Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/06—Making microcapsules or microballoons by phase separation
  • B01J13/14—Polymerisation; cross-linking
  • B01J13/18—In situ polymerisation with all reactants being present in the same phase
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G

Definitions

• the present invention relates to lubricant-containing resin particles, a method for producing lubricant-containing resin particles, a resin composition, a molded body, and a sliding member.
• sliding components such as bearings that require excellent sliding properties.
• metal materials have been widely used for such sliding components, but in recent years, the use of resin materials has increased in order to reduce weight.
• a molded body containing resin particles encapsulating a lubricant and a base component As a member with excellent sliding properties, a molded body containing resin particles encapsulating a lubricant and a base component has been reported. Specifically, the sliding properties of a molded body containing resin particles in which silicone oil is encapsulated as a lubricant in an acrylic resin as a shell and a thermoplastic olefin-based elastomer as a base component have been evaluated (Patent Documents 1 and 2).
• acrylic resins have low heat resistance and impact resistance.
• the resin particles demonstrated in Patent Documents 1 and 2 are made of, for example, a heat-resistant resin with a high melting point as the base component, if the resin particles and base component are mixed and extruded at high temperatures in an extruder, the resin particles may melt or crack or chip, resulting in a problem that the final molded product does not exhibit excellent sliding properties.
• Patent Documents 1 and 2 a sliding property durability evaluation is performed, but the evaluation is a comparison of the dynamic friction coefficient of the surface of the sheet, which is the molded body, between the initial state and after one month or two months of storage.
• the sliding property durability evaluation in Patent Documents 1 and 2 evaluates the decrease in sliding property during storage of the molded body (for example, the decrease in sliding property due to bleeding out of the lubricant), and does not evaluate the effect of sustaining sliding property in a sliding state.
• the present invention has been made to solve the above-mentioned problems of the prior art, and its main object is to provide lubricant-containing resin particles that can exhibit excellent heat resistance, excellent impact resistance, and long-lasting sliding properties in a sliding state. It also aims to provide a method for producing such lubricant-containing resin particles. It also aims to provide a resin composition containing such lubricant-containing resin particles, a molded body obtained by molding such a resin composition, a sliding member containing such a resin composition, and a sliding member containing such a molded body.
• a lubricant-encapsulated resin particle according to an embodiment of the present invention is a lubricant-encapsulated resin particle having a shell portion containing a lubricant, and the shell portion contains a polymer (P) having an ether structure represented by formula (1).
• the polymer (P) may be a polymer (AM) obtained by reacting a compound (A) having an ether structure and a radical reactive group represented by the above formula (1) with a monomer (M) that reacts with the compound (A).
• the amount of the compound (A) relative to the total amount may be 1 part by weight to 60 parts by weight.
• the monomer (M) may contain an aromatic monofunctional monomer (B) and an aromatic crosslinkable monomer (C).
• the amount of the aromatic monofunctional monomer (B) relative to the total amount may be 5 parts by weight to 60 parts by weight.
• the amount of the aromatic crosslinkable monomer (C) relative to the total amount may be 15 parts by weight to 65 parts by weight.
• the amount of the lubricant relative to the total amount may be 10 parts by weight to 100 parts by weight.
• the lubricant may be at least one selected from the group consisting of hydrocarbon-based oils, silicone-based oils, fluorine-based oils, ether-based oils, ester-based oils, and diester-based oils.
• the difference between the weight residual ratio at 250°C and the weight residual ratio at 400°C when the lubricant-encapsulated resin particle is heated at a rate of 10°C/min in a nitrogen atmosphere in a TG-DTA may be 40% or less.
• the lubricant-containing resin particles according to any one of [1] to [9] above may have a volume average particle diameter of 0.1 ⁇ m to 50 ⁇ m.
• a method for producing lubricant-encapsulated resin particles according to an embodiment of the present invention is a method for producing lubricant-encapsulated resin particles having a lubricant encapsulated in the shell portion, in which a compound (A) having an ether structure and a radical reactive group represented by formula (1) and a monomer (M) that reacts with the compound (A) are reacted in an aqueous medium in the presence of the lubricant and a compatibilizer.
• the amount of the compound (A) relative to the total amount may be 1 part by weight to 60 parts by weight.
• the monomer (M) may contain an aromatic monofunctional monomer (B) and an aromatic crosslinkable monomer (C).
• the amount of the aromatic monofunctional monomer (B) relative to the total amount may be 5 parts by weight to 60 parts by weight.
