JP6277962B2 - Composite aggregated resin particles and composition containing the particles - Google Patents

Description

  The present invention relates to composite aggregated resin particles. Specifically, the present invention relates to composite agglomerated resin particles excellent in light diffusion performance, a method for producing the same, and various compositions containing the particles.

  Conventionally, a light diffusion film imparted with light diffusibility by containing organic fine particles or inorganic fine particles is known. Among them, those using inorganic fine particles such as fine silicate as a light diffusing agent may cause a phenomenon in which the color of the ground becomes faint (white blurring phenomenon) due to poor transparency, the friction resistance of the film, There was a problem that it was inferior in breaking strength.

  On the other hand, when organic fine particles are used as the light diffusing agent, a film with good transparency and high light transmittance can be obtained although the light diffusion performance is inferior to that of inorganic fine particles. Therefore, for the purpose of supplementing the low light diffusion performance of organic fine particles, for example, for light diffusing agents with excellent light diffusion performance, which has a structure (micro phase separation structure) in which organic fine particles of different composition are finely phase separated inside Particles have been proposed (see Patent Document 1).

  However, in such particles for a light diffusing agent, particles less than 100 nm contained in the particles may hinder light transmission and reduce the transmittance of light irradiated from a backlight or the like. Further, in such particles, additives such as surfactants used in the production process remain, and thus there may be problems such as deterioration of physical properties and coloring during film molding or long-term use.

JP 2012-193244 A

  The present invention has been made based on the current state of the prior art, and can be widely used in various applications including light diffusion films, inks, paints, resin molded products, has few impurities, and has excellent handling properties. An object of the present invention is to provide composite agglomerated resin particles having excellent light diffusion performance.

  As a result of studying the above object, the present inventors have achieved the above object by combining the vinyl polymer with the raw material aggregated particles formed by agglomerating the fine resin particles and integrating the fine resin particles. The present invention was reached. That is, the object of the present invention is achieved by the following means.

[1] SEM image of the fine resin particles which are the aggregate resin particles in which the vinyl polymer not dissolved in the organic solvent is combined with the raw material aggregate particles formed by the aggregation of the fine resin particles, and constituting the raw material aggregate particles the average particle diameter determined by is 100-600 nm, the volume, wherein the fine resin particles present in at least a surface layer portion of the raw material agglomerated particles is in a state of being integrated by the vinyl polymer Composite aggregated resin particles having an average particle size of 3 to 150 μm.
[2] The composite aggregated resin particle according to [1], wherein the bulk density is 0.20 to 0.50 g / cm ³ .
[ 3 ] The composite agglomerated resin particle according to [1] or [ 2 ], which does not contain an emulsifier.
[ 4 ] The composite agglomerated resin particle according to any one of [1] to [ 3 ], which does not contain a flocculant.
[ 5 ] The composite according to any one of [1] to [ 4 ], wherein the content of the vinyl polymer not dissolved in the organic solvent is 0.1 to 200% by weight of the raw material aggregated particles. Aggregated resin particles.
[ 6 ] The raw material aggregated particles are 90 to 100% by weight of a vinyl monomer having a solubility in water of less than 3% by weight based on the total weight of the monomer, and 0.25 to 3 of a water-soluble polymerization initiator. The method for producing composite agglomerated resin particles according to any one of [1] to [ 5] , wherein the composite agglomerated resin particles are formed by polymerization in water using wt% .

[7] In the aqueous dispersion containing raw material agglomerated particles, by polymerizing a vinyl monomer which is insoluble in the solvent of the organic system by using a water-soluble polymerization initiator, the vinyl heavy on the raw material agglomerated particles The method for producing composite agglomerated resin particles according to any one of [1] to [ 5 ], wherein the composite is combined.
[ 8 ] A coating composition comprising the composite agglomerated resin particles according to any one of [1] to [ 5 ].

[ 9 ] An ink composition comprising the composite agglomerated resin particles according to any one of [1] to [ 5 ].
[ 10 ] A resin molded product comprising the composite agglomerated resin particle according to any one of [1] to [ 5 ].

