforehand. Likewise, the additives may be mixed with the resin composition.

As a method of obtaining the optical member of the form of said (ii), the method of laminating | stacking the layer which consists of the resin composition of this invention to the base material surface prepared previously is mentioned. The lamination method is not particularly limited, and an application method, a casting method, or the like is preferably exemplified. As a coating method, the coating composition containing the said resin composition can be apply | coated to a base material. Although the resin composition of this invention can also be used as a coating composition as it is, the said resin composition can be used as water or an organic solvent (for example, alcohol solvents, such as methanol, ethanol, isopropanol, ketone solvents, such as ethylene glycol and propylene glycol). It is preferable to use the coating composition prepared by dispersing and dissolving in an ester solvent such as ethyl acetate and aromatic hydrocarbons such as toluene and xylene. Although a base material is not specifically limited, For example, conventionally well-known colorless transparent resin films, such as a polyolefin resin film, a polyester resin film, and a polycarbonate resin film, are used preferably. As a specific coating method, well-known lamination | stacking methods, such as a reverse roll coating method, the gravure coating method, the die coating method, the comma coating method, and the spray coating method, are mentioned.

After application, the solvent contained in the coating film is dried as necessary, and then the coating film is solidified to form a resin composition layer. Moreover, from a viewpoint of ensuring heat resistance and weather resistance, it is preferable that the layer which consists of a resin composition hardens or crosslinks the binder resin contained in this resin composition.

Although the film thickness of the layer which consists of the resin composition (or coating composition) of this invention formed by said method is not specifically limited, In the case of the said light-diffusion film, the film thickness of the layer (light-diffusion layer) which consists of a resin composition is In the case of an anti-glare film, it is preferable that the film thickness of the layer (anti-glare layer layer) which consists of a resin composition is 20 micrometers or less, and the thickness of a light-diffusion plate is 2000 micrometers or less. Conventionally, when thickness is thin, it is difficult to express sufficient light-diffusion property and light transmittance. However, when the fine particle or resin composition of this invention is used, even if it is thin, very excellent light-diffusion property and light transmittance can be exhibited. In addition, the value of the said light-diffusion film and anti-glare film film thickness shows the thickness of the layer (namely, light-diffusion layer, anti-glare layer) containing the resin composition laminated | stacked on the base material, and the thickness of a base material is not included.

The microparticles of the present invention are chemically stable microparticles which can be suppressed at a low level with a very low content of coarse particles, and in addition to having a sharp particle size distribution, and are difficult to cause deterioration such as swelling in the coating composition. Uniform and fine unevenness can be formed in such optical members (light diffusing film, anti-glare film, light diffusing plate, etc.). Therefore, optical members such as a light diffusing film, an anti-glare film, and a light diffusing plate obtained by using the fine particles of the present invention are unlikely to generate optical foreign matters that cause local light loss or appearance defects derived from coarse particles. Moreover, since adjustment of an optical characteristic can also be performed by control of the average particle diameter of the microparticle of this invention, it can use suitably for an optical use.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is, of course, not limited by the following Examples. It is also possible to add and implement a change suitably in the range which can be suited for the purpose of the before and after, and they are all included in the technical scope of this invention. Moreover, unless otherwise indicated, a mass part may show "part" and mass% as "%."

Preparation of Fine Particles

Manufacturing example  One ( Polysiloxane  Particulates)

Into a reaction kettle equipped with a cooling device, a thermometer, and a dropping port, a mixed solution of 280 parts of ion-exchanged water, 5 parts of 25% ammonia water and 120 parts of methanol was added, and stirring of the mixed solution was carried out to remove the? -Methacryloxypropyl tree from the dropping port. 40 parts of methoxysilanes were added, and hydrolysis and condensation reaction of (gamma) -methacryloxypropyl trimethoxysilane was performed at the temperature of 30 degreeC for 2 hours, and the suspension of polysiloxane microparticles | fine-particles was adjusted. In addition, the weight average molecular weight of the polysiloxane particle | grains obtained at this time was 1800 (equivalent to about 7-mer of the silicone compound used).

Separately, in the reaction kettle 2 different from the above, 400 parts of styrene, 2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (3 parts of Wako Pure Chemical Industries, V-65), anionic 1.5 parts of surfactant (LA-10, Dai-ichi Kogyo Co., Ltd.) and 400 parts of ion-exchange water were emulsified-dispersed at room temperature (25 degreeC) for 15 minutes by the homomixer, and emulsion was adjusted (monomer solution).

