Particles and their applications

Abstract

To provide particles capable of maintaining the original soft touch of a composition containing a base component and suppressing the decrease in impact performance and poor appearance and to provide application for the same.SOLUTION: There are particles which contain a polymer of a polymerizable component containing the following monomer (A) and have an oleic acid absorption of 95 mL / 100 g or more and an average particle diameter of 2 to 100 μm. A monomer (A): a compound represented by the following general formula (1), which has an acryloyl group and / or a methacryloyl group, has a reactive carbon-carbon double bond other than the acryloyl group and the methacryloyl group and has a molecular weight of 200 or more. R1-O-R2-O-R3 (1) (wherein, R1 and R3 each are an acryloyl group or a methacryloyl group and R2 has the reactive carbon-carbon double bond.)SELECTED DRAWING: None

Description

[Technical Field] 【0001】 This invention relates to particles and their applications. [Background technology] 【0002】 Rubber and elastomers are preferably used as base materials for interior materials of vehicles, ships, etc. (e.g., car door trims, instrument panels, etc.) and gaskets (e.g., car weatherstrips, glass run channels, etc.) in order to provide a soft tactile feel. 【0003】 When using elastomers as a base material, methods have been proposed to impart flexibility to the resulting composition by adding oil as a flexible component, such as the styrene-based elastomer with excellent flexibility to which paraffin oil and silicone oil are added, as described in Patent Documents 1 and 2. [Prior art documents] [Patent Documents] 【0004】 [Patent Document 1] Japanese Patent Application Publication No. 4-73112 [Patent Document 2] Japanese Patent Application Publication No. 4-73142 [Overview of the project] [Problems that the invention aims to solve] 【0005】 In the case of compositions using oil, as described in Patent Documents 1 and 2, although the composition is flexible, it has been found that the surface of the composition becomes sticky due to the bleeding out of the contained oil, impairing its soft texture. To suppress oil bleed-out, a material with oil-absorbing properties is required, but no such material has been found to be sufficiently satisfactory. Furthermore, it has been confirmed that the addition of additives leads to problems such as a decrease in the impact performance and deterioration of the appearance of the resulting composition, resulting in a decline in the physical properties of the composition. 【0006】 The object of the present invention is to provide particles that can maintain the original soft feel of a composition containing a base component, suppress a decrease in impact performance and defects in appearance, and to provide applications for such particles. [Means for solving the problem] 【0007】 As a result of diligent research, the inventors of this invention discovered that the above problems can be solved if the particles satisfy certain conditions, and thus arrived at the present invention. In other words, the particles of the present invention contain a polymerizable component comprising the monomer (A) described below, have an oleic acid oil absorption capacity of 95 mL / 100 g or more, and an average particle diameter of 2 to 100 μm. Monomer (A): A compound having an acryloyl group and / or a methacryloyl group, and having a reactive carbon-carbon double bond in addition to the acryloyl group and methacryloyl group, having a molecular weight of 200 or more, and represented by the following general formula (1). R 1 -OR 2 -OR 3 (1) (In the formula, R 1 and R 3 Each of these is independently an acryloyl group or a methacryloyl group, and R 2 It has the aforementioned reactive carbon-carbon double bond. 【0008】 The particles of the present invention are R 2 It is preferable that the polymer chain has polymer chains, and that these polymer chains contain dienes as constituent units. In the particles of the present invention, it is preferable that the diene is butadiene and / or isoprene. The particles of the present invention preferably contain at least one polymerizable component selected from nitrile monomers, carboxyl group-containing monomers, (meth)acrylic acid ester monomers, and styrene monomers. The particles of the present invention preferably have an isopropyl alcohol swelling ratio defined by the following formula (I) of 3.0 or less. Isopropyl alcohol swelling ratio (times) = B / A (I) A: Average particle diameter of particles before swelling with isopropyl alcohol B: Average particle diameter of particles after swelling with isopropyl alcohol 【0009】 The wet powder particles of the present invention contain the particles described above, and a liquid organic compound and / or water. The composition of the present invention contains at least one selected from the above particles and the above wet powder particles, and a base material component, excluding rubber compositions for tires. [Effect of the Invention] 【0010】 The particles of the present invention can achieve excellent impact performance and excellent appearance while maintaining the soft touch originally possessed by the composition containing the base material component. The composition of the present invention has a soft touch and is excellent in impact performance and appearance. [Mode for Carrying Out the Invention] 【0011】 (Particles) The particles of the present invention contain a polymer of a polymerizable component. The polymerizable component means a monomer component having at least one or more reactive carbon-carbon double bonds in the molecule, and is a component that becomes a polymer constituting the particles by polymerization. Examples of the polymerizable component include a monomer having one reactive carbon-carbon double bond (hereinafter sometimes referred to as a monofunctional monomer) and a crosslinking agent which is a monomer having at least two reactive carbon-carbon double bonds. A crosslinked structure can be introduced into the polymer by the crosslinking agent. The reactive carbon-carbon double bond referred to here means a carbon-carbon double bond showing radical reactivity, and is not a carbon-carbon double bond in an aromatic ring such as a benzene ring or a naphthalene ring. For example, carbon-carbon double bonds contained in a vinyl group, an acryloyl group, a methacryloyl group, an allyl group, a vinylene group, etc. can be mentioned. The particles of the present invention are preferably polymer particles (solid) containing a polymer of a polymerizable component in terms of more exhibiting the effects of the present invention, and are also preferably spherical. 