  The composite agglomerated resin particles of the present invention have a sparse agglomerated structure, and voids exist inside the particles, so that the particle density is low and the area of the interface per unit weight of the particles is large. Therefore, a higher light diffusion effect can be obtained. Further, since the particle shape is indefinite, it is expected to have light diffusion performance that cannot be obtained with conventional resin particles. In addition, since the fine resin particles aggregated with the vinyl polymer are integrated, the aggregated state can be maintained even in an aqueous solvent or an organic solvent. Even if it exists, the coating film which expresses the desired frosting effect can be obtained, it is hard to generate | occur | produce a fine powder also about handling, and handling property is favorable.

The SEM image of the raw material aggregated particle obtained in Example 1 is shown. The SEM image of the composite aggregation resin particle obtained in Example 1 is shown.

  The present invention is described in detail below. The composite agglomerated resin particle of the present invention is an agglomerated resin particle in which a vinyl polymer is compounded with raw material agglomerated particles obtained by agglomerating fine resin particles, and the fine resin present in at least a surface layer portion of the raw material agglomerated particles The particles are characterized by being integrated with the vinyl polymer. Here, the “integrated state” is a state in which the fine resin particles are not simply agglomerated but adhered to each other by the vinyl polymer, and the organic resin is in an aqueous solvent. In any of the solvents, the aggregated state can be maintained and the primary particles are not formed.

  In such an “integrated state”, the appearance of the fine resin particles forming the composite agglomerated resin particles is not clear as shown in FIG. In many cases, they are connected to each other.

  Further, in the composite agglomerated resin particles of the present invention, the “combined state” means a state in which the vinyl polymer is adhered to the raw material agglomerated particles by immersing the raw material agglomerated particles in a solution of the vinyl polymer, Examples include a state obtained by polymerizing a vinyl monomer that is a raw material for a vinyl polymer in an aqueous dispersion of raw material aggregated particles.

  Moreover, it is desirable that the shape of the composite agglomerated resin particles of the present invention is indefinite. Here, the shape of the composite aggregated resin particles is not the detailed shape of the composite aggregated resin particles, but the overall shape. Further, “indefinite shape” means a state in which the shape of each composite aggregated resin particle varies. In such a state, most of the particles have a shape that is difficult to say spherical, and has an unevenness around the image of the particles viewed from one direction, that is, the particle projection image.

As a scale representing the degree of this irregular shape, the circularity defined by the following formula can be used.
Circularity of particle projection image = (circumference of a circle having the same area as the particle projection area) / (perimeter of particle projection image)
Average value of circularity of particle projection image = circularity of particle In other words, the circularity is 1 in the case of a perfect circle, and becomes a smaller value as the degree of irregularity increases. In the composite aggregated resin particles of the present invention, the circularity of the above particles is preferably in the range of 0.50 to 0.94, more preferably in the range of 0.70 to 0.90. The circularity can be measured using, for example, a flow type particle image analyzer “FPIA-3000S” manufactured by Sysmex Corporation.

  In the composite agglomerated resin particles of the present invention, since the fine resin particles are integrated with the vinyl polymer as described above, the composite agglomerated resin particles are easily handled even in a dry state. And fine particles do not scatter. In addition, in water-based solvents and organic solvents, it does not re-disperse to fine particle units, so when added to water-based paints or solvent-based paints to form a film, the agglomerated state is maintained. On the surface of the composite agglomerated resin particles, surfaces having various angles are present without being unevenly distributed, and an effect of scattering incident light from any direction without any spots can be obtained. In addition, when the composite agglomerated resin particles of the present invention have an irregular shape, it is possible to obtain an effect of scattering incident light in various directions. Furthermore, since the bulk density is lower than that of ordinary spherical particles, the number of particles per unit weight is increased, and more irregularities can be formed on the film surface. That is, compared with the light diffusing effect of a film using ordinary spherical particles, for example, the same light diffusing effect can be obtained even if the addition amount is halved.

  Furthermore, when the composite vinyl polymer is hydrophilic, it has excellent dispersion stability in an aqueous solvent and is suitable for addition to an aqueous paint or aqueous resin.

In the composite aggregated resin particles according the present invention, it is preferable that the bulk density is 0.20~0.50g / cm ^3, more preferably 0.25~0.40g / cm ^3. Such bulk density can be taken as a measure for confirming the aggregation state of the fine resin particles. If the bulk density is too high, the number of irregularities that can be formed on the surface, for example, when it is formed into a coating film decreases, and sufficient light diffusion performance may not be obtained.