2 hours after the start of preparation of the suspension of the polysiloxane particles (2 hours after the addition of γ-methacryloxypropyltrimethoxysilane), the emulsion was added through the dropping port of the reaction kettle (1). After continuing stirring for 1 hour and confirming that the polysiloxane particles absorbed the monomer component, 3500 parts of ion-exchanged water was added thereto, and the reaction solution was heated up to 65 ° C. under a nitrogen atmosphere, at 65 ± 2 ° C. for 2 hours. It retained and performed radical polymerization reaction, and the polymer particle (organic inorganic composite particle) dispersion liquid was obtained. The average particle diameter of the polymer particle disperse | distributed in a dispersion liquid was 10.1 micrometers, and the B-type viscosity (B-type viscometer, the Tokyo group make) of the dispersion liquid was 3.8 mPa * s, and solid content concentration was 10 mass%.

Manufacturing example  2-7 ( Polysiloxane  particle)

The polymer particle dispersion liquid was adjusted by the method similar to the manufacture example 1 except having changed the polysiloxane particle | grain raw material, radically polymerizable monomer species, and the usage-amount as shown in Table 1. In addition, the quantity of the ion-exchange water, methanol, and surfactant used for adjustment of the polysiloxane particle suspension and emulsion was adjusted suitably according to the conditions of each manufacture example.

[Measurement of Average Particle Diameter and Coarse Particle Size of Polymer Particles]

The polymer particle dispersion liquid obtained by the said manufacturing example was solid-liquid separated, 0.5g of dry polymer particles are disperse | distributed to 100g of ion-exchange water, the polymer particle dispersion liquid is adjusted, and a precision particle size distribution measuring apparatus (product name "Multi Sizer II") (Manufactured by Beckman Coulter, Inc.), the particle diameter of the polymer particles was measured, and the average particle diameter was calculated on a volume basis.

In addition, the measurement of the quantity of the coarse particle (coarse particle which has a particle diameter 2 times or more of average particle diameter) contained in a polymer particle dispersion liquid was performed as follows.

A polymer particle dispersion solution (viscosity: 3 mPa · s, solid content concentration: 0.5% by mass), in which 0.5 g of dried polymer particles were dispersed in 100 g of methanol, having a body of 1.75 to 2 times the average particle diameter (made of nickel) , Manufactured by Tokyo Process Service Co., Ltd., and a filtration bell equipped with a Buchner funnel, were filtered under reduced pressure, and the particles remaining on the mesh were then scanned using a scanning electron microscope (SEM, "S-3500N", manufactured by Hitachi Corporation, Acceleration Voltage: 25 kV), and visually counted the number of coarse particles that were two or more times the average particle diameter, and observed the field of view at 200 times magnification. In Table 1, "> average diameter x 2" is shown.

In addition, in the case of the coarse particle amount which has a particle diameter of 2.5 times or more of average particle diameters, it carried out similarly to the above-mentioned procedure except having used the mesh which has a 2.25-2.5 time of the average particle diameter. The results are shown in Table 1 as "> average diameter x 2.5".

[SiO ₂ content]

In the kiln apparatus, 1 g of the polymer particles were calcined at 800 degrees (under an atmosphere), and the produced ash was SiO ₂ , and the ratio of SiO ₂ to the mass of the used polymer particles was calculated.

[Solid content concentration]

Solid content concentration of the polymer particle dried 0.5g of polymer particle dispersion solutions at 120 degreeC x 20 minutes (in vacuum), and the ratio with respect to the mass of the polymer particle dispersion liquid of the mass of the residual solid content was made into solid content concentration.

Solid content concentration%) = [remained solid content mass / polymer particle dispersion mass] x 100

[Volume weight]

It measured by the powder tester (made by Hosokawa Microclon).

[Moisture content]

0.5 g of pulverized particles were used as a measurement sample and measured using a Karl Fischer moisture meter (manufactured by Hiranuma Industries, Ltd.).

[Weight average molecular weight]

The weight average molecular weight was measured using gel permeation chromatography (GPC, "HLC-8120GPC", manufactured by Tosoh Corporation) under the following measurement conditions. In addition, the measurement sample was diluted and adjusted with tetrahydrofuran (THF) so that solid content concentration might be 0.8%.