【0012】 The polymerizable component contains the following monomer (A). Monomer (A): A compound having an acryloyl group and / or a methacryloyl group, having a reactive carbon-carbon double bond other than the acryloyl group and the methacryloyl group, having a molecular weight of 200 or more, and represented by the following general formula (1) R 1 -O-R 2 -O-R 3 (1) (In the formula, R 1 and R 3 are each independently an acryloyl group or a methacryloyl group, and R 2 has a reactive carbon-carbon double bond.) 【0013】 Since the acryloyl group and the methacryloyl group have a structure with a reactive carbon-carbon double bond and polarity, they are considered to have very high radical reactivity. Therefore, the polymer obtained from the polymerizable component containing monomer (A) has a crosslinked structure with improved denseness. Since the molecular weight of monomer (A) is 200 or more, it is possible to increase the molecular weight of the polymer. Furthermore, since monomer (A) has a structure like the above general formula (1), it can have a carbon-carbon double bond in the polymer, and thus is considered to have high elasticity. Also, by having a carbon-carbon double bond in the polymer, it is considered that the affinity with oil can be adjusted. 【0014】 The molecular weight of monomer (A) is 200 or more, preferably 200 to 100000. If the molecular weight is less than 200, the elasticity becomes too high and the impact performance decreases. On the other hand, if the molecular weight is 100000 or less, the denseness of the polymer tends to improve. The upper limit of the molecular weight is more preferably 75000, further preferably 50000, particularly preferably 35000, and most preferably 25000. On the other hand, the lower limit of the molecular weight is preferably 500, more preferably 600, further preferably 1000, and particularly preferably 1500. 【0015】 In monomer (A), R in the above general formula (1) 2 It is preferable that the structure has polymer chains in order to better achieve the effects of the present invention. The reactive carbon-carbon double bond may be present in the polymer chain or in structural parts other than the polymer chain. In terms of achieving the effects of the present invention, it is preferable that the reactive carbon-carbon double bond is included in the polymer chain. Having a reactive carbon-carbon double bond in the polymer chain allows R 2 Because it can suppress bending, it is thought to have high elasticity, and thus its impact properties can be further improved. R 2 If the structure has polymer chains, the molecular weight of monomer (A) refers to the weight-average molecular weight. 【0016】 R 2 The polymer may have a structure composed solely of polymer chains, or a structure in which polymer chains are bonded to organic and / or inorganic groups other than polymer chains. Organic groups are defined as functional groups containing carbon. Examples of organic groups include alkyl groups, alkylene groups, alkenyl groups, alkynyl groups, alkoxy groups, oxyalkylene groups, carboxyl groups, anhydrous carboxyl groups, ester groups, carbonyl groups, amide groups, urethane groups, phenyl groups, phenylene groups, acryloyl groups, kryloyl groups, and allyl groups. One of these organic groups may be bonded to the polymer chain, or two or more may be bonded to the polymer chain. Furthermore, in this invention, an inorganic group is defined as a functional group that does not contain the element carbon. Examples of inorganic groups include hydroxyl groups, ether groups, amino groups, sulfo groups, halogen groups such as fluoro and chloro groups, and silanol groups. One of these inorganic groups may be bonded to the polymer chain, or two or more may be bonded to the polymer chain. Furthermore, R 2 The structure may be linear or branched. 【0017】 Furthermore, it is preferable for the polymer chain to contain a diene as a constituent unit, as this increases the number of reactive carbon-carbon double bonds in the monomer (A), thereby imparting elasticity and improving impact performance. 【0018】 Examples of dienes as constituent units of monomer (A) include 1,3-butadiene (also simply called butadiene in this invention); 1,3-pentadiene; 1,3-hexadiene; 2,4-hexadiene; 1,3-heptadiene; 1,3-octadiene; isoprene; chloroprene; 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1,3-butadiene, 2-hexyl- 2-alkyl-1,3-butadiene such as 1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, 2-neopentyl-1,3-butadiene; 2,3-dialkyl-1,3-butadiene such as 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene; 1-phenyl-1,3-butadiene; 2-phenyl-1,3-butadiene Dienes such as aryl-1,3-butadiene; 1-phenyl-2,4-pentadiene; 2-chloro-1,3-butadiene; 2-cyano-1,3-butadiene; conjugated dienes such as 3-methyl-1,3-pentadiene, 1,4-hexadiene; 3-methyl-1,4-hexadiene; 4-methyl-1,4-hexadiene; 5-methyl-1,4-hexadiene; 4,5-dimethyl-1,4-hexadiene; 7-methyl-1,6-octadiene; 8-methyl-4-ethylidene-1,7-nonadien Examples of non-conjugated dienes include 4-ethylidene-1,7-undecadiene; methyltetrahydroindene; 5-ethylidene-2-norbornene; 5-methylene-2-norbornene; 5-isopropylidene-2-norbornene; 5-vinylidene-2-norbornene; 6-chloromethyl-5-isopropenyl-2-norbornene; 5-vinyl-2-norbornene; 5-isopropenyl-2-norbornene; 5-isobutenyl-2-norbornene; cyclopentadiene; norbornadiene, etc. These dienes may be present one or more of them. Among the dienes, it is preferable to include at least one selected from butadiene, 1,3-pentadiene, isoprene, chloroprene, 1,3-pentadiene, and 1,3-hexadiene, in order to better achieve the effects of the present invention, and it is even more preferable to include butadiene and / or isoprene. When a polymer chain contains two or more dienes as constituent units, the polymer chain may be a polymer in which the constituent units of each diene are polymerized randomly, such as a random copolymer, or it may be a polymer in which the constituent units of each diene are polymerized in a group, such as a block copolymer. 【0019】 The polymer chain may contain components other than dienes, as long as they do not hinder the effects of the present invention. Examples of components other than dienes include polyene-based components having three or more reactive carbon-carbon double bonds in the component, such as 1,3,5-hexatriene; nitrile-based components such as acrylonitrile and methacrylonitrile; aromatic vinyl-based components such as styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene; and olefin-based components such as ethylene, polypropylene, and isobutylene. One or more of these components other than dienes may be included. If the polymer chain contains structural units other than dienes, the polymer chain may be a random copolymer in which dienes and other structural units are randomly polymerized, or a block copolymer in which dienes and other structural units are polymerized in a cohesive manner. 