  Moreover, it is preferable that the volume average particle diameter of the composite aggregation resin particle | grains of this invention is 3-150 micrometers, More preferably, it is 3-50 micrometers, More preferably, it is 3-30 micrometers. If the average particle size is less than 3 μm, the total light transmittance may be reduced due to light scattering when processed into a coating film, which is not desirable in applications that require light transmission such as light diffusion plates for LEDs. . On the other hand, if the average particle diameter exceeds 150 μm, the number of particles is reduced even if the weight added to the coating film is the same, so that sufficient haze may not be obtained. Moreover, it becomes easy to generate | occur | produce a spot at the time of coating, and besides giving a rough surface to a coating-film surface, the possibility of causing the fall of a coating-film physical property becomes high.

  Moreover, it is desirable that the composite agglomerated resin particles of the present invention do not contain a flocculant. Here, the aggregating agent is an additive added to agglomerate primary particles, and examples thereof include a polymer aggregating agent and inorganic salts. The agglomerated particles often contain an aggregating agent, but adding aggregated particles containing a large amount of the aggregating agent to the paint may deteriorate the properties of the paint or coating film.

  Moreover, it is desirable that the composite aggregated resin particles of the present invention do not contain an emulsifier. Here, the emulsifier refers to a surfactant. The emulsifier is generally added in a polymerization process or the like. If aggregated particles containing a large amount of emulsifier are added to the paint, the properties of the paint or coating film may be deteriorated.

  The average particle diameter of the fine resin particles contained in the composite agglomerated resin particles of the present invention is preferably 100 to 600 nm, and more preferably 150 to 500 nm. If this average particle diameter is too small, the cohesive force becomes strong and there are no gaps between the fine resin particles, which may increase the bulk density. Conversely, if it is too large, the aggregated state of the fine resin particles may not be maintained. Moreover, it is preferable to set it as the average particle diameter of this range also from a viewpoint of the effect of light scattering.

  Further, the type of resin of the fine resin particles is not particularly limited. For example, the resin can be obtained by selecting a resin having a refractive index difference as small as possible from the coating resin to which the composite agglomerated resin particles are added. The internal haze value of the resulting coating film is lowered and the transparency is improved. Conversely, by selecting a resin having a large refractive index difference as the resin of the fine resin particles, the internal haze value of the obtained coating film increases, and various optical characteristics such as anti-glare and ultraviolet scattering can be obtained. Accordingly, the type of resin may be arbitrarily selected according to the purpose. The internal haze value referred to here is not the surface structure such as irregularities but the haze value derived from the internal structure. If the coating film is as described above, the refractive index difference between the coating resin and the fine resin particles Is mainly derived from.

  From the viewpoint that the required characteristics vary depending on the application, the resin of the fine resin particles is preferably a vinyl resin rich in the types of monomers that can be used. Examples of vinyl monomers that can be used when adopting such vinyl resins include acrylic acid esters such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, dimethylaminoethyl acrylate, and diethylaminoethyl acrylate. Monomers, methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, lauryl methacrylate, dimethylaminoethyl methacrylate, styrene monomers such as styrene and p-methylstyrene, methyl vinyl ether, ethyl vinyl ether Vinyl ester monomers such as alkyl vinyl ethers such as vinyl acetate and vinyl butyrate, N-alkyl substituted (meth) acrylamides such as N-methyl acrylamide and N-ethyl acrylamide, acrylonitrile, Polyfunctional monomers such as nitrile monomers such as acrylonitrile, divinylbenzene, ethylene glycol di (meth) acrylate, polyethylene glycol mono (meth) acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Examples include the body. Such monomers may be used alone or in combination of two or more.

  The raw material agglomerated particles employed in the present invention are obtained by agglomerating the above-mentioned fine resin particles. For example, the raw material agglomerated particles are obtained by adding a flocculant to a dispersion of fine resin particles obtained by emulsion polymerization and aggregating them. be able to. However, it is more preferable to employ raw material aggregated particles obtained by a production method described later using a vinyl monomer having a solubility in water of less than 3% by weight such as methyl methacrylate or ethylene glycol dimethacrylate. This is because the raw material agglomerated particles obtained by such a production method contain neither an emulsifier nor a flocculant.

  In addition, the particle diameter of the fine resin particles in the present invention can be adjusted by polymerization conditions or the amount of emulsifier if used. Similarly, the particle diameter of the raw material agglomerated particles in the present invention can be adjusted by the polymerization conditions when the raw material agglomerated particles are produced, or the amount of the agglomerating agent if used.