Column: TSKgelG5000HXL-TSKgel2000HXL (manufactured by Tosoh Corporation)

Column temperature: 25 ℃

Eluent: THF

Pump: L6000 (manufactured by Hitachi, Ltd.)

Flow rate: 1.0 ml / min

Detection: R1 Model 504 (manufactured by Gl Science Co., Ltd.)

Sample concentration: 0.8%

Standard Sample / Calibration Curve: A standard polystyrene (TSK standard polystyrene, manufactured by Tosoh Corporation) and a calibration curve using 13 samples of Mw = 500 to 1000000 were used.

[Table 1]

Example  One

The polymer particle dispersion obtained in Production Example 1 was classified with a stainless steel wire mesh having a diameter of 20 µm (wet classification process). Subsequently, the polymer particle dispersion liquid after wet classification was solid-liquid separated by natural precipitation. The obtained cake was washed with ion-exchanged water and methanol, and then vacuum dried and steamed at 100 ° C. for 5 hours to obtain a dried product obtained by agglomeration of particles. Crushed particles were obtained by pulverizing the dried product (recovery rate 99% by mass).

At this time, the obtained pulverized particle was 0.7 g / cm <3> in volume ratio, the particle diameter of 10.1 micrometers, and the moisture content of 0.5 mass% or less.

The obtained pulverized particles are put into a high-precision airflow classifier ("DFX5 type", manufactured by Nippon Pneumatic Co., Ltd.) and classified by adjusting the balance of centrifugal force and drag given to the pulverized particles by high-speed swinging air and a suction blower. The fine particles were obtained at a recovery rate of 85% by mass with respect to the supplied pulverized particles (dry classification step). Moreover, the recovery rate of the microparticles | fine-particles from the polymer particle dispersion liquid at this time was 84 mass%.

Example  2

By the same process as in Example 1, the ground particles were adjusted from the polymer particle dispersion solution obtained in Production Example 2 (recovery rate 99% by mass). The obtained pulverized particle at this time was 0.7g / cm <3> by volume ratio, the particle diameter of 10.1 micrometers, and the water content of 0.5 mass% or less.

Subsequently, the obtained pulverized particles were put into a rotary rotor type classification apparatus ("Turboplex 100ATP", manufactured by Hosokawa Micron Co., Ltd.), and the centrifugal force and drag applied to the pulverized particles by the rotational speed of the classification rotor and the supply of air from the inlet port. Classification was performed by adjusting the balance of the fine particles to obtain fine particles at a recovery rate of 85% by mass with respect to the supplied pulverized particles (dry classification step). Moreover, the recovery rate of the microparticles | fine-particles from the polymer particle dispersion liquid at this time was 84 mass%.

Example  3

In the same manner as in Example 1, pulverized particles were adjusted from the polymer particle dispersion obtained in Production Example 3 (volume ratio of 0.7 g / cm 3, particle diameter of 10.1 μm, water content of 0.5 mass% or less, and recovery of 99 mass%).

The crushed particles are fed into a rotary rotor type airflow classifier ("Turbo Clash Fire TC-15", manufactured by Nisshin Engineering Co., Ltd.), and the centrifugal force applied to the crushed particles by the rotational speed of the classifying rotor and the supply of air from the inlet port. Classification was performed by adjusting the balance of drag, and microparticles | fine-particles were obtained by 85 mass% of recovery with respect to feed grinding particle | grains (dry classification process). Moreover, the recovery rate of the microparticles | fine-particles from the polymer particle dispersion liquid at this time was 84 mass%.

Example  4

In the same manner as in Example 1, pulverized particles were adjusted from the polymer particle dispersion obtained in Production Example 3 (volume ratio of 0.7 g / cm 3, particle diameter of 10.1 μm, moisture content of 0.5 mass% or less, and recovery rate of 99%).

The pulverized particles are introduced into a Coanda airflow classifier ("Elvozet EJ-15", manufactured by Nitetsu Mining Co., Ltd., feed air: 5 kgf, slim edge), and the inertial force and suction applied to the fine particles Classification was performed by adjusting the balance of drag by a blower, and microparticles | fine-particles were obtained by 85 mass% of recovery with respect to feed grinding particle | grains. Moreover, the recovery rate of the microparticles | fine-particles from the polymer particle dispersion liquid at this time was 84 mass%.

