Molding and curable composition

Abstract

To provide a molding capable of sustaining high abrasion resistance for a long period.SOLUTION: A molding has: a base part 2 containing, as a main component an organosilicon compound having a siloxane bond; and a fine particle 5 partly buried in the base part 2 and partly protruded from a surface, wherein the fine particle 5 contains, as a main component, any of silica, alumina, and titania, and a molding is obtained by dispersing a particle 4 forming a protrusion on a surface of the base part 2 in a matrix resin 1.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present disclosure relates to a molded article suitable for a sliding member and a curable composition suitable as a raw material thereof. [Background technology]

[0002] Resin materials are generally used for sliding components such as bearings, gears, cams, rollers, etc., because they have excellent self-lubricating properties, are lightweight, and produce little noise when sliding. In order to further reduce energy loss and noise and to inhibit deterioration of components, resin materials that exhibit sliding characteristics such as a lower friction coefficient and higher wear resistance are required. Patent Document 1 discloses that a resin molded body is obtained by using a resin composition containing a polycarbonate resin and irregularly shaped fine particles having a surface formed by concave faces of each of the faces of a polyhedron having 6 or more sides. Patent Document 2 discloses that lubricity and abrasion resistance can be imparted by adding composite particles made of organic resin particles coated with polyorganosiloxane to plastics. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2011-057785 A [Patent Document 2] JP 2014-162920 A Summary of the Invention [Problem to be solved by the invention]

[0004] According to the study by the present inventors, in the resin composition using the fine particles disclosed in Patent Document 1, the fine particles dispersed in the resin composition reduce the contact area with the opposing member on the sliding surface and act as a solid lubricant, which is expected to improve the sliding characteristics. In addition, since the surface of the fine particles has polyhedral recesses, the contact area with the matrix resin constituting the molded body is increased, which has the advantage that the fine particles are unlikely to separate from the matrix resin even under high-load sliding conditions. However, since the material surrounding the recesses is also silicone, there is a problem that the contact area with the opposing member increases due to long-term sliding or high-load sliding, as the convex parts on the surface of the fine particles or the entire fine particles are crushed or deformed, and the initial sliding characteristics cannot be maintained. According to the study by the present inventors, the resin material using the composite particles disclosed in Patent Document 2 has improved sliding properties due to the surfaces of the resin particles dispersed in the resin material being coated with silicone, but since the protrusions on the surface are also made of silicone, there is a problem in that the initial sliding properties cannot be maintained for the same reason as the particles described in Patent Document 1. In addition, with regard to the particles dispersed in the resin material, the relationship between the hardness of the resin particles inside the particles and the silicone constituting the protrusions on the surfaces of the resin particles is not disclosed, leaving room for improvement. In order to solve the above-mentioned problems, the present disclosure aims to provide a technique that is advantageous in realizing a molded article having good mechanical properties and a curable composition suitable as a raw material for the molded article. [Means for solving the problem]

[0005] A first molded body according to the present disclosure is a molded body including a matrix resin and a plurality of particles dispersed in the matrix resin, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, The convex portion is mainly composed of an inorganic material, The particle is characterized in that it has the base and fine particles, the base is particulate having a recess on its surface, and the fine particles have a first portion embedded in the recess of the base and a second portion forming the convex portion. A second molded body according to the present disclosure is a molded body including a matrix resin and a plurality of particles dispersed in the matrix resin, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, the protrusion has a higher Young's modulus than the base; The particle is characterized in that it has the base and fine particles, the base is particulate having a recess on its surface, and the fine particles have a first portion embedded in the recess of the base and a second portion forming the convex portion. A first curable composition according to the present disclosure is a curable composition including a plurality of particles and a curable resin material, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, The convex portion is mainly composed of an inorganic material, The particle is characterized in that it has the base and fine particles, the base is particulate having a recess on its surface, and the fine particles have a first portion embedded in the recess of the base and a second portion forming the convex portion. A second curable composition according to the present disclosure is a curable composition including a plurality of particles and a curable resin material, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, the protrusion has a higher Young's modulus than the base; The particle is characterized in that it has the base and fine particles, the base is particulate having a recess on its surface, and the fine particles have a first portion embedded in the recess of the base and a second portion forming the convex portion. Effect of the Invention

[0006] According to the present disclosure, it is possible to provide an advantageous technique for realizing a molded body having good mechanical properties. [Brief description of the drawings]

[0007] [Figure 1] FIG. 2 is a schematic diagram for explaining the function of protrusions of a particle. [Diagram 2] FIG. 2 is a schematic diagram for explaining the structure of one embodiment of a particle. [Diagram 3] FIG. 1 is a diagram showing an example of the configuration of a photo-lithography apparatus suitable for manufacturing a molded body. [Figure 4] 1 is an SEM image of particle No. 3. [Diagram 5] FIG. 1 is a diagram showing an example of the configuration of a machine equipped with a molded body. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] First, the molded body of this embodiment will be described, and then the curable composition suitable for producing the molded body will be described. The molded body of this embodiment can have good mechanical properties. The molded body of this embodiment can maintain high abrasion resistance for a long period of time. The molded body of this embodiment can also have good mechanical properties in terms of strength, elasticity, and other aspects.

[0009] [Molded body] FIG. 1 is a schematic cross-sectional view of the molded body of this embodiment, in which 1 is a matrix resin and 4 is a particle. The molded body of this embodiment contains a matrix resin 1 and a particle 4, and the particle 4 is dispersed in the matrix resin 1. The particle 4 has a base 2 and a protrusion 3. The surface of the base 2 and the surface of the protrusion 3 are each a part of the outer surface of the particle 4, and the surface of the protrusion 3 protrudes toward the outside of the particle 4 relative to the surface of the base 2. The particle 4 has a protrusion 3, which makes the particle 4 non-spherical. Therefore, the particle 4 can be called a non-spherical particle. The protrusion 3 contains a material harder than the base 2. The main component of the base 2 is an organic substance, and for example, the main component is an organosilicon compound (silicone) having a Si-O-Si bond (siloxane bond). The main component of the protrusion 3 is an inorganic substance, and for example, the main component is a material harder than silicone. Since the particle 4 is composed of materials with different hardnesses, the particle 4 can also be called a composite particle.

[0010] With this configuration, when a load is applied to the sliding surface, the harder protrusions 3 do not deform, and the load can be reduced by the deformation of the softer base 2. Therefore, in the molded product of this embodiment, the contact area with the opposing member on the sliding surface is unlikely to change, and since the contact area of ​​the particles 4 with the matrix resin 1 is large, they are unlikely to separate and are unlikely to be embedded inside the matrix resin 1. Therefore, it is presumed that the initial wear resistance is maintained for a long period of time.

[0011] In FIG. 1, (a) shows the initial state of the molded body, and (b) shows the state after use when the molded body is used as a sliding member. As shown in FIG. 1(a), in the initial state, a part of the particles 4 is exposed on the surface of the matrix resin 1. When the molded body is used as a sliding member in this state, the particles 4 on the surface come into contact with an opposing member and receive a load. However, the particles 4 according to this embodiment have a higher Young's modulus than the base 2, and do not collapse even when subjected to a load, and maintain a state of protruding from the surface of the particles 4. Therefore, due to the anchor effect of the protrusions 3, the particles 4 are less likely to fall off the matrix resin 1, and the state in which the particles 4 are embedded in the matrix resin 1 is maintained, and excellent sliding properties can be obtained for a long period of time. Hereinafter, the particles 4 and the matrix resin 1 contained in the molded product of this embodiment will each be described in detail.

[0012] <particle> The particle 4 according to this embodiment is, for example, a particle containing silicone, and has a base 2 made of silicone and a protrusion 3 supported by the base 2 and disposed on the surface of the particle 4, and the protrusion 3 is made of a material having a higher Young's modulus than silicone. The silicone in this embodiment is composed of at least one of silicon compounds (silane monomers) represented by any of the following structures (a), (b), and (c). The total content of structures (a), (b), and (c) in the base 2 is usually 80% by mass to 100% by mass. The base 2 may have a core-shell structure, in which case at least one of the core and the shell, preferably at least the core, and more preferably both the core and the shell, may be composed of silicone.

[0013] [ka] (R 1 , R 2 represents an alkyl group having 1 to 6 carbon atoms.

[0014] The Young's modulus of the base 2 is preferably 0.005 GPa or more and 25,000 GPa or less. Although it depends on the Young's modulus of the material constituting the protrusion 3, when the Young's modulus of the base 2 is 0.005 GPa or more and the particles 4 are deformed during stress relaxation, the protrusion 3 is less likely to be embedded in the base 2, the contact area with the opposing member is kept small, and the specific wear amount can be kept small. In addition, when the Young's modulus is 25,000 GPa or less, the stress received from the opposing member can be sufficiently relaxed, and crushing and embedding of the particles 4 in the matrix resin 1 can be suppressed, and the initial sliding characteristics can be maintained for a long period of time. Therefore, when the Young's modulus of the base 2 is within the above range, when a load is applied to the sliding surface, the stress due to the load can be relaxed, and crushing of the particles 4 and embedding of the particles 4 in the matrix resin 1 can be suppressed. The Young's modulus of the base 2 is more preferably 0.0100 GPa or more and 20,000 GPa or less.

[0015] The Young's modulus of the base 2 in this embodiment can be controlled by changing the material composition of the silane monomer constituting the organosilicon compound, which is the main component of the base 2, the temperature, time, pH, and type of catalyst in the hydrolysis step and condensation step. For example, when it is desired to increase the Young's modulus, it is possible to increase the mixing ratio of the silane monomer having the above-mentioned (a) structure, decrease the mixing ratio of the silane monomer having the above-mentioned (b) or (c) structure, increase the temperature of the hydrolysis step and condensation step, increase the time of the hydrolysis step and condensation step, increase the pH of the hydrolysis step and condensation step, etc. When it is desired to decrease the Young's modulus, it is possible to decrease the mixing ratio of the silane monomer having the above-mentioned (a) structure, increase the mixing ratio of the silane monomer having the above-mentioned (b) or (c) structure, add the silane monomer having the above-mentioned (a) structure after the hydrolysis step of the silane monomer having the above-mentioned (b) or (c) structure, decrease the temperature of the hydrolysis step and condensation step, decrease the time of the hydrolysis step and condensation step, decrease the pH of the hydrolysis step and condensation step, etc.

[0016] The method for producing the particles 4 according to this embodiment is not particularly limited, but it is preferable to form the particles 4 through hydrolysis of a silane monomer by a sol-gel method and a condensation polymerization reaction. Specifically, it is preferable to use at least one of a tetrafunctional silane monomer having the above structure (a), a trifunctional silane monomer having the above structure (b), and a bifunctional silane monomer having the above structure (c), hydrolyze and condense polymerize the silane monomer, and react any one of fine particles of silica, titania, and alumina therewith to form composite particles 4.

[0017] The proportion of silane monomers having the (a) structure is preferably 5 mol% or more and 70 mol% or less, more preferably 20 mol% or more and 65 mol% or less. The proportion of silane monomers having the (b) structure is preferably 90 mol% or less, more preferably 70 mol% or less. The proportion of silane monomers having the (c) structure is preferably 5 mol% or more and 90 mol% or less, more preferably 10 mol% or more and 80 mol% or less.

[0018] The method for producing the base 2 is not particularly limited, and for example, the base 2 can be obtained by dropping a silane monomer into water, hydrolyzing and condensing the resulting suspension with a catalyst, and then filtering and drying the resulting suspension. The particle size of the base 2 can be controlled by the type of catalyst, the compounding ratio, the reaction start temperature, the dropping time, etc. Examples of the catalyst include acidic catalysts such as hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, and examples of basic catalysts include ammonia water, sodium hydroxide, and potassium hydroxide, but are not limited to these.

[0019] The particles 4 are preferably produced by the following method. Specifically, the method preferably includes a first step of obtaining a hydrolyzate of a silane monomer, a second step of mixing the hydrolyzate with an alkaline aqueous medium and a metal oxide of silica, titania or alumina, polycondensing the hydrolyzate and reacting it with a metal oxide of silica, titania or alumina, and a third step of mixing the polycondensation reaction product with an aqueous solution to form particles. The silica, titania and alumina may be added by dispersing them in the aqueous solution in advance in the third step, or may be added after forming particles.

[0020] The particles 4 according to the present embodiment can be subjected to a surface treatment as necessary to adjust the dispersibility in a matrix resin or a radical polymerizable compound. For the surface treatment, a known means such as a disilazane compound or a silane coupling agent can be used.

[0021] In the first step, the silane monomer is brought into contact with the catalyst by stirring, mixing, or the like in an aqueous solution in which an acidic or alkaline substance serving as a catalyst is dissolved in water. Known catalysts can be suitably used. Specifically, examples of acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0022] The amount of the catalyst used may be appropriately adjusted depending on the type of silane monomer and catalyst. Preferably, the amount of the catalyst used is 1×10 -3 The amount is selected from the range of 1 part by mass to 1 part by mass. The amount of catalyst used is 1×10 -3 If the amount of catalyst used is 1 part by mass or more, the reaction proceeds sufficiently. On the other hand, if the amount of catalyst used is 1 part by mass or less, the concentration of impurities remaining in the fine particles is low, making hydrolysis easier. The amount of water used is preferably 2 moles or more and 15 moles or less per mole of silane monomer. If the amount of water is 2 moles or more, the hydrolysis reaction proceeds sufficiently, and if it is 15 moles or less, productivity is improved.