• the amount of the aromatic crosslinkable monomer (C) relative to the total amount may be 15 parts by weight to 65 parts by weight.
• the amount of the lubricant relative to the total amount may be 10 parts by weight to 100 parts by weight.
• the amount of the compatibilizer relative to the total amount may be 10 parts by weight to 100 parts by weight.
• a resin composition according to an embodiment of the present invention includes the lubricant-containing resin particles according to any one of [1] to [10] above and a base resin.
• a molded article according to an embodiment of the present invention is obtained by molding the resin composition described in [18] above.
• a slide member according to an embodiment of the present invention contains the resin composition according to the above [18].
• a slide member according to an embodiment of the present invention includes the molded article according to the above [19].
• lubricant-containing resin particles that can exhibit excellent heat resistance, excellent impact resistance, and a long-lasting effect of sliding properties in a sliding state. It is also possible to provide a method for producing such lubricant-containing resin particles. Furthermore, it is possible to provide a resin composition containing such lubricant-containing resin particles, a molded body obtained by molding such a resin composition, a sliding member containing such a resin composition, and a sliding member containing such a molded body.
• FIG. 2 is a photograph showing the appearance of particle (1).
• FIG. 2 is a cross-sectional photograph of particle (1).
• FIG. 2 is a photograph showing the appearance of particle (2).
• FIG. 2 is a cross-sectional photograph of particle (2).
• FIG. 2 is a photograph showing the appearance of particle (7).
• FIG. 2 is a cross-sectional photograph of particle (7).
• FIG. 2 is a photograph showing the appearance of particle (8).
• FIG. 2 is a cross-sectional photograph of particle (8).
• FIG. 2 is a photograph showing the appearance of particle (9).
• FIG. 2 is a cross-sectional photograph of particle (9).
• FIG. 2 is a photograph showing the appearance of particle (10).
• FIG. 2 is a cross-sectional photograph of particle (10).
• FIG. 1 is a cross-sectional photograph of particle (10).
• FIG. 1 shows the results of an evaluation of the long-term effect of sliding properties of a tablet-shaped molded body (1) in a sliding state (evaluation based on the presence or absence of fluctuation in the friction coefficient).
• FIG. 13 is a diagram showing the results of an evaluation of the long-term effect of sliding properties of a tablet-shaped molded body (8) in a sliding state (evaluation based on the presence or absence of fluctuation in the friction coefficient).
• FIG. 13 is a diagram showing the results of evaluation of the effect of long-term durability of slidability in a sliding state for a tablet-shaped molded body (C1) (evaluation based on the presence or absence of fluctuation in the friction coefficient).
• FIG. 13 is a diagram showing the results of evaluation of the effect of long-term durability of sliding properties in a sliding state for a tablet-shaped molded body (C7) (evaluation based on the presence or absence of fluctuation in the friction coefficient).
• salts include alkali metal salts and alkaline earth metal salts, and specific examples include sodium salts and potassium salts.
• the lubricant-containing resin particles according to the embodiment of the present invention are lubricant-containing resin particles having a shell portion and a lubricant encapsulated therein.
• the lubricant-containing resin particles according to the embodiment of the present invention typically have a shell portion and a hollow portion surrounded by the shell portion, and the lubricant is encapsulated in the hollow portion.
• the shell portion and the hollow portion surrounded by the shell portion may consist of one hollow region, or may consist of multiple hollow regions (porous structure). In order to better demonstrate the effects of the present invention, it is preferable that the shell portion and the hollow portion surrounded by the shell portion consist of one hollow region.
• Any suitable lubricant may be used as the lubricant as long as it does not impair the effects of the present invention.
• lubricants include at least one selected from the group consisting of hydrocarbon-based oils, silicone-based oils, fluorine-based oils, ether-based oils, ester-based oils, and diester-based oils. Only one type of lubricant may be used, or two or more types may be used.
• hydrocarbon oils examples include liquid paraffin, polybutene, polyisobutylene, 1-decene oligomer, 1-decene and ethylene co-oligomer, monoalkylbenzene, dialkylbenzene, polyalkylbenzene, monoalkylnaphthalene, dialkylnaphthalene, and polyalkylnaphthalene.
• Liquid paraffin is preferred as the hydrocarbon oil, as it can better exert the effects of the present invention.
• silicone oils examples include dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, and modified silicone oil.