【0020】 The ratio of the degree of polymerization of the diene constituent units to the degree of polymerization of all constituent units constituting the polymer chain is not particularly limited, but is preferred in the following order: (1) 10% or more, (2) 20% or more, (3) 40% or more, (4) 55% or more, (5) 65% or more, (6) 75% or more, (7) 90% or more, and (8) 100% (the higher the number in parentheses, the more preferable). When this ratio is 10% or more, the elasticity tends to improve. When a polymer chain contains a diene as a constituent unit, the polymer chain may have at least one of two structures: a cis structure and a trans structure. 【0021】 The weight percentage of monomer (A) in the polymerizable component is not particularly limited, but is preferably 0.05% by weight or more. When the weight percentage is within the above range, the elasticity of the particles tends to improve. The upper limit of the weight percentage is preferably 50% by weight, more preferably 40% by weight, even more preferably 25% by weight, particularly preferably 15% by weight, and most preferably 10% by weight. On the other hand, the lower limit of the weight percentage is more preferably 0.1% by weight, even more preferably 0.3% by weight, particularly preferably 0.5% by weight, and most preferably 1% by weight. 【0022】 The polymerizable component may include monomer (A), monomer components, and monomers other than monomer (A) that have at least two reactive carbon-carbon double bonds (hereinafter sometimes simply referred to as other crosslinking agents). Furthermore, in terms of achieving the effects of the present invention, it is preferable that the polymerizable component has a monofunctional monomer. 【0023】 Examples of monofunctional monomers include nitrile monomers such as acrylonitrile, methacrylonitrile, fumaronitrile, and maleonitrile; vinyl halogenated monomers such as vinyl chloride; vinylidene halogenated monomers such as vinylidene chloride; vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl butyrate; unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, and cinnamic acid, as well as maleic acid, itaconic acid, fumaric acid, citraconic acid, and chloronitrile. Carboxyl group-containing monomers such as unsaturated dicarboxylic acids like romaleic acid, anhydrides of unsaturated dicarboxylic acids, and unsaturated dicarboxylic acid monoesters such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconate, monoethyl itaconate, and monobutyl itaconate; methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate Examples include (meth)acrylic acid ester monomers such as 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate; (meth)acrylamide monomers such as acrylamide, substituted acrylamide, methacrylamide, and substituted methacrylamide; maleimide monomers such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene monomers such as styrene and α-methylstyrene; ethylene unsaturated monoolefin monomers such as ethylene, propylene, and isobutylene; vinyl ether monomers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; vinyl ketone monomers such as vinyl methyl ketone; N-vinyl monomers such as N-vinylcarbazole and N-vinylpyrrolidone; and vinylnaphthalene salts. In carboxyl group-containing monomers, some or all of the carboxyl groups may be neutralized during or after polymerization. In this invention, acrylic acid or methacrylic acid may be referred to as (meth)acrylic acid, and acrylate or methacrylate may be referred to as (meth)acrylate. Furthermore, (meth)acrylate means acrylate or methacrylate, and (meth)acrylic means acrylic or methacrylic. These monofunctional monomers may be used individually or in combination of two or more. 【0024】 The polymerizable component is preferably a monofunctional monomer containing at least one selected from nitrile monomers, carboxyl group-containing monomers, (meth)acrylic acid ester monomers, and styrene monomers, as this improves the impact resistance of the particles. When the polymerizable component contains at least one selected from nitrile monomers, carboxyl group-containing monomers, (meth)acrylic acid ester monomers, and styrene monomers, the total weight percentage of nitrile monomers, carboxyl group-containing monomers, (meth)acrylic acid ester monomers, and styrene monomers in the polymerizable component is not particularly limited, but is preferably 50 to 99.95% by weight. The upper limit of the total weight percentage is more preferably 99.9% by weight, even more preferably 99.7% by weight, particularly preferably 99.5% by weight, and most preferably 99% by weight. On the other hand, the lower limit of the total weight percentage is more preferably 75% by weight, even more preferably 85% by weight, and particularly preferably 90% by weight. 【0025】 It is preferable that the polymerizable component includes a nitrile monomer as a monofunctional monomer, as this improves the solvent resistance of the particles. When the polymerizable component includes a nitrile monomer, the weight percentage of the nitrile monomer in the polymerizable component is not particularly limited, but is preferably 0.05 to 90% by weight. The upper limit of this weight percentage is more preferably 80% by weight, even more preferably 60% by weight, particularly preferably 40% by weight, and most preferably 30% by weight. On the other hand, the lower limit of the total weight percentage is more preferably 1% by weight, even more preferably 5% by weight, particularly preferably 10% by weight, and most preferably 15% by weight. 【0026】 The inclusion of acrylonitrile in the nitrile monomer is preferable because it improves the heat resistance of the particles. When the nitrile monomer contains acrylonitrile, the weight percentage of acrylonitrile in the nitrile monomer is not particularly limited, but is preferably 5% by weight or more. The upper limit of this weight percentage is preferably 100% by weight, more preferably 75% by weight, and even more preferably 50% by weight. On the other hand, the lower limit of this weight percentage is more preferably 10% by weight, and particularly preferably 20% by weight. 【0027】 It is preferable that the polymerizable component includes a carboxyl group-containing monomer system monomer as a monofunctional monomer, as this improves the heat resistance of the particles. When the polymerizable component includes a carboxyl group-containing monomer, the weight percentage of the carboxyl group-containing monomer in the polymerizable component is not particularly limited, but is preferably 5 to 99.95% by weight. The upper limit of this weight percentage is more preferably 95% by weight, even more preferably 90% by weight, particularly preferably 85% by weight, and most preferably 80% by weight. On the other hand, the lower limit of the total weight percentage is more preferably 10% by weight, even more preferably 20% by weight, particularly preferably 40% by weight, and most preferably 50% by weight. 