Example  5

By the same process as in Example 1, pulverized particles were adjusted from the polymer particle dispersion solution obtained in Production Example 4 (volume ratio of 0.7 g / cm 3, particle diameter of 3.7 μm, water content of 0.5 mass% or less, and recovery rate of 99 mass%). .

Subsequently, the obtained pulverized particles are put into a high-precision airflow classifier ("DFX5 type", manufactured by Nippon Pneumatic Co., Ltd.), and the balance between centrifugal force and drag given to the pulverized particles by high-speed swirling air and a suction blower is adjusted. And fine particles were obtained at a recovery rate of 88% by mass with respect to the supplied pulverized particles (dry classification step). In this case, the recovery rate of the fine particles from the polymer particle dispersion was 87% by mass.

Example  6

By the same process as in Example 1, the pulverized particles were adjusted from the polymer particle dispersion solution obtained in Production Example 5 (volume ratio of 0.7 g / cm 3, particle diameter of 25.2 μm, water content of 0.5 mass% or less, recovery rate of 99 mass%). .

Subsequently, the obtained pulverized particles were put into a rotary rotor type classification apparatus ("Turboplex 100 ATP", manufactured by Hosokawa Micron Co., Ltd.), and the centrifugal force applied to the pulverized particles by the rotational speed of the classification rotor and the supply of air from the inlet port. Classification was performed by adjusting the balance of drag, and microparticles | fine-particles were obtained by 85 mass% of recovery with respect to the pulverized particle supplied (dry classification process). Moreover, the recovery rate of the microparticles | fine-particles from the polymer particle dispersion liquid at this time was 84 mass%.

Example  7

By the same process as in Example 1, the ground particles were adjusted from the polymer particle dispersion solution obtained in Production Example 6 (volume ratio of 0.7 g / cm 3, particle diameter of 4.2 μm, water content of 0.5 mass% or less, and recovery rate of 99 mass%). .

The crushed particles are fed into a rotary rotor type airflow classifier ("Turbo Clash Fire TC-15", manufactured by Nisshin Engineering Co., Ltd.), and the centrifugal force applied to the crushed particles by the rotational speed of the classifying rotor and the supply of air from the inlet port. Classification was performed by adjusting the balance of drag, and microparticles | fine-particles were obtained by 86 mass% of recovery with respect to the feed grinding particle (dry classification process). Moreover, the recovery rate of the microparticles | fine-particles from the polymer particle dispersion liquid at this time was 85 mass%.

Example  8

By the same process as in Example 1, pulverized particles were adjusted from the polymer particle dispersion solution obtained in Production Example 7 (volume ratio of 0.7 g / cm 3, particle diameter of 12.5 μm, water content of 0.5 mass% or less, recovery rate of 99 mass%). .

The pulverized particles are fed into a Coanda air flow classifier ("Elvojet EJ-15", manufactured by Nitetsu Mining Co., Ltd., feed air: 5 kgf, slim edge), and the inertial force and suction blower given to the fine particles. Classification was performed by adjusting the balance of drag by, and microparticles | fine-particles were obtained by 85 mass% of recovery with respect to feed grinding particle | grains. Moreover, the recovery rate of the microparticles | fine-particles from the polymer particle dispersion liquid at this time was 84 mass%.

Comparative Example  One

The polymer particle dispersion obtained in Production Example 1 was classified with a stainless steel wire mesh having a diameter of 20 µm (wet classification process). Subsequently, the polymer particle dispersion liquid after wet classification was solid-liquid separated by natural precipitation. The obtained cake was washed with ion-exchanged water and methanol, and then vacuum dried and scrubbed at 100 ° C. for 5 hours to obtain a dried product obtained by agglomeration of particles. Crushed particles were obtained by pulverizing the dried product.

Comparative Example  2

After dispersing the polymer particle dispersion obtained in Production Example 2 with a stainless steel wire mesh having a body diameter of 20 µm, one pass treatment was performed using a cartridge filter (manufactured by Nippon Poles Co., Ltd., trade name "Ultiplets Profile PUY1UY500") (wet classification process). ). Subsequently, the polymer particles were separated, washed and dried in the same manner as in Comparative Example 1 to obtain pulverized particles by pulverizing the obtained dried product.

Comparative Example  3

The polymer particle dispersion liquid obtained in manufacture example 5 was classified by the stainless steel wire mesh of 200 micrometers (wet classification process). Subsequently, the polymer particles were separated, washed and dried in the same manner as in Comparative Example 1 to obtain pulverized particles by pulverizing the obtained dried product.