[0023] The reaction temperature is not particularly limited and may be performed at room temperature or under heating, but since a hydrolysate can be obtained in a short time and a partial condensation reaction of the produced hydrolysate can be suppressed, it is preferable to carry out the reaction at a temperature maintained at 10° C. to 60° C. The reaction time is not particularly limited and may be appropriately selected in consideration of the reactivity of the silane monomer used, the composition of the reaction liquid obtained by mixing the silane monomer, acid, and water, and the productivity.

[0024] In the second step of the method for producing the particles 4, the raw material solution obtained in the first step is mixed with an alkaline aqueous medium to polycondense the particle precursor. This produces a polycondensation reaction liquid. The alkaline aqueous medium is a liquid obtained by mixing an alkaline component, water, and, if necessary, an organic solvent.

[0025] The alkaline component used in the alkaline aqueous medium is one whose aqueous solution is basic and acts as a neutralizer for the catalyst used in step 1 and as a catalyst for the polycondensation reaction in step 2. Examples of such alkaline components include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia; and organic amines such as monomethylamine and dimethylamine. The amount of the alkaline component used is an amount that neutralizes the acid and effectively acts as a catalyst for the polycondensation reaction. For example, when ammonia is used as the alkaline component, the amount is usually selected in the range of 0.01 parts by mass or more and 12.5 parts by mass or less per 100 parts by mass of the mixture of water and the organic solvent.

[0026] In the second step, in order to prepare an alkaline aqueous medium, an organic solvent may be used in addition to the alkaline component and water. The organic solvent is not particularly limited as long as it is compatible with water, but an organic solvent that dissolves 10 g or more of water per 100 g at room temperature and normal pressure is preferred.

[0027] Specific examples of the alcohol include alcohols such as methanol, ethanol, n-propanol, 2-propanol, and butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; ethers such as ethylene glycol monoethyl ether, acetone, diethyl ether, tetrahydrofuran, and diacetone alcohol; and amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Among the organic solvents listed above, preferred are alcohol solvents such as methanol, ethanol, 2-propanol, butanol, etc. Furthermore, from the viewpoint of hydrolysis and dehydration condensation reactions, it is more preferred to select as the organic solvent the same alcohol as the alcohol produced by elimination.

[0028] In the third step, the polycondensation reaction product obtained in the second step is mixed with an aqueous solution to form particles. As the aqueous solution, water (tap water, pure water, etc.) can be suitably used, but a component that is compatible with water, such as a salt, an acid, an alkali, an organic solvent, a surfactant, or a water-soluble polymer, may be further added to the water. The temperature of the polycondensation reaction liquid and the aqueous solution when they are mixed is not particularly limited, and is suitably selected in the range of 5°C to 70°C in consideration of their composition, productivity, etc.

[0029] The method for recovering the particles 4 can be any known method without any particular limitation. For example, a method of scooping floating particles or a filtration method can be mentioned, but a filtration method is preferred because of its simple operation. The filtration method is not particularly limited, and a known device such as reduced pressure filtration, centrifugal filtration, or pressure filtration can be selected. The filter paper, filter, filter cloth, etc. used in the filtration are not particularly limited as long as they are industrially available, and can be appropriately selected depending on the device to be used.

[0030] The silane monomer to be used can be appropriately selected based on the compatibility with the solvent and catalyst, hydrolysis property, etc. Examples of the tetrafunctional silane monomer having the above (a) structure include tetramethoxysilane, tetraethoxysilane, tetraisocyanatesilane, etc., among which tetraethoxysilane is preferred.

[0031] Examples of trifunctional silane monomers having the structure (b) include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, ethoxymethoxysilane, ethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxyhydroxy ...methoxyhydroxysilane, ethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysilane, ethoxymethoxyhydroxysil Examples of the silane include ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane. Of these, methyltrimethoxysilane is preferred.

[0032] Examples of the bifunctional silane monomer having the above (c) structure include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane, and the like. Of these, dimethyldimethoxysilane is preferred.

[0033] As described above, the Young's modulus of the protrusions 3 formed on the surface of the particle 4 according to this embodiment is higher than that of the base 2. This allows the load on the sliding surface to be reduced by deformation of the base 2 without deformation of the protrusions 3 having a high Young's modulus. Therefore, the contact area with the opposing member on the sliding surface is unlikely to change, and the initial sliding characteristics can be maintained for a long period of time. The Young's modulus of the protrusions 3 is preferably 50 GPa or more and 500 GPa or less. If the Young's modulus of the protrusions 3 is 50 GPa or more, the contact area with the opposing member is small and the wear resistance is high. If it is 500 MPa or less, the protrusions 3 tend not to detach from the base 2 easily.

[0034] The shape of the protrusions 3 is not particularly limited, but for example, the above metal oxides in the shape of rods or fibers can be used. In the case of fiber shapes, a mesh-like protrusion 3 can be formed on the surface. It is more preferable that the protrusions 3 are composed of spherical fine particles (fine particles) in which a part of the protrusions 3 is embedded in the base 2 while another part of the protrusions 3 protrudes from the surface of the base 2, because the fine particles are less likely to detach from the surface of the base 2 even when a load is applied to the sliding surface. Consider a sphere of radius r and a hemisphere cut by a plane (cross section) passing through the center of the sphere. The area of ​​the cross section of the hemisphere is πr. 2 and the area of ​​the hemisphere is 2πr 2 When the cross section of a hemispherical particle with a radius r is in contact with a spherical base 2 (X), the contact area between the particle and the base 2 is πr 2In contrast, when half of a spherical particle with a radius r is embedded in the base 2 and the hemispherical surface of the spherical particle with a radius r is in contact with the base 2 (Y), the contact area between the particle and the base 2 is 2πr 2 In this way, the contact area can be made larger in case (Y) than in case (X), and it can be seen that by burying the particles in the base 2, the particles are less likely to detach from the surface of the base 2. That is, it is preferable that the particle 4 is composed of a base 2 and fine particles, the base 2 is particulate with a recess on the surface, the fine particles have a first portion that is embedded in the recess and a second portion that is a protruding portion protruding from the base 2, and the second portion forms the protrusion 3. Examples of inorganic substances as the main component of the protrusion 3 include metals (including alloys) and metal compounds such as metal oxides, metal nitrides, metal carbides, and metal borides, but metal compounds, particularly metal oxides, are preferable. In this embodiment, the metalloid element can be treated as both a metal element and a nonmetallic element. For example, silicon (Si) is a typical example of a metalloid element, but metals include metallic silicon, and metal compounds include silicon oxide, silicon nitride, and silicon carbide. It is preferable that the fine particles are mainly composed of any of silica, titania, and alumina. Silica is a type of silicon oxide.

[0035] FIG. 2 shows a schematic cross-sectional view of a case where the convex portion 3 of the particle 4 according to the present embodiment is made of a fine particle. In FIG. 2, 4 is a particle, 2 is a base, and 5 is a fine particle. The fine particle 5 has a first portion 5a embedded in the base 2 and a second portion 5b protruding from the base 2. The second portion 5b of the fine particle 5 constitutes the convex portion 3. In FIG. 2, a circle including the outer surface of the base 2 is shown by a dashed line, and the boundary between the first portion 5a and the second portion 5b is represented by the portion of the dashed line that passes through the fine particle 5. The second portion 5b of the fine particle 5 constitutes the surface of the convex portion 3 and can constitute a part of the outer surface of the particle 4. The second portion 5b of the microparticles 5 may be covered with the same material as the base 2 (e.g., silicone), and the protrusions 3 may contain the same material as the base 2. In this case, at least a part of the surface of the protrusions 3 may contain the same material as the base 2. This may be a form in which the beans constituting the protrusions 3 on the outer surface of the salted bean mochi are covered with a thin mochi skin. The base 2 may have a core-shell structure, in which case it may be in a form similar to salted bean daifuku.

[0036] In this embodiment, the fine particles 5 are preferably any one of silica fine particles, titania fine particles, and alumina fine particles. From the viewpoint of controlling the reactivity with the binder component (base 2), silica fine particles, which are easy to modify on the surface, are more preferable. The silica fine particles used in this embodiment are silica (i.e., SiO 2 ) as a main component, and may be particles manufactured using water glass or silicon compounds such as alkoxysilane as raw materials, or may be particles obtained by crushing quartz.

[0037] Specifically, silica particles produced by the sol-gel method, precipitated silica particles produced by the precipitation method, aqueous colloidal silica particles, fumed silica particles obtained by the gas phase method, fused silica particles, etc. can be mentioned. Among these, aqueous colloidal silica particles are preferred in terms of reactivity with the above-mentioned binder components and dispersion stability. Aqueous colloidal silica particles are commercially available or can be prepared by known methods from various starting materials. Aqueous colloidal silica particles can be prepared from silicic acid derived from an alkali silicate solution having a pH of about 9 to about 11, and the silicate anion undergoes polymerization to produce silica particles in the form of an aqueous dispersion with the desired average particle size.

[0038] In this embodiment, the particle diameter D of the plurality of particles 4 dispersed in the matrix resin 1 F The particle diameter D of the plurality of particles 4 is preferably 0.02 μm or more and 15.00 μm or less. Fcan typically be evaluated using the average particle diameter (number-average particle diameter) of the particle diameters of a plurality of particles 4, but can also be evaluated using the median diameter or mode diameter. When the particle diameter is 0.02 μm or more, the function as a spacer for the opposing parts is well exhibited, and the effect of improving wear resistance is easily obtained. Also, when the particle diameter is 15.00 μm or less, the unevenness formed on the sliding surface by the particles 4 is kept to an appropriate size, and good wear resistance is obtained. Particle diameter D F may be 10.00 μm or more and 15.00 μm or less, 5.00 μm or more and less than 10.00 μm, 1.00 μm or more and less than 5.00 μm, or 0.02 μm or more and less than 1.00 μm. F More preferably, it is 0.04 μm or more and 11.00 μm or less. Particle diameter D of particle 4 F can be increased by lowering the reaction temperature, shortening the reaction time, and increasing the amount of catalyst in the hydrolysis and condensation steps.

[0039] In this embodiment, when the particle 4 is composed of a base 2 and a fine particle 5, the particle diameter D C The particle diameter D of the plurality of fine particles 5 is preferably 0.01 μm or more and 3.00 μm or less, and more preferably 0.02 μm or more and 2.00 μm or less. C Typically, the particle diameter D can be evaluated using the average particle diameter (number-average particle diameter) of the particle diameters of a plurality of particles 4, but it can also be evaluated using the median diameter or the mode diameter. F If the particle size is 5.00 μm or more, the particle size D C It is preferable that the particle size D is 0.50 μm or more. C If the particle size is less than 1.00 μm, the particle size D F It is preferred that the thickness is less than 5.00 μm.

[0040] In this embodiment, the particle diameter of the base 2 is D A , the particle diameter of microparticle 5 is D C When D A D C D is the ratio of C / D Ais preferably 0.050 or more and 0.650 or less. When this ratio is 0.050 or more, the size of the protrusions 3 relative to the base 2 becomes appropriate, the contact area between the opposing member and the surface of the base 2 is kept small, and the particles 4 tend to be less likely to fall off. When this ratio is 0.650 or less, a sufficient number of fine particles 5 can be present on the surface of the base 2, and when a load is applied to the sliding surface, the surface of the base 2 is less likely to come into contact with the opposing member. As a result, good wear resistance is obtained.

[0041] In this embodiment, the embedding ratio of the particles 5 defined by the following formula [1] is preferably 30% or more and 80% or less. Burial rate of fine particles 5 (%) = (depth of particle 5 buried in base 2 / diameter of particle 5) × 100 [1] When the embedment rate of the microparticles 5 is 30% or more, the microparticles 5 are less likely to come off when a load is applied to the sliding surface, and when the embedment rate is 80% or less, the surface of the base 2 and the opposing member are less likely to come into contact with each other, and the coefficient of friction is reduced, which is preferable. The embedment rate is more preferably 50% or more and 80% or less.

[0042] The content of the particles 4 in the molded body of this embodiment is preferably 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the matrix resin 1. When the particles 4 are 1 part by mass or more per 100 parts by mass of the matrix resin 1, a sufficient amount of the particles 4 can be present on the sliding surface to improve the sliding characteristics, and the wear resistance is improved. In addition, when the particles 4 are 50 parts by mass or less, a sufficient Young's modulus can be obtained in the molded body, and good processability can be obtained, so this is preferable.