  As described above, the vinyl polymer employed in the present invention is for maintaining the aggregated state of the composite aggregated resin particles of the present invention even in a dry state or in an aqueous or organic solvent. Such vinyl polymers are preferably those that do not dissolve in an aqueous or organic solvent, and are more compatible with the solvent used in consideration of dispersion stability in the solvent. Therefore, in selecting a vinyl polymer, for example, the solubility parameter of the solvent used for dispersion can be referred to, but generally, it is not soluble in an aqueous or organic solvent. It may be possible to select a vinyl polymer having a crosslinked structure. In order to obtain excellent dispersion stability in an aqueous solvent, it may be possible to select a hydrophilic polymer as the vinyl polymer.

  As will be described later, the vinyl polymer employed in the present invention is obtained by polymerizing a vinyl monomer using a water-soluble polymerization initiator in an aqueous dispersion containing raw material aggregated particles. It can be combined with aggregated particles. In this case, it is natural to select a vinyl monomer to be used so that a vinyl polymer to be combined is obtained, but also consider the affinity between the vinyl monomer and the fine resin particles. Should. That is, when the fine resin particles dissolve or vigorously swell when the vinyl monomer is added, optical properties such as matting performance may be deteriorated. However, the range of selection of the vinyl monomer can be expanded by introducing a crosslinked structure into the fine resin particles in advance to suppress dissolution and swelling.

  As a vinyl polymer employ | adopted for this invention described above, homopolymers and copolymers, such as a vinyl monomer employable in resin of the fine resin particle mentioned above, can be mentioned, for example. Specifically, poly (meth) acrylic acid ester, polyvinyl acetate, a copolymer of plural types of (meth) acrylic acid ester, and a crosslinkable monomer such as polyethylene glycol di (meth) acrylate were homopolymerized or copolymerized. A polymer etc. are illustrated. The expression “(meth) acrylic acid” indicates both “methacrylic acid” and “acrylic acid”.

  Further, the upper limit of the amount of the vinyl polymer combined with the raw material aggregated particles is preferably 200% by weight or less, more preferably 100% by weight or less, and more preferably 50% by weight or less of the raw material aggregated particles. Is more preferable. If the vinyl polymer exceeds 200% by weight, the gap between the fine resin particles may be filled with the vinyl polymer even in the innermost part of the raw material aggregated particles, and the bulk density may increase.

  On the other hand, the lower limit of the amount of the vinyl polymer combined with the raw material aggregated particles is preferably 0.1% by weight or more of the raw material aggregated particles, more preferably 1.0% by weight or more, and still more preferably 5.0%. % By weight or more. When the vinyl polymer is less than 0.1% by weight, the aggregation maintaining effect by the vinyl polymer is hardly obtained, fine powder is likely to be generated, and it may be difficult to handle.

  The composite agglomerated resin particles of the present invention described above can be obtained by combining a vinyl polymer with raw material agglomerated particles. From the viewpoint of the characteristics required for the above-described composite aggregated resin particles of the present invention, the raw material aggregated particles are desirably those in which the fine resin particles are aggregated while maintaining the shape before aggregation. The method for producing such raw material aggregated particles is not particularly limited as long as the desired raw material aggregated particles are obtained. As an example, raw material aggregated particles can be formed by a method in which droplets of a vinyl monomer are dispersed in water in which a water-soluble polymerization initiator is dissolved and polymerized while heating and stirring. In this method, raw material aggregated particles in which fine resin particles are aggregated can be obtained without adding any special operation or additive. The raw material aggregated particles thus obtained can be adjusted to an arbitrary particle size by pulverization and classification.

  As the vinyl monomer used in such a method, it is desirable to use a vinyl monomer having a solubility in water at 20 ° C. of less than 3% by weight, preferably less than 2% by weight. The body is used in an amount of 90% by weight or more, preferably 95% by weight or more based on the total monomer weight. Representative examples of such vinyl monomers include acrylate monomers such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Methacrylic acid ester monomers such as lauryl, styrene monomers such as styrene and p-methylstyrene, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl ester monomers such as vinyl acetate and vinyl butyrate, divinyl Examples include benzene, ethylene glycol di (meth) acrylate, polyethylene glycol mono (meth) acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate. That. When the monomer is less than 90% by weight, the fine resin particles may not aggregate. This is presumably because the amount of vinyl monomer having a solubility in water of 3% by weight or more increases the amount of such a monomer that preferentially polymerizes and acts as a dispersant. The ratio of the total monomer weight to the total charged weight is preferably 5 to 35% by weight.