• silicone oils include silicone oils having a kinetic viscosity (25°C) of 0.1 mm2 /s to 1,000,000 mm2 /s measured with an Ubbelohde viscometer according to ASTM D445-46T, and more preferably silicone oils having a kinetic viscosity (25°C) of 0.5 mm2/s to 100,000 mm2 /s. If the kinetic viscosity (25°C) is too high outside the above range, there is a risk that the particles will not contain the silicone oil, and long-term sliding properties may not be achieved.
• silicone oils having the above-mentioned preferred kinetic viscosity include dimethyl silicone oils "KF-96L-1cs”, “KF-96L-50cs”, “KF-96L-100cs”, “KF-96L-500cs”, “KF-96L-1000cs”, and "KF-96L-5000cs", manufactured by Shin-Etsu Chemical Co., Ltd.
• fluorine-based oils examples include fluoroethylene, trifluorochloroethylene, perfluoropolyether, and perfluoropolyalkyl ether.
• ether-based oils include polyethylene glycol, polypropylene glycol, polyethylene glycol monoether, polypropylene glycol monoether, monoalkyl triphenyl ether, alkyl diphenyl ether, dialkyl diphenyl ether, tetraphenyl ether, pentaphenyl ether, monoalkyl tetraphenyl ether, and dialkyl tetraphenyl ether.
• ester oils include trioctyl trimellitate, tridecyl trimellitate, tetraoctyl pyromellitate, trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate, and complex ester oils which are oligoesters of mixed fatty acids of monobasic and dibasic acids and polyhydric alcohols.
• diester oils examples include dibutyl sebacate, di(2-ethylhexyl) sebacate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate, diisotridecyl adipate, ditridecyl glutarate, and methyl acetyl ricinoleate.
• Hydrocarbon-based oils and silicone-based oils are preferred as lubricants, as they can better bring out the effects of the present invention.
• the weight ratio of the lubricant in the entire lubricant-containing resin particles according to the embodiment of the present invention may be any appropriate weight ratio within a range that does not impair the effects of the present invention.
• the weight ratio of such a lubricant is preferably 10% by weight to 60% by weight.
• the weight percentage of the lubricant in the entire lubricant-containing resin particles can be measured by any appropriate method.
• the weight percentage can be calculated from the weight of the lubricant-containing resin particles and the weight after removing the lubricant by washing with any appropriate solvent or the like.
• the volume average particle diameter of the lubricant-containing resin particles according to the embodiment of the present invention is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 0.2 ⁇ m to 40.0 ⁇ m, even more preferably 0.3 ⁇ m to 30.0 ⁇ m, and particularly preferably 0.4 ⁇ m to 25.0 ⁇ m. If the volume average particle diameter of the lubricant-containing resin particles according to the embodiment of the present invention is within the above range, the effects of the present invention can be more effectively achieved. If the volume average particle diameter of the lubricant-containing resin particles according to the embodiment of the present invention is too small outside the above range, the thickness of the shell portion becomes relatively thin, and the lubricant-containing resin particles may not have sufficient strength.
• volume average particle diameter of the lubricant-containing resin particles according to the embodiment of the present invention is too large outside the above range, phase separation between the polymer and the solvent produced by polymerization of the monomer component during suspension polymerization may be difficult to occur, which may make it difficult to form the shell portion.
• the lubricant-containing resin particles according to an embodiment of the present invention have a smaller difference between the weight residual rate at 250°C and the weight residual rate at 400°C when heated at 10°C/min in a nitrogen atmosphere in a TG-DTA, and the smaller the difference, the better, preferably 40% or less, more preferably 38% or less, and even more preferably 35% or less.
• the lower limit of the difference is preferably 0% or more. If the difference is within the above range, the lubricant-containing resin particles according to an embodiment of the present invention can exhibit excellent heat resistance. If the difference is too large outside the above range, the particles may be deformed by heating. For example, if the lubricant-containing resin particles and a heat-resistant resin with a high melting point are mixed and extruded at high temperature in an extruder, the lubricant-containing resin particles may melt or crack or chip.
• the difference between the weight retention rate at 250°C and the weight retention rate at 400°C when the temperature is increased at 10°C/min in a nitrogen atmosphere in the above TG-DTA can be smaller, preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less.
• the lower limit of the above difference is preferably 0% or more.
• the shell portion contains a polymer (P) having an ether structure represented by formula (1).
• the shell portion contains a polymer (P) having such a structure, the effects of the present invention can be more effectively exhibited.
• the polymer (P) may be of only one type or of two or more types.
• the polymer (P) may have only one type of ether structure represented by formula (1), or two or more types.