[0043] <Matrix resin> The matrix resin 1 constituting the molded body of this embodiment is not particularly limited, but preferably has a Young's modulus in the range of 1.0 GPa to 5.0 GPa. When the Young's modulus of the matrix resin 1 is 1.0 GPa or more, the particles 4 are less likely to be embedded in the matrix resin 1, and the friction coefficient is less likely to increase even in long-term sliding. When the Young's modulus of the matrix resin 1 is 5.0 GPa or less, the particles 4 are less likely to deform, and the wear resistance is less likely to deteriorate even in long-term sliding. Therefore, if the Young's modulus is within this range, a molded body suitable for a sliding member whose sliding characteristics do not change even in long-term sliding can be obtained. In this embodiment, the Young's modulus of the matrix resin 1 refers to the tensile modulus of elasticity determined by a tensile test method in accordance with JIS K 7161-1 or ISO 527-1, as will be described later.

[0044] The matrix resin 1 according to the present embodiment includes at least one of a thermoplastic resin, a thermosetting resin, and a photocurable resin. Among the thermoplastic resins, it is more preferable that the resin is one selected from the group consisting of a polyvinyl resin, a polyester resin, a polyamide resin, and a polyacetal resin. Among the thermosetting resins or photocurable resins, it is preferable that the resin is one of an acrylic resin and an epoxy resin. The matrix resin 1 may be a copolymer, or may be a compatible solution, a mixture, or a dispersion of a plurality of types of resins.

[0045] As the polyvinyl resin, for example, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polybutadiene resin, polymethyl methacrylate resin, copolymers thereof, and polymer alloys obtained by blending these resins can be used.

[0046] As the polyester resin, for example, polyethylene terephthalate resin, polybutylene terephthalate resin, polybutylene-2,6-naphthalate resin, polytrimethylene terephthalate resin, copolymers thereof, and polymer alloys obtained by blending these resins can be used.

[0047] As the polyamide resin, for example, nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612, copolymers thereof, and polymer alloys obtained by blending these can be used.

[0048] As the polyacetal resin, either a polyacetal homopolymer or a polyacetal copolymer can be used.

[0049] (Method of Manufacturing Molded Product) The molded body of this embodiment can be formed by curing a liquid curable composition containing the above-mentioned particles 4. As a curing method of the curable composition, photocuring is suitable, but heat curing may also be used. The matrix resin 1 can be formed by photocuring a curable composition containing a photocurable resin material or heat curing a thermosetting resin material. Alternatively, the above-mentioned particles 4 and a thermoplastic resin material can be mixed and melt-kneaded, and the thermoplastic resin material can be solidified by cooling to form the matrix resin 1. Furthermore, the matrix resin 1 can also be obtained by melting or dissolving a resin composition containing the particles 4 that has been solidified once and then solidifying it again. The molded body containing the above-mentioned particles 4 can be suitably used as a sliding member.

[0050] The shape of the molded product is not particularly limited. It may have a shape as a sliding member, or may be, for example, fibrous or pellet-shaped. The molded product in the form of fiber or pellet can be processed into any shape by using these as raw materials, such as compression molding, transfer molding, lamination molding, injection molding, extrusion molding, or blow molding.

[0051] In the molded body of the present embodiment, the particles 4 are preferably uniformly dispersed in the matrix resin 1 . When producing a molded article having a shape suitable for a sliding member, the particles 4 are uniformly dispersed in a liquid curable composition described below, and the molded article can be produced by a stereolithography method.

[0052] When producing a linear or pellet-shaped molded product, for example, a method of mixing and homogenizing all or a part of the matrix resin 1 and the particles 4 simultaneously or separately in a mixer such as a blender, kneader, roll, or extruder, or a method of mixing a part of the mixed parts simultaneously or separately in a blender, kneader, roll, extruder, etc., and further mixing and homogenizing the remaining components in such a mixer or extruder can be adopted. Furthermore, a method of melt-kneading and homogenizing a composition that has been dry-blended in advance in a heated extruder, extruding it into a wire shape, and then cutting it to a desired length to granulate it can also be applied.

[0053] The molded body of this embodiment has a volume of 1 mm 3 The volume can be more than 1 mm 3 The above-mentioned pellets and injection-molded articles are preferably applied. 3 The volume can be more than 100 mm 3 The present invention is preferably applied to the above-mentioned injection molded articles. The volume of the molded article referred to here is the sum of the volume of the continuous matrix resin 1 and the volume of the particles 4 dispersed in the continuous matrix resin 1. If the sum of the volume of the continuous matrix resin 1 and the volume of the particles 4 dispersed in the continuous matrix resin 1 is 1 mm 3 A number of micro-molded bodies can be arranged discontinuously on a substrate, but in this case the volume of the molded body (micro-molded body) is 1 mm 3 is less than.

[0054] [Curable composition] The curable composition containing particles in which the ratio of siloxane bonds and Si-OC bonds is adjusted can be suitably used as a paint for forming a film having excellent sliding properties, or as a raw material for forming a sliding member using a stereolithography method. The curable composition of this embodiment contains the above-mentioned particles 4 and a curable resin material that becomes a matrix resin by curing. The curable resin material contains a photocurable resin material or a thermosetting resin material. As the photocurable resin material, an acrylic resin material by radical polymerization or an epoxy resin material by cationic polymerization can be used. The curable resin material contains a polymerizable compound and a curing agent. The polymerizable compound is a radical polymerizable compound or a cationic polymerizable compound. The curing agent is a radical polymerization initiator or a cationic polymerization initiator. Hereinafter, an example in which the curable resin material contains a radical polymerizable compound and a curing agent will be described.

[0055] <Radical polymerizable compound> The radical polymerizable compound is not particularly limited, but when it contains a polyfunctional radical polymerizable compound (A) and a monofunctional radical polymerizable compound (B), a cured product with high toughness can be obtained.

[0056] The polyfunctional radical polymerizable compound (A) is a compound having two or more radical polymerizable functional groups in the molecule. Examples of the radical polymerizable functional group include ethylenically unsaturated groups. Examples of the ethylenically unsaturated group include (meth)acryloyl groups and vinyl groups. Examples of the polyfunctional radical polymerizable compound include (meth)acrylate-based compounds, vinyl ether group-containing (meth)acrylate-based compounds, (meth)acryloyl group-containing isocyanurate-based compounds, (meth)acrylamide-based compounds, urethane (meth)acrylate-based compounds, maleimide-based compounds, vinyl ether-based compounds, and aromatic vinyl-based compounds. Among them, (meth)acrylate-based compounds and urethane (meth)acrylate-based compounds are preferred from the viewpoints of availability and curability.

[0057] Although various compounds can be used for the polyfunctional radical polymerizable compound (A) of this embodiment, a polyfunctional radical polymerizable compound having a urethane structure is particularly preferred in that it is easy to synthesize, easy to obtain, and the Young's modulus of the resulting molded object is high. In addition, when the curable composition of this embodiment is used as a raw material for stereolithography, a polyfunctional radical polymerizable compound having a polyether structure is preferred in that it has low viscosity, has good liquid drainage during molding, and can produce a molded object with high accuracy. In addition, a polyfunctional radical polymerizable compound having a polyester structure or a polycarbonate structure is preferred in that it can produce a molded object with a high Young's modulus. The polyfunctional radical polymerizable compound (A) may be one type of compound selected from these compounds, or may contain two or more types. The polyfunctional radical polymerizable compound (A) in this embodiment is a name that collectively refers to one or more types of polyfunctional radical polymerizable compounds contained in the curable composition.

[0058] The polyfunctional radical polymerizable compound (A) having a urethane structure may be, for example, one obtained by reacting a hydroxyl group-containing (meth)acrylate compound with a polyisocyanate compound. Other examples include one obtained by reacting a hydroxyl group-containing (meth)acrylate compound with a polyisocyanate compound with a polyol compound. In terms of realizing a high Young's modulus, one obtained by reacting a hydroxyl group-containing (meth)acrylate compound with a polyisocyanate compound with a polyol compound is particularly preferred.

[0059] Examples of the hydroxyl group-containing (meth)acrylate compound include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethyl acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth)acrylate, fatty acid-modified glycidyl (meth)acrylate, and polyethylene glycol mono(meth)acrylate. acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, glycerin di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, etc. These hydroxyl group-containing (meth)acrylate compounds may be used alone or in combination of two or more.

[0060] Examples of the polyisocyanate-based compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples of the polyisocyanate include aliphatic polyisocyanates such as isocyanate and lysine triisocyanate, alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane, as well as trimer compounds or polymer compounds of these polyisocyanates, allophanate-type polyisocyanates, biuret-type polyisocyanates, and water-dispersible polyisocyanates. These polyisocyanate compounds may be used alone or in combination of two or more.

[0061] Examples of the polyol-based compound include polyether-based polyols, polyester-based polyols, polycarbonate-based polyols, polyolefin-based polyols, polybutadiene-based polyols, (meth)acrylic-based polyols, polysiloxane-based polyols, etc. These polyol-based compounds may be used alone or in combination of two or more kinds.

[0062] Examples of polyether polyols include alkylene structure-containing polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols.

[0063] Examples of polyester-based polyols include polycondensation products of polyhydric alcohols and polycarboxylic acids, ring-opening polymerization products of cyclic esters (lactones), and reaction products of three components: polyhydric alcohols, polycarboxylic acids, and cyclic esters.

[0064] Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol).

[0065] Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, and trimellitic acid.

[0066] Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

[0067] Examples of polycarbonate-based polyols include reaction products of polyhydric alcohols and phosgene, and ring-opening polymers of cyclic carbonates (such as alkylene carbonates).

[0068] Examples of the polyhydric alcohol include the polyhydric alcohols exemplified in the description of the polyester polyol, etc. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, etc. The polycarbonate-based polyol may be any compound having a carbonate bond in the molecule and a hydroxyl group at the end, and may have an ester bond in addition to the carbonate bond.

[0069] Examples of the polyfunctional radically polymerizable compound (A) having any one of a polyether structure, a polyester structure, and a polycarbonate structure include those obtained by reacting any one of the above-mentioned polyether-based polyols, polyester-based polyols, and polycarbonate-based polyols with a (meth)acrylic acid chloride or a (meth)acrylic acid compound.

[0070] The ethylenically unsaturated group equivalent of the polyfunctional radical polymerizable compound (A) of this embodiment is preferably in the range of 700 g / eq to 7000 g / eq. When the polyfunctional radical polymerizable compound (A) contained in the curable composition is a single compound, it is preferable to use a polyfunctional radical polymerizable compound having an ethylenically unsaturated group equivalent of 700 g / eq to 7000 g / eq. The ethylenically unsaturated group equivalent referred to here is a value obtained by dividing the weight average molecular weight (Mw) of the polyfunctional radical polymerizable compound by the number of ethylenically unsaturated groups in one molecule. When the curable composition contains multiple types of polyfunctional radical polymerizable compounds, the ethylenically unsaturated group equivalent of the polyfunctional radical polymerizable compound (A) can be calculated by weighting and averaging the ethylenically unsaturated group equivalents of each polyfunctional radical polymerizable compound at the mass ratio contained in the curable composition. Then, it is preferable to mix and use multiple types of polyfunctional radical polymerizable compounds at a ratio such that the value is 700 g / eq to 7000 g / eq. When the curable composition contains multiple types of polyfunctional radical polymerizable compounds, it preferably contains a polyfunctional radical polymerizable compound having an ethylenically unsaturated group equivalent of 700 g / eq or more and 7000 g / eq or less, and a polyfunctional radical polymerizable compound having an ethylenically unsaturated group equivalent of less than 700 g / eq.

[0071] The larger the ethylenically unsaturated group equivalent, the smaller the crosslink density of the cured product after curing, and the lower the Young's modulus of the resulting cured product. When the ethylenically unsaturated group equivalent of the polyfunctional radical polymerizable compound (A) is 7000 g / eq or less, the crosslink density of the cured product after curing is at least to a certain extent, and the cured product exhibits a moderate Young's modulus, so that the particles 4 are less likely to be embedded in the matrix resin 1, and the friction coefficient tends to be suppressed even in long-term sliding. On the other hand, when the ethylenically unsaturated group equivalent is 700 g / eq or more, the crosslink density of the cured product after photocuring is suppressed within a moderate range, and the Young's modulus of the cured product falls within a moderate range, so that the particles 4 are less likely to deform, and the friction coefficient tends to be suppressed even in long-term sliding.

[0072] The weight average molecular weight (Mw) of the polyfunctional radical polymerizable compound (A) in this embodiment is a weight average molecular weight calculated based on the molecular weight of standard polystyrene. The weight average molecular weight can be measured using high performance liquid chromatography. For example, a high-speed GPC device "HLC-8220GPC" manufactured by Tosoh Corporation is equipped with a column: Shodex GPCLF-804 (exclusion limit molecular weight: 2×10 6 , Separation range: 300 to 2×10 6 ) Two cables can be connected in series and measurements can be made.

[0073] The monofunctional radical polymerizable compound (B) is a compound having one radical polymerizable functional group in the molecule. Adding the monofunctional radical polymerizable compound (B) to the curable composition makes it easy to adjust the viscosity range. In addition, by adjusting the content of the monofunctional radical polymerizable compound (B) or appropriately selecting the type, the mechanical properties of the cured product obtained by curing the curable composition can be adjusted to a desired range.

