Elastomer composite particles, method for producing same, and method for producing elastomer spherical particles

Abstract

Provided are: elastomer composite particles containing elastomer spherical particles having, as a constituent unit, a (co) polymer having high degradation characteristics by external stimulation such as light; elastomer spherical particles; and a method for producing elastomer composite particles. The elastomer composite particles have polyorganosilsesquioxane or silica on the surface of spherical elastomer particles, which are cross-linked particles of a copolymer having a polyester structure and a polyether structure and having a volume average particle diameter of 0.5-200 m.

Description

Technical Field

[0001] This invention relates to an elastomer composite particle, a method for manufacturing the same, and a method for manufacturing spherical elastomer particles. Background Technology

[0002] In the past, rubber, as a raw material used in rubber products, can be exemplified as follows:

[0003] [1] Polymers whose repeating units consist only of conjugated diene units, such as butadiene rubber, isoprene rubber, chloroprene rubber, and natural rubber.

[0004] [2] Polymers with conjugated diene units and aromatic vinyl units as essential repeating units, represented by styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, and styrene-isoprene-butadiene copolymer rubber.

[0005] [3] Polymers with repetitive units consisting of conjugated diene units and α,β-unsaturated nitrile units, represented by acrylonitrile-butadiene copolymer rubber,

[0006] [4] Polymers with acrylic units as essential repeating units, represented by acrylic rubber,

[0007] [5] The repeating unit includes ethylene, α-olefins with 3 to 12 carbon atoms, and polymers such as ethylene-propylene rubber, which are non-conjugated polyenes used as needed.

[0008] [6] Polymers such as silicone rubber, which contain dimethylsiloxane units as repeating units, are widely used.

[0009] These raw rubber materials are used to obtain spherical elastomers (rubber), especially spherical elastomers (rubber) containing an organic framework, which are used primarily for electronic materials applications, including electronic devices, to improve various properties such as impact resistance, thermal shock resistance, and adhesion.

[0010] On the other hand, silicone rubber spherical particles and powders have previously been proposed for use in a wide range of industrial fields.

[0011] For example, it has been disclosed that it can be added to synthetic resin materials (Patent Documents 1 and 2), synthetic rubber materials (Patent Document 3), cosmetics (Patent Documents 4 to 7), etc.

[0012] Organosilicon rubber spherical particles are used, for example, as a low-stress agent for organic resins such as epoxy resins, taking advantage of their "softness". That is, due to the difference in the thermal expansion coefficients of electronic components and organic resins such as epoxy resins, cracks and fractures may sometimes occur due to stress applied to the resin. Therefore, by adding organosilicon rubber spherical particles, the occurrence of such cracks and fractures can be prevented.

[0013] Specifically, epoxy resins containing spherical particles of polymer cured with linear organopolysiloxane blocks (Patent Document 8) and epoxy resins containing spherical particles whose surfaces are coated with polyorganosilsesquioxanes (Patent Document 9) have been proposed.

[0014] In addition, a method for preparing organosilicon-containing rubber spherical particles by copolymerizing (meth)acrylate and a diorganopolysiloxane having an organic group containing a free radical polymerizable functional group at one end in an emulsion system is disclosed (Patent Document 10).

[0015] It should be noted that the organic rubber spherical particles were used for the purpose of imparting sliding properties to the thermoplastic resin.

[0016] Furthermore, organic cross-linked rubber spherical particles formed by cross-linking a liquid composition consisting of an organic compound with aliphatic saturated bonds and a silicon-containing organic compound with hydrogen atoms bonded to silicon atoms through a hydrosilylation reaction (Patent Document 11) have been proposed to have excellent dispersibility and processability for various resins, coatings and rubber components.

[0017] In addition, silicone rubber spherical particles are used in a wide range of cosmetics and cosmetic materials, such as foundation and foundation cream, cream and lotion, and sunscreen, to give cosmetics a soft and silky feel, to create a natural light-scattering effect, and to make pores and wrinkles less visible.

[0018] For example, cosmetics containing polymethylsilsesquioxane particles and powders have been proposed (Patent Document 12), color cosmetics having spherical silicone rubber particles and powders (Patent Document 13), and cosmetics containing silicone composite particles and powders containing polymethylsilsesquioxane resin coated onto silicone rubber spherical particles (Patent Document 14). These silicone rubber spherical particles, or composite particles formed by coating polymethylsilsesquioxane resin onto silicone rubber spherical particles, as described above, can also impart a soft touch and silky smoothness to the cosmetics.

[0019] Existing technical documents

[0020] Patent documents

[0021] Patent Document 1: Japanese Patent Publication No. 63-12489

[0022] Patent Document 2: Japanese Patent Publication No. 6-55805

[0023] Patent Document 3: Japanese Patent Application Publication No. 2-102263

[0024] Patent Document 4: Japanese Patent Application Publication No. 8-12546

[0025] Patent Document 5: Japanese Patent Application Publication No. 8-12545

[0026] Patent Document 6: Japanese Patent Publication No. 4-17162

[0027] Patent Document 7: Japanese Patent Publication No. 4-66446

[0028] Patent Document 8: Japanese Patent Application Publication No. 58-219218

[0029] Patent Document 9: Japanese Patent Application Publication No. 8-85753

[0030] Patent Document 10: Japanese Patent Application Publication No. 10-182987

[0031] Patent Document 11: Japanese Patent Application Publication No. 2001-40214

[0032] Patent Document 12: Japanese Patent Application Publication No. 63-297313

[0033] Patent Document 13: Japanese Patent Application Publication No. 8-12524

[0034] Patent Document 14: Japanese Patent Application Publication No. 9-20631 Summary of the Invention

[0035] The problem the invention aims to solve

[0036] However, these silicone rubber spherical particles, which are incorporated into various resins or cosmetics, cannot be degraded when released into natural environments such as soil, inland waterways, or seawater and oceans. This is because their particle structure lacks a degradable framework or units, and they are predicted to remain in the environment. Furthermore, due to the extremely small particle size, recycling is very difficult, and the current situation of them flowing into the ocean is currently unavoidable.

[0037] In addition, plastics flowing into the ocean and microplastics that have degraded and been miniaturized to the millimeter to micrometer scale have the ability to adsorb harmful substances and pathogens in the environment. These microplastics are often ingested by marine life, raising concerns that they may have adverse effects on the ecosystem. Therefore, there is a growing trend to restrict these microplastics.

[0038] For this reason, there is a need for silicone spherical particles or elastomer spherical particles that degrade in the environment after use and do not remain as particles (solids). To degrade these elastomer spherical particles in the environment, it is necessary to degrade and break the cross-linked structure that forms the particles. However, in the case of silicone rubber spherical particles, their structure is not degradable.

[0039] In view of the above-mentioned problems, the purpose of the present invention is to provide an elastomer composite particle, wherein the elastomer composite particle comprises spherical elastomer particles that are highly degradable (copolymer) polymers as structural units in natural environments including soil, inland water systems, oceans, and seawater, and are subjected to external stimuli such as light, heat, acid, alkali, and the action of microorganisms and fungi.

[0040] In addition, the present invention aims to provide a method for manufacturing elastomeric spherical particles and elastomeric composite particles that use highly degradable (copolymer) polymers as constituent units.

[0041] Methods for solving problems

[0042] In order to achieve the above-mentioned objectives, the inventors have repeatedly conducted in-depth research and found that an elastomeric composite particle, which uses elastomeric spherical particles, which are crosslinked particles of copolymers with specific polyester and polyether structures, as core particles, can solve the above-mentioned problems, thus completing the present invention.

[0043] Therefore, the present invention provides a method for manufacturing the following elastomeric composite particles, elastomeric spherical particles, and elastomeric composite particles.

[0044] [1] An elastomer composite particle, wherein the surface of the elastomer spherical particle, which is a crosslinked particle of a copolymer having a polyester structure and a polyether structure, has a volume average particle size of 0.5 to 200 µm, has a polyorganosilsesquioxane or silica.

[0045] [2]. According to the elastomeric composite particles described in [1], wherein the copolymer is a polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule.

[0046] [3]. The elastomeric composite particles according to [2], wherein the copolymer is a polyester-polyether copolymer represented by the following general formula (1) or general formula (2).

[0047] [Chemical Formula 1]

[0048]

[0049] (In general formula (1), R) 1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2 Each of the following general formulas (3a), (3b) or (3c) represents an organic group containing a free radical polymerizable functional group, where k is a number that is 1 ≤ k ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and n is a number that is 1 ≤ n ≤ 100.

[0050] In general formula (2), R 3 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 4 Each of the following general formulas (4a) and (4b) independently represents an organic group containing a free radical polymerizable functional group, where p is a number that is 1 ≤ p ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and q is a number that is 1 ≤ q ≤ 100.

[0051] [Chemical Formula 2]

[0052]

[0053] (In general formulas (3a), (3b), (3c), (4a), and (4b), R) 5 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 8 carbon atoms, R 6 Each can be independently represented by a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

[0054] [4]. The elastomeric composite particles according to [2], wherein the copolymer is a polyester-polyether copolymer represented by the following general formula (5).

[0055] [Chemical Formula 3]

[0056]

[0057] (In general formula (5), R) 1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2 Each of the following can be represented independently as an organic group containing a free radical polymerizable functional group, represented by general formula (3a), general formula (3b), or general formula (3c), where l is a number 1 ≤ l ≤ 1000, m is a number 1 ≤ m ≤ 1000, and r is a number 1 ≤ r ≤ 100.

[0058] [Chemical Formula 4]

[0059]

[0060] (In general formulas (3a), (3b) and (3c), R) 5 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 8 carbon atoms, R 6 Each can be independently represented by a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

[0061] [5]. A method for manufacturing spherical elastomeric particles, wherein the following steps i) to iii) are included.

[0062] i) The process of preparing a suspension composition by stirring and suspending the following components (A), (B), (C), and (D).

[0063] (A) A copolymer having polymerizable groups and possessing both polyester and polyether structures.

[0064] (B) is the aqueous or oil phase component in which component (A) is insoluble or sparingly soluble.

[0065] (C) Suspension agent,

[0066] (D) Polymerization initiator,

[0067] ii) A process of obtaining a dispersion of elastomeric spherical particles by free radical polymerization of component (A) in the suspension composition obtained by step i).

[0068] iii) A process of obtaining elastomeric spherical particles by washing and drying (B) as a continuous phase from the dispersion of elastomeric spherical particles obtained by step ii).

[0069] [6]. A method for manufacturing elastomeric composite particles according to any one of [1] to [4], wherein the following step iv) is included.

[0070] iv) A step in which component (I) is added to a liquid phase containing components (E), (F), (G), and (H), and component (I) is subjected to hydrolysis and polymerization reactions, wherein,

[0071] (E) Elastomer spherical particles manufactured by the method described in [5], having a volume average particle size of 0.5 to 200 µm, comprising crosslinked particles from copolymers having polyester and polyether structures.

[0072] (F) Alkaline substances,

[0073] (G) Selected from one or more cationic surfactants and cationic water-soluble polymers.

[0074] (H) water,

[0075] (I) Trialkoxysilane or tetraalkoxysilane.

[0076] The effects of the invention

[0077] The elastomeric composite particles of the present invention possess degradable polyester structures within their unit backbones. In the presence of moisture, the cross-linking structure of the particles is broken, thus exhibiting degradability. In particular, particles with poly-ε-caprolactone structures as the polyester structure within the particles, providing a microbial recognition backbone, are expected to exhibit both environmental and biodegradability in both elastomeric spherical particles and elastomeric composite particles.