• the content of polymer (P) in the shell portion is preferably 60% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even more preferably 80% by weight to 100% by weight, and particularly preferably 90% by weight to 100% by weight, in order to further exert the effects of the present invention.
• the shell portion may contain any other appropriate components as long as they do not impair the effects of the present invention.
• the polymer (P) may contain a phosphate ester structure.
• the phosphate ester structure may be of only one type, or of two or more types.
• the phosphate ester structure is typically represented by formula (2).
• the phosphate ester structure may be a phosphate monoester structure, a phosphate diester structure, or a phosphate triester structure.
• the phosphate ester structure is preferably a phosphate monoester structure or a phosphate diester structure.
• any appropriate polymer may be used as long as it has an ether structure represented by formula (1) and does not impair the effects of the present invention.
• a polymer (P) is preferably a polymer (AM) obtained by reacting a compound (A) having an ether structure represented by formula (1) and a radical reactive group with a monomer (M) that reacts with the compound (A).
• the compound (A) having an ether structure and a radical reactive group represented by formula (1) may be of only one type, or of two or more types.
• radical reactive group Any appropriate polymer may be used as the radical reactive group, provided that it is a group generally known as a radical reactive group and does not impair the effects of the present invention.
• radical reactive groups are preferably groups having a carbon-carbon unsaturated double bond, and specific examples include vinyl groups, acrylic groups, methacrylic groups, acrylamide groups, and allyl groups.
• the radical reactive group preferably has a structure represented by formula (3) in that the effect of the present invention can be more effectively exhibited.
• R 1 represents a methyl group or a hydrogen atom.
• the amount of compound (A) relative to the total amount is preferably 1 to 60 parts by weight, more preferably 3 to 55 parts by weight, even more preferably 5 to 53 parts by weight, and particularly preferably 7 to 50 parts by weight, in order to better demonstrate the effects of the present invention. If the amount of compound (A) is too small outside the above range, there is a risk of insufficient heat resistance. If the amount of compound (A) is too large outside the above range, there is a risk of it being difficult to form a shell portion and a hollow portion surrounded by the shell portion.
• the amount of compound (A) relative to 100 parts by weight of the total amount of compound (A) and monomer (M) is preferably 1 to 60 parts by weight, more preferably 10 to 55 parts by weight, even more preferably 20 to 50 parts by weight, and particularly preferably 25 to 50 parts by weight.
• Another embodiment of the amount of compound (A) relative to 100 parts by weight of the total amount of compound (A) and monomer (M) is preferably 1 part by weight to 60 parts by weight, more preferably 1 part by weight to 40 parts by weight, even more preferably 3 parts by weight to 30 parts by weight, and particularly preferably 5 parts by weight to 20 parts by weight.
• any suitable compound may be used as long as it has the ether structure represented by formula (1) and a radical reactive group, without impairing the effects of the present invention.
• polyphenylene ether is preferable as such a compound (A).
• polyphenylene ether products include, for example, the NORYL (registered trademark) series (NORYL (registered trademark) SA9000 and the like) (manufactured by SABIC), the Iupiace (registered trademark) series (manufactured by Mitsubishi Chemical Corporation), the ZYLON (registered trademark) series (manufactured by Asahi Kasei Corporation), and the OPE-2St series (manufactured by Mitsubishi Gas Chemical Co., Ltd.).
• NORYL registered trademark
• Iupiace registered trademark
• ZYLON registered trademark
• OPE-2St series manufactured by Mitsubishi Gas Chemical Co., Ltd.
• the polyphenylene ether is an oligomer, and that the number average molecular weight Mn is 500 to 3500.
• the amount of lubricant relative to the total amount of compound (A) and monomer (M) taken as 100 parts by weight is preferably 10 parts by weight to 100 parts by weight, more preferably 20 parts by weight to 90 parts by weight. If the amount of the lubricant is within the above range, the effects of the present invention can be more effectively achieved. If the amount of the lubricant is outside the above range and is too small, it may be difficult to obtain lubricant-encapsulated resin particles that can exhibit excellent sliding properties. If the amount of the lubricant is outside the above range and is too large, it may be difficult to smoothly obtain lubricant-encapsulated resin particles in which the lubricant is encapsulated in the shell portion.
• the amount of lubricant per 100 parts by weight of the total amount of compound (A) and monomer (M) is preferably 10 parts by weight to 100 parts by weight, more preferably 15 parts by weight to 90 parts by weight, even more preferably 20 parts by weight to 80 parts by weight, and particularly preferably 25 parts by weight to 75 parts by weight.