Table 2 shows the results of the classification treatment in Examples 1 to 8 and Comparative Examples 1 to 3, and the evaluation results regarding the obtained fine particles and powder particles. In addition, each evaluation method is as follows.

[Measurement of Average Particle Diameter and Coarse Particle Size]

0.5 g of the fine particles obtained in the above examples and comparative examples were dispersed in 100 g of methanol to adjust the polymer particle dispersion, and the particles were prepared using a precision particle size distribution measuring device (product name "Multi Sizer II", manufactured by Beckman Coulter, Inc.). The diameter was measured and the average particle diameter was calculated on the basis of volume.

The measurement of the quantity of the coarse particle 1 (coarse particle which has the particle diameter more than twice the average particle diameter) was performed as follows. The fine particle dispersion solution (viscosity: 3 mPa * s, solid content concentration: 0.5 mass%) adjusted by the method similar to the said average particle diameter measurement, the mesh which has a body of 1.75-2 times the average particle diameter (made by nickel, Tokyo process) Filtration was carried out under reduced pressure using a suction filtration apparatus provided with a Buchner funnel in Servi Corporation) and a filtration bell.

Subsequently, the particles remaining on the mesh were visually observed at 200 times using a scanning electron microscope (SEM, "S-3500N", Hitachi, Ltd., acceleration voltage: 25 kV), and visually doubled the average particle diameter. The number of the above coarse particles was measured (pieces / 0.5 g).

In the case of the coarse particle amount (coarse particle 2) having a particle diameter of 2.5 times or more of the average particle diameter, the same procedure as described above is used except that a mesh having a body of 2.25 to 2.5 times the average particle diameter is used. I went.

[Measurement of micro particle amount]

0.5 g of the fine particles obtained in Examples and Comparative Examples were dispersed in 100 g of ion-exchanged water to adjust the fine particle dispersion, and the particle size was measured using a precision particle size distribution measuring device (product name "Multi Sizer II", manufactured by Beckman Coulter, Inc.). The diameter and average particle diameter were measured (by volume). Based on the measurement result, the volume% of microparticles | fine-particles which have a particle diameter of 1/2 or less of the numerical value obtained by rounding off 1 decimal place of an average particle diameter was computed, and the obtained value was made into microparticle amount.

[Table 2]

In Table 2, "Rotor rotor airflow classifier 1" uses "Torboflex 100ATP" from Hosokawa Micron Co., Ltd., and "Rotor rotor airflow classifier 2" is "Turbo Clash Firer TC" of Nisshin Engineering Co., Ltd. -15 "is used. In addition, "coarse particle 1" is the number of particles having a particle diameter of 2 times or more (average / 0.5g), and "coarse particle 2" is the number of particles having a particle diameter of 2.5 times or more of the average particle diameter ( /0.5g), and "product recovery" means the ratio of the total mass of the fine particles recovered through the classification step to the total mass of the particles supplied to the classification step in the Examples and Comparative Examples.

Manufacturing example  8 (amino resin Crosslinked particles )

Into a reaction kettle equipped with a cooling line, a thermometer, and an inlet, 75 parts of melamine, 75 parts of benzoguanamine, 290 parts of formalin at 37% concentration and 1.16 parts of aqueous sodium carbonate solution at 10% concentration were injected, and the mixture for forming an amino resin precursor was prepared. Was adjusted. After heating up this mixture to 85 degreeC, stirring, it hold | maintained at that temperature for 1.5 hours, and obtained the initial condensate. Separately, 7.5 parts of an emulsion (non-ionic surfactant) 430 (Kao Co., Ltd., polyoxyethylene oleyl ether) was dissolved in 2455 parts of ion-exchanged water, and the prepared surfactant solution was kept at 50 ° C, under stirring, The initial condensate was added thereto to obtain an emulsion of an amino resin precursor. 90 parts of 5% dodecylbenzenesulfonic acid aqueous solution was added to this emulsion, and it condensed and hardened | cured at the temperature of 70-90 degreeC, and the suspension containing amino resin crosslinked particle was obtained.

Manufacturing example  9, 10 (amino resin Crosslinked particles )

A suspension containing amino resin crosslinked particles was prepared in the same manner as in Production Example 8 except that the amount of the amino compound and formalin was changed to the amount shown in Table 3.