[0078] Therefore, the elastomeric composite particles of the present invention are (bio)degradable particles and can be expected to be used as materials that reduce environmental burden.

[0079] Furthermore, the elastomeric composite particles of the present invention, being particles with low cohesion and high dispersibility, are expected to improve the stress relaxation effect when combined with various resins. Additionally, in cosmetic applications, by incorporating the elastomeric composite particles of the present invention, it is expected to improve the user experience, such as a soft touch and silky smoothness, as well as imparting a spreading effect.

[0080] The elastomeric composite particles of the present invention can also form hydrophilic particles by adjusting the amount of silica microparticles coated (attached) on the surface, and can also be incorporated into water-based cosmetics without the use of emulsifiers or other dispersants. Attached Figure Description

[0081] [ Figure 1 [Electron microscope image of the elastomeric spherical particles obtained in manufacturing example 1.]

[0082] [ Figure 2 [Image of an electron microscope photograph of the elastomeric spherical particles obtained in manufacturing example 3.]

[0083] [ Figure 3 [Electron microscope image (magnification × 1000) of the elastomeric composite particles (silica-coated elastomeric spherical particles) obtained in Example 3.]

[0084] [ Figure 4 [Electron microscope image (magnification × 7500) of the elastomeric composite particles (silica-coated elastomeric spherical particles) obtained in Example 3.] Detailed Implementation

[0085] The present invention will now be described in detail.

[0086] [Elastomer Composite Particles]

[0087] The elastomeric composite particles of the present invention are elastomeric composite particles having polyorganosilsesquioxane or silica on the surface of elastomeric spherical particles that are crosslinked particles of copolymers having polyester and polyether structures, preferably elastomeric composite particles having polyorganosilsesquioxane or silica with spherical microparticles attached to the particle surface of the elastomeric spherical particles.

[0088] The shape of the elastomeric composite particles of the present invention is preferably spherical. "Spherical" in this invention does not simply mean that the particle shape is round, but also includes the value of the average aspect ratio (length of the longest axis / length of the shortest axis), which is typically in the range of 1 to 4, preferably in the range of 1 to 2, more preferably in the range of 1.0 to 1.6, and even more preferably a deformed ellipsoid in the range of 1.0 to 1.4. As shown in the manufacturing method described later, when crosslinking copolymers having polyester and polyether structures by suspending and dispersing them using a suspending agent, the obtained particles are spherical. The shape of the elastomeric composite particles can be confirmed by observation using, for example, an optical microscope or an electron microscope, where the aspect ratio is calculated as the average value of the lengths of the longest and shortest axes of 50 particles arbitrarily measured from the microscope images.

[0089] In this invention, the volume average particle size of the elastomeric composite particles is in the range of 0.5 to 200 μm, more preferably in the range of 1.0 to 50 μm. When the volume average particle size of the elastomeric composite particles is larger than the upper limit mentioned above, the smoothness and silkiness of the particles may decrease, resulting in a rough feel and reduced light diffusion properties. Furthermore, when the volume average particle size of the elastomeric composite particles is smaller than the lower limit mentioned above, the particle fluidity decreases and cohesion increases, thus failing to adequately impart silkiness and light diffusion properties, which is not preferable.

[0090] The volume average particle size of the elastomeric composite particles of the present invention is expressed as a value measured by the following measurement method. Before measuring the volume average particle size, the particle size of 50 particles is randomly measured from a microscopic photograph of the elastomeric composite particles, and it is determined whether the average value is 1 µm or more or less than 1 µm. A dispersion in which the elastomeric composite particles are redispersed in water is prepared using various surfactants. If the previously determined value is 1 µm or more, the volume average particle size is expressed as a value measured by the resistance method; if the determined value is less than 1 µm, the volume average particle size is expressed as a value measured by the laser diffraction / scattering method.

[0091] The rubber (elastomer) used as a component of the elastomer composite particles is preferably a non-sticky and non-greasy rubber. The hardness of the rubber (elastomer) used as a component of the elastomer composite particles, when measured using a Type A hardness tester as specified in JIS K6253, is preferably in the range of 5 to 90, more preferably in the range of 10 to 80. Furthermore, when measured using a Type C ASKER rubber hardness tester as specified in the Japan Rubber Industry Association Standards (SRIS), the hardness of the rubber (elastomer) used as a component of the elastomer composite particles is preferably in the range of 5 to 90, more preferably in the range of 20 to 85, and even more preferably in the range of 40 to 85.

[0092] If the measured rubber hardness value is below 5, the particle cohesion may increase and the dispersibility may decrease. Furthermore, if the rubber hardness value is above 90, it may reduce the soft feel and is therefore not preferred.

[0093] - Elastomer spherical particles that are crosslinked particles of copolymers having polyester and polyether structures

[0094] The elastomeric spherical particles in the elastomeric composite particles of the present invention are more preferably particles composed of a polymer of polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule, that is, as crosslinked particles of polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule.

[0095] It should be noted that the aspect ratio of the elastomeric spherical particles in the elastomeric composite particles of the present invention is also defined in the same way as described above. The average value of the aspect ratio (length of the longest axis / length of the shortest axis) of the elastomeric spherical particles is typically in the range of 1 to 4, preferably in the range of 1 to 2, more preferably in the range of 1.0 to 1.6, and even more preferably in the range of 1.0 to 1.4.

[0096] Furthermore, the volume average particle size of the elastomeric spherical particles in the elastomeric composite particles of the present invention is also defined in the same manner as described above, wherein the volume average particle size of the elastomeric spherical particles is in the range of 0.5 to 200 μm, more preferably in the range of 1.0 to 50 μm.

[0097] A polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule, preferably a copolymer represented by the following general formula (1) or general formula (2).

[0098] [Chemical Formula 5]

[0099]

[0100] (In general formula (1), R)1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2 Each of the following general formulas (3a), (3b) or (3c) represents an organic group containing a free radical polymerizable functional group, where k is a number that is 1 ≤ k ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and n is a number that is 1 ≤ n ≤ 100.

[0101] In general formula (2), R 3 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 4 Each of the following general formulas (4a) and (4b) independently represents an organic group containing a free radical polymerizable functional group, where p is a number that is 1 ≤ p ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and q is a number that is 1 ≤ q ≤ 100.

[0102] [Chemical Formula 6]

[0103]

[0104] (In general formulas (3a), (3b), (3c), (4a), and (4b), R) 5 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 8 carbon atoms, R 6 Each can be independently represented by a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

[0105] As R 1 Examples of such alkylene compounds include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene, with methylene, ethylene, trimethylene, and tetramethylene being preferred.

[0106] As R 3 Examples of such alkylene compounds include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene, with methylene, ethylene, trimethylene, and tetramethylene being preferred.

[0107] R 2 R represents an organic group containing a free radical polymerizable functional group, represented by general formula (3a), general formula (3b) or general formula (3c). 4 It represents an organic group containing a free radical polymerizable functional group, represented by general formula (4a) or general formula (4b).

[0108] In general formulas (3b), (3c), (4a), and (4b), as R 5Examples of such compounds include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, and other alkylene compounds; preferably methylene, ethylene, trimethylene, or tetramethylene.

[0109] In general formulas (3a), (3b), (3c), (4a), and (4b), as R 6 Examples of such examples include hydrogen, alkyl groups with 1 to 3 carbon atoms such as methyl, ethyl, and propyl, with hydrogen or methyl atoms being preferred.

[0110] Organic groups containing free radical polymerizable functional groups, represented by these general formulas (3a), (3b), (3c), (4a), and (4b), are residues derived from polymerizable monomers. Specifically, examples of polymerizable monomers include (meth)acrylates containing hydroxyl groups, (meth)acrylates containing isocyanate groups, and (meth)acryloyl chloride.

[0111] Examples of hydroxyl-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and other hydroxyalkyl (meth)acrylates with 2 to 8 carbon atoms; and carboxylated (meth)acrylates such as carboxyethyl (meth)acrylate, methacryloyloxyethyl succinate, and methacryloyloxyethyl phthalate.

[0112] Examples of (meth)acrylates containing isocyanate groups include, for example, ethyl isocyanate (meth)acrylate, propyl isocyanate (meth)acrylate, butyl isocyanate (meth)acrylate, and hexyl isocyanate (meth)acrylate.

[0113] Examples of (meth)acryloyl chloride include, for example, acryloyl chloride, methacryloyl chloride, acryloyl bromide, methacryloyl bromide, etc.

[0114] The polyester structure (unit) of a polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule is preferably an aliphatic polyester with degradation ability or improved degradation ability.

[0115] Examples of aliphatic polyesters include poly-ε-caprolactone, poly-β-propiolactone, γ-butyrolactone, polylactic acid, polyhydroxybutyrate, polyglycolic acid, polyethylene adipate, polyhydroxybutyric acid, polybutylene succinate, and polybutylene succinate. In particular, from the viewpoint of degradability and ease of handling, a poly-ε-caprolactone structure is preferred.

[0116] In general formula (1), k is independently a number that is 1≤k≤10, preferably a number that is 1≤k≤6.

[0117] In general formula (2), p can be a number that is 1≤p≤10, preferably a number that is 1≤p≤6.

[0118] In general formula (1), n ​​can be a number that is 1≤n≤100, preferably a number that is 1≤n≤50, and even more preferably a number that is 2≤n≤20.

[0119] In general formula (2), q can be a number that is 1≤q≤100, preferably a number that is 1≤q≤50, and even more preferably a number that is 2≤q≤20.

[0120] When n and q are greater than the above upper limits, the crystallinity increases due to the intramolecular / intermolecular interactions of the polymer generated by the ester structure (unit). If the flowability of the copolymer is too low, it may affect the processability in the preparation process of the suspension composition described later.

[0121] In general formulas (1) and (2), l is a number that is 1≤l≤1000, preferably a number that is 2≤l≤100.

[0122] In general formulas (1) and (2), m is a number that is 1 ≤ m ≤ 1000, preferably a number that is 10 ≤ m ≤ 500.

[0123] When the value of l is greater than the aforementioned upper limit, the crystallinity of the polymer, generated by the intramolecular / intermolecular interactions of the polymer produced from the ethylene oxide (EO) structural units, may increase, potentially reducing the flowability of the copolymer. In this case, as described above, it may affect the processability in the preparation process of the suspension composition described later, and is therefore not preferred.

[0124] A polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule is preferably a copolymer represented by the following general formula (5) or general formula (6) from the viewpoint of raw material handling and ease of manufacturing.

[0125] [Chemical Formula 7]

[0126]

[0127] (In general formula (5), R) 1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2 Each of the following can be represented independently as an organic group containing a free radical polymerizable functional group, represented by general formula (3a), (3b), or (3c), where l is a number 1 ≤ l ≤ 1000, m is a number 1 ≤ m ≤ 1000, and r is a number 1 ≤ r ≤ 100.

[0128] (In general formula (6), R) 3 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 4 Each of the above represents an organic group containing a free radical polymerizable functional group, represented by general formula (4a) or general formula (4b), where l is a number 1 ≤ l ≤ 1000, m is a number 1 ≤ m ≤ 1000, and s is a number 1 ≤ s ≤ 100.

