WO2009128441A1 - Particules de résine composites et leur utilisation - Google Patents

Particules de résine composites et leur utilisation Download PDF

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Publication number
WO2009128441A1
WO2009128441A1 PCT/JP2009/057491 JP2009057491W WO2009128441A1 WO 2009128441 A1 WO2009128441 A1 WO 2009128441A1 JP 2009057491 W JP2009057491 W JP 2009057491W WO 2009128441 A1 WO2009128441 A1 WO 2009128441A1
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WO
WIPO (PCT)
Prior art keywords
composite resin
particles
resin particle
particle
silicone resin
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PCT/JP2009/057491
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English (en)
Japanese (ja)
Inventor
敏雄 関谷
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綜研化学株式会社
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Application filed by 綜研化学株式会社 filed Critical 綜研化学株式会社
Priority to KR1020107022645A priority Critical patent/KR101204963B1/ko
Priority to JP2010508213A priority patent/JP5706687B2/ja
Priority to CN2009801136487A priority patent/CN102007154B/zh
Publication of WO2009128441A1 publication Critical patent/WO2009128441A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0226—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures having particles on the surface
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties

Definitions

  • the present invention relates to a composite resin particle group containing silicone resin core particles and use thereof. More specifically, the present invention relates to a composite resin particle group formed using silicone resin core particles as seed particles and the use thereof.
  • the acrylic resin particles having an acrylic resin in the outer shell or the resin particles having polystyrene in the outer shell are used for various applications by utilizing the characteristics. Such resin particles are being widely used especially as optical members and cosmetic raw materials because the resin forming the outer shell is transparent.
  • Core particles are manufactured, and the core particles are used as seed particles, and an outer shell made of acrylic resin or styrene resin is formed around the core particles. It can be produced by seed polymerization to form.
  • Patent Document 1 Japanese Patent Laid-Open No. 7-96815
  • Patent Document 2 Japanese Patent Laid-Open No. 2002-138119
  • the silicone fine particles described in Patent Document 1 are obtained by coating the periphery of silicone rubber sphere fine particles with a polyorganosilsesquioxane resin, and the silicone fine particles have rubber elasticity,
  • the outer shell is made of a polyorganosilsesquioxane resin, so that it is not suitable as an optical material.
  • Patent Document 2 discloses that polymer particles in which a silicone compound represented by a specific formula or a partial hydrolysis condensate thereof is included in a polymer have a specific particle size distribution. The cited document 2 does not show in what form the obtained polymer particles include a silicone compound or a hydrolyzate thereof.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-177426
  • High low reflection transparent spherical particles are disclosed.
  • This particle forms a low-refractive index layer such as a fluorine-based polymer layer on the surface layer by two-stage polymerization by, for example, soap-free emulsion polymerization, and there is no description regarding the position of the core layer that forms this low-reflection transparent spherical particle
  • a low-refractive index layer such as a fluorine-based polymer layer
  • soap-free emulsion polymerization there is no description regarding the position of the core layer that forms this low-reflection transparent spherical particle
  • Patent Document 4 Japanese Patent Laid-Open No. 2007-091515 discloses a silica particle having a spherical or substantially spherical outer shell having a hollow structure and an inner shell that is in contact with the outer shell and forms a convex portion toward the center. The invention is disclosed.
  • a polymer is prepared by adding an acrylic monomer to a dispersion of colloidal silica to prepare a polymer, and then a polyalkoxysiloxane oligomer is added thereto to carry out a condensation reaction of the polyalkoxysiloxane oligomer.
  • a silica component derived from the polyalkoxysiloxane oligomer is locally attached to the surface to prepare composite polymer particles, which are baked at a temperature of about 500 ° C. to remove the polymer component.
  • the silica particles disclosed in Patent Document 4 are silica particles that are inorganic substances from which the polymer component has been removed by firing.
  • the object of the present invention is to provide a new composite resin particle group. Furthermore, the present invention provides an assembly of composite resin particles having a resin layer around the core material particles, and the core material particles present in each composite resin particle constituting the composite resin particle group are the composite resin particles. An object of the present invention is to provide a composite resin particle group containing a large number of unevenly distributed particles.
  • an object of the present invention is to provide a use of a composite resin particle group composed of composite resin particles in which core particles are unevenly distributed as described above, particularly a light diffusion sheet and a cosmetic.
  • a monomer component containing an acrylic monomer and / or a styrene monomer is copolymerized in the presence of silicone resin core particles having an average particle diameter in the range of 0.01 to 50 ⁇ m.
  • a composite resin particle group consisting of solid particles containing silicone resin core particles In the cross section of the composite resin particle cut so as to expose the substantially center of the silicone resin core material particle included in the composite resin particle constituting the composite resin particle group, It passes through the center of the cross section of the silicone resin core material particle, passes through the virtual straight line (A) having the longest distance between the intersections with the outer peripheral surface of the composite resin particle, and the center of the cross section of the silicone resin core material particle.
  • the center point (P) of the silicone resin core particle is from the center point (P) of the silicone resin core particle to the point where the virtual straight line (A) or (B) is in contact with the surface of the composite resin particle.
  • the shortest distance (R mini ) and the longest distance (R) from the center point (P) of the silicone resin core particle to the point where the virtual line (A) or (B) contacts the surface of the composite resin particle 50% by number or more of composite resin particles in a position having a relationship represented by the following formulas (1) and (2) with respect to max ).
  • Dsi represents the diameter of the silicone resin core particle in the cross section, and is usually in the range of 0.01 to 50 ⁇ m, preferably in the range of 0.5 to 10 ⁇ m. It is in.
  • the silicone resin core particle is a condensate of a silicone compound, but an alkoxide of titanium / zirconium may be blended in the silicone resin core particle.
  • the cosmetic of the present invention is characterized by being formed using the composite resin particle group as described above.
  • the light diffusion sheet of the present invention is characterized by being formed using the composite resin particle group as a reflective material.
  • the composite resin particles forming the composite resin particle group of the present invention have a shell layer obtained by seed polymerization of an acrylic resin or a styrene resin on a silicone particle core material, and the silicone resin core material forming the core layer includes The composite resin particles are not in the center and are unevenly distributed in either one of them.
  • the light reflection peak angle of each composite resin particle does not show a constant angle, but the reflection peel peels off due to the presence of a large number of particles. The variation in reflected light depending on the angle is reduced.