  As the polymerization initiator, any type of initiator such as azo, persulfate, peroxide, and redox can be used as long as it is a water-soluble polymerization initiator. Good. Representative examples include 2,2′-Azobis (2-methylpropionamidine) dihydrochloride, 2,2′-Azobis (1-imino-1-pyrrolidino-2-methylpropylane) dihydrochloride, t-Butylhydrogen sulfate, Examples thereof include potassium and hydrogen peroxide / iron (II) ion systems.

  The water-soluble polymerization initiator is used in an amount of 0.25 to 3% by weight, preferably 0.25 to 2% by weight, based on the total monomer weight. By setting it within such a range, it is possible to obtain particles having a moderate size in which the fine resin particles are in an aggregated state and are not agglomerated.

  As described above, the raw material aggregated particles employed in the present invention can be obtained. However, the obtained raw material aggregated particles can be pulverized as necessary to be adjusted to a desired particle diameter. In the pulverization process, a special apparatus is not required, and a general-purpose pulverization apparatus such as a blade mill, a Banbury mixer, a kneader mixer, or a roll can be used. In the pulverization treatment, it is not necessary to dry the particles, and the particles can be pulverized in a wet state such as after the polymerization.

  Moreover, in the manufacturing method mentioned above, you may add polyvinyl alcohol at the stage which superpose | polymerizes raw material aggregated particles, or after superposition | polymerization as needed. Thereby, the dispersion stability of the aqueous dispersion of the raw material aggregated particles obtained can be improved. The added amount of polyvinyl alcohol is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.1 part by weight, with respect to 100 parts by weight of the raw material aggregated particles.

  As described above, since the production method described in detail above can obtain raw material aggregated particles in an appropriate aggregated state without using an emulsifier or an aggregating agent, the composite aggregated resin particles of the present invention can be obtained. It is a suitable method. However, in this production method, an emulsifier and a flocculant can be used as necessary.

  In addition, as a method of combining the vinyl polymer with the raw material aggregated particles, for example, a method of polymerizing a vinyl monomer using a water-soluble polymerization initiator in an aqueous dispersion containing the raw material aggregated particles. Can be mentioned.

  In this method, as the aqueous dispersion containing the raw material aggregated particles, the raw material aggregated particle dispersion produced by the polymerization in the raw material aggregated particle production method described in detail above may be used as it is. In addition, as a method of adding the vinyl monomer and the water-soluble polymerization initiator to the aqueous dispersion, the whole amount may be added at once, or may be dropped little by little while the polymerization proceeds. Further, the addition amount of the vinyl monomer is preferably 200% by weight or less, more preferably 100% by weight of the raw material aggregated particles as the upper limit from the viewpoint of the amount of the vinyl polymer combined with the raw material aggregated particles. % By weight or less, more preferably 50% by weight or less. The lower limit is preferably 0.1% by weight or more of the raw material aggregated particles, more preferably 1.0% by weight or more, and further preferably 5.0% by weight or more.

  In addition, when making a vinyl polymer compound by this method, it is desirable that the fine resin particles constituting the raw material aggregated particles have a crosslinked structure. When it does not have a cross-linked structure, there is a possibility that the fine resin particles are dissolved by the added vinyl monomer and the composite aggregated resin particles of the present invention cannot be obtained. Examples of a method for introducing a crosslinked structure include a method of copolymerizing a vinyl monomer having two or more vinyl groups in the case of the raw material aggregated particle production method described in detail above.

  Although the use of the composite aggregation resin particle of this invention is described below, this use is an example and the composite aggregation resin particle of this invention can be used also for the other wide use.

  The composite agglomerated resin particles of the present invention can be used by being contained in a resin molded product in addition to a paint and an ink composition. When these are included, stirring and kneading are often performed, but even in such a case, the composite agglomerated resin particles of the present invention can maintain an agglomerated state with almost no loosening, and thus are described above. Such optical characteristics can be expressed.