[0129] [Manufacturing method of polyester-polyether copolymer]

[0130] As a method for manufacturing the polyester-polyether copolymer constituting the elastomeric composite particles of the present invention, examples include, for instance, using various polyethers containing active hydrogen, such as hydroxyl-containing polyethers, carboxyl-modified polyethers, and amino-modified polyethers, as starting materials, and obtaining poly-ε-caprolactone-modified polyethers and poly-γ-butyrolactone-modified polyethers by ring-opening polymerization of cyclic-ε-caprolactone, γ-butyrolactone, etc., and then introducing polymerizable monomers having unsaturated groups capable of free radical polymerization through ester bonds, ether bonds, urethane bonds, amide bonds, etc.

[0131] It should be noted that, from the perspective of reactivity during manufacturing, the terminal structure of various polyethers is preferably a structure in which reactive functional groups are bonded to primary carbon atoms.

[0132] Examples of reaction conditions in the above manufacturing method include the following, but the method is not limited to these reaction conditions.

[0133] For example, 3.0 to 4.0 equivalents (functional group equivalent ratio) of cyclic ε-caprolactone are added to 1.0 equivalents of polyether or carboxyl-modified polyether containing active hydrogen, and the reaction is carried out at 120°C for 4 to 6 hours in the presence of a known ring-opening polymerization catalyst to obtain poly-ε-caprolactone modified polyether.

[0134] Next, for example, 1.0 to 1.25 mol (functional group equivalent ratio) of (meth)acryloyl chloride or (meth)acrylate containing isocyanate groups, such as isocyanate ethyl ester of (meth)acrylate, is added to the hydroxyl groups of 1.0 mol of the obtained poly-ε-caprolactone modified polyether, and a reaction catalyst is added as needed, and the reaction is carried out at 40 to 100 °C for more than 4 hours.

[0135] After the reaction, the crude product is rapidly cooled with alcohol or the like, and byproducts are removed by filtration, washing with water and / or adsorption treatment. Finally, the solvent is removed by distillation, thereby obtaining acrylic acid-modified poly-ε-caprolactone polyether (polyester-polyether copolymer).

[0136] When a polyether having hydroxyl groups is used as the starting material, examples of polyester-polyether copolymers can be cited, for example, those represented in general formulas (7a) and (7b) (only the one-sided structure is described due to the symmetrical structure).

[0137] [Chemical Formula 8]

[0138]

[0139] In general formulas (7a) and (7b), R 5 R is a divalent hydrocarbon group with 1 to 8 carbon atoms. 6 It consists of hydrogen atoms or hydrocarbon groups with 1 to 3 carbon atoms.

[0140] l, m, and r are 1≤l≤1000, 1≤m≤1000, and 1≤r≤30, respectively, and preferably 2≤l≤100, 10≤m≤500, and 2≤r≤10, respectively.

[0141] When carboxyl-modified polyether is used as the starting material, examples of polyester-polyether copolymers can be cited, for example, those represented in general formulas (8a) and (8b) (only single-end copolymers are described due to their symmetrical structure).

[0142] [Chemical Formula 9]

[0143]

[0144] In general formulas (8a) and (8b), R 5 R is a divalent hydrocarbon group with 1 to 8 carbon atoms. 6 It consists of hydrogen atoms or hydrocarbon groups with 1 to 3 carbon atoms.

[0145] In addition, l, m, s and t are 1≤l≤1000, 1≤m≤1000, 1≤s≤30 and 0≤t≤10 respectively, and preferably 2≤l≤100, 10≤m≤500, 2≤s≤10 and 1≤t≤10 respectively.

[0146] As a catalyst for the ring-opening polymerization of cyclic ε-caprolactone, conventionally known catalysts can be used, but are not limited thereto.

[0147] Specifically, examples include organotitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetran-propoxytitanium, and tetran-butoxytitanium; organotin compounds such as di-n-butyltin dilaurate, diisobutyltin oxide, and dibutyltin diacetate; acetates of magnesium, calcium, zinc, etc.; antimony oxide; stannous halides; and perchloric acid.

[0148] The amount of the above-mentioned ring-opening polymerization catalyst added, relative to the ε-caprolactone monomer (cyclic ε-caprolactone), can be in the range of 1 to 10,000 ppm, preferably in the range of 10 to 1,000 ppm.

[0149] As a method for introducing polymerizable monomers with unsaturated groups capable of free radical polymerization into poly-ε-caprolactone-modified polyethers, the reaction matrix (reactive functional group) of the polymerizable monomer and various catalysts corresponding to the formation of the framework can be used. Conventionally known catalysts can be used as catalysts.

[0150] Examples of esterification catalysts for the esterification reaction in which the reaction of polymerizable monomers with poly-ε-caprolactone-modified polyether is an esterification reaction include Lewis acid catalysts such as alkoxides of titanium, zirconium, tin, aluminum, and zinc; carboxylates of titanium, zirconium, tin, aluminum, and zinc; chelates of titanium, zirconium, tin, aluminum, and zinc; and boron trifluoride and boron trifluoride ethers; acid catalysts such as hydrochloric acid, sulfuric acid, hydrogen bromide, acetic acid, trifluoroacetic acid, methanesulfonic acid, and p-toluenesulfonic acid; and amine catalysts such as pentamethyldiethylenetriamine (PMDETA), 1,4,7-trimethyl-1,4,7-triazacyclononane (TACN), triethylamine (TEA), 4-(N,N-dimethylamino)pyridine (DMAP), 1,4-diazabicyclo(2,2,2)octane (DABCO), and tetramethylethylenediamine (TMEDA). Among these, amine catalysts are preferred from the viewpoint of the stability and economy of the product obtained by the esterification reaction.

[0151] It should be noted that, when using amine-based catalysts, dehydrating condensing agents can also be added to improve reaction efficiency. Commonly known dehydrating condensing agents include, for example, 1,1'-carbonyldiimidazole (CDI), N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC), 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC·HCl), and 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU), but are not limited to these.

[0152] Examples of catalysts for carbamate reactions in which the reaction of polymeric monomers with poly-ε-caprolactone-modified polyethers is a carbamate reaction include, for example, amines such as triethylamine, triethylenediamine, pentamethylenediethylenetriamine, N,N-dimethylethanolamine, 1,4-diazabicyclo(2,2,2)octane (DABCO), pyridine, and N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA); and amines such as dibutyltin dilaurate, diisobutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate (DBTL), and dioctyl dinedecyltin oxide. Organotin compounds such as dineodecanoate; organotitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetran-propoxytitanium, tetrabutoxytitanium, tetraoctyloxytitanium, acetylacetone titanium, tetraacetylacetone titanium, dodecylbenzenesulfonate titanium compounds, phosphate titanium complexes, triethanolamine titanium, diisopropoxybis(acetoethyl acetoethyl) titanium, etc.; organozirconium compounds such as n-propylzirconate, n-butylzirconate, tetraacetylacetone zirconium, dibutoxybis(acetoethyl acetoethyl) zirconium, zirconium octanoate compounds, etc.; organoiron compounds such as tri(2,4-pentanedione)iron(III), etc.

[0153] The amount of catalyst added when introducing these polymerizable monomers with unsaturated groups capable of free radical polymerization can be in the range of 1 to 10,000 ppm, preferably in the range of 10 to 1,000 ppm, relative to the polymerizable monomer.

[0154] In order to inhibit the polymerization of (meth)acrylate groups during the above reaction, polymerization inhibitors and antioxidants can be used.

[0155] Examples of polymerization inhibitors or antioxidants include, but are not limited to, hydroquinone, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, 2,4-dimethyl-6-tert-butylphenol, p-benzoquinone, dibutylhydroxytoluene, 2,5-dihydroxy-p-benzoquinone, p-methoxyphenol, etc.

[0156] As a method for manufacturing polyester-polyether copolymers, when carboxyl-modified polyether is used as the starting material, an example is a method of manufacturing by esterifying the above-mentioned carboxyl-modified polyether with poly-ε-caprolactone-modified (meth)acrylate represented by the following formula (9).

[0157] Commercially available products of poly-ε-caprolactone-modified (meth)acrylates include, for example, PLACEL FA2D, PLACEL FA10L, PLACEL FN2D, and PLACEL FM4 (manufactured by Daicel Corporation).

[0158] [Chemical Formula 10]

[0159]

[0160] In general formula (9), R 7 It is a monovalent hydrocarbon group with 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. v is 1 ≤ v ≤ 50, preferably 1 ≤ v ≤ 30.

[0161] Examples of manufacturing methods for the aforementioned polyester-polyether copolymers include, but are not limited to, the methods shown below.

[0162] Relative to 1.0 mole of carboxyl group in the carboxyl-modified polyether, 1.0 to 1.25 moles (functional group equivalent ratio) of poly-ε-caprolactone-modified (meth)acrylate (formula (9)) are added and mixed, and further 0.1 to 5.0 moles of esterification catalyst are added and mixed, and the mixture is stirred at 15 to 150 °C for 10 to 30 minutes. Optionally, 1.0 to 1.25 moles of dehydrating condensing agent are added, and the mixture is reacted at 15 to 150 °C for 4 to 20 hours.

[0163] After the reaction, byproducts are removed by filtering, washing and / or adsorption of the crude product, and finally the solvent is removed by distillation, thereby obtaining an acrylic-modified polyester (poly-ε-caprolactone)-polyether copolymer.

[0164] The obtained polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule is preferably in liquid form, and its weight-average molecular weight (M) is determined by gel permeation chromatography (GPC). W The value of .) is preferably in the range of 100 to 100,000, more preferably in the range of 500 to 50,000.

[0165] If the weight-average molecular weight is less than the lower limit mentioned above, the crosslinking density of the elastomer in the obtained elastomer spherical particles / composite particles may become higher, and the degradation performance may become worse, which is not preferred; if the weight-average molecular weight is greater than the upper limit mentioned above, the viscosity of the copolymer may increase, and the preparation of elastomer spherical particles may become more difficult.

[0166] In the filtration process, hydrophobic organic solvents can also be used for dilution to adjust the viscosity of the crude reaction product.

[0167] There are no particular limitations on the hydrophobic organic solvent used, but from the viewpoint of solubility and affinity for polyester-polyether copolymers, toluene, hexane, ethyl acetate, etc. are preferred.

[0168] The adsorption treatment process is a process performed to remove hydrochloric acid salts that cannot be completely removed by water washing, and to dehydrate, decolorize, and deodorize.

[0169] As for the adsorbent material used, any conventionally known adsorbent material is acceptable, and multiple adsorbent materials can be used in combination. Preferred adsorbent materials include, for example, desiccants such as magnesium sulfate and sodium sulfate; activated carbon; silica gel; and the KYOWAAD series (manufactured by Kyowa Chemical Industry Co., Ltd., Japan).

[0170] Using the copolymer having a polyester structure and a polyether structure manufactured by the above method, for example by a method having steps i) to iii) described later, elastomeric spherical particles can be manufactured.

[0171] -[Polyorganosilsesquioxane]

[0172] In this invention, the polyorganosilsesquioxane present on the surface of the elastomeric spherical particles is in the form of R... 7 SiO 3 / 2 The units represented are cross-linked into a three-dimensional network of resinous solids.

[0173] R in the above formula 7 It is a monovalent hydrocarbon group with 1 to 20 carbon atoms, either unsubstituted or substituted. As R 7 Examples of such groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl; alkenyl groups such as vinyl and allyl; aromatic groups such as phenyl, tolyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; and hydrocarbon groups formed by replacing some or all of the hydrogen atoms bonded to the carbon atoms of these groups with halogen atoms (fluorine, chlorine, bromine, iodine), and / or substituents such as amino, acryloyloxy, methacryloyloxy, epoxy, glycidyloxy, hydrogen sulfide, and carboxyl.