【0028】 It is preferable that the polymerizable component contains (meth)acrylic acid ester monomers as monofunctional monomers, as this allows for adjustment of particle hardness. When the polymerizable component contains (meth)acrylic acid monomers, the weight percentage of (meth)acrylic acid monomers in the polymerizable component is not particularly limited, but is preferably 10 to 99.95% by weight. The upper limit of this weight percentage is more preferably 99.9% by weight, even more preferably 99.7% by weight, particularly preferably 99.5% by weight, and most preferably 99% by weight. On the other hand, the lower limit of this weight percentage is more preferably 20% by weight, even more preferably 30% by weight, particularly preferably 40% by weight, and most preferably 50% by weight. 【0029】 It is preferable that the polymerizable component contains a styrene monomer as a monofunctional monomer, as this improves the heat resistance of the particles. When the polymerizable component contains a styrene monomer, the weight percentage of the styrene monomer in the polymerizable component is not particularly limited, but is preferably 5 to 90% by weight. The upper limit of this weight percentage is more preferably 85% by weight, even more preferably 80% by weight, particularly preferably 75% by weight, and most preferably 70% by weight. On the other hand, the lower limit of the total weight percentage is more preferably 10% by weight, even more preferably 20% by weight, and particularly preferably 30% by weight. 【0030】 The polymerizable component may also contain other crosslinking agents as described above. The inclusion of other crosslinking agents in the polymerizable component is preferable because it further improves the particle strength. Other crosslinking agents include, for example, aromatic divinyl monomers such as divinylbenzene and divinylnaphthalene; and bifunctional or more (meth)acrylate monomers such as allyl methacrylate, triacrylic formal, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, PEG200# di(meth)acrylate, PEG400# di(meth)acrylate, PEG600# di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and 2-butyl-2-ethyl 1,3-propanediol di(meth)acrylate. These other crosslinking agents may be used individually or in combination of two or more. If the polymerizable component contains other crosslinking agents, the amount is not particularly limited, but is preferably 0 to 30 parts by weight per 100 parts by weight of the polymerizable component. When the amount of other crosslinking agents is 30 parts by weight or less, it tends to be possible to adjust the affinity with oil while maintaining the strength of the particles. The upper limit of the content is more preferably 15 parts by weight, and even more preferably 10 parts by weight. On the other hand, the lower limit of the content is more preferably 0.1 parts by weight, even more preferably 0.5 parts by weight, particularly preferably 1 part by weight, and most preferably 3 parts by weight. 【0031】 The weight percentage of the polymer obtained by polymerizing the above polymerizable component in the particles of the present invention is not particularly limited, but is preferably 80% by weight or more, more preferably 85% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight. That's all. , most preferably 97% by weight That's all. The effects of the present invention tend to be more pronounced when the weight percentage is 80% by weight or more. On the other hand, the upper limit of the weight percentage is preferably 100% by weight. 【0032】 The particles of the present invention may also contain inorganic components as components other than polymers obtained by polymerizing the above polymerizable components. Examples of inorganic components include silica, alumina, calcium carbonate, magnesium carbonate, calcium phosphate, magnesium oxide, magnesium hydroxide, talc, mica, and kaolin. These inorganic components may be pre-surface-treated with a coupling agent such as a silane coupling agent. These inorganic components may consist of one or more types. 【0033】 The weight percentage of inorganic components in the particles is not particularly limited, but is preferably 20% by weight or less, more preferably 15% by weight or less, even more preferably 10% by weight, particularly preferably 5% by weight or less, and most preferably 3% by weight or less. When the weight percentage is 20% by weight or less, it tends to result in a softer feel. The lower limit of the weight percentage is 0% by weight. If the particles contain inorganic components, these inorganic components may be present on the surface of the particles, inside the particles, or both. 【0034】 The oleic acid absorption capacity of the particles of the present invention is 95 mL / 100 g That's all. The oil absorption rate is preferably 95 to 300 mL / 100 g. If the oil absorption rate is less than 95 mL / 100 g, the oil's oil absorption capacity is low, resulting in a sticky surface and an inferior soft feel when used in a composition. The upper limit of the oil absorption rate is more preferably 250 mL / 100 g. On the other hand, the lower limit of the oil absorption rate is preferably 120 mL / 100 g. The amount of oleic acid absorbed by the particles is determined by the method described in the examples. 【0035】 The average particle diameter of the particles of the present invention is 2 to 100 μm. If the average particle diameter is less than 2 μm, the elasticity of the particles decreases, and the impact performance decreases. On the other hand, if the average particle diameter exceeds 100 μm, the appearance is impaired. The upper limit of the average particle diameter is preferably 90 μm, more preferably 75 μm, even more preferably 60 μm, and particularly preferably 50 μm. On the other hand, the lower limit of the average particle diameter is preferably 2 μm, more preferably 5 μm, and even more preferably 7 μm. The average particle size of the particles is determined by the method described in the examples. 【0036】 The coefficient of variation CV of the particle size distribution of the present invention is not particularly limited, but is preferably 1 to 70% in terms of suppressing defects in the appearance of the resulting composition. The upper limit of the CV is more preferably 65%, and even more preferably 50%. On the other hand, the lower limit of the CV is more preferably 3%, even more preferably 5%, particularly preferably 10%, and most preferably 15%. The CV was calculated using the following formulas (1) and (2). 