  • the silicone resin core particles contained in each particle constituting the particle group are not present at the center of the composite resin particle but are present unevenly. For this reason, when the individual particles are viewed, the reflection peaks of the light do not coincide with each other. Therefore, the reflection peaks vary depending on the viewing angle. However, when such a composite resin particle group is applied to form a layer, the reflection peaks that are scattered among the particles cancel each other, and the dispersion of the reflection peaks depending on the viewing angle disappears.
  • the cosmetic of the present invention has a dull and clean finish.
  • the light diffusion sheet of the present invention can obtain a light diffusion sheet with very high uniformity by using the above-described composite resin particles with high reflection uniformity.
  • FIG. 1 is a perspective view having a notch portion showing an example of composite resin particles forming the composite resin particle group of the present invention.
  • 2 is a cross-sectional view taken along the line XX in FIG. 3 is a cross-sectional view taken along the line YY in FIG.
  • FIG. 4 is a cross-sectional view showing the center position of the silicone resin core material particles in the composite resin particles constituting the composite resin particle group of the present invention.
  • FIG. 5 is a cross-sectional view showing an example of composite resin particles having a relatively high sphericity.
  • FIG. 6 is a cross-sectional view showing another example of composite resin particles having a relatively high sphericity.
  • FIG. 7 is a cross-sectional view showing an example of the composite resin of the present invention having a substantially elliptical cross section and a relatively low sphericity.
  • FIG. 8 is a cross-sectional view showing an example of the composite resin particle of the present invention having a low sphericity.
  • FIG. 9 is a cross-sectional view showing an example of composite resin particles having an irregular cross-section.
  • FIG. 10 is an SEM photograph of the composite resin particle group of Example 1.
  • FIG. 11 is an SEM photograph showing a cross section of the composite resin particle shown in FIG. 10 obtained in Example 1.
  • FIG. 12 is an SEM photograph of the composite resin particle group obtained in Example 2.
  • FIG. 13 is an SEM photograph showing a cross section of the composite resin particle shown in FIG. 12 obtained in Example 2.
  • FIG. 14 is an SEM photograph of the composite resin particle group obtained in Example 3.
  • FIG. 15 is an SEM photograph showing a cross section of the composite resin particle shown in FIG. 14 obtained in Example 3.
  • FIG. 16 is an SEM photograph of the composite resin particle group obtained in Example 4.
  • FIG. 17 is an SEM photograph showing a cross section of the composite resin particle shown in FIG. 16 obtained in Example 4.
  • FIG. 18 is an SEM photograph of the composite resin particle group obtained in Example 5.
  • FIG. 19 is an SEM photograph showing a cross section of the composite resin particle shown in FIG. 18 obtained in Example 5.
  • FIG. 20 is an SEM photograph of the composite resin particle group obtained in Example 6.
  • FIG. 21 is a SEM photograph showing a cross section of the composite resin particle shown in FIG. 20 obtained in Example 6.
  • FIG. 22 is an SEM photograph of the composite resin particle group obtained in Example 7.
  • FIG. 23 is a SEM photograph showing a cross section of the composite resin particle shown in FIG. 22 obtained in Example 7.
  • FIG. 24 is a graph showing the rate of change in reflected light of the particle group obtained in Example 6.
  • FIG. 25 is a graph showing the rate of change in reflected light of the particle group obtained in Comparative Example 3.
  • FIG. 26 is a SEM photograph of the silicone resin core particles obtained in Production Example 3 used in Example 8.
  • FIG. 27 is a SEM photograph of the composite resin particle group produced in Example 8.
  • FIG. 28 is a graph showing the rate of change in reflected light of the particle group obtained in Example 8.
  • FIG. 1 is a perspective view having a cutout portion showing an example of composite resin particles forming the composite resin particle group of the present invention
  • FIG. 2 is a sectional view taken along line XX in FIG. 1, and FIG. FIG.
  • the individual composite resin particles 10 constituting the composite resin particle group of the present invention are composed of a silicone resin core particle 30 and an acrylic resin layer (shell layer) 20 formed on the outer periphery of the silicone resin core particle 30. Is formed.
  • the center P of the silicone resin core particle 30 that is the core material of the composite resin particle 10 and the center Q of the composite resin particle 10 do not coincide with each other. Is shifted to either one.
  • the silicone resin core particles 30 are shifted to the right. This state is clearly shown in FIG. 3 showing the YY cross section of FIG. 1, and the center point Q of the composite resin particle 10 and the center point P of the silicone resin core particle do not coincide with each other.
  • the center P of the silicone resin core particle 30 does not coincide with the Q of the composite resin particle 10.
  • the silicone resin core particle 30 is not displaced in the vertical direction, and in FIG. 2 showing the XX cross section in FIG. 1, the center point P of the silicone resin core particle 30 and the composite resin particle 10 It coincides with the center point Q.
  • Such a shift of the silicone resin core particle 30 in the composite resin particle 10 can be expressed as follows. In the cross section of the composite resin particle 10 cut so as to include at least a part of the silicone resin core particle 30, it passes through the center of the silicone resin core particle in this cross section, and the outer peripheral surface of the composite resin particle 10 in this cross section. And the virtual straight line (A) having the longest distance between the intersections with each other and the virtual straight line having the shortest distance between the intersections with the outer peripheral surface of the composite resin particles while passing through the center of the cross section of the silicone resin core particle 30 Virtualize (B).
  • the center point (P) of the silicone resin core particle is from the center point (P) of the silicone resin core particle to the point where the virtual straight line (A) or (B) is in contact with the surface of the composite resin particle.
  • the shortest distance is R mini and the longest distance from the center point (P) of the silicone resin core particle to the point where the virtual line (A) or (B) is in contact with the surface of the composite resin particle is R.
  • R mini and R max are at positions having a relationship represented by the following expressions (1) and (2).
  • Dsi represents the diameter of the silicone resin core particles in the cross section.
  • R mini and R max are equal to R mini and R max because there is no vertical displacement of the composite resin particle 10 of the silicone resin core particle 30, but as shown in FIG. Since the material particles 30 are displaced in the lateral direction of the composite resin particles 10, R mini and R max show different values.
  • the unevenly distributed particles in which the silicone resin core material particles 30 are ubiquitously present in the composite resin particles 10 as described above are at least 50 number /%, preferably 60 number /%. It is contained at a rate in the range of up to 100 pieces /%.
  • the silicone resin core material particles 30 are unevenly distributed in the composite resin particles 10 as described above, light incident on the individual particles is reflected in various directions depending on the uneven distribution state of the silicone resin core material particles 30. At first glance, it seems that the reflected light intensity becomes unstable due to the reflected light coming out in various directions, but the reflection peak is unexpectedly offset and the composite resin particle group of the present invention was applied. The light emitted from the layer is very stable with little fluctuation due to the viewing angle.