[0174] According to the manufacturing method of the present invention described later, in order to allow the polyorganosilsesquioxane to adhere to the surface of the elastomeric spherical particles, the above-mentioned R is preferred. 7 More than 50 mol% of which are methyl, vinyl or phenyl, preferably R 7 More than 80 mol% of the substance is methyl, vinyl, or phenyl, with the above-mentioned R being more preferred. 7 More than 90 mol% of it is methyl, vinyl or phenyl.

[0175] Without compromising the non-cohesive, dispersible, or other properties of the obtained elastomer composite particles, and within the limits of usability or soft touch such as a smooth, silky feel, polyorganosilsesquioxanes, except for R... 7 SiO 3 / 2 In addition to the unit, it may also include R 7 2SiO 2 / 2 Unit, R7 3SiO 1 / 2 unit and SiO 4 / 2 At least one of the units.

[0176] In such polyorganosilsesquioxanes, R 7 SiO 3 / 2 The content of the unit is preferably 70-100 mol% of all siloxane units, more preferably 80-100 mol%.

[0177] -Silica

[0178] In this invention, the silicon dioxide on the surface of the elastomeric spherical particles is made of R 8 SiO 4 / 2 The units represented are cross-linked into a three-dimensional network of inorganic solids.

[0179] R in the above formula 8 It is a monovalent hydrocarbon group with 1 to 6 carbon atoms, either unsubstituted or substituted. As R 8 Examples of such compounds include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0180] Silica is obtained through the hydrolysis and condensation reaction of tetraalkoxysilane and is mainly composed of SiO2 units.

[0181] In addition, silicon dioxide is not only composed of SiO2 units; it may also contain alkoxy groups derived from tetraalkoxysilanes used as raw materials, and silanol groups that have not undergone condensation reactions.

[0182] In this invention, the polyorganosilsesquioxane or silicon dioxide is preferably spherical in shape.

[0183] The particle sizes of the polyorganosilsesquioxane and silica are preferably 10-500 nm, more preferably 20-200 nm.

[0184] When the particle size of the polyorganosilsesquioxane and silica is less than 10 nm, the light scattering property of the resulting elastomer composite particles may be reduced. Conversely, when the particle size of the polyorganosilsesquioxane and silica is greater than 500 nm, the resulting elastomer composite particles may lack a soft tactile feel and exhibit reduced light scattering property.

[0185] Polyorganosilsesquioxane or silica can be attached to a portion of the surface of the elastomeric spherical particles, or it can be attached in a manner that covers the entire surface of the particles, i.e., it can also cover the entire surface of the particles, but it is preferred that it be covered substantially without gaps on the entire surface of the elastomeric spherical particles.

[0186] It should be noted that by observing the particle surface of the obtained elastomer composite particles using an electron microscope, the particle size, shape, and adhesion density of the polyorganosilsesquioxane and silica on the surface of the spherical elastomer particles can be confirmed. The particle size of the polyorganosilsesquioxane and silica refers to the value calculated by averaging the particle size of any 50 particles measured from electron microscope images of the particle surface of the separately obtained elastomer composite particles.

[0187] In the elastomeric composite particles of the present invention, the amount of polyorganosilsesquioxane or silica attached to the surface of the elastomeric spherical particles is preferably 0.5 to 200 parts by mass, more preferably 1.0 to 50 parts by mass, relative to 100 parts by mass of the elastomeric spherical particles.

[0188] When the amount of polyorganosilsesquioxane or silica is less than the lower limit mentioned above, the cohesiveness is high and the dispersibility is poor, which may lead to reduced light scattering or a lack of a soft feel. In addition, when the amount of polyorganosilsesquioxane or silica exceeds the upper limit mentioned above, the soft touch of the elastomer composite particles may be lacking.

[0189] [Manufacturing methods for elastomeric spherical particles and elastomeric composite particles]

[0190] The method for manufacturing the elastomeric spherical particles of the present invention comprises the following steps i) to iii).

[0191] i) The process of preparing a suspension composition by stirring and suspending the following components (A), (B), (C), and (D).

[0192] (A) A copolymer having polymerizable groups and possessing both polyester and polyether structures.

[0193] (B) The aqueous or oil phase components in which component (A) is insoluble or sparingly soluble.

[0194] (C) Suspension agent,

[0195] (D) Polymerization initiator.

[0196] ii) A process of free radical polymerization of component (A) in the suspension composition obtained by step i) to obtain a dispersion of elastomeric spherical particles.

[0197] iii) A process of obtaining elastomeric spherical particles by washing and drying the dispersion of elastomeric spherical particles obtained by step ii) to remove (B) as a continuous phase.

[0198] The elastomeric composite particles of the present invention can be manufactured, for example, by a method having the following step iv).

[0199] iv) A step of adding component (I) to a liquid phase containing components (E), (F), (G), and (H), and subjecting component (I) to a hydrolysis and polymerization reaction.

[0200] (E) The elastomeric spherical particles manufactured by processes i) to ii) or i) to iii) are copolymer crosslinked particles with a volume average particle size of 0.5 to 200 μm and having a polyester structure and a polyether structure.

[0201] (F) Alkaline substances,

[0202] (G) Selected from one or more cationic surfactants and cationic water-soluble polymers.

[0203] (H) water

[0204] (I) Trialkoxysilane or tetraalkoxysilane.

[0205] That is, the method for manufacturing the elastomeric composite particles of the present invention can be roughly divided into two stages: manufacturing elastomeric spherical particles (i) to (iii) and assembling the elastomeric spherical particles (iv). Each stage will be described below.

[0206] The aqueous dispersion of elastomer composite particles obtained in step iv) can be used directly as an aqueous dispersion depending on the application. Alternatively, it can be further processed by a dehydration process to remove water and a powdering process to produce elastomer composite particle powder for the desired application.

[0207] - Manufacturing process of elastomeric spherical particles

[0208] The elastomeric spherical particles constituting the elastomeric composite particles of the present invention are polymers (crosslinked particles) obtained by the free radical polymerization reaction of the above-mentioned polyester-polyether copolymer, and are elastomeric spherical particles manufactured by a manufacturing method having the following steps i) to iii).

[0209] Project i)

[0210] In step i), the following components (A), (B), (C) and (D) are stirred and suspended to prepare a suspension composition.

[0211] The components used in engineering i) are as follows.

[0212] (A) The component is a copolymer having polymerizable groups and having a polyester structure and a polyether structure, preferably a polyester-polyether copolymer having unsaturated groups that can be free radical polymerized.

[0213] The constituent units of the elastomer composite particles of the present invention are derived from the constituent units of copolymers having polyester and polyether structures, preferably polyester-polyether copolymers having at least two unsaturated groups capable of free radical polymerization in one molecule.

[0214] As a specific example of component (A), examples include, for example, polyester-polyether copolymers represented by the general formula (1) or general formula (2), and more preferably, polyester-polyether copolymers represented by the general formula (5) or general formula (6).

[0215] The content of component (A) in the suspension composition prepared in step i) is preferably 1.0 to 80 parts by mass relative to 100 parts by mass of the composition. Since production efficiency may decrease if the amount of component (A) is less than the lower limit, and poor suspension may sometimes occur if the amount of component (A) is greater than the upper limit, making it difficult to obtain a dispersion of elastomeric spherical particles, this is not preferred.

[0216] (B) is a component that forms a continuous phase in the suspension composition, and is an aqueous or oil phase component in which (A) is insoluble or sparingly soluble.

[0217] When component (B) is an aqueous phase, the water contained in the aqueous phase can be exemplified by, for example, distilled water, ion-exchanged water, pure water, ultrapure water, etc.

[0218] In the aqueous phase, additives may be optionally incorporated to the extent that their function as a continuous phase is not impaired. Examples of additives include, but are not limited to, preservatives, salts, pH adjusters, chelating agents, vitamins, amino acids, humectants, and antioxidants. Since component (A) is an insoluble or poorly soluble component, the water content in the aqueous phase is preferably 90-100% by mass.

[0219] When component (B) is an oil phase component, examples of oil phase components include silicone oil, hydrocarbon oil, higher fatty acids, ester oil, liquid fats, etc. They can be used alone or in combination of two or more appropriately, but are not limited thereto.

[0220] Examples of silicone oils include, for example, dimethylpolysiloxane, methylhydropolysiloxane, methylphenylpolysiloxane, octamethylsiloxane, decamethyltetrasiloxane, decamethylcyclopentasiloxane, hexamethylcyclotrisiloxane, and octamethylcyclotetrasiloxane.

[0221] Examples of hydrocarbon oils include, for example, liquid paraffin, α-olefin oligomers, isododecane, isohexadecane, squalane, crude ceresin, squalene, refined ceresin, alkanes, isoalkanes, paraffin, polyethylene wax, polyethylene-polypropylene wax, squalane, polyisobutylene, petrolatum, and microcrystalline wax.

[0222] Examples of high-grade fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, benzolic acid, undecenoic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, and 12-hydroxystearic acid.

[0223] Examples of ester oils include, for example, isopropyl myristate, hexadecyl octanoate, octyl dodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, tetradecyl myristate, decyl oleate, hexyl decyl dimethyl octanoate, hexadecyl lactate, tetradecyl lactate, lanolin acetate, isohexadecanyl stearate, isohexadecanyl isostearate, isononyl isononanoate, 12-hydroxystearate cholesterol ester, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl diol monoisostearate, neopentyl glycol didecanoate, diisostearate malate, glyceryl di-2-heptyl undecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, tetra-2- Pentaerythritol ethylhexanoate, tri-2-ethylhexanoate, trioctanoate, triisopalmitoate, trimethylolpropane triisostearate, hexadecyl 2-ethylhexanoate, 2-ethylhexyl palmitate, trimyristic acid glyceride, tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleic acid oleyl alcohol ester, acetylglycine ester, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate, etc.

[0224] Examples of liquid oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, almond oil, wheat germ oil, camellia oil, castor oil, flaxseed oil, safflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea seed oil, torreya nut oil, rice bran oil, tung oil, Japanese tung oil, jojoba oil, wheat germ oil, and triglycerides.

[0225] (B) The kinematic viscosity of component B at 25°C is preferably 100,000 mm³ / s. 2 / s or less, more preferably 10000mm2 / s or less. When the kinematic viscosity is greater than the above-mentioned upper limit, suspension in step (i) becomes difficult, and it is sometimes difficult to obtain suspension compositions and elastomeric spherical particles with narrow particle size distribution.

[0226] (C) Suspension agents for the components include, for example, water-soluble polymers such as conventionally known natural polymers, semi-synthetic polymers, and synthetic polymers, or polymers used as thickeners. It should be noted that they can be used alone or in combination of two or more appropriately.

[0227] Examples of natural macromolecular compounds include xanthan gum, cellulose, tamarind gum, tamarind gum, locust bean gum, gellan gum, HM pectin, carrageenan, guar gum, flaxseed gum, gum arabic, pullulan, agarose, agar gum, alginic acid, cannabidiol, succinoglycan, starch, dextrin, gelatin, and casein.

[0228] Examples of semi-synthetic polymers include methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, cationic xanthan gum, LM pectin (acid-treated / alkali-treated), cationic guar gum, alginate, soluble starch, and cellulose nanofibers.

[0229] Examples of synthetic polymers include polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymers, polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, polyacrylamide, polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol.