[0074] Examples of the monofunctional radical polymerizable compound (B) include acrylamide compounds, (meth)acrylate compounds, maleimide compounds, styrene compounds, acrylonitrile compounds, vinyl ester compounds, N-vinyl compounds, conjugated diene compounds, vinyl ketone compounds, vinyl halide / vinylidene halide compounds, etc. However, the present invention is not limited to these. Among these, acrylamide compounds, (meth)acrylate compounds, maleimide monomers, and N-vinyl compounds are particularly preferred in that the curing properties of the composition and the mechanical properties of the resulting shaped object are excellent.

[0075] Examples of acrylamide compounds include (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-methylol(meth)acrylamide, N,N-diacetone(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-dibutyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-(meth)acryloylpiperidine, N-[3-(dimethylamino)propyl]acrylamide, and N-tert-octyl(meth)acrylamide.

[0076] Examples of the (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, i-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 3,5-Dihydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, 3-methyl-3-oxetanyl-methyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylate, phenyl glycidyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, phenyl cellosolve (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, biphenyl (meth)acrylate, 2-hydroxyethyl (meth)acryloyl phosphate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, benzyl (meth)acrylate, butoxytriethylene glycol (meth) ) acrylate, 2-ethylhexyl polyethylene glycol (meth)acrylate, nonylphenyl polypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, glycerol (meth)acrylate, trifluoromethyl (meth)acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, octafluoropentyl acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, allyl (meth)acrylate acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H,octafluoropentyl (meth)acrylate, epichlorohydrin modified butyl (meth)acrylate, epichlorohydrin modified phenoxy (meth)acrylate, ethylene oxide (EO) modified phthalic acid (meth)acrylate, EO modified succinic acid (meth)acrylate, caprolactone modified 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,Examples of such compounds include N-diethylaminoethyl (meth)acrylate, morpholino (meth)acrylate, EO-modified phosphate (meth)acrylate, methyl allyloxyacrylate (product name: AO-MA, manufactured by Nippon Shokubai Co., Ltd.), (meth)acrylates having an imide group (product name: M-140, manufactured by Toagosei Co., Ltd.), and monofunctional (meth)acrylates having a siloxane structure.

[0077] Examples of maleimide monomers include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide.

[0078] Examples of the N-vinyl compound include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, and N-vinylacetamide.

[0079] Other examples of the monofunctional radically polymerizable compound (B) include styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and its salts, vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate, and vinyl cyanide compounds such as (meth)acrylonitrile. These monofunctional radically polymerizable compounds may be used alone or in combination of two or more kinds.

[0080] When the curable composition of the present embodiment is used as a raw material for stereolithography, it is particularly preferable to include a polyfunctional radical polymerizable compound (A) and a monofunctional radical polymerizable compound (B). In that case, the amount of the polyfunctional radical polymerizable compound (A) contained in the curable composition is preferably 20 parts by mass or more and 75 parts by mass or less in a total of 100 parts by mass of the polyfunctional radical polymerizable compound (A) and the monofunctional radical polymerizable compound (B). If the content of the polyfunctional radical polymerizable compound (A) is 20 parts by mass or more, the curable composition exhibits good curability, and a molded object having a good elastic modulus can be obtained. If the content of the polyfunctional radical polymerizable compound (A) is 75 parts by mass or less, a curable composition with a viscosity suitable for stereolithography can be obtained. More preferably, it is 30 parts by mass or more and 75 parts by mass or less. Even more preferably, it is 40 parts by mass or more and 65 parts by mass or less.

[0081] <Hardening agent> As the curing agent added to the curable composition of the present embodiment, a photoradical polymerization initiator is preferably used, and the photoradical polymerization initiator may be used in combination with a thermal radical polymerization initiator. By including a thermal radical polymerization initiator in the curable composition, a polymerization reaction can be promoted by carrying out a heat treatment after modeling by light irradiation, and the mechanical properties of the modeled object can be further improved.

[0082] Photoradical polymerization initiators are mainly classified into intramolecular cleavage type and hydrogen abstraction type. In the intramolecular cleavage type, a bond at a specific site is cut by absorbing light of a specific wavelength, and a radical is generated at the cut site, which becomes a polymerization initiator and starts polymerization of the polyfunctional radical polymerizable compound (A) and the monofunctional radical polymerizable compound (B). In the hydrogen abstraction type, light of a specific wavelength is absorbed and becomes excited, and the excited species causes a hydrogen abstraction reaction from a hydrogen donor in the vicinity, generating a radical. Then, the generated radical becomes a polymerization initiator and starts polymerization of the polyfunctional radical polymerizable compound (A) and the monofunctional radical polymerizable compound (B). In this embodiment, two or more types of photoradical polymerization initiators may be used in combination, or they may be used alone.

[0083] Known intramolecular cleavage type photoradical polymerization initiators include alkylphenone-based photoradical polymerization initiators, acylphosphine oxide-based photoradical polymerization initiators, and oxime ester-based photoradical polymerization initiators, which undergo α-cleavage of the bond adjacent to the carbonyl group to generate radical species.

[0084] Examples of the alkylphenone-based photoradical polymerization initiator include a benzyl methyl ketal-based photoradical polymerization initiator, an α-hydroxyalkylphenone-based photoradical polymerization initiator, and an aminoalkylphenone-based photoradical polymerization initiator. Specific examples of the compounds include a benzyl methyl ketal-based photoradical polymerization initiator, such as 2,2'-dimethoxy-1,2-diphenylethan-1-one (Irgacure(R) 651, manufactured by BASF), and an α-hydroxyalkylphenone-based photoradical polymerization initiator, such as 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocure(R) 1173, manufactured by BASF), 1-hydroxycyclohexyl phenyl ketone (Irgacure(R) 184, manufactured by BASF), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure(R) 185, manufactured by BASF), and the like. Examples of the aminoalkylphenone-based photoradical polymerization initiator include, but are not limited to, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Irgacure(R) 907, BASF), 2-benzylmethyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (Irgacure(R) 369, BASF), and the like.

[0085] Examples of acylphosphine oxide-based photoradical polymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin(R) TPO, manufactured by BASF), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad(R) 819, manufactured by IGMResins), and the like, but are not limited to these.

[0086] Examples of oxime ester-based photoradical polymerization initiators include, but are not limited to, (2E)-2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (Irgacure® OXE-01, manufactured by BASF).

[0087] Examples of the hydrogen abstraction type photoradical polymerization initiator include anthraquinone derivatives such as 2-ethyl-9,10-anthraquinone and 2-tert-butyl-9,10-anthraquinone, and thioxanthone derivatives such as isopropylthioxanthone and 2,4-diethylthioxanthone, but are not limited to these.

[0088] The amount of the photoradical polymerization initiator contained in the curable composition is preferably 0.1 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the radical polymerizable compound. More preferably, it is 0.1 parts by mass or more and 10 parts by mass or less. In order to perform sufficient polymerization, a certain amount of the photoradical polymerization initiator is necessary, but in order to maintain light transmittance and perform uniform polymerization, it is preferable to limit the amount of the photoradical polymerization initiator to an appropriate amount.

[0089] The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and any conventionally known compound can be used. For example, preferred examples include azo compounds, peroxides, and persulfates.

[0090] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-azobis(1-acetoxy-1-phenylethane).

[0091] Examples of peroxides include benzoyl peroxide, di-tert-butylbenzoyl peroxide, tert-butyl peroxypivalate, and di(4-tert-butylcyclohexyl)peroxydicarbonate.

[0092] Examples of the persulfates include ammonium persulfate, sodium persulfate, potassium persulfate, and the like.

[0093] The amount of the thermal radical polymerization initiator added is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the radical polymerizable compound. By using the thermal radical polymerization initiator in an appropriate range, the molecular weight of the cured product is increased and good physical properties are obtained.

[0094] <Other additives> The curable composition of the present embodiment may contain various additives as other optional components within a range that does not impair the object and effect of the present embodiment. Examples of the additives include resins such as epoxy resins, polyurethanes, polybutadiene, polychloroprene, polyesters, styrene-butadiene block copolymers, polysiloxanes, petroleum resins, xylene resins, ketone resins, and cellulose resins, engineering plastics such as polycarbonates, modified polyphenylene ethers, polyamides, polyacetals, polyethylene terephthalates, polybutylene terephthalates, polyphenylsulfones, polysulfones, polyarylates, polyetherimides, polyetheretherketones, polyphenylene sulfides, polyethersulfones, polyamideimides, liquid crystal polymers, polytetrafluoroethylenes, polychlorotrifluoroethylenes, and polyvinylidene fluorides, fluorine-based oligomers, silicone-based oligomers, and polysulfide-based oligomers. Examples of the additives include reactive monomers such as monomers, fluorine-containing monomers, and siloxane structure-containing monomers; soft metals such as gold, silver, and lead; layered crystal structure substances such as graphite, molybdenum disulfide, tungsten disulfide, boron nitride, graphite fluoride, calcium fluoride, barium fluoride, lithium fluoride, silicon nitride, and molybdenum selenide; polymerization inhibitors such as phenothiazine and 2,6-di-tert-butyl-4-methylphenol; photosensitizers such as benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds; polymerization initiator assistants, leveling agents, wettability improvers, surfactants, plasticizers, ultraviolet absorbers, silane coupling agents, inorganic fillers, pigments, dyes, antioxidants, flame retardants, thickeners, and defoamers.

[0095] <Method of producing curable composition> The curable composition of the present embodiment is produced by adding an appropriate amount of other optional components to the particles 4 and the curable resin material as necessary. Specifically, these components are charged into a stirring vessel and usually stirred at 30°C to 120°C, preferably 50°C to 100°C. The stirring time is usually 1 minute to 6 hours, preferably 10 minutes to 2 hours. The total amount of the particles 4 and the curable resin material is preferably 25 parts by mass to 100 parts by mass in 100 parts by mass of the curable composition excluding the curing agent. More preferably, it is 75 parts by mass to 100 parts by mass. The remaining parts by mass of 100 parts by mass of the curable composition excluding the particles 4 and the radical polymerizable compound are occupied by the curing agent and other components.

[0096] The viscosity of the curable composition of this embodiment at 25° C. is preferably 50 mPa·s or more and 30,000 mPa·s or less, and more preferably 50 mPa·s or more and 10,000 mPa·s or less.

[0097] <Method of manufacturing a sliding member using a curable composition> The curable composition of the present embodiment can be cured by irradiating light. Examples of the light to be irradiated include ultraviolet light and infrared light. Among them, light having a wavelength of 300 nm or more and 450 nm or less can be preferably used because it is versatile and easy to obtain, and the energy is easily absorbed by the photoradical polymerization initiator. As the light source that emits light, a laser light source (for example, an Ar laser, a He-Cd laser, etc.), a mercury lamp, a xenon lamp, a halogen lamp, a fluorescent lamp, etc. can be used. Among them, a laser light source is preferably used because it can shorten the modeling time by increasing the energy level, and can reduce the irradiation diameter to obtain high modeling accuracy. The light to be irradiated can be appropriately selected according to the type of radical polymerization initiator contained in the curable composition, and a combination of multiple light sources can also be used.

[0098] The curable composition of the present embodiment is suitable as a raw material for producing a slide member by stereolithography. That is, the curable composition of the present embodiment is irradiated with a light energy beam in accordance with slice data generated from three-dimensional shape data of the slide member to be modeled, and energy required for curing is supplied to produce a slide member of a desired shape.

[0099] FIG. 3 shows an example of the configuration of a photo-lithography apparatus 100 using a free liquid surface method suitable for manufacturing a sliding member. The photo-lithography apparatus 100 has a tank 11 filled with a liquid curable composition 10. The bottom surface of the tank 11 is made of a light-transmitting material, and a modeling stage 12 is disposed inside the tank 11 so as to be driven vertically by a drive shaft 13. A light beam 15 emitted from a light source 14 can change the irradiation position and perform scanning according to the inclination of a galvanometer mirror 16 controlled by a control unit 18 according to slice data. In FIG. 3, an example of the scanning range of the light beam 15 is shown by a dashed line.

[0100] The thickness d of the curable composition 10 cured by the light energy beam 15 is a value determined based on the settings at the time of generating the slice data, and affects the accuracy (reproducibility of the shape data of the three-dimensional model of the article to be molded) of the obtained three-dimensional object 17. The thickness d is achieved by the control unit 18 controlling the drive amount of the drive shaft 13.

[0101] First, the control unit 18 controls the drive shaft 13 based on the settings, and the curable composition 10 is supplied to a thickness d on the modeling stage 12. The liquid curable composition on the modeling stage 12 is selectively irradiated with light energy rays based on the slice data to form a cured layer having a desired pattern. Next, the modeling stage 12 is moved in the direction of the white arrow to supply uncured curable composition to a thickness d on the surface of the cured layer. Then, light energy rays 15 are irradiated based on the slice data to form a cured product integrated with the previously formed cured layer. In this way, a three-dimensional three-dimensional object 17 can be obtained by repeating the process of stacking the cured layers cured to a predetermined thickness d.