  • the virtual straight line (C) is temporarily mounted radially outward from the center point Q with Q being the center point of any composite resin particle constituting the composite resin particle group.
  • the center point P of the silicone resin core particles contained in the composite resin particles is present on the virtual straight line (C).
  • the center point Q of the composite resin particle which is the base point of the virtual line (C)
  • the length between the virtual line (C) and the outer peripheral surface of the composite resin particle is 100.
  • the center point P of the silicone resin core particles contained in the composite resin particles is preferably in the position of more than 0% and 99% or less, and more preferably in the range of 10 to 95%. It is particularly preferred.
  • the composite resin particles in which the silicone resin core particles are unevenly distributed as described above are 50 number /% or more of the entire composite resin particle group, and further 60 to 100 number. /% Is preferable.
  • the composite resin particles constituting the composite resin particle group of the present invention have an average particle diameter ( ⁇ cp) in the range of 0.02 to 100 ⁇ m, preferably in the range of 1 to 20 ⁇ m.
  • the average particle diameter ( ⁇ si) of the silicone resin core particles included in the composite resin particles is in the range of 0.01 to 50 ⁇ m, preferably in the range of 0.5 to 10 ⁇ m.
  • the average particle diameter of the silicone resin core particles usually used for seed polymerization can be applied. It is preferable to obtain the average particle diameter ( ⁇ cp) of the composite resin particles and the average particle diameter ( ⁇ si) of the silicone resin core particles from the SEM photograph of the cross section passing through the approximate center point Q of the composite resin particles.
  • the composite resin particle is not substantially spherical, that is, when the cross-sectional shape is not substantially circular, the diameter of a virtual circle that can be drawn based on the arc of the composite resin particle that can be visually recognized in the SEM photograph is obtained.
  • the center point P of the silicone resin core material particle does not coincide with the center point Q of the composite resin particle and is unevenly distributed, the center point Q of the composite resin particle And a certain distance between the center point P of the silicone resin core particles. In FIG. 4, this distance is indicated by x.
  • the average distance x between the center point Q of the composite resin particles and the center point P of the silicone resin core particles is usually in the range of 0.005 to 50 ⁇ m, preferably in the range of 0.1 to 20 ⁇ m. Is in.
  • the average distance x between the center point Q of the composite resin particles constituting the composite resin particle group and the center point P of the silicone resin core particles, and the average particle diameter ( ⁇ cp of the composite resin particles )) (X / ⁇ cp) is usually in the range of 0.01 to 0.5, preferably in the range of 0.1 to 0.4.
  • the ratio represented by (x / ⁇ cp) represents the degree of uneven distribution of the silicone resin core particles in the composite resin particle group, and as this value approaches 0, the silicone resin core material This means that the uneven distribution of particles is reduced.
  • the ratio represented by (x / ⁇ cp) is set to 0.1 to 0.00. By setting it within the range of 35, it is possible to extract extremely uniform reflected light.
  • the composite resin particle group of the present invention having a large number of composite resin particles in which the silicone resin core particles are unevenly distributed cancels reflected light appropriately, so that when a layer coated with such a composite resin particle group is visually observed Variation in reflected light due to angle does not occur.
  • grains which comprise the composite resin particle group of this invention are not necessarily a sphere.
  • the cross section is substantially elliptical as shown in FIG. 7, there are cases where the cross section is irregular as shown in FIGS. 8 and 9, but in these cases, the convex portions of these particles Assuming the sphere that contacts the most, the above definition is applied with the center point of the virtual sphere as the center point Q of the composite resin sphere.
  • the silicone resin core particles in the composite resin particles constituting such a composite resin particle group are usually covered with an acrylic resin and / or a styrene resin, but the composite resin forming the composite resin particle group
  • the resin particles may contain composite resin particles in which, for example, 10 to 80% by volume of the silicone resin core particles are exposed on the surface of the particles.
  • the composite resin particles constituting the composite resin particle group of the present invention do not particularly need to be a perfect sphere as described above, and the composite resin particle group of the present invention is usually 0.1 to It is desirable to contain composite resin particles having a sphericity in the range of 1.00 in an amount of 50% by number or more.
  • FIGS. 5 and 6 show examples of composite resin particles having a relatively high sphericity.
  • FIGS. 7 substantially oval in cross section
  • FIGS. 8 and 9 show the composite of the present invention having a low sphericity.
  • the shape of the composite resin particle which forms the composite resin particle group of this invention is not limited by these.
  • the fluctuation rate of the reflection intensity is a numerical value represented by an average value of reflectance at a light receiving angle of 0 ° / reflectance at a light receiving angle of ⁇ 35 °, and the closer this value is to 1, 0,
  • the individual particles forming the particle group vary depending on the angle of the reflection peak because the position of the silicone resin core particle serving as the core material is different.
  • the composite resin particle group of the present invention which is an aggregate of particles, variations due to the angle of the reflection peak as seen in individual particles cancel each other, and a layer having a very uniform reflection peak regardless of the angle is formed. Can be formed.
  • the composite resin particle group of the present invention is copolymerized with, for example, a silicone resin core material particle as a seed particle and a monomer component containing an acrylic monomer and / or a styrene monomer as a shell layer so that the seed particles are unevenly distributed. Can be manufactured.
  • the silicone resin core particles used in the present invention can be obtained by a known method using a silicon-containing compound such as a silane compound and a silane coupling agent.
  • a silicon-containing compound such as a silane compound and a silane coupling agent.
  • the silane compound include those represented by the general formula (1) in Patent Document 2 (Japanese Patent Laid-Open No. 2002-138119).
  • R 1 O 4-a SiR 2 a
  • R 1 is the same or different, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms
  • R 2 is The same or different alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms or aralkyl group having 7 to 10 carbon atoms, a is an integer of 0 to 2) and / or a silicon compound thereof
  • Specific examples of the partial hydrolysis condensate include tetramethyl silicate, methyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane.
  • silane coupling agent for example, the general formula (2) X 3-n (CH 3 ) n Si (R 3 ) n Y (2) Wherein R 3 is a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms, X is an alkoxy group or a halogen atom, Y is an amino group, a vinyl group, (meth) acrylic.
  • n is an integer of 0 or 1)
  • Specific examples include 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, 3-methacrylate.
  • silicon-containing compounds include reactive silicone (trade name: Silaplane) manufactured by Chisso Corporation.
  • the above silicon-containing compounds can be used alone or in combination of two or more compounds, but preferably a silane compound and a silane coupling agent are used in combination.