[0230] As component (C), from the viewpoint that the above-mentioned component (A) can be suspended in a small amount to obtain fine elastomeric spherical particles, xanthan gum, tamarind gum, carrageenan, guar gum, gum arabic, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, cationic xanthan gum, cationic guar gum, polyvinyl alcohol, and polyvinylpyrrolidone are preferred.

[0231] The amount of component (C) added relative to 100 parts by weight of the suspension composition is preferably 0.01 to 25 parts by weight, more preferably 0.05 to 15 parts by weight. If the amount added is less than the lower limit mentioned above, poor emulsification or failure to obtain fine elastomeric spherical particles may occur, which is not preferred. Furthermore, if the amount added is greater than the upper limit mentioned above, the viscosity of the composition increases significantly, and fine elastomeric spherical particles may not be obtained, leading to insufficient particle dispersion, which is also not preferred.

[0232] As the polymerization initiator for component (D), conventionally known free radical polymerization initiators can be used. In the presence of the polymerization initiator, free radicals can be generated by external stimuli such as heating, light irradiation, and UV irradiation, thereby enabling reaction and curing (crosslinking).

[0233] (D) Polymerization initiator, specifically, peroxide, azo initiator, photoinitiator or redox initiator combining oxidant and reductant can be used.

[0234] Examples of peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, 2,4-dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert-butyl peroxide, tert-butyl peroxide, and hydrogen peroxide.

[0235] Alternatively, it can be perchlorate such as potassium perchlorate or sodium perchlorate.

[0236] Examples of azo initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(methyl 2-methylpropionate), 2,2'-azobis(methyl isobutyrate), tert-butyl peroxy-2-ethylhexanoate, and 2,2-azobis(2-aminodipropane) dihydrochloride.

[0237] Examples of photoinitiators include, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one, methyl benzoylformate, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide.

[0238] In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether can also be used.

[0239] Examples of redox initiators include initiators that combine ferrous sulfate / sodium pyrophosphate / glucose / hydrogen peroxide and initiators that combine ferrous sulfate / disodium ethylenediaminetetraacetate / sodium formaldehyde sulfoxylate / hydrogen peroxide.

[0240] In addition, this redox initiator can also be used in combination with an azo initiator and a photoinitiator.

[0241] Considering the stability of the suspension composition during (free radical) polymerization and the ease of handling, peroxide, azo initiators, and photoinitiators used in heating or light irradiation methods are preferred as polymerization initiators.

[0242] The amount of polymerization initiator added is preferably in the range of 0.01 to 5.0 parts by mass relative to 100 parts by mass of component (A).

[0243] If the amount of polymerization initiator added is less than the lower limit mentioned above, poor curing (crosslinking) may occur. If the amount of polymerization initiator added is greater than the upper limit mentioned above, odors or leaching may occur due to the mixing (contamination) of reaction residues, etc., which is not preferred.

[0244] [Other additives]

[0245] In the method for manufacturing the elastomer composite particles of the present invention, in the preparation of the suspension composition in step i), in addition to the above-mentioned components (A), (B), (C) and (D), various additives may also be added as needed.

[0246] Examples of additives include, for example, thickeners, pH adjusters, preservatives, antioxidants, and polymerization inhibitors. They can be used individually or in appropriate combinations of two or more, and in appropriate amounts without impairing the effects of the invention.

[0247] There is no particular limitation on the order in which the components are added and mixed in step i). For example, components (A) and (D) can be mixed beforehand, and then components (B) and (C) can be added to the mixture of components (A) and (D) to prepare a suspension composition; or components (D) can be added after the suspension composition is prepared from components (A), (B) and (C).

[0248] Alternatively, after preparing a suspension composition from components (A), (B), (C), and (D), component (B) may be further added to dilute it to the desired concentration before submission to step ii).

[0249] In addition, when the polyester-polyether copolymer of component (A) with unsaturated groups that can be free radical polymerized has temperature dependence such as having a cloud point (by heating, the solubility of component (A) decreases rapidly and the phase separates as a boundary at a certain temperature), the preparation of the suspension composition in step i) can be carried out under temperature conditions corresponding to the temperature characteristics of component (A), for example, by stirring and suspending under heating conditions.

[0250] The temperature conditions for heating can be, for example, below 100°C, preferably in the range of 30 to 90°C, and more preferably in the range of 40 to 70°C. If the continuous phase is aqueous, and the heating temperature exceeds the above-mentioned upper limit, water may evaporate or violently boil, which is not preferred.

[0251] When preparing the suspension composition in step i), conventionally known emulsifying dispersers can be used. Examples of common emulsifying dispersers include, for example, high-speed rotary shear mixers such as HOMO MIXER, high-speed centrifugal radial mixers such as HOMO DISPER, combined emulsifying mixers that combine a homogenizer and a homogenizer, mixing-emulsifying mixers (vacuum homogenizers (Agi-Homo Mixer)) that combine a homogenizer or a homogenizer and an anchor mixer, high-pressure jet emulsifying dispersers such as homogenizers, colloid mills, ultrasonic emulsifiers, and paddle mixers.

[0252] Process (ii)

[0253] Step (ii) is a process in which component (A) in the suspension composition prepared in step (i) is reacted and solidified (crosslinked) by (free radical) polymerization to obtain a dispersion of elastomeric spherical particles.

[0254] In step ii), the conditions of the polymerization reaction can be appropriately determined according to the type of polymerization initiator (D).

[0255] Examples of methods include, for instance, a heating method using peroxide or azo initiators, where the reaction is carried out at a temperature of 30–80°C for 10–24 hours; and a redox method using redox initiators, where the reaction is carried out at a temperature of 30–70°C for 2–24 hours. When using photoinitiators, a photoirradiation method is used, where the reaction is carried out under light irradiation conditions. Regarding the light source and wavelength range used for light or UV irradiation, conventionally known light sources and wavelength ranges can be used.

[0256] Process iii)

[0257] Step iii) is a process of obtaining elastomeric spherical particles by washing, drying and removing the (B) component, which is a continuous phase, from the dispersion of elastomeric spherical particles obtained in step ii).

[0258] When the continuous phase (dispersion medium) of component (B) is an aqueous phase, specific methods for step iii) can be exemplified as follows: After concentrating the dispersion by methods such as heating and dehydration, (pressure) filtration, centrifugation, and decantation, water washing is performed by adding pure water as needed, followed by heating and drying under normal or reduced pressure; spray drying is performed by spraying the dispersion into a heated airflow; heating and drying is performed using a flowing heat medium; or freeze-drying is performed by reducing pressure after solidifying the dispersion to remove the dispersion medium, thereby obtaining spherical elastomer particles. It should be noted that if the spherical elastomer particles agglomerate after washing and drying to remove the dispersion medium, they can also be crushed using a mortar, ball mill, or jet mill.

[0259] When the continuous phase (dispersion medium) of component (B) is an oil phase, as a specific method in step iii), for example, component (B) is cleaned, removed, and solvent replaced by adding a hydrophobic organic solvent to the dispersion of elastomer spherical particles, stirring for a specified time, and then pressure filtering. By repeating the cleaning operation multiple times, component (B) can be thoroughly removed and solvent replaced. Examples of hydrophobic organic solvents used at this time include toluene and hexane. Finally, elastomer spherical particles are obtained by performing methods such as heating and drying under normal or reduced pressure; spraying the dispersion in a heated gas stream for heating and drying (spray drying); using a flowing hot medium for heating and drying; or freeze-drying to remove the dispersion medium by solidifying the dispersion and then depressurizing.

[0260] The elastomeric spherical particles manufactured by the methods described in steps i) to iii) above are fine particles with a volume average particle size in the range of 0.5 to 200 μm, more preferably in the range of 1.0 to 50 μm. Therefore, the elastomeric spherical particles obtained by the method for manufacturing elastomeric spherical particles of the present invention are particularly suitable for manufacturing the elastomeric composite particles of the present invention.

[0261] - Manufacturing process of elastomer composite particles (resin or silica-coated elastomer spherical particles)

[0262] Engineering (iv)

[0263] Process iv) is a process of adding component (I) to a liquid phase containing components (E), (F), (G) and (H) to cause component (I) to undergo hydrolysis and polymerization.

[0264] (E) The elastomer spherical particles of component (E) are used in the elastomer spherical particles obtained in the processes described above (i) to (ii) or (i) to (iii).

[0265] Alternatively, if component (B) used in step i) is an aqueous component, step iii) can be omitted, and the aqueous dispersion of the elastomeric spherical particles obtained by steps i) and ii) can be provided to step iv as a mixture of components (E) and (H).

[0266] The amount of (E) elastomer spherical particles is preferably in the range of 1.0 to 150 parts by mass, more preferably in the range of 3.0 to 70 parts by mass, relative to 100 parts by mass of water in the liquid phase containing (E) to (H) components. If the amount of (E) component is less than the lower limit mentioned above, the production efficiency of the target elastomer composite particles may decrease. In addition, if the amount of (E) component is higher than the upper limit mentioned above, it is difficult to coat the polyorganosilsesquioxane and silica on the surface of the elastomer spherical particles, which may lead to particle aggregation or fusion, and is therefore not preferred.

[0267] (F) The basic substance is a substance that acts as a catalyst in the hydrolysis or condensation reaction of trialkoxysilanes or tetraalkoxysilanes. One basic substance may be used alone, or two or more may be used in appropriate combination.

[0268] There are no particular limitations on the alkaline substances used; for example, alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as potassium carbonate and sodium carbonate; ammonia; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and amines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, dimethylamine, diethylamine, trimethylamine, triethanolamine, and ethylenediamine. It should be noted that these alkaline substances can be used alone or in appropriate combinations.

[0269] Ammonia is the most preferred alkaline substance, considering its ease of removal from the obtained elastomeric composite particle powder by evaporation. Commercially available ammonia solutions of various concentrations can be used as ammonia.

[0270] (F) The amount of alkaline substance added is preferably such that the pH value of the liquid phase containing components (E) to (H) at 25°C is 9.0 to 13.0, more preferably such that the pH value is in the range of 10.0 to 12.0. If an amount is added to make the pH value 9.0 to 13.0, the hydrolysis and condensation reaction of the trialkoxysilane or tetraalkoxysilane can be sufficiently carried out, and the resin or silica can be sufficiently coated on the surface of the elastomer spherical particles.

[0271] (G) Cationic surfactants and cationic water-soluble polymers promote the condensation reaction of hydrolyzed trialkoxysilanes or tetrakoxysilanes, producing resins or silica. They also facilitate the adsorption of the resulting resins or silica onto the surface of elastomeric spherical particles. Cationic surfactants and cationic water-soluble polymers can be used alone or in appropriate combinations of two or more.

[0272] Examples of cationic surfactants include, for example, alkyl trimethylammonium salts, dialkyl dimethylammonium salts, polyoxyethylene alkyl dimethylammonium salts, dipolyoxyethylene alkyl methylammonium salts, trimeroxyethylene alkylammonium salts, alkyl benzyl dimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, and monoalkyl amide amine salts.

[0273] Examples of cationic water-soluble polymers include, for example, polymers of dimethyl diallyl ammonium chloride (DMDAAC), polymers of vinyl imidazoline, polymers of methyl vinyl imidazoline chloride, polymers of ethyl trimethyl ammonium chloride acrylate, polymers of ethyl trimethyl ammonium chloride methacrylate, polymers of acryloylaminopropyl trimethyl ammonium chloride, polymers of methacrylaminopropyl trimethyl ammonium chloride, polymers of epichlorohydrin (ECH) / dimethylamine, polymers of ethyleneimine, quaternary compounds of ethyleneimine polymers, polymers of allylamine hydrochloride, polylysine, cationic starch, cationic cellulose, chitosan, and copolymers thereof with monomers having nonionic and anionic groups, and their derivatives.