• the amount of lubricant per 100 parts by weight of the total amount of compound (A) and monomer (M) is preferably 10 parts by weight to 100 parts by weight, more preferably 20 parts by weight to 95 parts by weight, even more preferably 30 parts by weight to 90 parts by weight, particularly preferably 40 parts by weight to 85 parts by weight, and most preferably 45 parts by weight to 85 parts by weight.
• the monomer (M) a monomer that reacts with the terminal group of the compound (A) is preferred, and examples thereof include a monofunctional monomer and a crosslinkable monomer.
• the monomer (M) preferably contains an aromatic monofunctional monomer (B) and an aromatic crosslinkable monomer (C).
• aromatic monofunctional monomer (B) Any appropriate aromatic monofunctional monomer may be used as the aromatic monofunctional monomer (B) as long as it does not impair the effects of the present invention.
• aromatic monofunctional monomers (B) include styrene, ⁇ -methylstyrene, ethylvinylbenzene, vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, vinylbiphenyl, and vinylnaphthalene, with styrene and ethylvinylbenzene being preferred.
• the aromatic monofunctional monomer (B) may be of only one type, or of two or more types.
• the amount of the aromatic monofunctional monomer (B) relative to the total amount is preferably 5 parts by weight to 60 parts by weight, more preferably 5 parts by weight to 55 parts by weight, and even more preferably 10 parts by weight to 50 parts by weight, in order to better demonstrate the effects of the present invention.
• the amount of the aromatic monofunctional monomer (B) is within the above range, the effects of the present invention can be better demonstrated. If the amount of the aromatic monofunctional monomer (B) is too small outside the above range, there is a risk that the shell portion may crack or chip, and the lubricant may not be sufficiently encapsulated in the shell portion. If the amount of the aromatic monofunctional monomer (B) is too large outside the above range, there is a risk that the heat resistance may be insufficient.
• the amount of aromatic monofunctional monomer (B) relative to 100 parts by weight of the total amount of compound (A) and monomer (M) is preferably 5 parts by weight to 60 parts by weight, more preferably 5 parts by weight to 50 parts by weight, even more preferably 5 parts by weight to 40 parts by weight, and particularly preferably 10 parts by weight to 30 parts by weight.
• the amount of aromatic monofunctional monomer (B) relative to 100 parts by weight of the total amount of compound (A) and monomer (M) is preferably 5 parts by weight to 60 parts by weight, more preferably 10 parts by weight to 60 parts by weight, even more preferably 20 parts by weight to 55 parts by weight, and particularly preferably 30 parts by weight to 50 parts by weight.
• aromatic crosslinkable monomer Any appropriate aromatic crosslinkable monomer may be used as the aromatic crosslinkable monomer (C) as long as it does not impair the effects of the present invention.
• aromatic crosslinkable monomers (C) include divinylbenzene, divinylnaphthalene, and diallyl phthalate, with divinylbenzene being preferred.
• the aromatic crosslinkable monomer (C) may be of only one type, or of two or more types.
• the amount of the aromatic crosslinkable monomer (C) relative to the total amount is preferably 15 to 65 parts by weight, more preferably 20 to 60 parts by weight, in order to better demonstrate the effects of the present invention. If the amount of the aromatic crosslinkable monomer (C) is within the above range, the effects of the present invention can be better demonstrated. If the amount of the aromatic crosslinkable monomer (C) is too small outside the above range, the degree of crosslinking may be reduced, resulting in reduced heat resistance.
• the amount of the aromatic crosslinkable monomer (C) is too large outside the above range, the polymerization of the aromatic crosslinkable monomer (C) and the aromatic monofunctional monomer (B) is promoted, making it difficult to polymerize with the compound (A), and the particles may chip or crack due to the formation of parts with different degrees of crosslinking throughout the particles.
• the amount of aromatic crosslinkable monomer (C) relative to 100 parts by weight of the total amount of compound (A) and monomer (M) is preferably 15 to 65 parts by weight, more preferably 15 to 60 parts by weight, and even more preferably 20 to 60 parts by weight.
• the amount of aromatic crosslinkable monomer (C) relative to 100 parts by weight of the total amount of compound (A) and monomer (M) is preferably 15 to 65 parts by weight, more preferably 20 to 60 parts by weight, even more preferably 30 to 55 parts by weight, particularly preferably 35 to 55 parts by weight, and most preferably 40 to 55 parts by weight.