  • the silicone resin core particles may contain an alkoxide such as titanium alkoxide or zirconium alkoxide. These contents are usually 1 to 30 parts by weight with respect to 100 parts by weight of the silicone resin core particles.
  • the silicone resin core particle is a particle made of a hydrolyzate of a silicone compound reacted by a hydrolysis reaction.
  • this reaction At least a part of the ionic double bond is present in the silicone resin core particle in a state where the activity is not lost.
  • the silicone resin core particles in the present invention have a very high affinity with acrylic monomers or styrene monomers that form a shell layer. ing.
  • the slurry thus obtained is passed through, for example, a 200-mesh wire net to remove a lump, and then the reaction solution is separated by filtration under reduced pressure to obtain a silicone resin core particle cake. Silicone resin core particles can be obtained by heating and drying this cake to remove moisture and crush it.
  • the average particle diameter is in the range of 0.01 to 50 ⁇ m, preferably in the range of 0.5 to 20 ⁇ m.
  • the CV value is usually in the range of 1 to 100, preferably 1 to 10.
  • the silicone resin core particles obtained as described above as seed particles, seed polymerization is performed to form a transparent resin layer (shell layer) containing acrylic resin and / or styrene resin on the outer periphery of the silicone resin core particles.
  • the transparent resin layer may be formed by one-stage polymerization, or the transparent resin layer may be formed by multi-stage polymerization such as two-stage polymerization.
  • the transparent resin layer formed on the outer periphery of the silicone resin core particle is formed of an acrylic resin, a styrene resin, or a transparent resin containing a copolymer resin thereof.
  • acrylic resins used here methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid Isobutyl, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl ester having a hydrocarbon group having 1 to 20 carbon atoms which may have a branched or unsaturated bond such as
  • styrene resin used in the present invention examples include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, iso-propyl styrene, iso -Propyl styrene, iso-propyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-hexyl styrene, p-methoxy styrene, pn-nonyl styrene, pn-decyl styrene, 3,4- Examples thereof include a styrene
  • acrylic resin and styrene derivative can be used alone or in combination.
  • other polymerizable monomers can be blended.
  • Examples of such other monomers include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persamic acid, vinyl laurate, vinyl stearate, benzoic acid.
  • Vinyl esters such as vinyl acid, pt-butyl vinyl benzoate and vinyl salicylate; Vinylidene chloride, vinyl chlorohexanecarboxylate, etc .: Unsaturated carboxylic acids such as tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid; And maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride and the like. These can be used appropriately within a range not impairing the identification of the composite resin particle group of the present invention. Furthermore, these monomers can be used alone or in combination.
  • a polyfunctional monomer in order to form a crosslinked structure in the shell layer, a polyfunctional monomer can be used.
  • polyfunctional monomers include divinylbenzene, ethylene glycol di (meth) acrylate, diethyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene Di (meth) acrylates of alkylene glycols such as di (meth) acrylates of glycols, di (meth) acrylates of tripropylene glycolose; Examples thereof include polyvalent (meth) acrylates such as trimethylolpropane tri (meth) acrylate. These can be used alone or in combination.
  • the polyfunctional monomer may be used at any stage. However, in order to increase the uneven distribution of the silicone resin core particles, the polyfunctional monomer is used in the first stage. However, it is desirable to use a polyfunctional monomer at a later stage, preferably the last stage.
  • the above-mentioned silicone-based resin core particles are dispersed in an aqueous medium, and the above monomer is added to this dispersion to perform seed polymerization using the silicone-based resin core particles as seed particles.
  • the monomer added to the aqueous medium in which the silicone resin core particles are dispersed is incorporated into the silicone resin particles and polymerized, and the diameter of the silicone resin core particles is 1 of the original particle diameter. .1-10 times.
  • the core particles are thus formed of a silicone-based resin, it is extremely rare for the monomer to be uniformly incorporated into the silicone resin core particles, and the monomer concentration in the silicone resin core particles is uniform.
  • the uneven distribution of such a monomer is not centered in the composite resin particle of the present invention, and the center of the silicone resin core particle is not centered. It is considered that this is not the same as the center of the particles constituting the composite resin particle group to be obtained, and becomes a cause of uneven distribution of the core material particles.
  • the center of the silicone resin core material particles, which are seed particles, and the center of the individual particles constituting the composite resin particle group are not matched, and the silicone resin core material particles are unevenly distributed in the individual particles. Therefore, after the silicone resin core particles as seed particles are uniformly dispersed in an aqueous medium, preferably water, the above monomer components, and if necessary, a dispersant and a surfactant are blended while stirring, The monomer component is dispersed in the medium. After uniformly dispersing the silicone resin core particles and the monomer components as seed particles in the aqueous medium, the monomer component adsorbed on the silicone resin core particles is polymerized by adding a polymerization initiator and heating. Thus, the composite resin particle group of the present invention is obtained.
  • the monomer component is adsorbed in the same manner as described above, and the monomer component is polymerized, whereby the particle diameter of the composite resin particles can be increased.
  • the monomer component is 20 to 5000 parts by weight, preferably 200 to 3000 parts by weight based on 100 parts by weight of seed particles (silicone resin core particles or composite resin particles), and the aqueous medium is seed particles (silicone resin core material). Particles or composite resin particles) and the monomer component in a total amount of 100 parts by weight, 100 to 900 parts by weight, preferably 150 to 300 parts by weight. .1 to 10 parts by weight, preferably 0.2 to 3 parts by weight.
  • polymerization initiator As the polymerization initiator used here, it is desirable to use a polymerization initiator having a 10-hour half-life temperature of usually 40 to 95 ° C., preferably 60 to 85 ° C.
  • examples of such polymerization initiator include: Cumene hydroperoxide (CHP), ditertiary butyl peroxide, dicumyl peroxide, benzoyl peroxide (BPO), lauryl peroxide (LPO), tertiary butyl (2-ethylhexanoyl) peroxide, dimethyl bis (tertiary) Butylperoxy) hexane, dimethylbis (tertiarybutylperoxy) hexyne-3, bis (tertiarybutylperoxyisopropyl) benzene, bis (tertiarybutylperoxy) trimethylcyclohexane, butyl-bis (tertiarybutylperoxy) ) Valerato, Gibe
  • the reaction temperature at this time varies depending on the type of polymerization initiator used, but is usually 50 to 80 ° C., preferably 60 to 75 ° C. Under these conditions, it is usually 2 to 10 hours, preferably 3 to By reacting for 6 hours, the composite resin particle group of the present invention is obtained. This reaction can be carried out in a single stage or in multiple stages.