[0274] As component (G), alkyltrimethylammonium salts of cationic surfactants are preferred, with dodecyltrimethylammonium salts and hexadecyltrimethylammonium salts being more preferred.

[0275] Relative to 100 parts by mass of water in the liquid phase containing components (E) to (H), the amount of cationic surfactant and cationic water-soluble polymer compound added is preferably in the range of 0.01 to 2.0 parts by mass, more preferably in the range of 0.1 to 1.0 parts by mass. If the amount of component (G) added is less than the lower limit mentioned above, resin or silica that is not coated on the surface of the elastomeric spherical particles may be generated; if the amount added is greater than the upper limit mentioned above, resin or silica that is not coated on the surface of the elastomeric spherical particles may also be generated.

[0276] There are no special limitations on (H) water. For example, pure water, ion-exchanged water, pure water, etc. can be used. (B) component is an aqueous component. If the aqueous dispersion of the elastomeric spherical particles obtained in step ii) is provided directly to step iv) without going through the above step iii), it also includes the water in the aqueous dispersion and water added as needed.

[0277] There is no particular limitation on (I) trialkoxysilanes and tetraalkoxysilanes; any conventionally known substances may be used. However, from the viewpoint of reactivity, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane are preferred, and methyltrimethoxysilane and tetramethoxysilane are more preferred. Tetraalkoxysilanes may be tetraalkoxysilanes obtained by hydrolyzing some or all of the alkoxy groups, or tetraalkoxysilanes obtained by condensing some of the alkoxy groups.

[0278] The amount of trialkoxysilane added is preferably 1.0 to 50 parts by mass relative to 100 parts by mass of (E) elastomer spherical particles, more preferably 2 to 25 parts by mass.

[0279] Furthermore, the amount of tetraalkoxysilane added is preferably 0.5 to 200 parts by mass of silica, more preferably 1.0 to 50 parts by mass, relative to 100 parts by mass of the (E) elastomer spherical particles.

[0280] Hydrolysis reaction, condensation reaction

[0281] In a liquid phase containing components (E) to (H), add component (I) trialkoxysilane or tetraalkoxysilane, and allow it to undergo hydrolysis and condensation reactions.

[0282] Specifically, in an aqueous dispersion prepared by dispersing (E) spherical elastomer particles in (H) water, and then dissolving one or more of (F) an alkaline substance, (G) a cationic surfactant, and a cationic water-soluble polymer, (I) a trialkoxysilane or tetraalkoxysilane is added, followed by hydrolysis and condensation. Through hydrolysis and condensation, as a condensate of the trialkoxysilane or tetraalkoxysilane, a polyorganosilsesquioxane or silica adheres to the surface of the spherical elastomer particles, thereby coating the surface of the spherical elastomer particles with the polyorganosilsesquioxane or silica.

[0283] The addition of trialkoxysilanes and tetraoxosilanes is preferably carried out under stirring conditions using a conventional mixer equipped with impeller blades, flat blades, etc. They can be added all at once, but it is preferable to add them over a period of time. The preferred addition time is in the range of 1 minute to 6 hours, more preferably in the range of 10 minutes to 3 hours.

[0284] Furthermore, the temperature of the liquid phase is preferably in the range of 0 to 60°C, and more preferably in the range of 0 to 40°C. If the temperature is within the above range, the polyorganosilsesquioxane or silica can be perfectly attached to and coated on the surface of the elastomeric spherical particles in the liquid phase.

[0285] After adding trialkoxysilane or tetrakoxysilane, continue stirring until these hydrolysis and polycondensation reactions are complete. To complete the hydrolysis and polycondensation reactions, the reactions can be carried out at room temperature or under heating conditions of about 40~100°C. In addition, an alkaline substance may be added as appropriate.

[0286] Dehydration process, powdering process

[0287] Following the hydrolysis and condensation reaction in step iv), water is optionally removed from the aqueous dispersion of the elastomeric composite particles of the present invention. Water removal can be performed by heating the aqueous dispersion after the reaction under normal or reduced pressure.

[0288] Specifically, examples include methods such as heating and drying under normal or reduced pressure, spraying the dispersion into a heated airflow for heating and drying (spray drying), using a flowing heat medium for heating and drying, or freeze drying to remove the dispersion medium by reducing pressure after solidification of the dispersion, thereby obtaining elastomer composite particles.

[0289] It should be noted that, as a pretreatment step for this operation, the dispersion can also be concentrated by methods such as heating and dehydration, filtration and separation, centrifugation and decantation. If necessary, the aqueous dispersion can also be washed with water or alcohol.

[0290] In the case of powder agglomeration of elastomeric composite particles obtained by removing water from the aqueous dispersion after reaction, they can be crushed using pulverizers such as jet mills, ball mills, and hammer mills.

[0291] [Example]

[0292] The present invention will be described in more detail below with examples and comparative examples, but the present invention is not limited to the following examples.

[0293] It should be noted that, in the following examples, unless otherwise specified, "%" indicating concentration and content ratio refers to "mass %" and "parts" refers to "parts by mass". Additionally, the kinematic viscosity is the value measured at 25°C. Furthermore, in the following examples, the volume average particle size and aspect ratio of the elastomeric spherical particles and elastomeric composite particles represent values ​​measured using the methods described above.

[0294] The hardness of the cured rubber (elastomer) is the value measured in accordance with the Japan Rubber Industry Association Standard Specification (SRIS).

[0295] The molecular weight of a copolymer having both polyester and polyether structures (a polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule) is the weight-average molecular weight (M) of polystyrene as a standard substance, which will be determined by GPC under the following conditions. W . )).

[0296] [Measurement Conditions]

[0297] Elution solvent: Tetrahydrofuran (THF)

[0298] Flow rate: 0.60 mL / min

[0299] Detector: Differential Refractive Index Detector (RI)

[0300] Column: TSK Guardcolumn SuperH-H

[0301] TSKgel SuperHM-N

[0302] TSKgel SuperH2500 (all manufactured by Tosoh Corporation, Japan)

[0303] Column temperature: 40℃

[0304] Sample injection volume: 50 µL (0.5% by mass THF solution)

[0305] [Methods for determining and evaluating biodegradability]

[0306] Biodegradability was determined using activated sludge from a microbial (degradation) source, according to the OECD Guidelines for the Testing of Chemicals, No. 301F, July 17, 1992, “Ready Biodegradability: MANOMETRIC RESPIROMETRY TEST” standard, and evaluated based on the degree of biodegradability. The activated sludge used was from a municipal wastewater treatment plant, with a suspended solids concentration of 2400 mg / L. Sodium benzoate was used as a standard (control).

[0307] As a method for determining biodegradability, a BOD measuring instrument was used to measure the oxygen consumption (biochemical oxygen consumption (BOD)) in the closed system inside the incubator, and the biodegradability was calculated according to the following formula.

[0308] Biodegradability (%) = BOD - B / TOD × 100

[0309] BOD: Biochemical oxygen demand of the test suspension or control (measured value: mg)

[0310] B: Mean biochemical oxygen demand (measured value: mg) of plant-derived blank samples

[0311] TOD: The theoretical oxygen consumption required for the complete oxidation of the tested substance or sodium benzoate (calculated value: mg).

[0312] [Synthesis of Acrylic-Modified Poly-ε-Caprolactone / Polyether Copolymer 1 - Synthesis Example 1]

[0313] In a 2L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 500g of terminally carbide EO (ethylene oxide) / PO (propylene oxide) polyether (molecular weight: approximately 2000, OH group equivalent: 0.09~0.10mol / 100g), 183.6g of ε-caprolactone (molecular weight 114.1), and 350g of dehydrated toluene were added and heated to 90°C under nitrogen flow. After reaching the target temperature, 0.68g of tetrabutyl titanate (molecular weight 340.0) was added as a catalyst, and the mixture was aged at 120°C for 4~6 hours.

[0314] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 60.7 g of triethylamine (molecular weight 101.2), 100 g of dehydrated toluene, and 0.22 g of butylated hydroxytoluene (BHT) (molecular weight 220.4) as a polymerization inhibitor were added. After stirring for a specified time to ensure uniform dissolution, 49.7 g of acryloyl chloride (molecular weight 90.5) was added dropwise using a dropping funnel. After confirming the heating effect, the mixture was cured at 60°C for 4 hours.

[0315] After pressure filtration of the obtained crude product, washing with sodium chloride aqueous solution using a separatory funnel, centrifugation, etc., magnesium sulfate, silica gel, activated carbon, etc. were added, and impurities were adsorbed and removed by vibrating powder treatment. After removing the above powders by pressure filtration, 0.22g of butylated hydroxytoluene (BHT) was added, and the solvent was removed by distillation at 60~70℃ and below 50mmHg, thereby obtaining acrylic modified poly-ε-caprolactone / polyether copolymer 1 (weight average molecular weight of formula (11) below: 2880).

[0316] [Chemical Formula 11]

[0317]

[0318] [Synthesis of Acrylic-Modified Poly-ε-Caprolactone / Polyether Copolymer 2 - Synthesis Example 2]

[0319] In a 1L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 300g of terminally carbonized EO / PO polyether (similar to that in Synthesis Example 1), 110.2g of ε-caprolactone, and 200g of dehydrated toluene were added, and the mixture was heated to 90°C under nitrogen flow. After reaching the target temperature, 0.41g of tetrabutyl titanate was added as a catalyst, and the mixture was aged at 120°C for 4–6 hours.

[0320] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 100g of dehydrated toluene, 0.96g of dioctyl dinecaproyltin oxide (molecular weight 687.7) and 0.12g of dibutylhydroxytoluene (BHT) as catalysts were added, and the mixture was stirred for a specified time. After it was uniformly dissolved, 44.4g of ethyl 2-isocyanate acrylate (molecular weight 141.1) was added dropwise using a dropping funnel. After confirming that the mixture was heating up, it was cured at 60°C for 4 hours.

[0321] After cooling the obtained crude product to below 40°C, 0.8 g of ethanol was added, and a rapid cooling treatment was performed to react with the unreacted (residual) isocyanate groups. Then, magnesium sulfate, silica gel, activated carbon, etc. were added, and impurities were adsorbed and removed by vibrating powder treatment. After removing the above powders by pressure filtration, 0.12 g of butylated hydroxytoluene (BHT) was added, and the solvent was removed by distillation at 60~70°C and below 50 mmHg, thereby obtaining acrylic modified poly-ε-caprolactone / polyether copolymer 2 (hereinafter, formula (12), weight average molecular weight 3120).

[0322] [Chemical Formula 12]

[0323]

[0324] [Synthesis of Acrylic-Modified Poly-ε-Caprolactone / Polyether Copolymer 3 - Synthesis Example 3]

[0325] In a 1L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 300g of terminally carbonized EO / PO polyether (molecular weight: approximately 2600, OH group equivalent: 0.09~0.10mol / 100g), 115.2g of ε-caprolactone, and 200g of dehydrated toluene were added, and the mixture was heated to 90°C under nitrogen flow. After reaching the target temperature, 0.42g of tetrabutyl titanate was added as a catalyst, and the mixture was aged at 120°C for 4~6 hours.