【0037】 TIFF0007873559000001.tif33140(In the formula, s is the standard deviation of the particle size, <x>x is the average particle diameter. i (where n is the particle diameter of the i-th particle, and n is the number of particles.) 【0038】 The circularity of the particles of the present invention is not particularly limited, but is preferably 0.70 to 1.0 in terms of improving impact performance. The lower limit of the circularity is more preferably 0.75, even more preferably 0.80, particularly preferably 0.85, and particularly preferably 0.90. The circularity of the particles is determined by the method described in the examples. 【0039】 The particles of the present invention preferably have an isopropyl alcohol swelling ratio defined by the following formula (I) of 3.0 or less. Isopropyl alcohol swelling ratio (times) = B / A (I) A: Average particle size of particles before swelling with isopropyl alcohol B: Average particle size of particles after swelling with isopropyl alcohol When the swelling ratio is 3.0 or less, surface stickiness is suppressed when used with the composition, and the texture tends to be softer. The upper limit of the swelling ratio is more preferably 2.5, and even more preferably 2.0. On the other hand, the lower limit of the swelling ratio is preferably 1.0, more preferably 1.05, even more preferably 1.08, particularly preferably 1.1, and most preferably 1.2. 【0040】 (Particle manufacturing method) The method for producing the particles of the present invention is not particularly limited, and conventionally known methods (for example, suspension polymerization, dispersion polymerization, seed polymerization, etc.) can be employed. Among these, suspension polymerization is preferred because it allows for the efficient production of the particles of the present invention. In suspension polymerization, a suspension is typically prepared by dispersing an oily mixture containing polymerizable components in an aqueous dispersion medium in the presence of a dispersant. The suspension is then heated to polymerize the polymerizable components, thereby producing particles. The following describes the case where the particle of the present invention is manufactured by suspension polymerization. 【0041】 The method for producing the particles includes a step of dispersing an oily mixture containing polymerizable components in an aqueous dispersion medium and polymerizing the polymerizable components (hereinafter referred to as the polymerization step). In the polymerization process, it is preferable to polymerize the polymerizable components in the presence of a polymerization initiator using an oily mixture containing a polymerization initiator. 【0042】 There are no particular limitations on the polymerization initiator, but examples include peroxides and azo compounds. Examples of peroxides include peroxydicarbonates such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-octyl peroxydicarbonate, and dibenzyl peroxydicarbonate; peroxyesters such as t-butyl peroxypivalate, t-hexyl peroxypivalate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, and t-butyl peroxy 3,5,5-trimethylhexanoate; and diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide. 【0043】 Examples of azo compounds include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionate), and 2,2'-azobis(2-methylbutyronitrile). These polymerization initiators may be used individually or in combination of two or more. As polymerization initiators, oil-soluble polymerization initiators that are soluble in polymerizable components are preferred. The content of the polymerization initiator in the oily mixture is not particularly limited, but is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, and even more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the polymerizable component. 【0044】 Aqueous dispersion media are water-based media used to disperse oily mixtures. The water used in the aqueous dispersion media can be distilled water, deionized water, tap water, industrial water, etc. While water is the main component of the aqueous dispersion media, hydrophilic organic solvents such as methanol, ethanol, propanol, or acetone may also be used in combination with water. Using a mixture of water and a hydrophilic organic solvent allows for the formation of pores on the surface and within the particles. Here, "hydrophilic" means being able to be freely miscible with water. The weight percentage of water in the aqueous dispersion medium is not particularly limited, but is preferably 50 to 99.5% by weight. 【0045】 The aqueous dispersion medium may further contain an electrolyte. Examples of electrolytes include sodium chloride, magnesium chloride, calcium chloride, sodium sulfate, magnesium sulfate, ammonium sulfate, and sodium carbonate. These electrolytes may be used individually or in combination of two or more. The electrolyte content in the aqueous dispersion medium is not particularly limited, but it is preferably 0.1 to 30% by weight per 100% by weight of the aqueous dispersion medium. 【0046】 The aqueous dispersion medium may contain at least one water-soluble compound selected from water-soluble 1,1-substituted compounds having a structure in which a hydrophilic functional group selected from a hydroxyl group, a carboxylic acid (salt) group, and a phosphonic acid (salt) group and a heteroatom are bonded to the same carbon atom, potassium dichromate, alkali metal nitrites, metal (III) halides, boric acid, water-soluble ascorbic acids, water-soluble polyphenols, water-soluble vitamin B compounds, and water-soluble phosphonic acid (salts). In this invention, "water-soluble" means a state in which 1 g or more dissolves per 100 g of water. 【0047】 The amount of water-soluble compound contained in the aqueous dispersion medium is not particularly limited, but is preferably 0.0001 to 1.0 part by weight, more preferably 0.0003 to 0.1 parts by weight, and even more preferably 0.001 to 0.05 parts by weight, per 100 parts by weight of polymerizable component. If the amount of water-soluble compound is too small, the effect of the water-soluble compound may not be sufficiently obtained. Conversely, if the amount of water-soluble compound is too large, the polymerization rate may decrease or the amount of residual monomer, which is the raw material, may increase. 【0048】 The aqueous dispersion medium preferably contains a dispersant and / or a surfactant in addition to water and a hydrophilic organic solvent. Examples of dispersants include poorly water-soluble inorganic compounds such as colloidal silica, calcium phosphate, magnesium phosphate, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium pyrophosphate, and magnesium pyrophosphate; and water-soluble polymers such as polyvinyl alcohol, methylcellulose, and polyvinylpyrrolidone. These dispersants may be used individually or in combination of two or more. Among these, poorly water-soluble inorganic compounds are preferred, and colloidal silica is particularly preferred. The amount of dispersant contained in the aqueous dispersion medium is not particularly limited, but is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, per 100 parts by weight of polymerizable component. 