[0102] The molded body 17 thus obtained is taken out of the tank 11, and the unreacted curable composition remaining on the surface is removed, followed by cleaning and post-processing as necessary. As the cleaning agent used for cleaning, an alcohol-based organic solvent, such as alcohols such as isopropyl alcohol and ethyl alcohol, can be used. In addition, a ketone-based organic solvent, such as acetone, ethyl acetate, methyl ethyl ketone, or an aliphatic organic solvent, such as terpenes, may be used. After cleaning with the cleaning agent, post-processing is performed as necessary. For example, post-curing by light irradiation and / or heat irradiation may be performed. Post-curing can harden the unreacted curable composition remaining on the surface and inside of the molded object, and can suppress the stickiness of the surface of the molded object and can improve the initial strength of the molded object. As post-processing, removal of the support, polishing of the surface, shape processing such as providing a screw hole, etc. may be performed.

[0103] 3 shows an example in which the curable composition is irradiated with light in a pointillist or line drawing manner to cure it, but light may be irradiated in other ways. For example, the curable composition may be cured by irradiating light in a planar manner through a planar drawing mask formed by arranging a plurality of micro-light shutters such as liquid crystal shutters or digital micromirror shutters. Although FIG. 3 shows a stereolithography apparatus using a free liquid surface method, the curable composition of the present embodiment is not limited to a specific modeling method and can also be used in a restricted liquid surface method.

[0104] The molded body of this embodiment can be a molded body having a desired shape obtained by, for example, injection molding, extrusion molding, or layered molding such as stereolithography using a melt-kneaded material composition, and can be used as it is as a component. The obtained molded body can also be used after being combined with another molded body by a process such as thermocompression bonding. The molded body of this embodiment also includes a film-like form (coating film) obtained by forming a liquid film made of the composition on a substrate surface using a dip coating method, inkjet coating method, spray coating method, or other means, and then drying and / or curing the composition.

[0105] The molded article having good mechanical properties can be used in machines. A machine using the molded article of this embodiment can include the molded article of this embodiment as a mechanical part such as a bearing, a gear, a cam, or a roller. A machine using the molded article of this embodiment can realize various devices. For example, it can be used in the mirror drive unit of a single-lens reflex camera in an imaging device, in the lens drive unit of an interchangeable lens in an optical device, and in the drive unit of an inkjet device or an electrophotographic device in a printing device. It can also be applied to industrial equipment such as robots and electronic device manufacturing equipment, and medical equipment such as CT and MRI.

[0106] A machine using the molded body as a sliding member includes the molded body as a sliding member and another member, and the molded body and the other member slide against each other. The other member can also be called a member to be slid or an opposing member. In the machine, the sliding member and the other member may be either movable or fixed, or both may be movable. The presence of the particles 4 on the sliding surface between the molded body and the other member can provide good sliding characteristics on the sliding surface.

[0107] FIG. 5 illustrates a cross-sectional view of a printing device equipped with an electrophotographic device as the device 200. For example, the photosensitive drum 23, various rollers (charging roller 22, developing roller 24, transfer roller, fixing roller 26, pressure roller 27), and various belts (transfer belt 25, fixing belt) equipped in the electrophotographic device may have the molded body of this embodiment. In addition, the device 200 may have a housing 21 and other mechanical parts 29 such as bearings, gears, and cams. At least one of the drum, roller, and belt has the molded body of this embodiment. For example, a film-like molded body can be used as a protective film provided on at least one surface of the drum, roller, and belt. At least one of the drum, roller, and belt may slide with other members (drum, roller, belt). In the printing device illustrated in FIG. 5, a printing medium such as paper passes through a path 28. The molded body may be used for a part that slides against the printing medium. In an electrophotographic device using the molded body of this embodiment, good operation is expected for a long time.

[0108] The molded article of the present embodiment can maintain good properties for a long period of time, and therefore has high durability as a resin member, which contributes to reducing the frequency of part replacement and extending the product life, thereby suppressing the generation of waste. Materials having sliding properties include organic fluorine compounds such as perfluoroalkyl compounds and polyfluoroalkyl compounds (collectively referred to as PFAS), and the molded body and composition of the present embodiment can also be used as an alternative material to such organic fluorine compounds. The technology described in this specification can contribute to the realization of a sustainable society, such as a carbon-free / recycling-based society.

[0109] [Included configuration] The disclosure of this embodiment includes the following configuration. (Configuration 1) A molded article comprising a matrix resin and a plurality of particles dispersed in the matrix resin, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, the particle has the base and fine particles, the base is in a particulate form having a recess on a surface, the fine particles have a first portion embedded in the recess of the base and a second portion forming the protrusion, A molded article, wherein the convex portions are mainly composed of an inorganic material. (Configuration 2) A molded article comprising a matrix resin and a plurality of particles dispersed in the matrix resin, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, the particle has the base and fine particles, the base is in a particulate form having a recess on a surface, the fine particles have a first portion embedded in the recess of the base and a second portion forming the protrusion, A molded article, wherein the convex portion has a higher Young's modulus than the base portion. (Configuration 3) The molded body according to configuration 2, wherein the Young's modulus of the base is 0.005 GPa or more and 25,000 GPa or less, and the Young's modulus of the protrusions is 50 GPa or more and 500 GPa or less.

[0110] (Configuration 4) 4. The molded article according to any one of configurations 1 to 3, wherein the fine particles are mainly composed of any one of silica, alumina, and titania. (Configuration 5) 5. The molded article according to any one of configurations 1 to 4, wherein the particle diameter of the plurality of particles is 0.02 μm or more and 15.00 μm or less. (Configuration 6) The particle diameter of the base is D A , the particle diameter of the fine particles is D C When D C / D A 6. The molded article according to any one of configurations 1 to 5, wherein the ratio is 0.050 or more and 0.650 or less. (Configuration 7) 7. The molded article according to any one of configurations 1 to 6, wherein the embedding ratio of the fine particles defined by the following formula [1] is 30% or more and 80% or less. Particle embedding rate (%) = (depth of particle buried in base / diameter of particle) x 100 [1]

[0111] (Configuration 8) 8. The molded article according to any one of configurations 1 to 7, wherein the matrix resin has a Young's modulus in the range of 1.0 GPa or more and 5.0 GPa or less. (Configuration 9) 9. The molded article according to any one of configurations 1 to 8, wherein the matrix resin contains at least one of a polyvinyl resin, a polyester resin, a polyamide resin, a polyacetal resin, an acrylic resin, and an epoxy resin. (Configuration 10) 10. The molded article according to any one of configurations 1 to 9, which is a film. (Configuration 11) 11. The molded article according to any one of configurations 1 to 10, wherein the content of the particles is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the matrix resin. (Configuration 12) The volume of the molded body is 1 mm 3 12. The molded article according to any one of configurations 1 to 11, characterized in that: (Configuration 13) The volume of the molded body is 100 mm 3 12. The molded article according to any one of configurations 1 to 11, characterized in that:

[0112] (Configuration 14) A curable composition comprising a plurality of particles and a curable resin material, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, the particle has the base and fine particles, the base is in a particulate form having a recess on a surface, the fine particles have a first portion embedded in the recess of the base and a second portion forming the protrusion, The curable composition, wherein the convex portions are mainly composed of an inorganic material. (Configuration 15) A curable composition comprising a plurality of particles and a curable resin material, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, the particle has the base and fine particles, the base is in a particulate form having a recess on a surface, the fine particles have a first portion embedded in the recess of the base and a second portion forming the protrusion, The curable composition, wherein the convex portion has a higher Young's modulus than the base portion. (Configuration 16) 16. The curable composition according to claim 15, wherein the Young's modulus of the base is 0.005 GPa or more and 25,000 GPa or less, and the Young's modulus of the protrusions is 50 GPa or more and 500 GPa or less.

[0113] (Configuration 17) 17. The curable composition according to any one of configurations 14 to 16, wherein the fine particles are mainly composed of any one of silica, alumina, and titania. (Configuration 18) 18. The curable composition according to any one of claims 14 to 17, wherein the particle diameter of the plurality of particles is 0.02 μm or more and 15.00 μm or less. (Configuration 19) The particle diameter of the base is D A , the particle diameter of the fine particles is D C When D C / D A 19. The curable composition according to any one of claims 14 to 18, wherein (Configuration 20) 20. The curable composition according to any one of claims 14 to 19, wherein the embedding ratio of the fine particles defined by the following formula [1] is 30% or more and 80% or less. Particle embedding rate (%) = (depth of particle buried in base / diameter of particle) x 100 [1]

[0114] (Configuration 21) 21. The curable composition according to any one of configurations 14 to 20, wherein the content of the particles is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the curable resin material. (Configuration 22) 22. The curable composition according to any one of claims 14 to 21, wherein the curable resin material contains a radically polymerizable compound. (Configuration 23) the curable resin material contains a polyfunctional radical polymerizable compound (A) and a monofunctional radical polymerizable compound (B); 23. The curable composition according to any one of claims 14 to 22, wherein the polyfunctional radically polymerizable compound (A) has an ethylenically unsaturated group equivalent of 700 g / eq or more and 7000 g / eq or less. (Configuration 24) The curable composition according to claim 23, characterized in that the polyfunctional radically polymerizable compound (A) is a (meth)acrylate-based compound or a urethane (meth)acrylate-based compound having any one of a polyether structure, a polyester structure, and a polycarbonate structure. (Configuration 25) 25. The curable composition according to any one of configurations 14 to 24, wherein the curable resin material contains a photoradical polymerization initiator.

[0115] (Configuration 26) A step of disposing the curable composition according to any one of configurations 14 to 25 to a predetermined thickness; and curing the curable composition having the predetermined thickness by irradiating the curable composition with light in accordance with shape data of a three-dimensional model. (Configuration 27) A machine comprising the molded body according to any one of configurations 1 to 13 and a member, wherein the molded body and the member slide against each other. (Configuration 28) 28. The machine according to configuration 27, characterized in that the particles are present on a sliding surface of the molded body with respect to the member. (Configuration 29) A machine comprising the molded article according to any one of configurations 1 to 13 as a bearing, gear, cam or roller. (Configuration 30) 14. An electrophotographic apparatus comprising at least one of a photosensitive drum, a roller, and a belt, the molded article according to any one of claims 1 to 13. EXAMPLES

[0116] Examples will be given below to explain the present embodiment in detail, but the present embodiment is not limited to these examples. (Methods for measuring various physical properties) The methods for measuring various physical properties are described below.

[0117] <Separation of particles contained in compacts> The particles contained in the molded body can be isolated after dissolving the matrix resin using a good solvent for the matrix resin forming the molded body. The solvent used is not particularly limited as long as it dissolves the matrix resin but does not dissolve the particles, but for example, when the matrix resin is a polyacetal resin, only the matrix resin can be dissolved using hexafluoroisopropanol (HFIP). When the particles could not be separated by the above method, the molded body was subjected to a freezing treatment, and then the molded body was cut by a known method, and the following various measurements were carried out on the particles present on the cut surface.

[0118] <How to capture particle images> Images of particles are obtained using a Hitachi ultra-high resolution field emission scanning electron microscope "S-4800" (Hitachi High-Technologies Corporation).

[0119] (1) Sample preparation Apply a thin layer of conductive paste to a sample stage (aluminum sample stage 15 mm x 6 mm) and spray the particles onto it. Then use air to remove excess particles from the sample stage and dry thoroughly. Set the sample stage in the sample holder and adjust the sample stage height to 36 mm using the sample height gauge.

[0120] (2) S-4800 observation condition setting Pour liquid nitrogen into the anti-contamination trap attached to the S-4800 housing until it overflows, and leave it for 30 minutes. Start the S-4800's "PC-SEM" and perform flushing (cleaning the FE chip, which is the electron source). Click the accelerating voltage display area on the control panel on the screen, and press the [Flushing] button to open the flushing execution dialog. Check that the flushing intensity is 2, and execute it. Check that the emission current due to flushing is between 20 μA and 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.

[0121] Click the accelerating voltage display to open the HV setting dialog, and set the accelerating voltage to [1.1kV] and the emission current to [20μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select the SE detector to [Upper (U)] and [+BSE], and select [LA100] in the selection box to the right of [+BSE] to set the mode to observation with backscattered electron images. In the same [Basic] tab of the operation panel, set the probe current in the electron optical system condition block to [Normal], the focus mode to [UHR], and the WD to [4.5mm]. Press the [ON] button in the accelerating voltage display of the control panel to apply the accelerating voltage.

[0122] (3) Focus adjustment Rotate the focus knob [COARSE] on the operation panel, and adjust the aperture alignment once the image is in focus to a certain extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture], and rotate the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the image movement or adjust it so that it moves as little as possible. Close the aperture dialog, and adjust the focus using autofocus. After that, set the magnification to 50,000 (50k), and adjust the focus using the focus knob and STIGMA / ALIGNMENT knob as above, and then adjust the focus using autofocus again. Repeat this operation to adjust the focus. Here, if the inclination angle of the observation surface is large, the measurement accuracy of the coverage rate is likely to be low, so when adjusting the focus, select an observation surface with as little surface inclination as possible for analysis by selecting one that can simultaneously bring the entire observation surface into focus.

[0123] (4) Image storage Adjust the brightness in ABC mode, take a photo with a size of 640 x 480 pixels, and save it. Use this image file for the following analysis. Obtain images of at least 25 particles.