[Table 3]

Manufacturing example  11 (polystyrene particles)

50 parts of styrene, 50 parts of ethylene glycol dimethacrylate, 5 parts of azo polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.), 0.5 parts of t-butylhydroquinone, 0.5 parts of sodium lauryl sulfate and 100 parts of ion-exchanged water. The mixture was stirred and emulsified to obtain an aqueous dispersion of the polymerizable monomer.

40 parts of monodisperse polystyrene latex (5% solids concentration) having a particle diameter of 1 μm were added to 200 parts of ion-exchanged water, and dispersed in a reaction kettle having a cooling line, a thermometer, and a dropping outlet. The temperature was raised to ° C, and the total amount of the aqueous dispersion of the polymerizable monomer and 200 parts of a 2% aqueous solution of polyvinyl alcohol were added dropwise continuously over 5 hours. After completion of the dropwise addition, the temperature was raised to 85 ° C, the temperature was further maintained at this temperature for 3 hours, and a suspension containing polystyrene particles was obtained.

Manufacturing example  12 (polystyrene particles)

As shown in Table 4, except that the combination of radically polymerizable monomers was changed and the addition amount of monodisperse polystyrene latex (particle diameter: 0.6 micrometer (production example 12), 0.7 micrometer (production example 13)) was adjusted suitably, In the same manner as in Production Example 11, the polystyrene latex fine particle dispersion solution was adjusted.

[Table 4]

Example  9

The polymer dispersion obtained in Production Example 3 was subjected to a filtration treatment using a configuration in which a plurality of cartridge filters were combined (prefilter 1: HC-75, prefilter 2: HC-25, final filter: SLP300, manufactured by Rocky Techno Co., Ltd.). (Wet classification process).

Next, the dispersion was solid-liquid separated by natural sedimentation, and the obtained cake was washed with ion-exchanged water and methanol, and then vacuum-dried and vacuum-dried at 100 ° C for 5 hours to obtain a dried product obtained by agglomeration of particles. Particles were obtained by pulverizing the dried product.

The pulverized microparticles | fine-particles obtained at this time were 0.7 g / cm <3> in volume ratio, 6.9 micrometers of particle diameters, 0.5 mass% or less of water content, and 97 mass% of recovery.

This is put into a Coanda airflow classifier (Elvojet EJ-15, manufactured by Nitetsu Mining Co., Ltd., feed air: 5 kgf, using a slim edge), and the inertia force provided to the fine particles and the drag due to the suction blower are provided. The fine particles classified by adjusting and classifying with 89 mass% of recovery with respect to the supplied grinding | pulverization particle | grain were obtained (dry classification process).

Example  10

By the same process as in Example 9, the ground particles were adjusted from the polymer dispersion solution obtained in Production Example 8 (0.6 g / cm 3 in volume ratio, 8.5 µm in particle diameter, 1.0 mass% or less in water content, and 96 mass% in recovery).

The pulverized particles are introduced into a high-precision airflow classifier (DFX 5, manufactured by Nippon Pneumatic Co., Ltd.) and classified by adjusting the balance between the centrifugal force applied to the pulverized particles by the high-speed swirling air and the drag caused by the suction blower. And fine particles classified at a recovery rate of 85% by mass with respect to the supplied pulverized particles were obtained (dry classification step).

Example  11

By the same process as in Example 9, pulverized fine particles were prepared from the polymer dispersion solution obtained in Production Example 11 (volume ratio of 0.7 g / cm 3, particle diameter of 4.0 μm, water content of 0.5 mass% or less, and recovery rate of 97 mass%).

The pulverized particles are fed into a rotary rotor air flow classifier (Turbo Clash Fire TC-15, manufactured by Nisshin Engineering Co., Ltd.), and the centrifugal force and drag force applied to the pulverized particles by the rotational speed of the classification rotor and the supply of air from the inlet port. By adjusting the balance, classification was performed to obtain fine particles classified at a recovery rate of 85% by mass with respect to the supplied pulverized particles (dry classification step).

Example  12

In the same manner as in Example 1, pulverized fine particles were prepared from the polymer particle dispersion obtained in Production Example 10 (volume ratio 0.6 g / cm 3, particle diameter 13.1 μm, water content 1.0 mass% or less, and recovery 99 mass%).