  • the monomer component infiltrates into the silicone resin core particles that are seed particles in a non-uniform manner and the polymerization reaction proceeds, so that the center of the silicone resin core particles exists at the center of the composite resin particles.
  • the center point of the silicone resin core particle and the center point of each composite resin particle do not coincide with each other, and the refraction property of each particle is not uniform and is individual.
  • the refractive properties of the individual particles cancel each other, and when viewed as a whole of the composite resin particle group, very uniform reflected light can be obtained.
  • the variation rate of reflection intensity measured under the condition of 100 is usually in the range of 0.8 to 1.00 Of these, it is preferably in the range of 0.9 to 1.00, and reflected light with very high uniformity can be obtained.
  • the composite particles of the present invention having an average particle diameter of 5 ⁇ m, in which the core particles are unevenly distributed, obtained by seed polymerization of styrene and methyl methacrylate on the silicone resin core particles are coated with a base material (trade name: The intensity of reflected light measured by applying to the surface of Bioskin # 30 (manufactured by Beaulux Co., Ltd.) and measuring a projection angle of 45 °, a measurement range of ⁇ 85 ° to + 85 °, and a measurement interval of 1 ° is shown.
  • the phenomenon that the reflection intensity becomes uniform as described above by using the composite resin particle group of the present invention cannot be predicted from the reflection intensity of the individual particles constituting the composite resin particle group. This is an effect that is exhibited only for the particle group.
  • the composite resin particle group of the present invention as described above has a characteristic that it can reflect a very uniform reflected light when it is layered as described above.
  • the composite resin particle group of the present invention as described above can be used as a cosmetic raw material. That is, the cosmetic of the present invention is a foundation using the above-mentioned composite resin particle group, or a cosmetic such as a liquid foundation, blusher, or mascara in which the composite resin particle group of the present invention is dispersed in a liquid.
  • the component normally used when manufacturing cosmetics can be used.
  • the cosmetic obtained in this way has high uniformity of light reflection, it has no dullness and has a clean finish.
  • the composite resin particle group of the present invention may be used together with other raw material components that are usually used when manufacturing the cosmetic. it can.
  • a light diffusion sheet with very high uniformity can be produced. That is, by forming the composite resin particle group layer in which the composite resin particle group is disposed on the substrate, the reflection of light in the composite resin particle group layer is made uniform, and the light can be diffused uniformly.
  • a light diffusion layer may be formed using the composite resin particle group of the present invention described in detail above.
  • the slurry was passed through a 200-mesh wire mesh and then filtered under reduced pressure using a filter paper with a Buchner funnel to obtain a cake of silicone resin core particles.
  • the obtained silicone resin core material particles were observed with a scanning electron microscope (SEM), the particle shape was a true sphere, and the average particle size ( ⁇ si) was a monodisperse particle with 2.70 ⁇ m.
  • Production Example 2 In Production Example 1, the same conditions as in Production Example 1 were used, except that 28 parts by weight of methyltrimethoxysilane (KBM-13) and 2 parts by weight of 3-methacryloxypropyltrimethoxysilane (KBM-503) were used. A cake of silicone resin core particles was obtained.
  • KBM-13 methyltrimethoxysilane
  • KBM-503 3-methacryloxypropyltrimethoxysilane
  • Example 1 75 parts by weight of methyl methacrylate, 5 parts by weight of ethylene glycol dimethacrylate, 0.67 parts by weight of benzoyl peroxide, 0.5 parts by weight of sodium dodecylbenzenesulfonate, 0.1 parts by weight of sodium nitrite, and 200 parts by weight of ion-exchanged water was stirred at 10000 rpm for 3 minutes using a homomixer (Special Machine Industries Co., Ltd., model: TK homomixer III, the same applies hereinafter).
  • a homomixer Specific Machine Industries Co., Ltd., model: TK homomixer III, the same applies hereinafter.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas inlet tube, and 20 parts by weight of the silicone resin core particles prepared in Production Example 1 and 40 parts by weight of ion-exchanged water were added. The mixture was added and reacted at 75 ° C. for 1 hour, followed by reaction at 90 ° C. for 2 hours.
  • the aqueous dispersion obtained was filtered under reduced pressure using a filter paper with a Buchner funnel to give resin particle cake, and the obtained cake was dried using a hot air dryer set at 105 ° C. to obtain a composite resin particle group (I) was obtained.
  • FIG. 1 SEM photograph of the obtained composite resin particle group (I) is shown in FIG.
  • a microtome is used so that the cross section of the silicone resin core particles that are impregnated with epoxy resin and become the core material of the composite resin particles is exposed. A cross section was cut out. This sectional view is shown in FIG.
  • the diameter (Dsi) of the silicone resin particles is 2.54 ⁇ m
  • the shortest is the point through the center point (P) of the silicone resin particles to the surface of the composite resin particles.
  • a virtual straight line (B) is drawn, and the shortest (R mini ) from the center point (P) of the silicone resin particle in this cross section to the point where the virtual straight line (B) contacts the surface of the composite resin particle is 1. It was 69 ⁇ m.
  • the composite resin particles satisfy the following formulas (1) and (2).
  • the cross section was cut out and the position of the silicone resin core particles was measured as described above. As a result, at least the composite resin particle group (I) was measured. In 95% by number of the particles, the uneven distribution of the silicone resin core particles was observed.
  • Example 2 In Example 1, except that it was changed to 88.33 parts by weight of methyl methacrylate and 6.67 parts by weight of the silicone resin core particles prepared in Production Example 1, it was prepared under the same conditions as in Example 1, and the composite resin particle group ( II) was obtained.
  • FIG. 13 the SEM photograph of the obtained composite resin particle group (II) is shown in FIG.
  • the diameter (Dsi) of the silicone resin particles is 2.83 ⁇ m
  • the shortest is the point through the center point (P) of the silicone resin particles to the surface of the composite resin particles.
  • a virtual straight line (B) is drawn, and the shortest (R mini ) from the center point (P) of the silicone resin particle in this cross section to the point where the virtual straight line (B) contacts the surface of the composite resin particle is 1. It was 46 ⁇ m.
  • the composite resin particles satisfy the following formulas (1) and (2).
  • the cross section was cut out and the position of the silicone resin core particles was measured as described above. As a result, at least the composite resin particle group (I) was measured. In 98% by number of particles, uneven distribution of the silicone resin core particles was observed.