[0326] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 70 g of dehydrated toluene, 0.18 g of tris(2,4-pentanedione)ferro(III) (also known as acetylacetone ferro(III) (molecular weight: 353.2) as a catalyst and 0.13 g of butylated hydroxytoluene (BHT) were added. The mixture was stirred for a specified time until it was uniformly dissolved. Then, 46.4 g of ethyl 2-isocyanate acrylate was added dropwise using a dropping funnel. After confirming that the mixture was heating up, it was aged at 60°C for 4 hours.

[0327] Similar to the method described in Synthesis Example 2 above, acrylic-modified poly-ε-caprolactone / polyether copolymer 3 was obtained by post-processing and refining the crude product. Acrylic-modified poly-ε-caprolactone / polyether copolymer 3 has the structure of formula (12), in which l≈18~21, m≈34~38, r≈3~4, and weight-average molecular weight: 4870.

[0328] [Synthesis of Acrylic-Modified Poly-ε-Caprolactone / Polyether Copolymer 4 - Synthesis Example 4]

[0329] In a 1L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 300g of terminally carbonized EO / PO polyether (similar to that used in Synthesis Example 3), 115.2g of ε-caprolactone, and 200g of dehydrated toluene were added, and the mixture was heated to 90°C under nitrogen flow. After reaching the target temperature, 0.42g of tetrabutyl titanate was added as a catalyst, and the mixture was aged at 120°C for 4–6 hours.

[0330] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 70g of dehydrated toluene, 2.77g of tetraacetylacetone zirconium (molecular weight: 487.7) as a catalyst and 0.13g of butylated hydroxytoluene (BHT) were added. The mixture was stirred for a specified time until it was uniformly dissolved. Then, 46.4g of ethyl 2-isocyanate acrylate was added dropwise using a dropping funnel. After confirming that the mixture was heating up, it was aged at 60°C for 4 hours.

[0331] Similar to the method described in Synthesis Example 2 above, the acrylic-modified poly-ε-caprolactone / polyether copolymer 4 was obtained by post-processing and refining the crude product. The acrylic-modified poly-ε-caprolactone / polyether copolymer 4 has the structure of formula (12), in which l≈18~21, m≈34~38, r≈3~4, and weight-average molecular weight: 4990.

[0332] [Synthesis of Acrylic-Modified Poly-ε-Caprolactone / Polyether Copolymer 5 - Synthesis Example 5]

[0333] In a 1L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 300g of terminally carbonized EO / PO polyether (molecular weight: approximately 3200, OH group equivalent: 0.062mol / 100g), 106.3g of ε-caprolactone, and 200g of dehydrated toluene were added, and the mixture was heated to 90°C under nitrogen flow. After reaching the target temperature, 0.41g of tetrabutyl titanate was added as a catalyst, and the mixture was aged at 120°C for 4–6 hours.

[0334] Next, after cooling the poly-ε-caprolactone / polyether copolymer obtained through the above operation to near room temperature, 70g of dehydrated toluene, 1.01g of dioctyl dinecaproyltin oxide as a catalyst, and 0.13g of dibutylhydroxytoluene (BHT) were added. The mixture was stirred for a specified time until it was uniformly dissolved. Then, 28.4g of ethyl 2-isocyanate acrylate was added dropwise using a dropping funnel. After confirming that the mixture was heating up, it was aged at 60°C for 4 hours.

[0335] Similar to the method described in Synthesis Example 2 above, by subjecting the obtained crude product to post-treatment and refining processes, acrylic-modified poly-ε-caprolactone / polyether copolymer 5 (Formula (13), weight average molecular weight: 7940) was obtained.

[0336] [Chemical Formula 13]

[0337]

[0338] [Synthesis of Acrylic-Modified Poly-ε-Caprolactone / Polyether Copolymer - Synthesis Example 6]

[0339] In a 1L detachable flask equipped with a stirrer, thermometer, cooling tube, and dropping funnel, 300g of carboxyl-modified organosilicon (molecular weight: approximately 1200, COOH equivalent: 0.19mol / 100g), 202.8g of poly(ε-caprolactone) monoacrylate (OH equivalent: 0.29mol / 100g, molecular weight 344.0), 200g of dehydrated toluene, and 6.85g of 4-dimethylaminopyridine (DMAP) (molecular weight 122.2) were added and stirred and mixed under ice bath conditions.

[0340] After sufficient cooling, using a dropping funnel, a solution containing 168.9 g of N,N'-dicyclohexylcarbodiimide (DCC) (molecular weight: 206.3) dissolved in 173.6 g of dehydrated toluene was added to the above mixture. The mixture was reacted and matured at room temperature for 20 hours. After maturation, 200 g of toluene and 300 g of 0.5 mol / L hydrochloric acid were added for washing (to remove DMAP). Then, a water washing operation was performed in the order of saturated sodium bicarbonate aqueous solution and 10% sodium chloride aqueous solution.

[0341] After performing the above operations, magnesium sulfate, silica gel, activated carbon, and KYOWAAD700 (manufactured by Kyowa Chemical Industry Co., Ltd., Japan) were added, and impurities were adsorbed and removed by vibration. After removing the various powders by pressure filtration, 0.09 g of butylated hydroxytoluene (BHT) was added, and the solvent was removed by distillation at 60-70°C and below 10 mmHg, thereby obtaining acrylic-modified poly-ε-caprolactone / organosilicon copolymer (formula (14) below, weight average molecular weight: 2130).

[0342] [Chemical Formula 14]

[0343]

[0344] [Manufacturing of Elastomer Spherical Particles - Manufacturing Example 1]

[0345] 250g of a 2.6% aqueous solution of hydroxypropyl methylcellulose (trade name: METOLOSE60 SH-4000, manufactured by Shin-Etsu Chemical Co., Ltd., Japan) was placed into a 1L container of vacuum homogenizer. The homogenizer and anchor mixer were operated while the mixture was stirred and mixed under heating conditions of 55~60°C.

[0346] Meanwhile, 100g of the acrylic-modified poly-ε-caprolactone / polyether copolymer 4 described in Synthesis Example 4 above and 1.0g of 2,2'-azobis(2-methylpropionate) (molecular weight: 230.3) were placed into a graduated cup, mixed in advance using a dispersion mixer, and preheated to 60~65°C.

[0347] Next, the pre-mixed acrylic-modified poly-ε-caprolactone / polyether copolymer was added to a 1L vacuum homogenizer containing a heated aqueous solution of hydroxypropyl methylcellulose. The mixture was stirred for more than 10 minutes at a temperature of 55-60°C and a speed of 4500 rpm in a homogenizer to suspend it, thus obtaining an O / W type suspension composition.

[0348] Subsequently, the obtained suspension composition was stirred and matured for 8 hours using a paddle impeller at 200 rpm and 70°C. After adding 50 g of pure water, it was matured again at 80°C for 6 hours at the same speed to obtain a dispersion of elastomer spherical particles.

[0349] The shape of the spherical elastomer particles in the obtained dispersion was observed using an optical microscope and confirmed to be spherical. The volume average particle size was measured using a resistive particle size distribution measuring device (Multisizer 3, manufactured by Beckman Coulter, Inc.) and the result was 5 µm.

[0350] Using a filter screen (#100), the obtained dispersion of elastomer spherical particles was checked for the presence of agglomerates. If agglomerates were found, they were removed. Then, solid-liquid separation by pressure filtration was performed to remove pure water, which served as the continuous phase. The above washing and separation process was repeated three times with pure water to remove moisture. It should be noted that if solid-liquid separation is not perfectly achieved in the pressure filtration process, centrifugation can also be used to remove moisture.

[0351] Finally, by allowing the concentrate of the elastomer spherical particles obtained above to stand and dry for more than 8 hours, a white to light yellow powder of the target elastomer spherical particles was obtained.

[0352] The obtained spherical elastomer particle powder was observed using an electron microscope (S-4700 scanning microscope, manufactured by Hitachi High Technology Co., Ltd., Japan), and was confirmed to be spherical particles with a particle size of approximately 5 μm. Furthermore, the aspect ratio of the obtained spherical elastomer particles was 1.0.

[0353] In addition, the results of measuring and evaluating the dispersion of elastomeric spherical particles redispersed in water using lauryl alcohol polyoxyethylene ether as a surfactant by resistance method were confirmed to have a volume average particle size of 5 μm.

[0354] The hardness of the elastomer (rubber) constituting the elastomeric spherical particles was measured using the method described below.

[0355] 30g of the synthesized acrylic-modified poly-ε-caprolactone / polyether copolymer 4 and 0.24g of 2'-azobis-(2,4-dimethylpentanonitrile) (molecular weight: 248.4) were stirred and mixed, and then poured into an aluminum petri dish to form a thickness of 10mm. After standing in an air-controlled thermostat at 70℃ for 1-2 hours, a non-sticky, flat rubber was obtained. The hardness of the obtained flat rubber was measured to be 72 using an Asker C hardness tester and 55 using an Asker A hardness tester.

[0356] [Manufacturing of Elastomer Spherical Particles - Manufacturing Example 2]

[0357] Except that the 250g of 2.6% aqueous solution of hydroxypropyl methylcellulose in Manufacturing Example 1 was replaced with 173g of 3.8% aqueous solution of hydroxypropyl methylcellulose, elastomeric spherical particles were manufactured using the same method as in Manufacturing Example 1. As a result, elastomeric spherical particles with a volume average particle size of 2μm were obtained.

[0358] [Manufacturing of elastomeric spherical particles: Manufacturing example 3]

[0359] Except that the hydroxypropyl methylcellulose (trade name: METOLOSE 60 SH-4000, manufactured by Shin-Etsu Chemical Co., Ltd., Japan) used in Manufacturing Example 1 was replaced with hydroxypropyl methylcellulose (trade name: METOLOSE 60 SH-50, manufactured by Shin-Etsu Chemical Co., Ltd., Japan), elastomeric spherical particles were manufactured using the same method as in Manufacturing Example 1. As a result, elastomeric spherical particles with a volume average particle size of 11 μm were obtained.

[0360] [Manufacturing of Elastomer Spherical Particles - Manufacturing Example 4]

[0361] Except that the 2.6% aqueous solution of hydroxypropyl methylcellulose (trade name: METOLOSE 60 SH-4000, manufactured by Shin-Etsu Chemical Co., Ltd., Japan) in 250g of Manufacturing Example 1 was replaced with a 5.2% aqueous solution of xanthan gum in 250g of Manufacturing Example 1, elastomeric spherical particles were manufactured using the same method as in Manufacturing Example 1. As a result, elastomeric spherical particles with a volume average particle size of 20μm were obtained.

[0362] [Manufacturing of Elastomer Composite Particles - Example 1]

[0363] 100g of a dispersion of 20% solids elastomer spherical particles obtained in Manufacturing Example 1, 184.9g of pure water, and 0.2g of a 30% dodecyltrimethylammonium chloride aqueous solution were added to a 500ml glass flask equipped with a paddle impeller. After the aqueous dispersion was heated to 5-10°C, while maintaining the aqueous dispersion with 0.75g of 5.0% ammonia at 5-10°C, 11.2g of tetramethoxysilane (an amount that reduces the amount of silica after hydrolysis and condensation reaction to 22.0 parts by mass relative to 100 parts by mass of the elastomer spherical particles) was added dropwise over 15-30 minutes, while maintaining the liquid temperature at 5-10°C and stirring for 1 hour.

[0364] Next, the mixture was heated to 55-60°C and stirred and matured for 1 hour while maintaining the temperature, thus completing the hydrolysis and condensation reaction of tetramethoxysilane.