【0049】 As surfactants, low molecular weight surfactants with a molecular weight of less than 1000 are preferred, and examples include anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkylnaphthalene sulfonates, and alkyl phosphate salts; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, and adipic acid-diethanolamine condensates; and amphoteric surfactants such as lauryldimethylamine oxide and lauryldimethylaminoacetic acid betaine. These surfactants may be used individually or in combination of two or more. The amount of surfactant contained in the aqueous dispersion medium is not particularly limited, but is preferably 0.01 to 5 parts by weight per 100 parts by weight of the monomer mixture. 【0050】 Aqueous dispersion media are prepared, for example, by adding hydrophilic organic solvents, electrolytes, water-soluble compounds, dispersants, surfactants, etc., to water (ion-exchanged water) as needed. The pH of the aqueous dispersion media during polymerization is appropriately determined depending on the type of dispersant used. There are no particular limitations on the amount of water in the aqueous dispersion medium, but it is preferably 100 to 1000 parts by weight per 100 parts by weight of polymerizable component. 【0051】 In the polymerization process, first, an oily mixture is dispersed in an aqueous dispersion medium so that spherical oil droplets of a predetermined particle size are prepared. Methods for dispersing oily mixtures include, for example, stirring with a homomixer (e.g., manufactured by Primix), homodisperser (e.g., manufactured by Primix), or Clearmix (manufactured by M-Technique), or using a static dispersion device such as a static mixer (e.g., manufactured by Noritake Engineering), or general dispersion methods such as membrane emulsification, ultrasonic dispersion, or microchannel methods. 【0052】 Next, polymerization is initiated by heating the dispersion (suspension) in which the oily mixture is dispersed as oil droplets in an aqueous dispersion medium. The polymerization temperature can be freely set depending on the type of polymerization initiator, but is preferably controlled within the range of 40 to 100°C, more preferably 45 to 90°C. The time for maintaining the reaction temperature is preferably about 1 to 20 hours. The initial polymerization pressure is in the range of 0 to 5 MPa, more preferably 0.1 to 3 MPa, in gauge pressure. During the polymerization reaction, it is preferable to stir the dispersion, and the stirring should be done gently enough to prevent, for example, the monomer from floating to the surface and the polymerized particles from settling. By carrying out the polymerization process in this manner, an aqueous dispersion (slurry) containing particles can be obtained. 【0053】 The particle manufacturing method may include, as necessary, steps for decomposing the dispersant, filtration, washing, drying, grinding, and classification, in addition to the polymerization step, and may also include steps for attaching inorganic powder. The order and number of times these steps are performed are not particularly limited. The step for decomposing the dispersant refers to the step of decomposing the poorly water-soluble inorganic compound used as a dispersant by adding an acid or base to an aqueous dispersion (slurry) containing the particles. 【0054】 The filtration process involves separating the solid and liquid components of an aqueous dispersion (slurry) containing particles using a filtration device to obtain a wet cake with a water content of 5 to 50% by weight, preferably 7 to 30% by weight. Examples of filtration devices include centrifugal separators, pressure presses, and vacuum dewatering machines. By appropriately changing the settings of these devices, the water content of the resulting wet cake can be adjusted. In the drying process, the wet cake can be dried using a shelf dryer, indirect heating dryer, fluidized bed dryer, vacuum dryer, vibrating dryer, airflow dryer, etc., to obtain a dry powder with a moisture content of 5% by weight or less. Alternatively, the slurry can be dried using a spray dryer, fluidized bed dryer, etc., to obtain a dry powder. 【0055】 When the particles consist of a polymer of the polymerizable component described above, inorganic powder may be attached to the particles as described above. The inorganic powder may be the same as the inorganic component described above. There are no particular limitations on the method of attaching the inorganic powder, but examples include mixing the particles and the inorganic powder using a known powder mixer, etc., while heating as necessary. There are no particular limitations on the amount of inorganic powder to be attached, but it is preferably 1 to 15 parts by weight per 100 parts by weight of particles. 【0056】 (wet powder particles) The wet powder particles of the present invention are in a wet powder state containing the above-mentioned particles and a liquid organic compound and / or water, and can improve the handling properties of the particles. Alternatively, the wet powder particles may be the above-mentioned wet cake. Examples of liquid organic compounds include alkylene glycol, polyalkylene glycol, glycerin, process oil, liquid paraffin, naphthenic oil, aromatic oil, fats and oils, silicone oil, and the hydrophilic organic solvents mentioned above. For the water used, distilled water, deionized water, tap water, or industrial water may be used, for example. 【0057】 In the wet powder particles of the present invention, the total content of the liquid organic compound and water is not particularly limited, but is preferably 1 to 100 parts by weight per 100 parts by weight of particles. When the total content is within the above range, it tends to maintain high handling properties. The upper limit of the total content is more preferably 45 parts by weight, even more preferably 30 parts by weight, and particularly preferably 20 parts by weight. On the other hand, the lower limit of the total content is more preferably 5 parts by weight. 