• the monomer (M) may contain a monofunctional monomer other than the aromatic monofunctional monomer (B).
• monofunctional monomers include alkyl (meth)acrylic acid esters having 1 to 16 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cetyl (meth)acrylate; dicarboxylic acid ester monomers, such as dimethyl maleate, diethyl fumarate, dimethyl fumarate, and diethyl fumarate; maleic anhydride; N-vinyl carbazole; and (meth)acrylonitrile.
• the monofunctional monomer other than the aromatic monofunctional monomer (B) may be of one type only, or of two or more types.
• the monomer (M) may contain a crosslinking monomer other than the aromatic crosslinking monomer (C).
• crosslinking monomers include polyfunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and glycerin tri(meth)acrylate; polyfunctional acrylamide derivatives such as N,N'-methylene bis(meth)acrylamide and N,N'-ethylene bis(meth)acrylamide; and polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane.
• the crosslinking monomer other than the aromatic crosslinking monomer (C) may be of only one type or of two or more types.
• the monomer (M) may contain a compound (D) having a phosphate ester structure and a radical reactive group.
• the polymer (P) may contain the above-mentioned phosphate ester structure.
• the compound (D) having a phosphate ester structure and a radical reactive group may be of only one type, or of two or more types.
• the amount of compound (D) relative to said total amount is preferably 0.001 to 0.2 parts by weight, more preferably 0.005 to 0.15 parts by weight, and even more preferably 0.01 to 0.1 parts by weight. If the amount of compound (D) is too small outside the above range, the average particle size may become small and the dispersion stability of the oil droplets may become insufficient, and the formation of polymerized lumps and coarse particles may occur frequently. If the content of compound (D) is too large outside the above range, it may be difficult to form a shell portion and a hollow portion surrounded by the shell portion.
• any appropriate compound may be adopted as long as it has a phosphate ester structure and a radical reactive group, as long as the effects of the present invention are not impaired.
• a compound (B) is preferably a compound represented by formula (4).
• R 1 represents a methyl group or a hydrogen atom.
• R 2 and R 3 represent a linear or branched alkylene group having 1 to 30 carbon atoms.
• m represents 1 to 300.
• n represents 1 to 3.
• a is 0 or 1
• b is 0 to 300
• c is 0 or 1.
• R 2 is preferably a linear or branched alkylene group having 1 to 50 carbon atoms, more preferably a linear or branched alkylene group having 1 to 40 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 30 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 25 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 20 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 15 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 10 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 8 carbon atoms, particularly preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and most preferably a linear or branched alkylene group having 1 to 4 carbon atoms.
• R 3 is preferably a linear or branched alkylene group having 1 to 50 carbon atoms, more preferably a linear or branched alkylene group having 1 to 40 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 30 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 25 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 20 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 15 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 13 carbon atoms, particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and most preferably a linear or branched alkylene group having 1 to 8 carbon atoms.
• m is preferably 1 to 100, more preferably 1 to 50, even more preferably 1 to 30, even more preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 3.
• b is preferably 0 to 100, more preferably 0 to 50, even more preferably 0 to 10, particularly preferably 0 to 5, and most preferably 0 or 1.
• the compound (D) a commercially available product may be used. From the viewpoint of compatibility, for example, an example of such a compound (D) is the product name "KAYAMER (registered trademark) PM-21" (manufactured by Nippon Kayaku Co., Ltd.).
• the lubricant-containing resin particles according to the embodiment of the present invention can be produced by any suitable method within the scope that does not impair the effect of the present invention.In terms of being able to more effectively express the effect of the present invention, the lubricant-containing resin particles according to the embodiment of the present invention can be produced by reacting the compound (A) having an ether structure and a radical reactive group represented by formula (1) with the monomer (M) that reacts with the compound (A) in the presence of a lubricant and a compatibilizer in an aqueous medium.
• the method for producing lubricant-encapsulated resin particles is a method for producing lubricant-encapsulated resin particles in which a lubricant is encapsulated in the shell portion, and involves reacting a compound (A) having an ether structure and a radical reactive group represented by formula (1) with a monomer (M) that reacts with the compound (A) in an aqueous medium in the presence of a lubricant and a compatibilizer.
• the reaction between compound (A) and monomer (M) is preferably a suspension polymerization reaction.
• an oil phase containing compound (A), monomer (M), a lubricant, and a compatibilizer is added to an aqueous phase containing an aqueous medium and dispersed.
• Any suitable dispersion method can be used as long as it can cause the oil phase to exist in droplets in the aqueous phase, without impairing the effects of the present invention.