[0124] <Particle diameter at base D A Measurement method> From the particle images obtained by the above method, the particle diameter at the base D A First, a Bezier curve is drawn along the outer shape of the base of the particle to define the base outline. In addition, if there are convex parts or fine particles on the surface of the base and the outer diameter is unknown, the outline is drawn by interpolation. The maximum diameter is measured for the outline of the base defined by the above method. The number of particles analyzed is 20, and the average of the maximum diameters is taken as D in this example. A It was decided.

[0125] <Particle size D C Measurement method and D C / D ACalculation of > From the particle images obtained by the above method, the particle diameter D C The particle is assumed to be approximately spherical, and the outer part of the particle protruding from the base is fitted with a circle. The diameter of the fitted circle is measured and taken as the diameter of the particle. The number of particles analyzed is 20, and the average value is taken as D in this example. C The particle diameter D of the base part mentioned above was set as the value. A and the particle diameter D C From D C / D A Calculate.

[0126] <Method for measuring particle size of particles in dispersion> The particle size of the particles and microparticles in the dispersion liquid during production was measured by centrifugal sedimentation. Specifically, 1 g of the dispersion liquid containing particles or microparticles was taken and placed in a 25 ml glass vial. 0.2 g of 5% Triton aqueous solution and 19.8 g of distilled water were added to the vial to prepare a solution. Next, the tip of the ultrasonic disperser probe was immersed in the above solution, and ultrasonic dispersion was performed for 15 minutes at an output of 20 W to obtain a dispersion. Next, the number average particle size of the primary particles was measured using this dispersion with a centrifugal sedimentation particle size distribution analyzer DC24000 manufactured by CPS Instruments. The disk rotation speed was set to 18000 rpm, and the true density was 1.3 g / cm. 3 Prior to the measurement, the instrument was calibrated using polyvinyl chloride particles with an average particle size of 0.476 μm.

[0127] <Method for measuring Young's modulus of matrix resin> The Young's modulus of the matrix resin is a tensile modulus determined by a tensile test method in accordance with JIS K 7161-1 or ISO 527-1.

[0128] <Method for measuring Young's modulus of base> The Young's modulus of the base is determined by a microcompression test using a Hysitron PI 85L pico-indenter (manufactured by BRUKER).

[0129] Young's modulus (MPa) is calculated from the slope of the profile (load-displacement curve) of the displacement (nm) and test force (μN) obtained in the measurement. Equipment and fixtures Base system: Hysitron PI-85L Measurement indenter: 1 μm diameter circular flat end indenter SEM used: Thermo Fisher Versa 3D SEM conditions: -10°tilt, 13pA at 10keV Measurement conditions Measurement mode: Displacement control Maximum displacement: 30nm Displacement speed: 1 nm / sec Hold time: 2 seconds Unloading speed: 5nm / sec ·Analysis method Hertz analysis is applied to the curve obtained when compressed from 0 nm to 10 nm in the load-displacement curve, and the Young's modulus of the base is calculated. Sample preparation A base identical to the base of the particles used in each Example was prepared and attached onto a silicon wafer.

[0130] <Method of measuring Young's modulus of fine particles or protrusions> First, the composition of the fine particles or the convex portions is identified. The measurement is performed using a scanning electron microscope "S-4800" (product name; manufactured by Hitachi, Ltd.). In the image obtained by the above <particle image acquisition method>, the particles in which there is a difference in image contrast between the part originating from the fine particles or convex portions, which are inorganic, and the part originating from the base, which is organic, are classified as the particles of this embodiment, and the particles in which there is no difference in contrast are classified as particles other than the particles of this embodiment. Note that the fine particles, which are inorganic, are observed to have a higher brightness. The particles are observed with the S-4800, and the composition of the base and the fine particles or the convex portions is identified with an energy dispersive X-ray analyzer in a field of view magnified up to 2 million times. After the composition of the fine particles or the convex portions is identified, fine particles having the same composition as the fine particles or the convex portions are prepared, and the same measurement as the measurement of the Young's modulus of the base described above is performed to obtain the Young's modulus of the fine particles or the convex portions. When the fine particles are silica, titania, or alumina, a powder having a particle size of 50 nm or more that is widely available on the market, or a plate-shaped molded body, is used to measure the Young's modulus in the same manner as in the measurement of the Young's modulus of the base portion described above.

[0131] <Method for measuring the embedding rate of fine particles> The particles separated from the molded body are thoroughly dispersed in a visible light curable resin (product name: Aronix LCR series "D-800"; manufactured by Toagosei Co., Ltd.), and then irradiated with short wavelength light to cure. The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to prepare a 250 nm thin sample. Next, the cut sample is magnified at a magnification of 40,000 to 50,000 times using a transmission electron microscope (JEM-2800 electron microscope manufactured by JEOL Ltd.) (TEM-EDX) to observe the particle cross section. The diameter of the microparticle and the depth of the microparticle buried in the base are measured from the cross-sectional image. Five microparticles are randomly selected for each particle, and the buried rate of the microparticles is calculated using the following formula [1]. In addition, the number of particles analyzed is 20 or more, and the average value is taken as the buried rate of the microparticles. Particle embedding rate (%) = (depth of particle buried in base / diameter of particle) x 100 [1]

[0132] <Performance evaluation of molded products> Test pieces of the molded bodies produced by the method described below were evaluated by the following methods. (specific wear rate) The specific wear rate was measured in accordance with JIS K 7218A under the conditions shown below. Measurement equipment: A&D friction and wear tester MODEL EMF-III-F Test environment: 23℃±2℃, humidity 50%±5%RH Test piece: Test piece Y (size 30mm x 30mm, thickness 4mm) Mating material: S45C, ring shape, surface roughness approx. 0.8μmRa, contact area 2cm 2 Load: 50N Sliding speed: 50cm / s Test duration: 100 minutes Sliding distance: 3km

[0133] (Evaluation Criteria) (1) Specific wear rate The counter material was pressed against the 30 mm x 30 mm surface of test piece Y with the above load and slid at the above sliding speed. The sliding was stopped after 100 minutes, and the wear mass was measured from the mass of the test piece before and after the sliding. The wear volume was calculated from the measured wear mass and the specific gravity of the test piece. The calculated wear volume was divided by the sliding distance and load to obtain the specific wear amount (unit: mm 3 N -1 km -1 ) was used as an index of wear resistance. The evaluation criteria for wear resistance are shown below. If the wear depth exceeded 1.5 mm within 100 minutes after the start of sliding, the evaluation was rated D as this was the measurement limit. If evaluation criterion B is met, it is determined that good wear resistance has been obtained, and if evaluation criterion A is met, it is determined that excellent wear resistance has been obtained. A: 0.3 mm 3 N -1 km -1 less than. B: 0.3 mm 3 N -1 km -1 More than 0.5mm 3 N -1 km -1 less than C: 0.5 mm 3 N -1 km -1 More than 0.66mm 3 N -1 km -1 less than D: 0.66 mm 3 N -1 km -1 End

[0134] (2) Evaluation of particle adhesion to matrix resin The counter material was pressed against the 30 mm x 30 mm surface of test piece Y with the above load, and slid at the above sliding speed for 5 minutes. The sliding surface at that time was cut out to 5 mm x 5 mm, and the surface was air-blowed to remove large wear debris. After that, electron microscope images were taken of 10 fields of view at 10,000 times magnification using the same procedure as the particle image acquisition method described above. The number of particles present in the acquired images was counted, and the number of particles per unit area P 5 After sliding for 10 minutes at the above sliding speed, the number of particles per unit area P was calculated using the same method. 15 The rate of change ΔP obtained from the following formula [2] was used as an index of adhesion. If evaluation criterion B is met, it is judged that the adhesion between the resin and the particles has good durability, and if evaluation criterion A is met, it is judged that excellent durability has been obtained. ΔP[%]=((P 5 -P 15 ) / P 5 )×100 [2] A: Less than 10% B: 10% or more but less than 30% C: 30% or more but less than 40% D: 40% or more

[0135] <Aqueous dispersion for forming convex portions> Table 1 shows the particle size and solid concentration of the fine particles in the aqueous dispersion of fine particles used in this example for forming the convex portion. The colloidal silica aqueous dispersions A to F, the titania aqueous dispersion, and the alumina aqueous dispersion were commercially available products, while the silicone fine particle aqueous dispersions A and B and the polyester resin fine particle aqueous dispersion were produced by the method described below. Among the commercially available products, the powder products were dispersed in water to adjust the concentration (mass%) shown in Table 1, and the dispersion products were concentrated with an evaporator or water was added to adjust the solid concentration to the concentration (mass%) shown in Table 1.

[0136] [Table 1]

[0137] <Production of Silicone Fine Particle Aqueous Dispersion A> [Hydrolysis and Polycondensation Process] (1) 21.6 g of RO water, 120.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 13.0 g of dimethyldimethoxysilane were charged into a 500 ml beaker and stirred at 45° C. for 5 minutes. (2) 1.0 g of 28% aqueous ammonia and 14.5 g of tetraethoxysilane were added thereto and stirred at 30° C. for 3.0 hours to obtain a raw material solution.

[0138] [Particle formation process] 60.0 g of RO water was placed in a 1000 ml beaker, and the raw material solution obtained in the above [Hydrolysis and Polycondensation Process] step was added dropwise over 5 minutes while stirring at 25°C. The mixture was then heated to 60°C and stirred for 2.0 hours while maintaining the temperature at 60°C. The mixture was concentrated using an evaporator to obtain a silicone microparticle aqueous dispersion A for forming convex portions, with a solid content of 30% by mass. The particle diameter of the silicone microparticles was 1.04 μm.

[0139] <Production of Silicone Fine Particle Aqueous Dispersion B> [Hydrolysis and Polycondensation Process] (1) 21.6 g of RO water, 120.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 9.5 g of dimethyldimethoxysilane were charged into a 500 ml beaker and stirred at 45° C. for 5 minutes. (2) 1.0 g of 28% aqueous ammonia and 10.5 g of tetraethoxysilane were added thereto and stirred at 30° C. for 2.5 hours to obtain a raw material solution.

[0140] [Particle formation process] 200.0 g of RO water was placed in a 1000 ml beaker, and the raw material solution obtained in the above [hydrolysis and condensation polymerization process] step was added dropwise over 5 minutes while stirring at 25°C. The mixture was then heated to 60°C and stirred for 3.0 hours while maintaining the temperature at 60°C. The mixture was concentrated using an evaporator to obtain a silicone microparticle aqueous dispersion B for forming convex portions, with a solid content of 20% by mass. The particle diameter of the silicone microparticles was 0.03 μm.

[0141] <Production of Water Dispersion of Polyester Resin Fine Particles> [Synthesis of polyester resin] 50 mol% polyoxypropylene(2,2)-2,2-bis(4-hydroxyphenyl)propane, 48 mol% terephthalic acid, and 2 mol% trimellitic acid were mixed in a two-neck flask that had been thoroughly heated and dried. 0.05 parts by mass of dibutyltin oxide was added to 100 parts by mass of this mixture, and the mixture was heated while maintaining an inert atmosphere by introducing nitrogen gas into the container, and then subjected to a co-condensation polymerization reaction at 150°C to 230°C for about 12 hours. Thereafter, the pressure was reduced, the temperature was raised to 210°C to 250°C, and the co-condensation polymerization reaction was further performed for 2 hours to synthesize a polyester resin.

[0142] [Preparation of Polyester Resin Fine Particle Aqueous Dispersion] 1200 parts by mass of the polyester resin was dissolved in 2400 parts by mass of THF, and then dimethylaminoethanol (0.5 equivalents relative to the acid value of the polyester resin) was added and stirred for 10 minutes. Then, 3600 parts by mass of ion-exchanged water was added dropwise while stirring at a rotation speed of 5000 r / min using a homogenizer (IKA: Ultra Turrax T50). The resulting mixture was treated under reduced pressure (50 mmHg) at 50°C to remove THF, and an aqueous dispersion of polyester resin fine particles was obtained (solid content concentration: 25% by mass, particle size: 1.00 μm).

[0143] <Production of Particle No. 1> [Hydrolysis and Polycondensation Process] (1) 21.6 g of RO water, 135.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 12.2 g of dimethyldimethoxysilane were charged into a 500 ml beaker and stirred at 45° C. for 5 minutes. (2) 2.0 g of 28% aqueous ammonia and 15.0 g of tetraethoxysilane were added thereto and stirred at 30° C. for 3.0 hours to obtain raw material solution 1.

[0144] [Particleization process 1] 120.0 g of RO water was placed in a 1000 ml beaker, and the entire amount of the raw material solution 1 obtained in the above [Hydrolysis and Polycondensation Step] was added dropwise while stirring at 25° C. After the dropwise addition was completed, the mixture was heated to 60° C. and stirred for 2.0 hours while maintaining the temperature at 60° C., to obtain a seed particle dispersion having a particle size of 0.12 μm.

[0145] [Particleization process 2] In a reaction vessel other than that of the above [Particle formation process 1], 43.2 parts by mass of RO water and 0.008 parts by mass of acetic acid as a catalyst were charged and stirred at 40° C. 29.9 parts by mass of tetraethoxysilane and 24.5 parts by mass of dimethyldimethoxysilane were added thereto and stirred for 1.5 hours. 350 parts by mass of methanol and 58.8 parts by mass of RO water were added to prepare raw material solution 2.