【0058】 (Method for producing wet powder particles) In the wet powder particles of the present invention, there are no particular limitations on the method of manufacturing them, but examples include the following (1) to (4). (1) A method of separating the slurry obtained in the polymerization step from solid to liquid and converting the resulting wet cake into wet powder particles. (2) A method of obtaining a wet cake by separating the slurry obtained in the polymerization step from solid and liquid, and then mixing the obtained wet cake with a liquid organic compound and / or water to obtain wet powder particles. (3) A method of obtaining wet cake by solid-liquid separation of the slurry obtained in the polymerization step, then drying the obtained wet cake to obtain dried particle powder, and then mixing the obtained dried particle powder with a liquid organic compound and / or water to obtain wet powder particles. In the methods described in (2) and (3) above, a general powder mixer such as a ribbon mixer, a vertical screw mixer, or a super mixer can be used as the apparatus for mixing the wet cake or dried powder particles with the liquid organic compound and / or water. 【0059】 (composition) The composition of the present invention comprises at least one selected from the above-mentioned particles and the above-mentioned wet powder particles, and a base component, excluding rubber compositions for tires. The base material is not particularly limited and includes rubbers such as natural rubber, butyl rubber, silicone rubber, and ethylene-propylene-diene rubber (EPDM); thermosetting resins such as unsaturated polyester, epoxy resin, and phenolic resin; waxes such as polyethylene wax and paraffin wax; ethylene-vinyl acetate copolymer (EVA), ionomer, polyethylene, polypropylene, polyvinyl chloride (PVC), acrylic resin, thermoplastic polyurethane, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polystyrene (PS), polyamide resin (nylon 6, nylon 66, etc.), polycarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacetal (POM), and polyphenylene sulfide. Examples of base materials include thermoplastic resins such as PPS; thermoplastic elastomers such as olefin-based elastomers and styrene-based elastomers; bioplastics such as polylactic acid (PLA), cellulose acetate, PBS, PHA, and starch resins; sealing materials such as silicone-based, modified silicone-based, polysulfide-based, modified polysulfide-based, urethane-based, acrylic-based, polyisobutylene-based, and butyl rubber-based materials; liquid components such as emulsions and plastisols of urethane-based, ethylene-vinyl acetate copolymer-based, vinyl chloride-based, and acrylic-based materials; inorganic materials such as cement, mortar, and cordierite; and organic fibers such as cellulose, kenaf, wheat bran, aramid fibers, phenol fibers, polyester fibers, acrylic fibers, polyolefin fibers such as polyethylene and polypropylene, polyvinyl alcohol-based fibers, and rayon. These base materials may be used individually or in combination of two or more types. 【0060】 The weight percentage of at least one type selected from particles and wet powder particles in the composition of the present invention is not particularly limited, but is preferably 0.01 to 80% by weight. When the weight percentage is within this range, the composition tends to have a soft feel and excellent impact performance and appearance. The upper limit of the weight percentage is more preferably 65% ​​by weight, even more preferably 50% by weight, particularly preferably 25% by weight, and most preferably 10% by weight. On the other hand, the lower limit of the weight percentage is more preferably 0.05% by weight, even more preferably 0.1% by weight, particularly preferably 0.3% by weight, and most preferably 0.5% by weight. 【0061】 The composition of the present invention may further contain various additives as needed, such as inorganic fillers, vulcanizing or crosslinking agents, vulcanizing or crosslinking accelerators, antioxidants, anti-aging agents, foaming agents, and coloring pigments. The content of these additives can also be in conventional amounts, as long as it does not hinder the objective of the present invention. 【0062】 The method of manufacturing the composition of the present invention is not particularly limited, but any conventionally known method may be used. For example, a method of mechanically mixing or molding the composition uniformly using a homomixer, static mixer, Henschel mixer, tumbler mixer, planetary mixer, kneader, roll, mixing roll, mixer, single-screw kneader, twin-screw kneader, multi-screw kneader, etc. [Examples] 【0063】 The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples described herein. Unless otherwise specified, the particles used in the measurements refer to dry particles. 【0064】 [Measurement of average particle diameter and particle size distribution] The particle size distribution was measured using a wet measurement method with a laser diffraction particle size distribution analyzer (Microtrac 9320HRA×100, manufactured by Nikkiso Co., Ltd.), and the D50 value obtained by volume-based measurement was used as the average particle size. 【0065】 [Measurement of absorption amount for oleic acid] 1 g of particles was accurately weighed (Wg) onto a smooth glass plate, oleic acid was added dropwise from a burette, and kneaded with a metal spatula. This process was repeated, and the amount of oleic acid added just before it began to seep out (VmL) was measured when the spatula was pressed down at the end. The amount absorbed was then calculated using the following formula. Absorption amount (mL / 100g) = V (mL) / W (g) × 100 【0066】 [Measurement of isopropyl alcohol swelling ratio] Approximately 10 mg of particles were placed on a glass slide, and the average particle size (A) was measured using an optical microscope and Mac-View Ver.4, an image analysis-based particle size distribution software manufactured by Mountec Co., Ltd. Then, 0.5 mL of IPA was dropped onto the particles and left at 23°C, and the swelling process was observed using an optical microscope. The average particle size (B) was then measured when the swelling reached equilibrium. The swelling ratio (times) of isopropyl alcohol is calculated according to the following formula. Isopropyl alcohol swelling ratio (times) = B / A A: Average particle size (μm) of particles before swelling with isopropyl alcohol. B: Average particle size (μm) of particles after swelling with isopropyl alcohol. The above measurement was performed five times, and the average value was used as the isopropyl alcohol swelling ratio of the particles. 【0067】 [Measurement of circularity] Approximately 10 mg of particles were placed on adhesive tape, sputtered with platinum, and then observed using an electron microscope. The circularity of 100 randomly selected particles was measured using Mac-View Ver.4, an image analysis particle size distribution software manufactured by Mountec Co., Ltd. 