  Examples of the method for producing the coating composition or ink composition of the present invention include a method of adding the composite agglomerated resin particles and binder resin of the present invention to an organic solvent. The binder resin is not particularly limited, and examples thereof include thermoplastic resins, thermosetting resins, and photocurable resins. Specifically, for example, acrylic resins, polyester resins, polyvinyl chloride, polyurethane, silicone resins And melamine resin. In addition, when providing transparency to a coating film, it is preferable to use acrylic resin, acrylic-silicone resin, etc. suitably.

  The organic solvent is not particularly limited. For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethyl acetate, butyl acetate, isopropyl Alcohol, acetone, anisole, etc. are mentioned. These may be used alone or in combination of two or more. Various known additives such as a leveling agent, a surface modifier, a defoaming agent, and a colorant such as a pigment may be added to the paint and ink composition.

  For example, the above composition is prepared by dissolving the binder resin in an organic solvent and then adding the composite agglomerated resin particles of the present invention, and uniformly dispersing using a sand mill, a ball mill, an attritor, a high-speed rotating stirrer, a triple roll, etc. It can also be produced by mixing.

  The composite agglomerated resin particles of the present invention are not limited to solvent-based paints and ink compositions as described above, and can also be used in various paints and ink compositions such as solvent-free, water-based, and powder.

  The composite aggregated resin particles of the present invention can be molded by kneading into a thermoplastic or thermosetting matrix resin to produce a resin molded product containing the composite aggregated resin particles. As these matrix resins, resins having excellent transparency, good weather resistance, and rigidity such as polymethyl methacrylate resin, MS resin, polycarbonate resin, and polyester resin are preferably used.

  The resin molded product of the present invention can be obtained by mixing a resin and composite agglomerated resin particles with a mixer, kneading with a melt kneader, and then extruding the resin molded product. The molded product can also be obtained by taking out as pellets after melt-kneading, and injection-molding the pellets after melting.

  Hereinafter, the effects of the present invention will be described with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples.

(1) Circularity and volume average particle diameter of sample particles The circularity and volume average particle diameter of the particles as defined above were measured by a flow type particle image analyzer (FPIA-3000S: manufactured by Sysmex Corporation).

(2) Average particle diameter of fine resin particles In the SEM image of the raw material aggregated particles, 20 fine resin particles were arbitrarily selected, each diameter was measured, and an average value was calculated.

(3) Bulk density A container A (cm ³ ) having a known volume was filled with particles, the weight B (g) was measured, and the bulk density was calculated according to the following formula.
Bulk density (g / cm ³ ) = B (g) / A (cm ³ )

(4) Haze value 12 parts by weight of sample particles and 200 parts by weight of methyl ethyl ketone are added to 100 parts by weight of an oil-based topcoat paint (Acridic (acrylic resin, resin concentration: 51% by weight): manufactured by DIC Corporation). Stir for minutes. The obtained coating composition was coated on a PET film (Cosmo Shine # A4300 (thickness 100 μm: manufactured by Toyobo Co., Ltd.)) with a bar coater, and then dried in a hot air dryer at 60 ° C. for 30 minutes. The haze value of the obtained coating film was measured with a haze meter (NDH 2000: manufactured by Nippon Denshoku Co., Ltd.).

[Example 1]
300 parts by weight of water was charged into the reaction vessel, and 0.6 part by weight of 2,2′-Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride was dissolved as a polymerization initiator. Next, 99 parts by weight of methyl methacrylate and 1 part by weight of ethylene glycol methacrylate were added as monomers and reacted at 45 ° C. for 2 hours with stirring to obtain an aqueous dispersion of raw material aggregated particles. Subsequently, 30 parts by weight of polyethylene glycol # 400 dimethacrylate (NK-ester 9G, manufactured by Shin-Nakamura Chemical Co., Ltd.) and 2,2′-, based on 100 parts by weight of the solid content of the aqueous dispersion, were added to the aqueous dispersion. Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride 0.3 parts by weight was added and reacted again at 45 ° C. for 2 hours. Next, after filtering, washing with water, and drying, classification was performed to remove coarse particles, and composite agglomerated resin particles of Example 1 were obtained. The results of measuring the characteristics of the particles are shown in Table 1. Further, FIG. 1 shows the raw material aggregated particle SEM image, and FIG. 2 shows an SEM image of the composite aggregated resin particle.

[Example 2]
The aggregated resin particles obtained in Example 1 were classified with a finer sieve to obtain composite aggregated resin particles of Example 2. The results of measuring the characteristics of the particles are shown in Table 1.