The pulverized fine particles thus obtained were put into a Coanda type air flow classifier (Elvozette EJ-15, manufactured by Nitetsu Mining Co., Ltd., feed air: 5 kgf, using a slim edge), and the rotation speed of the classifying rotor and the intake port were Classification was performed by adjusting the balance of centrifugal force and drag applied to the pulverized particles by supplying air, thereby obtaining fine particles classified at a recovery rate of 85% by mass with respect to the supplied pulverized particles (dry classification step).

Example  13

In the same manner as in Example 1, pulverized fine particles were prepared from the polymer particle dispersion obtained in Production Example 9 (volume ratio of 0.6 g / cm 3, particle diameter of 2.0 μm, water content of 1.0 mass% or less, recovery rate of 99 mass%).

The pulverized fine particles thus obtained are put into a high-precision airflow classifier (DFX 5, manufactured by Nippon Pneumatic Co., Ltd.) and classified by adjusting the balance of the centrifugal force given to the pulverized particles by the high-speed swirling air and the drag by the suction blower. And fine particles classified at a recovery rate of 80% by mass with respect to the supplied pulverized particles were obtained.

Example  14

In the same manner as in Example 1, pulverized fine particles were prepared from the polymer particle dispersion obtained in Production Example 12 (0.7 g / cm 3 in volume ratio, 6.5 µm in particle diameter, 0.5 mass% or less in water content, and 99 mass% in recovery).

The pulverized fine particles thus obtained were put into a Coanda type air flow classifier (Elvozette EJ-15, manufactured by Nitetsu Mining Co., Ltd., feed air: 5 kgf, using a slim edge), and the rotation speed of the classifying rotor and the intake port were The fine particles were classified by adjusting the balance of centrifugal force and drag applied to the pulverized particles by supplying air to obtain a 87% by mass recovery rate for the supplied pulverized particles.

Example  15

In the same manner as in Example 1, ground fine particles were prepared from the polymer particle dispersion obtained in Production Example 13 (volume ratio of 0.7 g / cm 3, particle diameter of 9.3 μm, water content of 0.5 mass% or less, and recovery rate of 99 mass%).

The obtained pulverized fine particles were put into a rotary rotor type air flow classification device (Turbo Clash Fire TC-15, manufactured by Nisshin Engineering Co., Ltd.), and the centrifugal force and drag force applied to the pulverized particles by the rotational speed of the classification rotor and the supply of air from the inlet port. Classification was performed by adjusting the balance, and fine particles classified at a recovery rate of 83% by mass with respect to the feed milled particles were obtained.

Comparative Example  4

In the same manner as in Example 1, pulverized fine particles were prepared from the polymer particle dispersion obtained in Production Example 12 (0.7 g / cm 3 in volume ratio, 6.5 µm in particle diameter, 0.5 mass% or less in water content, and 99 mass% in recovery).

The pulverized fine particles thus obtained were put into a Coanda type air flow classifier (Elvozette EJ-15, manufactured by Nitetsu Mining Co., Ltd., feed air: 5 kgf, using a slim edge), and the rotation speed of the classifying rotor and the intake port were The fine particles were classified by adjusting the balance of the centrifugal force and drag applied to the pulverized particles by supplying air to obtain a 75% by mass recovery rate for the supplied pulverized particles.

Comparative Example  5

In the same manner as in Example 1, except that wet classification was not performed, pulverized fine particles were prepared from the polymer particle dispersion obtained in Preparation Example 3 (volume ratio 0.7 g / cm 3, particle diameter 6.9 μm, water content 0.5 mass%). Below).

The obtained pulverized fine particles were put into a rotary rotor type air flow classification device (Turbo Clash Fire TC-15, manufactured by Nisshin Engineering Co., Ltd.), and the centrifugal force and drag force applied to the pulverized particles by the rotational speed of the classification rotor and the supply of air from the inlet port. By adjusting the balance, classification was performed to obtain fine particles classified at a recovery rate of 90% by mass with respect to the supplied pulverized particles (the first time for dry classification). Thereafter, the same dry classification process was repeated to obtain fine particles classified at a recovery rate of 90% by mass with respect to the supplied pulverized particles (the second time for dry classification).

Table 5 shows the evaluation results of the contents of the classification treatments in Examples 9 to 13 and Comparative Example 4 and the obtained fine particles and powder particles. In addition, each evaluation method is as above-mentioned.

[Table 5]

In addition, Comparative Example 5 is an example of repeating dry classification twice as a classification step. Repeated dry classification did not sufficiently remove coarse particles. In addition, the tendency of the product recovery rate to fall by repeating dry classification was shown, and it turned out that industrial product yield is difficult to be obtained only by dry classification.