【0068】 <Example 1> An aqueous dispersion medium was prepared by adding 50 parts by weight of sodium chloride, 20 parts by weight of colloidal silica containing 20% ​​by weight of silica as the active ingredient, and 0.5 parts by weight of an aqueous solution of adipic acid-diethanolamine condensate (effective concentration 50% by weight), a low molecular weight nonionic surfactant, to 200 parts by weight of deionized water and mixing, and then adjusting the pH to 2.8 to 3.2. Separately, 99 parts by weight of n-butyl acrylate, 1 part by weight of polybutadiene diacrylate (Sartomer Co., Ltd., product code CN-307), and 0.5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed and dissolved to obtain an oily mixture. The aqueous dispersion medium and oily mixture obtained above were stirred (8000 rpm x 1 min) in a TK Homomixer Type 2.5 (Primix Corporation) to prepare a suspension. This suspension was transferred to a 1.5-liter pressurized reactor, purged with nitrogen, and the initial reaction pressure was set to 0.2 MPa. Polymerization was carried out at a polymerization temperature of 65°C for 15 hours while stirring at 80 rpm to obtain an aqueous dispersion containing particles. The aqueous dispersion containing the obtained particles was filtered and dried to obtain the particles themselves. Their physical properties are shown in Table 1. 【0069】 <Examples 2-11, Comparative Examples 1-3> In Examples 2-11 and Comparative Examples 1-3, particles were obtained in the same manner as in Example 1, except that the type and amount of raw materials used were changed to those shown in Table 1. The physical properties of the obtained particles are shown in Tables 1-2. Note that the abbreviations shown in Table 3 are used in Tables 1 and 2. 【0070】 <Preparation and evaluation of compositions> A styrene-based elastomer mixture was prepared by uniformly kneading 90 parts by weight of styrene-based elastomer (hardness A: 26) and 10 parts by weight of the particles obtained in Example 1 in a kneader. Next, this styrene-based elastomer mixture was extruded using a vented single-screw extruder (screw diameter φ65 mm) to produce a composition. The molding temperature during extrusion was 160°C, and the die shape was a rectangle with a width of 150 mm and a thickness of 20 mm. The impact performance and tackiness of the prepared composition were evaluated by the methods described. The results are shown in Table 1. The particles obtained in Examples 2-11 and Comparative Examples 1-3 were used to prepare styrene-based elastomer mixtures in the same manner as described above, and the compositions were evaluated. The results are shown in Tables 1-2. 【0071】 [Evaluation of impact performance] The impact performance of the obtained compositions was measured using a rebound elasticity tester (FR-2 type, manufactured by Polymer Instruments Co., Ltd.) in accordance with JIS K6400-3. The impact performance of the composition was determined based on the following evaluation criteria. ○: The rebound elasticity of the composition containing particles is maintained at 80% or more compared to the molded product without particles, and there is no dent in the molded product after the test. ×: The rebound elasticity of the composition containing particles is less than 80% of that of the molded product without particles, or the molded product is indented after testing. 【0072】 [Evaluation of stickiness] After leaving the compositions at 23°C for two days, five panelists evaluated them by touch. A ○ was given if all five panelists evaluated that there was no stickiness, a △ was given if 3-4 panelists evaluated that there was no stickiness, and a × was given for all other cases. 【0073】 [Table 1] 【0074】 [Table 2] 【0075】 [Table 3] 【0076】 As can be seen from the results in Tables 1 and 2, when particles containing a polymerizable component including monomer (A), with an oleic acid oil absorption of 95 mL / 100 g or more and an average particle diameter of 2 to 100 μm, it was possible to suppress the decrease in impact performance and appearance defects while maintaining the soft tactile feel that the base material component originally possesses. On the other hand, when particles that did not use monomer (A) (Comparative Example 1), particles with an oleic acid oil absorption of less than 95 mL / 100 g (Comparative Example 2), and particles with an average particle diameter outside the range of 2 to 100 μm (Comparative Example 3) were used, it was not possible to solve all of the problems of the present invention, namely maintaining the soft tactile feel that the base material component originally possesses, suppressing the decrease in impact performance, and suppressing appearance defects. [Industrial applicability] 【0077】 The particles of the present invention can be used as an additive to base components. They can also be used as ingredients in cosmetics and topical pharmaceuticals.< / x>

Claims

[Claim 1] A solid polymer particle comprising a monomer having one reactive carbon-carbon double bond and a polymerizable component containing the monomer (A) described below, The weight percentage of monomer (A) in the polymerizable component is 0.3 to 15% by weight. Polymer particles having an oleic acid absorption capacity of 95 mL / 100 g or more and an average particle size of 2 to 100 μm. Monomer (A): A compound having an acryloyl group and / or a methacryloyl group, and having a reactive carbon-carbon double bond in addition to the acryloyl group and methacryloyl group, having a molecular weight of 200 or more, and represented by the following general formula (1). R １ -O-R ２ -O-R ３ (1) (In the formula, R １ and R ３ Each of these is independently an acryloyl group or a methacryloyl group, and R ２ (It has polymer chains, and these polymer chains have reactive carbon-carbon double bonds.) [Claim 2] The particles according to claim 1, wherein the weight percentage of the monomer having one reactive carbon-carbon double bond in the polymerizable component is 78 to 99.7% by weight. [Claim 3] The particle according to claim 1 or 2, wherein the polymer chain contains a diene as a constituent unit. [Claim 4] The particle according to claim 3, wherein the diene is butadiene and / or isoprene. [Claim 5] The particle according to any one of claims 1 to 4, wherein the monomer having one reactive carbon-carbon double bond comprises at least one selected from nitrile monomers, carboxyl group-containing monomers, (meth)acrylic acid ester monomers, and styrene monomers. [Claim 6] Moist powdery particles comprising the particles according to any one of claims 1 to 5, and a liquid organic compound and / or water. [Claim 7] A composition comprising at least one selected from the particles described in any one of claims 1 to 5 and the wet powdery particles described in claim 6, and a base component (excluding rubber compositions for tires).

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