[0365] Using a pressure filter, the dispersion of tetramethoxysilane in the dispersion of elastomer spherical particles, obtained through hydrolysis and condensation, was dehydrated to approximately 30% moisture content. Next, the dehydrated material was transferred to a 1L glass flask equipped with an anchor stirrer, 500g of water was added, and the mixture was stirred for 30 minutes. Dehydration was then carried out by pressure filtration. The dehydrated material, obtained by repeating the washing and dehydration process three times, was dried at 105°C in a hot air flow dryer. The dried material was then crushed using a jet mill to obtain free-flowing particles.

[0366] When the obtained particles were observed using an electron microscope, it was confirmed that spherical silica adhered and coated the entire surface of the elastomeric spherical particles, thereby obtaining silica-coated elastomeric spherical particles (elastomeric composite particles). Furthermore, the aspect ratio of the silica-coated elastomeric spherical particles (elastomeric composite particles) obtained in Example 1 was 1.0.

[0367] The obtained silica-coated elastomer spherical particles (elastomer composite particles) were dispersed in water using a surfactant (lauryl alcohol polyoxyethylene ether). The particle size distribution was measured using a resistivity particle size distribution measuring device (Multisizer 3, manufactured by Beckman Coulter, Inc.). The particle size distribution was confirmed to be the same as that of the aqueous dispersion of the above-mentioned elastomer spherical particles, with a volume average particle size of approximately 5 µm.

[0368] [Manufacturing of Elastomer Composite Particles - Example 2]

[0369] Except that the elastomeric spherical particles of Manufacturing Example 2 were used instead of the elastomeric spherical particles of Manufacturing Example 1, elastomeric composite particles were manufactured using the same method as in Example 1. As a result, silica-coated elastomeric spherical particles (elastomeric composite particles) with a volume average particle size of about 2 µm were obtained, in which spherical silica is attached and coated on the entire particle surface of the elastomeric spherical particles.

[0370] [Manufacturing of Elastomer Composite Particles - Example 3]

[0371] Except that the elastomeric spherical particles of Manufacturing Example 3 were used instead of the elastomeric spherical particles of Manufacturing Example 1, elastomeric composite particles were manufactured using the same method as in Example 1. As a result, silica-coated elastomeric spherical particles (elastomeric composite particles) with a volume average particle size of about 11 µm were obtained, in which spherical silica particles were attached and coated on the entire particle surface of the elastomeric spherical particles.

[0372] [Manufacturing of Elastomer Composite Particles - Example 4]

[0373] Except that the elastomeric spherical particles of Manufacturing Example 4 were used instead of the elastomeric spherical particles of Manufacturing Example 1, elastomeric composite particles were manufactured using the same method as in Example 1. As a result, silica-coated elastomeric spherical particles (elastomeric composite particles) with a volume average particle size of about 20 µm were obtained, in which spherical silica is attached and coated on the entire particle surface of the elastomeric spherical particles.

[0374] [Manufacturing of Elastomer Composite Particles - Example 5]

[0375] 100g of a dispersion of 20% solids elastomer spherical particles obtained in Manufacturing Example 3, 184.9g of pure water, and 0.2g of a 30% dodecyltrimethylammonium chloride aqueous solution were added to a 500ml glass flask equipped with a paddle impeller. After the aqueous dispersion was heated to 5-10°C, while maintaining the aqueous dispersion with 0.84g of 5.0% ammonia at 5-10°C, 12.5g of methyltrimethoxysilane (an amount that, relative to 100 parts by mass of the elastomer spherical particles, results in 22.0 parts by mass of silane after hydrolysis and condensation) was added dropwise over 15-20 minutes, maintaining the liquid temperature at 5-10°C during this period, and stirring was performed for 1 hour. Subsequent operations were performed in the same manner as in Example 1, resulting in flowable particles.

[0376] When the obtained particles were observed using an electron microscope, it was confirmed that the spherical polyorganosilsesquioxane was attached and coated across the entire surface of the elastomer spherical particles, thus obtaining resin (polyorganosilsesquioxane) coated elastomer spherical particles (elastomer composite particles). Furthermore, the resin (polyorganosilsesquioxane) coated elastomer spherical particles (elastomer composite particles) obtained in Example 5 had an aspect ratio of 1.0.

[0377] Using a surfactant (lauryl alcohol polyoxyethylene ether), the obtained resin (polyorganosilsesquioxane) was coated with elastomer spherical particles (elastomer composite particles) and dispersed in water. The results of measuring the particle size distribution of the resin-coated elastomer spherical particles using a resistivity particle size distribution measuring device (Multisizer3, manufactured by Beckman Coulter, Inc.) were confirmed to be the same as that of the aqueous dispersion of the elastomer spherical particles, with a volume average particle size of approximately 11 µm.

[0378] [Manufacturing of Elastomer Composite Particles - Example 6]

[0379] Except that the amount of tetramethoxysilane added was adjusted from 11.2 g (to 22.0 parts of silica after hydrolysis and condensation reaction relative to 100 parts of elastomeric spherical particles) to 5.6 g (to 11.0 parts of silica after hydrolysis and condensation reaction relative to 100 parts of elastomeric spherical particles), elastomeric composite particles were manufactured using the same method as in Example 1. As a result, silica-coated elastomeric spherical particles (elastomeric composite particles) with a volume average particle size of approximately 5 µm were obtained, in which spherical silica was attached and coated on the entire particle surface of the elastomeric spherical particles.

[0380] The particle size of the spherical silica or resin (polyorganosilsesquioxane) attached to and coated on the surface of the elastomeric spherical particles obtained in each embodiment is as shown in the table below.

[0381] [Table 1]

[0382]

[0383] [Biodegradability Evaluation]

[0384] According to the evaluation method, the biodegradability of acrylic-modified poly-ε-caprolactone / polyether copolymer 1 was evaluated after 60 days of cultivation at a temperature of 22±1℃. The average biodegradability of acrylic-modified poly-ε-caprolactone / polyether copolymer 1 after 28 days was 62%, and the average biodegradability after 60 days was 73%. Since it met the criterion of 60% biodegradability after 28 days, it was judged as a "biodegradable substance".

[0385] Therefore, it can be inferred that the elastomeric spherical particles and composite particles, which are crosslinked particles of acrylic-modified poly-ε-caprolactone / polyether copolymer 1, will not remain in the environment as particles after being used and will eventually degrade if they flow directly into the ocean through land water systems.

[0386] The biodegradability evaluation results of acrylic-modified poly-ε-caprolactone / polyether copolymers 2~4 after 60 days of cultivation at a temperature of 22±1℃ showed that the average biodegradability of acrylic-modified poly-ε-caprolactone / polyether copolymers 2~4 was 40% after 28 days and 65% after 60 days. Since it met the criterion of 60% biodegradability after 60 days, it was judged as an "inherently biodegradable substance".

[0387] Therefore, it can be inferred that the elastomeric spherical particles and composite particles, which are 2-4 crosslinked particles of acrylic-modified poly-ε-caprolactone / polyether copolymer, will not remain in the environment as particles after being used and flow directly into the ocean through land water systems, and will eventually degrade.

[0388] The results of the biodegradability evaluation of acrylic-modified poly-ε-caprolactone / organosilicon copolymer after 28 days of cultivation at a temperature of 22±1℃ showed that the biodegradability of acrylic-modified poly-ε-caprolactone / organosilicon copolymer stopped at an average value of 26% after 28 days, and no further increase in biodegradability was observed thereafter.

[0389] Because it failed to meet the criterion of 60% biodegradability after 28 days, it was judged to be "not (easily) biodegradable".

[0390] The elastomeric composite particles (elastomeric spherical particles coated with resin or silica) of the present invention are expected to be particularly useful for cosmetics and the like, based on their characteristic structural composition.

[0391] In addition, since the powder and particle skeleton contain degradable polyester structures (especially poly-ε-caprolactone) and polyether structures, it is expected to exhibit or be endowed with high biodegradability.

Claims

1. An elastomer composite particle, wherein, The surface of the elastomeric spherical particles, which are cross-linked particles of copolymers with polyester and polyether structures, have a volume average particle size of 0.5~200µm and contain polyorganosilsesquioxane or silica.

2. The elastomer composite particle according to claim 1, wherein, The copolymer is a polyester-polyether copolymer having at least two unsaturated groups capable of free radical polymerization in one molecule.

3. The elastomer composite particle according to claim 2, wherein, The copolymer is a polyester-polyether copolymer represented by the following general formula (1) or general formula (2). [Chemical Formula 1] In general formula (1), R 1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2 Each of the following formulas (3a), (3b), or (3c) represents an organic group containing a free radical polymerizable functional group, where k is a number that is 1 ≤ k ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and n is a number that is 1 ≤ n ≤ 100. In general formula (2), R 3 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 4 Each of the following formulas (4a) and (4b) represents an organic group containing a free radical polymerizable functional group, where p is a number that is 1 ≤ p ≤ 10, l is a number that is 1 ≤ l ≤ 1000, m is a number that is 1 ≤ m ≤ 1000, and q is a number that is 1 ≤ q ≤ 100. [Chemical Formula 2] In general formulas (3a), (3b), (3c), (4a), and (4b), R 5 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 8 carbon atoms, R 6 Each can be used independently to represent a hydrocarbon group consisting of 1 to 3 hydrogen atoms or carbon atoms.

4. The elastomer composite particle according to claim 2, wherein, The copolymer is a polyester-polyether copolymer represented by the following general formula (5). [Chemical Formula 3] In general formula (5), R 1 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 10 carbon atoms, R 2 Let each of the following be an independent representation of an organic group containing a free radical polymerizable functional group, represented by general formulas (3a), (3b), and (3c), where l is a number 1 ≤ l ≤ 1000, m is a number 1 ≤ m ≤ 1000, and r is a number 1 ≤ r ≤ 100. [Chemical Formula 4] In general formula (3a), general formula (3b) or general formula (3c), R 5 Each of the following groups independently represents a divalent hydrocarbon group with 1 to 8 carbon atoms, R 6 Each can be used independently to represent a hydrocarbon group consisting of 1 to 3 hydrogen atoms or carbon atoms.

5. A method for manufacturing elastomeric spherical particles, wherein, It has the following processes i) to iii). i） The process of preparing a suspension composition by stirring and suspending the following components (A), (B), (C), and (D) is described. (A) A copolymer having polymerizable groups and possessing both polyester and polyether structures. (B) is the aqueous or oil phase component in which component (A) is insoluble or sparingly soluble. (C) Suspension agent, (D) Polymerization initiator, ii) The process of obtaining a dispersion of elastomeric spherical particles by free radical polymerization of component (A) in the suspension composition obtained by step i). iii) The process of obtaining elastomeric spherical particles by washing and drying (B), which is a continuous phase, from the dispersion of elastomeric spherical particles obtained by step ii).

6. The method for manufacturing elastomeric composite particles according to any one of claims 1 to 4, wherein, It has the following process iv), iv) The process involves adding component (I) to a liquid phase containing components (E), (F), (G), and (H), and subjecting component (I) to a hydrolysis and polymerization reaction, wherein... (E) Elastomeric spherical particles manufactured by the method of claim 5, It consists of cross-linked particles of copolymers with polyester and polyether structures, having a volume average particle size of 0.5–200 µm. (F) Alkaline substances, (G) Selected from one or more cationic surfactants and cationic water-soluble polymers. (H) water, (I) Trialkoxysilane or tetraalkoxysilane.

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