[Example 3]
In Example 1, the composite aggregation of Example 3 was performed in the same manner as in Example 1 except that 30 parts by weight of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles was changed to 30 parts by weight of vinyl acetate. Resin particles were obtained. The results of measuring the characteristics of the particles are shown in Table 1.

[Example 4]
Example 1 is the same as Example 1 except that the blending amount of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles is changed from 30 parts by weight to 0.1 parts by weight. 4 composite agglomerated resin particles were obtained. The results of measuring the characteristics of the particles are shown in Table 1.

[Example 5]
In Example 1, except that the blending amount of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles was changed from 30 parts by weight to 10 parts by weight, Composite aggregated resin particles were obtained. The results of measuring the characteristics of the particles are shown in Table 1.

[Example 6]
In Example 1, except that the blending amount of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles was changed from 30 parts by weight to 250 parts by weight, Particles were obtained. The results of measuring the characteristics of the particles are shown in Table 1.

[Example 7]
In Example 1, composite aggregated resin particles of Example 7 were obtained in the same manner as in Example 1 except that 0.04 parts by weight of polyvinyl alcohol was added after the reaction of the raw material aggregated particles. The results of measuring the characteristics of the particles are shown in Table 1.

[Comparative Example 1]
The aqueous dispersion of the raw material aggregated particles of Example 1 was directly filtered, washed with water, dried, and classified to obtain particles of Comparative Example 1. The results of measuring the characteristics of the particles are shown in Table 1.

  As shown in Table 1, in Examples 1 to 7, composite agglomerated resin particles having high dispersion stability in a solvent and few fine powders were obtained. Moreover, when these particles were added to the solvent paint to form a coating film, a higher haze value was obtained as compared with the raw material aggregated particles of Comparative Example 1. In other words, in Examples 1 to 7, a high haze value was obtained because the aggregated state of the composite agglomerated resin particles was maintained even when added to the paint due to the effect of compounding the vinyl polymer. it is conceivable that. On the other hand, in Comparative Example 1, since the vinyl polymer is not combined, it is inferior in handling properties such as scattering at the time of classification or preparation, and it is considered that the agglomerated particles are loosened in the solvent and the haze value is lowered. . In addition, since the composite aggregation resin particle of Example 6 had many composite amounts of a vinyl polymer, the bulk density was high and the haze value became low compared with the composite aggregation resin particle of another Example.

Claims (10)

Aggregated resin particles in which a vinyl polymer that does not dissolve in an organic solvent is combined with raw material aggregated particles obtained by agglomerating fine resin particles, and measured by an SEM image of the fine resin particles constituting the raw material aggregated particles average particle diameter of 100-600 nm, at least the fine resin particles present in the surface layer portion is a volume average particle diameter, characterized in that in a state of being integrated by the vinyl polymer of the raw material agglomerated particles Composite agglomerated resin particles having a diameter of 3 to 150 μm. 2. The composite aggregated resin particle according to claim 1, having a bulk density of 0.20 to 0.50 g / cm ³ . The composite agglomerated resin particles according to claim 1 or 2 , which do not contain an emulsifier. The composite agglomerated resin particle according to any one of claims 1 to 3 , which does not contain an aggregating agent. The composite agglomerated resin particles according to any one of claims 1 to 4 , wherein the content of the vinyl polymer not dissolved in the organic solvent is 0.1 to 200% by weight of the raw material agglomerated particles. The raw material aggregated particles comprise 90 to 100% by weight of a vinyl monomer having a solubility in water of less than 3% by weight and 0.25 to 3% by weight of a water-soluble polymerization initiator based on the total monomer weight. It is formed by using and polymerizing in water, The manufacturing method of the composite aggregation resin particle in any one of Claims 1-5 characterized by the above-mentioned . In aqueous dispersion containing raw material agglomerated particles, by polymerizing a vinyl monomer which is insoluble in the solvent of the organic system by using a water-soluble polymerization initiator, the vinyl polymer to the raw material agglomerated particle composite method of producing composite aggregated resin particles according to any one of claims 1 to 5, characterized in that is obtained by. A coating composition comprising the composite agglomerated resin particles according to any one of claims 1 to 5 . An ink composition comprising the composite agglomerated resin particles according to any one of claims 1 to 5 . A resin molded product comprising the composite agglomerated resin particles according to any one of claims 1 to 5 .

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