  • Example 3 First stage polymerization> Using the apparatus used in Example 1, 66.6 parts by weight of methyl methacrylate, 0.014 parts by weight of ethylene glycol dimethacrylate, 0.5 parts by weight of benzoyl peroxide, 0.5 parts by weight of sodium dodecylbenzenesulfonate, nitric acid 0.1 part by weight of sodium and 200 parts by weight of ion-exchanged water were stirred at 10,000 rpm for 3 minutes using a homomixer.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas inlet tube, and 33.3 parts by weight of the silicone resin particles prepared in Production Example 2 and 40 parts by weight of ion-exchanged water were added. And gently stirred at 50 ° C. for 30 minutes.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas inlet tube, and 19.2 parts by weight of the dispersion (III-1) of the composite resin particle group was added, The mixture was reacted at 75 ° C. for 1 hour and subsequently reacted at 90 ° C. for 2 hours to obtain a dispersion of composite resin particle group (III-2).
  • the aqueous dispersion thus obtained was filtered under reduced pressure using a filter paper with a Buchner funnel to obtain a resin particle cake.
  • the obtained cake was dried using a hot air dryer set at 105 ° C. to obtain a composite resin particle group ( III-2) was obtained.
  • FIG. 15 An SEM photograph of the obtained composite resin particle group (III-2) is shown in FIG. With respect to the composite resin particles constituting the composite resin particle group (III-2) thus obtained, the cross section was cut out so that the cross section of the silicone resin core material particles serving as the core material of the composite resin particles was exposed.
  • This sectional view is shown in FIG.
  • the diameter (Dsi) of the silicone resin particles is 2.76 ⁇ m
  • the shortest distance is from the center point (P) of the silicone resin particles to the point of contact with the surface of the composite resin particles.
  • the virtual straight line (B) is drawn, and the shortest (R mini ) from the center point (P) of the silicone resin particle in this cross section to the point where the virtual straight line (B) contacts the surface of the composite resin particle is 1. It was 50 ⁇ m.
  • the composite resin particles satisfy the following formulas (1) and (2).
  • the cross section of the composite resin particles constituting the composite resin particle group (III-2) was cut out and the position of the silicone resin core particles was measured as described above.
  • Example 4 First stage polymerization> Using the apparatus used in Example 1, 93.35 parts by weight of methyl methacrylate, 0.0185 parts by weight of ethylene glycol dimethacrylate, 1.0 part by weight of benzoyl peroxide, 0.5 parts by weight of sodium dodecylbenzenesulfonate, nitric acid 0.1 part by weight of sodium and 200 parts by weight of ion-exchanged water were stirred at 10,000 rpm for 3 minutes using a homomixer.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas inlet tube, and 6.65 parts by weight of the silicone resin particles prepared in Production Example 1 and 40 parts by weight of ion-exchanged water were added. And gently stirred at 50 ° C. for 30 minutes.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas inlet tube, and 76.2 parts by weight of the dispersion liquid (IV-1) of the composite resin particle group was added.
  • the mixture was reacted at 75 ° C. for 3 hours, and subsequently reacted at 90 ° C. for 3 hours to obtain a dispersion of composite resin particle group (IV-2).
  • the aqueous dispersion thus obtained was filtered under reduced pressure using a filter paper with a Buchner funnel to obtain a resin particle cake.
  • the obtained cake was dried using a hot air dryer set at 105 ° C. to obtain a composite resin particle group ( IV-2) was obtained.
  • FIG. 17 An SEM photograph of the obtained composite resin particle group (IV-2) is shown in FIG. With respect to the composite resin particles constituting the composite resin particle group (IV-2) thus obtained, the cross section was cut out so that the cross section of the silicone resin core material particles serving as the core material of the composite resin particles was exposed.
  • This sectional view is shown in FIG.
  • the diameter (Dsi) of the silicone resin particles is 2.25 ⁇ m
  • the shortest distance is from the center point (P) of the silicone resin particles to the point of contact with the surface of the composite resin particles.
  • the virtual straight line (B) is drawn, and the shortest (R mini ) from the center point (P) of the silicone resin particle in this cross section to the point where the virtual straight line (B) contacts the surface of the composite resin particle is 1. It was 51 ⁇ m.
  • an imaginary straight line (A) that passes through the center of the cross section of the silicone resin core particle and has the longest distance between the intersection points with the outer peripheral surface of the composite resin particle is drawn, and the center of the silicone resin core particle in this cross section is drawn.
  • the longest distance (R max ) from the point (P) to the point where the virtual straight line (A) is in contact with the surface of the composite resin particles was 9.81 ⁇ m.
  • the composite resin particles satisfy the following formulas (1) and (2).
  • the cross section of the composite resin particles constituting the composite resin particle group (IV-2) was cut out and the positions of the silicone resin core particles were measured as described above.
  • Example 5 First stage polymerization> Using the apparatus used in Example 1, 66.7 parts by weight of methyl methacrylate, 0.0078 parts by weight of ethylene glycol dimethacrylate, 1.0 part by weight of benzoyl peroxide, 0.5 parts by weight of sodium dodecylbenzenesulfonate, nitric acid 0.1 part by weight of sodium and 200 parts by weight of ion-exchanged water were stirred at 10,000 rpm for 3 minutes using a homomixer.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas inlet tube, and 33.3 parts by weight of the silicone resin particles prepared in Production Example 1 and 40 parts by weight of ion-exchanged water were added. And gently stirred at 50 ° C. for 30 minutes.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas inlet tube, and 76.2 parts by weight of the dispersion liquid (V-1) of the composite resin particle group was added.
  • the mixture was reacted at 75 ° C. for 3 hours, and subsequently reacted at 90 ° C. for 3 hours to obtain a dispersion of composite resin particle group (V-2).
  • the aqueous dispersion thus obtained was filtered under reduced pressure using a filter paper with a Buchner funnel to obtain a resin particle cake.
  • the obtained cake was dried using a hot air dryer set at 105 ° C. to obtain a composite resin particle group ( V-2) was obtained.
  • FIG. 19 An SEM photograph of the obtained composite resin particle group (V-2) is shown in FIG. With respect to the composite resin particles constituting the composite resin particle group (V-2) thus obtained, the cross section was cut out so that the cross section of the silicone resin core material particles serving as the core material of the composite resin particles was exposed.
  • This sectional view is shown in FIG.
  • the diameter (Dsi) of the silicone resin particles is 2.45 ⁇ m
  • the shortest is the point through the center point (P) of the silicone resin particles to the surface of the composite resin particles.
  • the virtual straight line (B) is drawn, and the shortest (R mini ) from the center point (P) of the silicone resin particle in this cross section to the point where the virtual straight line (B) contacts the surface of the composite resin particle is 1. It was 23 ⁇ m.