• Representative examples of such dispersion methods include dispersion methods using a homomixer or homogenizer, such as a polytron homogenizer, ultrasonic homogenizer, or high-pressure homogenizer.
• the stirring speed is preferably more than 1500 rpm, more preferably 1600 rpm or more, even more preferably 2000 rpm or more, particularly preferably 3000 rpm or more, and most preferably 4000 rpm or more, in order to better express the effects of the present invention.
• the upper limit of the stirring speed for dispersion may be any appropriate upper limit within a range that does not impair the effects of the present invention, and is preferably 20,000 rpm or less, more preferably 15,000 rpm or less, even more preferably 12,000 rpm or less, and particularly preferably 10,000 rpm or less.
• Any suitable polymerization temperature may be used as long as it is suitable for suspension polymerization and does not impair the effects of the present invention.
• Such a polymerization temperature is preferably 30°C to 80°C.
• Any appropriate polymerization time may be used as long as it is suitable for suspension polymerization and does not impair the effects of the present invention.
• Such a polymerization time is preferably 1 hour to 48 hours.
• post-heating After polymerization, post-heating may be performed. By performing post-heating, heat resistance can be further improved.
• Any appropriate temperature may be used for the post-heating as long as it does not impair the effects of the present invention.
• Such a post-heating temperature is preferably 70°C to 120°C.
• any appropriate time may be used for the post-heating time as long as it does not impair the effects of the present invention.
• Such a post-heating time is preferably 1 hour to 24 hours.
• compound (A) and monomer (M) are reacted in an aqueous medium in the presence of a lubricant and a compatibilizer, and the resulting particles are then separated and, if necessary, purified and dried to obtain lubricant-encapsulated resin particles.
• Lubricant-containing resin particles ⁇ can be used as is.
• a compatibilizer is used in the lubricant-encapsulated resin particles according to an embodiment of the present invention.
• a compatibilizer By using a compatibilizer, the effects of the present invention can be more effectively achieved, and in particular, lubricant-encapsulated resin particles having a lubricant encapsulated in the shell portion can be easily obtained. If a compatibilizer is not used, it may be difficult to easily obtain lubricant-encapsulated resin particles having a lubricant encapsulated in the shell portion.
• the compatibilizer is preferably a non-polymerizable organic compound having a boiling point of 30°C to 200°C, and specific examples include saturated aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, cyclohexane, and n-heptane; aromatic hydrocarbons such as toluene and benzene; and acetates such as ethyl acetate and butyl acetate.
• the compatibilizer is preferably a saturated aliphatic hydrocarbon, and more preferably n-heptane.
• the amount of the compatibilizer relative to the total amount is preferably 10 parts by weight to 100 parts by weight, more preferably 10 parts by weight to 90 parts by weight, and even more preferably 10 parts by weight to 85 parts by weight, in order to better demonstrate the effects of the present invention.
• the amount of the compatibilizer is within the above range, the effects of the present invention can be better demonstrated. If the amount of the compatibilizer is too small outside the above range, it may be difficult to smoothly obtain lubricant-encapsulated resin particles in which the lubricant is encapsulated in the shell portion. If the amount of the compatibilizer is too large outside the above range, it may be difficult to form the shell portion and the hollow portion surrounded by the shell portion.
• the amount of the compatibilizer relative to 100 parts by weight of the total amount of compound (A) and monomer (M) is preferably 10 parts by weight to 100 parts by weight, more preferably 10 parts by weight to 90 parts by weight, even more preferably 10 parts by weight to 85 parts by weight, even more preferably 20 parts by weight to 80 parts by weight, particularly preferably 30 parts by weight to 80 parts by weight, and most preferably 40 parts by weight to 80 parts by weight.
• the amount of the compatibilizer relative to 100 parts by weight of the total amount of compound (A) and monomer (M) is preferably 10 parts by weight to 100 parts by weight, more preferably 10 parts by weight to 90 parts by weight, even more preferably 10 parts by weight to 85 parts by weight, even more preferably 10 parts by weight to 75 parts by weight, particularly preferably 10 parts by weight to 65 parts by weight, and most preferably 10 parts by weight to 60 parts by weight.
• the oil phase may contain any other appropriate component that does not fall under any of the above-mentioned compounds (A), monomers (M), lubricants, and compatibilizers, as long as the effect of the present invention is not impaired.
• the other component may be only one type, or two or more types. Note that the other components referred to here do not include the aqueous medium used in the aqueous phase, or the dispersion stabilizer described below.