[0146] The raw material solution 2 was added dropwise at 15 mL / hr to the seed particle dispersion liquid while stirring at 25° C. The change in particle diameter of the particles in the dispersion liquid over time was measured, and when the particle diameter reached 2.00 μm, 5.0 g of the colloidal silica aqueous dispersion liquid A was added to the seed particle dispersion liquid (D F When the particle diameter reached 3.20 μm, the dropping of the raw material solution 2 was stopped, and particles No. 1 were obtained.

[0147] <Production of Particle No. 2> In the [granulation step 2], the colloidal silica aqueous dispersion A was not used, and when the particle diameter of the particles in the dispersion reached 3.20 μm, 5.0 g of the colloidal silica aqueous dispersion B was added to obtain a particle diameter (D F Particle No. 2 was obtained in the same manner as for Particle No. 1, except that the dropping of Raw Material Solution 2 was stopped when the particle diameter reached 8.50 μm.

[0148] <Production of Particle No. 3> [Hydrolysis and Polycondensation Process] (1) 21.6 g of RO water, 135.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 12.2 g of dimethyldimethoxysilane were charged into a 500 ml beaker and stirred at 45° C. for 5 minutes. (2) To this was added 2.0 g of 28% ammonia water, 15.0 g of tetraethoxysilane, and 5.0 g of colloidal silica aqueous dispersion C, and the mixture was stirred at 30° C. for 3.0 hours to obtain a raw material solution.

[0149] [Particle formation process] 120.0 g of RO water was placed in a 1000 ml beaker, and the entire amount of the raw material solution obtained in the above [Hydrolysis and Polycondensation Step] was added dropwise while stirring at 25°C. After the dropwise addition was completed, the mixture was heated to 60°C and stirred for 2.0 hours while maintaining the temperature at 60°C to measure the particle diameter (D F ) yielded particle No. 3 of 0.12 μm. Figure 4 shows an SEM image of particle No. 3. The scale in Figure 4 is 200 nm.

[0150] <Production of Particle No. 4> In the [Particleization Process 1], the particle diameter (D F ) yielded particle No. 4 with a diameter of 0.04 μm.

[0151] <Production of Particle No. 5> In the [Particle formation process 2], when the particle diameter of the particles in the dispersion liquid reaches 7.0 μm, 5.0 g of colloidal silica aqueous dispersion liquid B is added to the dispersion liquid, and the particle diameter (D F Particle No. 5 was obtained in the same manner as for Particle No. 2, except that the dropwise addition of Raw Material Solution 2 was terminated when the particle diameter reached 11.0 μm.

[0152] <Production of Particle No. 6> Particles No. 6 were obtained in the same manner as for Particles No. 1, except that colloidal silica aqueous dispersion B was used instead of colloidal silica aqueous dispersion A in the [Particle formation step 2].

[0153] <Production of Particle No. 7> Particle No. 7 was obtained in the same manner as for Particle No. 6, except that colloidal silica aqueous dispersion D was used instead of colloidal silica aqueous dispersion B in [Particle formation step 2].

[0154] <Production of Particle No. 8> In the [Particle formation process 2], the particle diameter (D F ) yielded particle No. 8 of 3.20 μm.

[0155] <Production of Particle No. 9> The particle diameter (D F ) yielded particle No. 9 with a diameter of 3.20 μm.

[0156] <Production of Particle No. 10> In the [Particle formation process 2], when the particle diameter of the particles in the dispersion reached 2.50 μm, the particle diameter (D F ) yielded particle No. 10 with a diameter of 3.20 μm.

[0157] <Production of Particle No. 11> In the [Particle formation process 2], when the particle diameter of the particles in the dispersion reached 3.00 μm, the particle diameter (D F ) yielded particle No. 11 with a diameter of 3.20 μm.

[0158] <Production of Particle No. 12> The particle diameter (D F ) yielded particle No. 12 with a diameter of 3.20 μm.

[0159] <Production of Particle No. 13> The particle diameter (D F ) yielded particle No. 13 with a diameter of 3.20 μm.

[0160] <Production of Particle No. 14> [Hydrolysis and Polycondensation Process] (1) 21.6 g of RO water, 135.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 24.5 g of dimethyldimethoxysilane were charged into a 500 ml beaker and stirred at 45° C. for 5 minutes. (2) To this was added 2.0 g of 28% aqueous ammonia, 1.5 g of tetraethoxysilane, and 1.5 g of trimethoxysilane, followed by stirring at 30° C. for 3.0 hours to obtain raw material solution 1.

[0161] [Particleization process 1] 120.0 g of RO water was placed in a 1000 ml beaker, and the entire amount of the raw material solution 1 obtained in the above [Hydrolysis and Polycondensation Step] was added dropwise while stirring at 25° C. After the dropwise addition was completed, the mixture was heated to 60° C. and stirred for 2.0 hours while maintaining the temperature at 60° C., to obtain a seed particle dispersion having a particle size of 0.31 μm.

[0162] [Particleization process 2] In a reaction vessel other than that of the above [Particle formation process 1], 43.2 parts by mass of RO water and 0.008 parts by mass of acetic acid as a catalyst were charged and stirred at 40° C. 5.0 parts by mass of tetraethoxysilane, 5.0 parts by mass of trimethoxysilane, and 45.0 parts by mass of dimethyldimethoxysilane were added thereto and stirred for 1.5 hours. 350 parts by mass of methanol and 58.8 parts by mass of RO water were added to prepare raw material solution 2.

[0163] The raw material solution 2 was added dropwise at 15 mL / hr to the seed particle dispersion while stirring at 25° C. The change in particle diameter of the particles in the dispersion over time was measured, and when the particle diameter reached 2.00 μm, 5.0 g of the colloidal silica aqueous dispersion F was added to the seed particle dispersion (D F When the particle diameter reached 4.90 μm, the dropwise addition of the raw material solution 2 was stopped, and particles No. 14 were obtained.

[0164] <Production of Particle No. 15> [Hydrolysis and Polycondensation Process] (1) 21.6 g of RO water, 135.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 8.3 g of dimethyldimethoxysilane were charged into a 500 ml beaker and stirred at 45° C. for 5 minutes. (2) 2.0 g of 28% aqueous ammonia and 19.2 g of tetraethoxysilane were added thereto and stirred at 30° C. for 3.0 hours to obtain raw material solution 1.

[0165] [Particleization process 1] 90.0 g of RO water was placed in a 1000 ml beaker, and the entire amount of the raw material solution 1 obtained in the above [Hydrolysis and Polycondensation Step] was added dropwise while stirring at 25° C. After the dropwise addition was completed, the mixture was heated to 60° C. and stirred for 2.0 hours while maintaining the temperature at 60° C., to obtain a seed particle dispersion having a particle size of 0.29 μm.

[0166] [Particleization process 2] In a reaction vessel other than that of the above [Particle formation process 1], 43.2 parts by mass of RO water and 0.008 parts by mass of acetic acid as a catalyst were charged and stirred at 40° C. 38.1 parts by mass of tetraethoxysilane and 16.3 parts by mass of dimethyldimethoxysilane were added thereto and stirred for 1.5 hours. 350 parts by mass of methanol and 58.8 parts by mass of RO water were added to prepare raw material solution 2.

[0167] The raw material solution 2 was added dropwise at 15 mL / hr to the seed particle dispersion liquid while stirring at 25° C. The change in particle diameter of the particles in the dispersion liquid over time was measured, and when the particle diameter reached 2.00 μm, 5.0 g of the colloidal silica aqueous dispersion liquid A was added to the seed particle dispersion liquid (D F When the particle diameter reached 3.20 μm, the dropwise addition of the raw material solution 2 was stopped, and particle No. 15 was obtained.

[0168] <Production of Particle No. 16> [Hydrolysis and Polycondensation Process] (1) 21.6 g of RO water, 135.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 5.5 g of dimethyldimethoxysilane were charged into a 500 ml beaker and stirred at 45° C. for 5 minutes. (2) 2.0 g of 28% aqueous ammonia and 22.0 g of tetraethoxysilane were added thereto and stirred at 30° C. for 3.0 hours to obtain raw material solution 1.

[0169] [Particleization process 1] 120.0 g of RO water was placed in a 1000 ml beaker, and the entire amount of the raw material solution 1 obtained in the above [Hydrolysis and Polycondensation Step] was added dropwise while stirring at 25° C. After the dropwise addition was completed, the mixture was heated to 60° C. and stirred for 2.0 hours while maintaining the temperature at 60° C., to obtain a seed particle dispersion having a particle size of 0.12 μm.

[0170] [Particleization process 2] In a reaction vessel separate from the one used in the above [Particle formation process 1], 43.2 parts by mass of RO water and 0.008 parts by mass of acetic acid as a catalyst were charged and stirred at 40° C. 43.5 parts by mass of tetraethoxysilane and 10.9 parts by mass of dimethyldimethoxysilane were added thereto and stirred for 1.5 hours. 350 parts by mass of methanol and 58.8 parts by mass of RO water were added to prepare raw material solution 2.

[0171] The raw material solution 2 was added dropwise at 15 mL / hr to the seed particle dispersion liquid while stirring at 25° C. The change in particle diameter of the particles in the dispersion liquid over time was measured, and when the particle diameter reached 2.00 μm, 5.0 g of the colloidal silica aqueous dispersion liquid A was added to the seed particle dispersion liquid (D F When the particle diameter reached 3.20 μm, the dropwise addition of the raw material solution 2 was stopped, and particles No. 16 were obtained.

[0172] <Production of Particle No. 17> [Hydrolysis and Polycondensation Process] (1) 21.6 g of RO water, 135.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 5.5 g of dimethyldimethoxysilane were charged into a 500 ml beaker and stirred at 45° C. for 5 minutes. (2) 2.0 g of 28% aqueous ammonia and 22.0 g of tetraethoxysilane were added thereto and stirred at 30° C. for 3.0 hours to obtain raw material solution 1.

[0173] [Particleization process 1] 90.0 g of RO water was placed in a 1000 ml beaker, and the entire amount of the raw material solution 1 obtained in the above [Hydrolysis and Polycondensation Step] was added dropwise while stirring at 25° C. After the dropwise addition was completed, the mixture was heated to 60° C. and stirred for 2.0 hours while maintaining the temperature at 60° C., to obtain a seed particle dispersion having a particle size of 0.27 μm.

[0174] [Particleization process 2] In a separate reaction vessel, 43.2 parts by mass of RO water and 0.008 parts by mass of acetic acid as a catalyst were charged and stirred at 40° C. 43.5 parts by mass of tetraethoxysilane and 10.9 parts by mass of dimethyldimethoxysilane were added thereto and stirred for 1.5 hours. 350 parts by mass of methanol and 58.8 parts by mass of RO water were added to prepare raw material solution 2.

[0175] The raw material solution 2 was added dropwise at 15 mL / hr to the seed particle dispersion while stirring at 25° C. The change in particle size of the particles in the dispersion over time was measured, and when the particle size reached 2.00 μm, 25.0 g of the silicone microparticle aqueous dispersion A was added to the seed particle dispersion (D F When the particle diameter reached 3.20 μm, the dropwise addition of the raw material solution 2 was stopped, and particles No. 17 were obtained.

[0176] <Production of Particle No. 18> The particle diameter (D F ) yielded particle No. 18 with a diameter of 0.04 μm.

[0177] <Production of Particle No. 19> The particle diameter (D F ) yielded particle No. 19 with a diameter of 3.20 μm.

[0178] <Production of Particle No. 20> [Hydrolysis and Polycondensation Process] (1) 21.6 g of RO water, 135.0 g of methanol, 0.004 g of acetic acid as a catalyst, and 12.2 g of dimethyldimethoxysilane were charged into a 500 ml beaker and stirred at 45° C. for 5 minutes. (2) 2.0 g of 28% aqueous ammonia and 15.0 g of tetraethoxysilane were added thereto and stirred at 30° C. for 3.0 hours to obtain raw material solution 1.

[0179] [Particleization process 1] 120.0 g of RO water was placed in a 1000 ml beaker, and the entire amount of the raw material solution 1 obtained in the above [Hydrolysis and Polycondensation Step] was added dropwise while stirring at 25° C. After the dropwise addition was completed, the mixture was heated to 60° C. and stirred for 2.0 hours while maintaining the temperature at 60° C., to obtain a seed particle dispersion having a particle size of 0.12 μm.

[0180] [Particleization process 2] In a reaction vessel other than that of the above [Particle formation process 1], 43.2 parts by mass of RO water and 0.008 parts by mass of acetic acid as a catalyst were charged and stirred at 40° C. 29.9 parts by mass of tetraethoxysilane and 24.5 parts by mass of dimethyldimethoxysilane were added thereto and stirred for 1.5 hours. 350 parts by mass of methanol and 58.8 parts by mass of RO water were added to prepare raw material solution 2.