  • an imaginary straight line (A) that passes through the center of the cross section of the silicone resin core particle and has the longest distance between the intersection points with the outer peripheral surface of the composite resin particle is drawn, and the center of the silicone resin core particle in this cross section is drawn.
  • the longest distance (R max ) from the point (P) to the point where the virtual straight line (A) is in contact with the surface of the composite resin particle was 3.92 ⁇ m.
  • the composite resin particles satisfy the following formulas (1) and (2).
  • Example 6 First stage polymerization> Using the apparatus used in Example 1, 93.3 parts by weight of methyl methacrylate, 0.02 part by weight of ethylene glycol dimethacrylate, 1.0 part by weight of benzoyl peroxide, 0.5 part by weight of sodium dodecylbenzenesulfonate, nitric acid 0.1 parts by weight of sodium and 200 parts by weight of ion-exchanged water were stirred at 10,000 rpm for 3 minutes using a homomixer.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas inlet tube, and 6.7 parts by weight of the silicone resin particles prepared in Production Example 1 and 40 parts by weight of ion-exchanged water were added. And gently stirred at 50 ° C. for 30 minutes.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas introduction tube, and 37.7 parts by weight of the dispersion liquid (VI-1) of the composite resin particle group was added.
  • the mixture was reacted at 75 ° C. for 3 hours and then reacted at 90 ° C. for 3 hours to obtain a dispersion of composite resin particle group (VI-2).
  • the aqueous dispersion thus obtained was filtered under reduced pressure using a filter paper with a Buchner funnel to obtain a resin particle cake.
  • the obtained cake was dried using a hot air dryer set at 105 ° C. to obtain a composite resin particle group ( VI-2) was obtained.
  • FIG. 1 An SEM photograph of the obtained composite resin particle group (VI-2) is shown in FIG. With respect to the composite resin particles constituting the composite resin particle group (VI-2) thus obtained, the cross section was cut out so that the cross section of the silicone resin core material particles serving as the core material of the composite resin particles was exposed. This sectional view is shown in FIG.
  • the diameter (Dsi) of the silicone resin particles is 2.50 ⁇ m, and the shortest distance is from the center point (P) of the silicone resin particles to the point of contact with the surface of the composite resin particles.
  • a virtual straight line (B) is drawn, and the shortest (R mini ) from the center point (P) of the silicone resin particle in this cross section to the point where the virtual straight line (B) contacts the surface of the composite resin particle is 2. It was 69 ⁇ m.
  • an imaginary straight line (A) that passes through the center of the cross section of the silicone resin core particle and has the longest distance between the intersection points with the outer peripheral surface of the composite resin particle is drawn, and the center of the silicone resin core particle in this cross section is drawn.
  • the longest distance (R max ) from the point (P) to the point where the virtual straight line (A) is in contact with the surface of the composite resin particle was 9.04 ⁇ m.
  • the composite resin particles satisfy the following formulas (1) and (2).
  • the cross section of the composite resin particles constituting the composite resin particle group (IV-2) was cut out and the positions of the silicone resin core particles were measured as described above.
  • Example 7 The change rate of the reflection intensity of the particle group obtained here is shown in FIG. Example 7 ⁇ First stage polymerization> Using the apparatus used in Example 1, 66.7 parts by weight of methyl methacrylate, 0.013 parts by weight of ethylene glycol dimethacrylate, 1.0 part by weight of benzoyl peroxide, 0.05 part by weight of sodium dodecylbenzenesulfonate, nitric acid 0.01 parts by weight of sodium and 200 parts by weight of ion-exchanged water were stirred at 10,000 rpm for 3 minutes using a homomixer.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas inlet tube, and 33.6 parts by weight of the silicone resin particles prepared in Production Example 1 and 40 parts by weight of ion-exchanged water were added. And gently stirred at 50 ° C. for 30 minutes.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas introduction tube, and 76.9 parts by weight of the dispersion (V-1) of the composite resin particle group was added.
  • the mixture was reacted at 75 ° C. for 3 hours, and subsequently reacted at 90 ° C. for 3 hours to obtain a dispersion of composite resin particle group (V-2).
  • the aqueous dispersion thus obtained was filtered under reduced pressure using a filter paper with a Buchner funnel to obtain a resin particle cake.
  • the obtained cake was dried using a hot air dryer set at 105 ° C. to obtain a composite resin particle group ( V-2) was obtained.
  • FIG. 23 An SEM photograph of the obtained composite resin particle group (V-2) is shown in FIG. With respect to the composite resin particles constituting the composite resin particle group (V-2) thus obtained, the cross section was cut out so that the cross section of the silicone resin core material particles serving as the core material of the composite resin particles was exposed.
  • This sectional view is shown in FIG.
  • the diameter (Dsi) of the silicone resin particles is 2.63 ⁇ m
  • the shortest is the point through the center point (P) of the silicone resin particles to the surface of the composite resin particles.
  • the virtual straight line (B) is drawn, and the shortest (R mini ) from the center point (P) of the silicone resin particle in this cross section to the point where the virtual straight line (B) contacts the surface of the composite resin particle is 1. It was 38 ⁇ m.
  • an imaginary straight line (A) that passes through the center of the cross section of the silicone resin core particle and has the longest distance between the intersection points with the outer peripheral surface of the composite resin particle is drawn, and the center of the silicone resin core particle in this cross section is drawn.
  • the longest distance (R max ) from the point (P) to the point where the virtual straight line (A) is in contact with the surface of the composite resin particles was 4.06 ⁇ m.
  • the composite resin particles satisfy the following formulas (1) and (2).
  • the cross section of the composite resin particles constituting the composite resin particle group (V-2) was cut out and the positions of the silicone resin core particles were measured as described above.
  • the composite resin particle group (V- In at least 95% by number of the particles of 2) uneven distribution of the silicone resin core particles was observed.
  • the sphericity was determined by the following method.
  • the composite resin particle group is photographed using an electron microscope, and the obtained image is measured for circularity using image analysis software (Mitani Corporation, WinROOF). About 50 measurement values are averaged, and this is defined as sphericity.
  • the circularity is calculated by the following formula.
  • Circularity 4 ⁇ ⁇ area / (perimeter length ⁇ perimeter length)
  • Example 8 40 parts by weight of MMA, 10 parts by weight of EGDMA, 1 part by weight of benzoyl peroxide, 0.3 part by weight of sodium lauryl sulfate, 300 parts by weight of ion-exchanged water, and 0.1 part by weight of sodium nitrite are mixed at 10000 rpm with a homomixer. Stir for minutes.