Example  16 Blooming  Production of film

3 mass parts of each resin particle and 20 mass parts of toluene obtained by Example 1, 9, 10, and the comparative example 4 were fully stirred and mixed. 40 mass parts of acrylic ionizing radiation hardening resin, 2 mass parts of photoinitiators (Ciba Specialty Chemicals company, "Irugacure (registered trademark) 907)), 23 mass parts of methyl ethyl ketones, and ethylene glycol monobutyl ether to the said mixture liquid 2 mass parts and a leveling agent (BYK320 by the company made) were added, and it fully stirred, and prepared coating liquid.

The coating liquid was apply | coated by the bar coater to the single side | surface of the triacetyl cellulose film (The Fuji Photo Film company make, "Fuji Tak (trademark)") of 80 micrometers in thickness. After drying the obtained coating film with a 80 degreeC dryer, the anti-glare film was produced by irradiating the ultraviolet-ray of 300mJ / cm <2> using a high pressure mercury lamp, and hardening a resin component.

The black film was laminated | stacked on the back surface of each anti-glare film, the fluorescent lamp of 10000 cd / m <2> was lighted at the position 2 m from this film, and the degree of blur of the reflection image was evaluated by the following reference | standard. The results are shown in Table 6.

(Circle): The outline of a fluorescent lamp cannot be discriminated.

X: The outline of a fluorescent lamp can be distinguished clearly.

In addition, about each anti-glare film, transmission sharpness (image sharpness) was measured in accordance with JIS K7105 using a mapping measuring instrument (made by Suga Tester Co., Ltd., ICB-IDD) and an optical comb of 0.5 mm width.

Each anti-glare film was laminated on the surface of a liquid crystal monitor (15 inch XGA, TFT-TN method, front luminance: 350 cd / m 2, front contrast: 300: 1, surface AG: none) connected to a personal computer. The cloudy state of was evaluated by the following criteria. The results are shown in Table 6.

(Circle): The outline of a character is not blurred at all.

X: The outline of a character is blurred, and a strong sense of incongruity is felt.

[Table 6]

As can be seen from Table 6, the antiglare films obtained using the particles of Examples 1, 9 and 10 all had excellent anti-glare properties and visibility (no character blurring). On the other hand, the antiglare film produced using the particles of Comparative Example 4 having a large amount of coarse particles more than twice the average particle diameter has antiglare properties, but coarse particles contained in the antiglare film act like a lens, or the coarse particles Due to this, scratches occurred on the surface of the film, and as a result, it is considered that it is difficult to visually recognize characters.

The microparticles | fine-particles of this invention reduce content of coarse particle | grains and microparticles beyond the suitable range of particle diameter to low level. Therefore, various optical films or sheets (anti-glare sheet, light-diffusion film, etc.) manufactured using such microparticles | fine-particles are considered to produce the fault which originates in coarse particle, and the fall of transparency which originate in a microparticle hardly generate | occur | produce. . Moreover, since unevenness | corrugation is formed uniformly in surface, it is thought to exhibit the outstanding optical characteristic (for example, anti-glare property and light diffusivity).

Claims (11)

A step of wet classifying a fine particle dispersion having a solid content concentration of 0.5 to 50% by mass and a type B viscosity of 0.5 to 20 mPa · s,
Drying the fine particles after wet classification into powder fine particles having a water content of 0.05 to 2% by mass, and
Characterized in that it comprises a step of dry classification of the powder fine particles,
The manufacturing method of microparticles | fine-particles for optical films containing microparticles which have a particle diameter of 1/2 or less of an average particle diameter in 10 volume% or less. The method for producing particulates according to claim 1, wherein the dry classification is performed by an air flow classifier. 3. The airflow classifier according to claim 2, wherein the airflow classifier is a device for classifying coarse powder and fine powder from particles by the balance of centrifugal force and drag force, a rotary rotor type airflow classifier, and a airflow classifier and network using a Coanda effect. A method for producing microparticles, which is at least one member selected from the group consisting of an airflow classifier using a body. The method for producing particulates according to claim 1, wherein the wet classification is performed by a filtration device or a liquid cyclone device. The method for producing fine particles according to claim 1, which contains coarse particles having a particle diameter of twice or more the average particle diameter in an amount of 1000 / 0.5 g or less. delete delete delete delete delete delete