[0181] The raw material solution 2 was added dropwise at 15 mL / hr to the seed particle dispersion liquid while stirring at 25° C. The change in particle diameter of the particles in the dispersion liquid over time was measured, and the particle diameter (D F When the particle diameter reached 3.20 μm, the dropwise addition of the raw material solution 2 was stopped, and particles No. 20 were obtained.

[0182] The physical properties of the particles Nos. 1 to 20 obtained above are shown in Table 2.

[0183] [Table 2]

[0184] <Preparation of Molded Bodies 1 to 28> (Molded body 1) 100 parts by mass of polyoxymethylene (POM) resin (Duracon M90-44, manufactured by Polyplastics Co., Ltd., Young's modulus: 2.7 GPa) was added to 10 parts by mass of particle No. 1 and mixed uniformly with a tumbler mixer. Then, a twin-screw extruder (Process 11, manufactured by Thermo Fisher Scientific Co., Ltd.) was used to knead at a kneading temperature of 200°C and 200 rpm to obtain a resin composition of Example 1. The obtained composition was pulverized with a cutter mill, and then molded into a molded body 1 as a test piece for evaluation (size 30 mm x 30 mm, thickness 4 mm) using an injection molding machine (HAAKE MiniJetPro, manufactured by Thermo Fisher Scientific Co., Ltd.). The molding conditions were a cylinder temperature of 200°C, a mold temperature of 80°C, and an injection pressure of 100 MPa.

[0185] (Molded objects 2 to 16) Molded bodies 2 to 16 were produced in the same manner as in Example 1, except that particle No. 1 was changed to particle Nos. 2 to 16 as shown in Table 3.

[0186] (Molded bodies 17 and 18) Compacts 17 and 18 were produced in the same manner as compact 1, except that the amount of particle No. 1 added was changed from 10 parts by mass to 40 parts by mass and 2 parts by mass, as shown in Table 3.

[0187] (Molded body 19) Molded body 19 was produced in the same manner as molded body 1, except that the polyoxymethylene resin was changed to a polybutylene terephthalate (PBT) resin (Novaduran 5010R5, manufactured by Mitsubishi Engineering Plastics Corporation, Young's modulus: 2.4 GPa) and the kneading temperature and the cylinder temperature during injection molding were changed to 240°C.

[0188] (Molded body 20) Molded body 20 was produced in the same manner as molded body 1, except that the polyoxymethylene resin was changed to a polypropylene (PP) resin (Novatec PP EG7FTB, manufactured by Japan Polypropylene Corporation, Young's modulus: 1.2 GPa), the kneading temperature and the cylinder temperature during injection molding were both set to 220°C, and the mold temperature was set to 50°C.

[0189] (Molded body 21) Molded body 21 was produced in the same manner as molded body 1, except that the polyoxymethylene resin was changed to a polyamide (PA) resin (Ultramid A3K, manufactured by BASF, Young's modulus: 3.1 GPa), the kneading temperature and the cylinder temperature during injection molding were both 280°C, and the mold temperature was 60°C.

[0190] (Molded body 22) Molded body 22 was produced in the same manner as molded body 1, except that the polyoxymethylene resin was changed to polyethylene (PE) resin (Suntech HD J340, manufactured by Asahi Kasei Corporation, Young's modulus: 0.8 GPa), the kneading temperature and the cylinder temperature during injection molding were both set to 200°C, and the mold temperature was set to 40°C.

[0191] (Molded objects 23 to 26) Compacts 23 to 26 were produced in the same manner as compact 1, except that compact No. 1 was changed to compact Nos. 17 to 20 as shown in Table 3.

[0192] (Molded body 27) Compact 1 was produced in the same manner as compact 1, except that particle No. 1 was not added.

[0193] (Molded body 28) Compact 28 was produced in the same manner as compact 1, except that the amount of particle No. 1 added was changed from 10 parts by mass to 0.5 parts by mass.

[0194] <Evaluation of Molded Articles 1 to 28> The molded bodies 1 to 28 obtained above were evaluated for the specific wear rate and the adhesion of the particles to the matrix resin (rate of change ΔP) by the above-mentioned evaluation method. The results are shown in Table 3.

[0195] [Table 3]

[0196] <Preparation of Molded Bodies 29 to 34> A curable composition was prepared using the following components, and molded bodies 29 to 34 were produced using a stereolithography method.

[0197] [Polyfunctional radically polymerizable compound (A)] A-1: Urethane acrylate (Shiko UV-6630B, manufactured by Mitsubishi Chemical Corporation, ethylenically unsaturated group equivalent: 1500 g / eq) A-2: Alicyclic diacrylate (UV-6630B, manufactured by Mitsubishi Chemical Corporation, ethylenically unsaturated group equivalent: 1500 g / eq) A-3: Ethoxylated bisphenol diacrylate (NK Ester ABE-300, Shin-Nakamura Chemical Co., Ltd., ethylenically unsaturated group equivalent 466 g / eq) A-4: Urethane acrylate compound (Shiko UV-3550AC, manufactured by Mitsubishi Chemical Corporation, ethylenically unsaturated group equivalent 7000g / eq) A-5: Urethane acrylate (EBECRYL8210, Daicel-Allnex, ethylenically unsaturated group equivalent: 150 g / eq)

[0198] [Monofunctional radically polymerizable compound (B)] B-1: N,N'-Dimethylacrylamide (DMAA, KJ Chemical Co.) B-2: Isobornyl acrylate (Tokyo Chemical Industry Co., Ltd.) B-3: N-acryloylmorpholine (ACMO, KJ Chemical Co.)

[0199] [Hardening agent] C-1: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) (photoradical polymerization initiator)

[0200] (Molded body 29) The following components were mixed and stirred at 75° C. for 2 hours to prepare a curable composition. A-1 40 parts by mass A-2 15 parts by mass A-3 20 parts by mass B-1 25 parts by mass C-1 1 part by mass Particle No.1 25 parts by mass The polyfunctional radically polymerizable compound (A), which is a mixture of A-1 to A-3, has an ethylenically unsaturated group equivalent of 893 g / eq.

[0201] The prepared curable composition was used to model a three-dimensional rectangular parallelepiped shape of 30 mm x 30 mm x 4 mm using a 3D printer (DWS-020X, a photolithography device using the regulated liquid surface method). The model was produced by stacking 30 mm x 4 mm x 50 μm thick cured layers to a height of 30 mm. The obtained model was irradiated with ultraviolet light for 30 minutes using a UVCuringUnitM (DWS), and then placed in a heating oven at 50 ° C for 1 hour and then placed in a heating oven at 100 ° C for 2 hours to perform heat treatment, thereby producing a molded body 29 as a test piece.

[0202] (Molded body 30) A curable composition was prepared in the same manner as for molded body 29, except that the composition of each component was changed as follows, and molded body 30 was produced. A-4 40 parts by mass B-2 30 parts by mass B-3 30 parts by mass C-1 1 part by mass Particle No.1 25 parts by mass

[0203] (Molded body 31) A curable composition was prepared in the same manner as in the case of molded body 29, except that the composition of each component was changed as follows, and molded body 31 was produced. A-5 55 parts by mass B-4 45 parts by mass C-1 1 part by mass Particle No.1 25 parts by mass

[0204] (Molded body 32) A curable composition was prepared in the same manner as for molded body 29, except that particle No. 1 was not added, and molded body 32 was produced.

[0205] (Molded bodies 33 and 34) Molded bodies 33 and 34 were produced by preparing a curable composition in the same manner as for molded body 29, except that particle No. 1 was replaced with particle No. 17 or 18.

[0206] <Evaluation of Molded Articles 29 to 34> The thus obtained molded bodies 29 to 34 were evaluated in the same manner as the molded bodies 1 to 28. The results are shown in Table 4. The Young's modulus of the matrix resin was 3.6 GPa in all the molded bodies.

[0207] [Table 4] [Explanation of symbols]

[0208] 1: matrix resin, 2: base, 3: protrusion, 4: particle, 5: fine particle, 5a: first portion, 5b: second portion

Claims

1. A molded article comprising a matrix resin and a plurality of particles dispersed in the matrix resin, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, The convex portion is mainly composed of an inorganic material, A molded body characterized in that the particle has the base and fine particles, the base is particulate having a recess on its surface, and the fine particles have a first portion embedded in the recess of the base and a second portion forming the convex portion.

2. A molded article comprising a matrix resin and a plurality of particles dispersed in the matrix resin, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, the protrusion has a higher Young's modulus than the base; A molded body characterized in that the particle has the base and fine particles, the base is particulate having a recess on its surface, and the fine particles have a first portion embedded in the recess of the base and a second portion forming the convex portion.

3. 3. The molded article according to claim 2, wherein the Young's modulus of the base portion is 0.005 GPa or more and 25,000 GPa or less, and the Young's modulus of the protrusions is 50 GPa or more and 500 GPa or less.

4. 3. The molded article according to claim 1, wherein the fine particles are composed mainly of any one of silica, alumina and titania.

5. 3. The molded article according to claim 1, wherein the particle diameter of the plurality of particles is 0.02 μm or more and 15.00 μm or less.

6. The particle diameter of the base is D A , the particle diameter of the fine particles is D C When this is done, D C / D A The molded article according to claim 1 or 2, characterized in that the ratio is 0.050 or more and 0.650 or less.

7. 3. The molded article according to claim 1, wherein the embedding ratio of the fine particles defined by the following formula [1] is 30% or more and 80% or less. Buried rate of fine particles (%) = (depth of particle buried in base / diameter of particle) x 100 [1]

8. 3. The molded article according to claim 1, wherein the matrix resin has a Young's modulus in the range of 1.0 GPa or more and 5.0 GPa or less.

9. 3. The molded article according to claim 1, wherein the matrix resin contains at least one of a polyvinyl resin, a polyester resin, a polyamide resin, a polyacetal resin, an acrylic resin, and an epoxy resin.

10. 3. The molded article according to claim 1, which is a film.

11. 3. The molded article according to claim 1, wherein the content of the particles is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the matrix resin.

12. The volume of the molded body is 1 mm 3 3. The molded article according to claim 1 or 2, characterized in that:

13. The volume of the molded body is 100 mm 3 3. The molded article according to claim 1 or 2, characterized in that:

14. A curable composition comprising a plurality of particles and a curable resin material, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, The convex portion is mainly composed of an inorganic material, A curable composition characterized in that the particle has the base and fine particles, the base is particulate having a recess on its surface, and the fine particles have a first portion embedded in the recess of the base and a second portion forming the convex portion.

15. A curable composition comprising a plurality of particles and a curable resin material, the particle has a base mainly composed of an organosilicon compound having a siloxane bond, and a protrusion supported by the base and disposed on a surface of the particle, the protrusion has a higher Young's modulus than the base; A curable composition characterized in that the particle has the base and fine particles, the base is particulate having a recess on its surface, and the fine particles have a first portion embedded in the recess of the base and a second portion forming the convex portion.

16. The curable composition according to claim 15, wherein the Young's modulus of the base is 0.005 GPa or more and 25,000 GPa or less, and the Young's modulus of the protrusions is 50 GPa or more and 500 GPa or less.

17. 16. The curable composition according to claim 14, wherein the fine particles are mainly composed of any one of silica, alumina, and titania.

18. The curable composition according to claim 14 or 15, wherein the particle diameter of the plurality of particles is 0.02 μm or more and 15.00 μm or less.

19. The particle diameter of the base is D A , the particle diameter of the fine particles is D C When this is done, D C / D A The curable composition according to claim 14 or 15, wherein the σ is 0.050 or more and 0.650 or less.

20. The curable composition according to claim 14 or 15, characterized in that the embedding ratio of the fine particles defined by the following formula [1] is 30% or more and 80% or less. Buried rate of fine particles (%) = (depth of particle buried in base / diameter of particle) x 100 [1]

21. 16. The curable composition according to claim 14, wherein the content of the particles is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the curable resin material.

22. The curable composition according to claim 14 or 15, wherein the curable resin material contains a radically polymerizable compound.

23. the curable resin material contains a polyfunctional radical polymerizable compound (A) and a monofunctional radical polymerizable compound (B), The curable composition according to claim 14 or 15, wherein the polyfunctional radically polymerizable compound (A) has an ethylenically unsaturated group equivalent of 700 g / eq or more and 7000 g / eq or less.

24. The curable composition according to claim 23, wherein the polyfunctional radically polymerizable compound (A) is a (meth)acrylate-based compound or a urethane (meth)acrylate-based compound having any one of a polyether structure, a polyester structure, and a polycarbonate structure.

25. The curable composition according to claim 14 or 15, wherein the curable resin material contains a photoradical polymerization initiator.

26. A step of disposing the curable composition according to claim 14 or 15 to a predetermined thickness; and curing the curable composition having the predetermined thickness by irradiating the curable composition with light in accordance with shape data of a three-dimensional model.

27. A machine comprising the molded body according to claim 1 or 2 and a member, the molded body and the member sliding against each other.

28. The machine according to claim 27, characterized in that the particles are present on a sliding surface of the molded body that slides against the member.

29. A machine comprising the molded article according to claim 1 or 2 as a bearing, gear, cam or roller.

30. 3. An electrophotographic apparatus, comprising at least one of a photosensitive drum, a roller, and a belt, the molded article according to claim 1.

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