  • this mixture was transferred to a 1-liter four-necked flask equipped with a thermometer and a nitrogen gas inlet tube, and 50 parts by weight of the polyorganosiloxane particles prepared in Production Example 3 were added, followed by stirring at 40 ° C. for 30 minutes. .
  • the obtained cake was dried using a hot air dryer set at 105 ° C. to obtain core-shell particles.
  • the shortest distance (R mini ) from the point of contact with the composite particle through the center point P of the silicone resin particle to the point of contact with the composite particle is 1.
  • An imaginary straight line A having the longest distance between the intersections with the outer surface of the silicone core particle is drawn, and the imaginary straight line (A) is drawn from the center point (P) of the silicone resin core particle in this cross section.
  • the longest distance (R max ) to the contact point on the surface of the composite resin particle was 2.68 ⁇ m.
  • Table 1 shows the characteristics of the obtained composite particle group.
  • the SEM photograph of the silicone resin core particles used in Example 8 is shown in FIG. 26, the SEM particle group of the composite resin particle group is shown in FIG. 27, and the reflected light of the particle group obtained in Example 8 is shown in FIG. Indicates the rate of change.
  • Comparative Examples 1 to 3 As comparative examples, commercially available silicone particles (Comparative Example 1, manufactured by Momentive Performance Materials Japan, trade name: Tospearl 145A, average particle size ( ⁇ si) 4.5 ⁇ m), crosslinked polymethyl methacrylate particles (Comparative Example 2) , Manufactured by Soken Chemical Co., Ltd., trade name: MX-500, average particle diameter 5.0 ⁇ m), styrene particles (Comparative Example 3, manufactured by Soken Chemical Co., Ltd., trade name: SX-500H, average particle diameter 5. Table 1 shows the rate of change in the reflection intensity of these particles.
  • the change rate of the reflection intensity of the particle group obtained in Comparative Example 3 is shown in FIG. [Comparative Example 4]
  • the mixed particles were adjusted by mixing at a ratio of 6.7 parts by weight of the particles of Comparative Example 1, 13.3 parts by weight of the particles of Comparative Example 2, and 80 parts by weight of the particles of Comparative Example 3, and the change in reflection intensity of the mixed particles The rates are shown in Table 1.
  • the core material particles are composed of silicone resin particles, and in the composite resin particles constituting the composite resin particles of the present invention, the silicone resin particles as the core material particles are the center of the composite resin particles. It is ubiquitously present. That is, despite the seed polymerization using resin core particles, the center point of the silicone resin core particles, which are seed particles, matches the center point of the composite resin particles obtained as a result of seed polymerization.
  • the silicone resin core particles are present in a biased direction in any direction in the composite resin particles, and the composite resin particles occupy more than half, preferably the majority.
  • the unified reflection direction is not shown, but the composite of the present invention containing a large number of these composite resin particles.
  • the resin particle group when the reflection direction of the light is viewed, the reflected light cooperates to obtain reflected light with very high uniformity.
  • the reflection characteristics of each particle become obvious, and the reflection characteristics that each particle does not have deteriorated.
  • the reflected light does not weaken and uniform reflected light can be obtained over all wavelengths.

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Abstract

L'invention concerne des particules de résine composites qui renferment une particule cœur de résine de silicone, qui sont obtenues par copolymérisation de composants monomères comprenant un monomère acrylique ou similaire en présence de particules cœur de résine de silicone dont le diamètre moyen de particules est compris entre 0,01 et 50 μm.  Une couche comprenant ces particules de résine composites réfléchit uniformément une lumière incidente.
PCT/JP2009/057491 2008-04-14 2009-04-14 Particules de résine composites et leur utilisation WO2009128441A1 (fr)

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KR1020107022645A KR101204963B1 (ko) 2008-04-14 2009-04-14 복합 수지 입자군 및 그 용도
JP2010508213A JP5706687B2 (ja) 2008-04-14 2009-04-14 複合樹脂粒子群およびその用途
CN2009801136487A CN102007154B (zh) 2008-04-14 2009-04-14 复合树脂颗粒团及其用途

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JP2011081123A (ja) * 2009-10-06 2011-04-21 Nippon Shokubai Co Ltd コアシェル型粒子、光拡散剤、および光拡散媒体
JP2012211222A (ja) * 2011-03-30 2012-11-01 Aica Kogyo Co Ltd 複合微粒子
JP2012220714A (ja) * 2011-04-08 2012-11-12 Canon Inc 屈折率分布構造体とその製造方法、屈折率分布構造体を備えた画像表示装置
US9562993B2 (en) 2011-04-08 2017-02-07 Canon Kabushiki Kaisha Refractive index distribution structure and manufacturing method of the same, and image display apparatus having the refractive index distribution structure
US9527969B2 (en) 2011-06-30 2016-12-27 Sekisui Plastics Co., Ltd. Non-spherical resin particles, manufacturing method thereof, and use thereof
US9980885B2 (en) 2013-11-01 2018-05-29 Nissin Chemical Industry Co. Ltd. Silicone-based copolymer resin powder, making method, and cosmetics
JP2015110738A (ja) * 2013-11-01 2015-06-18 日信化学工業株式会社 シリコーン系共重合樹脂粉体、その製造方法及び化粧料
US10066123B2 (en) 2013-12-09 2018-09-04 3M Innovative Properties Company Curable silsesquioxane polymers, compositions, articles, and methods
US9725561B2 (en) 2014-06-20 2017-08-08 3M Innovative Properties Company Curable polymers comprising silsesquioxane polymer core and silsesquioxane polymer outer layer and methods
US10370564B2 (en) 2014-06-20 2019-08-06 3M Innovative Properties Company Adhesive compositions comprising a silsesquioxane polymer crosslinker, articles and methods
US10392538B2 (en) 2014-06-20 2019-08-27 3M Innovative Properties Company Adhesive compositions comprising a silsesquioxane polymer crosslinker, articles and methods
US9957416B2 (en) 2014-09-22 2018-05-01 3M Innovative Properties Company Curable end-capped silsesquioxane polymer comprising reactive groups
US9957358B2 (en) 2014-09-22 2018-05-01 3M Innovative Properties Company Curable polymers comprising silsesquioxane polymer core silsesquioxane polymer outer layer, and reactive groups
JP2017197684A (ja) * 2016-04-28 2017-11-02 株式会社日本触媒 架橋アクリル系有機微粒子

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KR101204963B1 (ko) 2012-11-26
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JPWO2009128441A1 (ja) 2011-08-04
KR20100134021A (ko) 2010-12-22

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