• the content of other components in the oil phase is preferably 0% to 50% by weight, more preferably 0% to 30% by weight, even more preferably 0% to 10% by weight, and particularly preferably 0% to 5% by weight.
• Other components include, for example, polymerization initiators, polymerization retarders, surfactants, and non-crosslinkable polymers.
• any suitable polymerization initiator may be used as the polymerization initiator as long as it does not impair the effects of the present invention.
• suitable polymerization initiators include organic peroxides such as lauroyl peroxide, benzoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, and di-t-butyl peroxide; azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, and 2,2'-azobis(2,4-dimethylvaleronitrile); and the like.
• the polymerization initiator may be of only one type, or of two or more types.
• the amount of the polymerization initiator may be any appropriate amount as long as it does not impair the effects of the present invention.
• the amount of such a polymerization initiator is preferably 0.1% by weight to 5% by weight relative to the total amount of compound (A) and monomer (M), when the total amount of the compound (A) and monomer (M) is taken as 100 parts by weight.
• Any suitable polymerization retarder may be used as long as it does not impair the effects of the present invention.
• Examples of such polymerization retarders include mercaptans such as t-dodecanethiol, 1-dodecanethiol, 1-octanethiol, and 2-mercaptoethanol.
• the polymerization retarder may be of one type or of two or more types.
• the amount of polymerization retarder may be any appropriate amount as long as it does not impair the effects of the present invention.
• the amount of such polymerization retarder is preferably 0.1% to 5% by weight relative to the total amount of compound (A) and monomer (M), when the total amount of compound (A) and monomer (M) is taken as 100 parts by weight.
• the surfactant is preferably at least one selected from amphoteric surfactants and anionic surfactants, from the viewpoint of being able to more effectively exert the effects of the present invention, and more preferably at least an amphoteric surfactant is selected.
• amphoteric surfactant any appropriate amphoteric surfactant may be used as long as it does not impair the effects of the present invention.
• an amphoteric surfactant a known amphoteric surfactant that can be used in the production of resin particles may be used.
• amphoteric surfactants include lauryl dimethylamine oxide, lauryl dimethylaminoacetate betaine, phosphate surfactants, and phosphite surfactants. Only one type of amphoteric surfactant may be used, or two or more types may be used.
• anionic surfactant any suitable anionic surfactant may be used as long as it does not impair the effects of the present invention.
• anionic surfactants include fatty acid salts, polysulfonates, polycarboxylates, alkyl sulfate ester salts, alkylaryl sulfonates, alkylnaphthalenesulfonates, dialkylsulfonates, dialkylsulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates, naphthalenesulfonate-formaldehyde condensates, polyoxyethylene alkyl phosphate sulfonates, glycerol borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters.
• anionic surfactants include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, polyoxyethylene nonylphenyl ether sulfate ester salts, and sodium salts of ⁇ -naphthalenesulfonate-formaldehyde condensates.
• the anionic surfactant may be one type only, or two or more types.
• the amount of surfactant may be any appropriate amount as long as it does not impair the effects of the present invention.
• the non-crosslinkable polymer may be, for example, at least one selected from the group consisting of polyolefins, styrene-based polymers, (meth)acrylic acid-based polymers, and styrene-(meth)acrylic acid-based polymers.
• a non-crosslinkable polymer phase separation between the polymer (P) and the solvent that is produced as the reaction proceeds can be promoted, facilitating shell formation.
• polyolefins examples include polyethylene, polypropylene, and poly- ⁇ -olefins. From the viewpoint of solubility in the monomer composition, it is preferable to use side-chain crystalline polyolefins using long-chain ⁇ -olefins as the raw material, and low-molecular-weight polyolefins and olefin oligomers produced with metallocene catalysts.
• styrene-based polymers include polystyrene, styrene-acrylonitrile copolymers, and acrylonitrile-butadiene-styrene copolymers.
• Examples of (meth)acrylic acid-based polymers include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and polypropyl (meth)acrylate.
• styrene-(meth)acrylic acid polymers examples include styrene-methyl (meth)acrylate copolymers, styrene-ethyl (meth)acrylate copolymers, styrene-butyl (meth)acrylate copolymers, and styrene-propyl (meth)acrylate copolymers.
• the aqueous phase includes an aqueous medium.
• aqueous medium any appropriate aqueous medium may be used as the aqueous medium as long as it does not impair the effects of the present invention.
• aqueous media include water and mixed media of water and lower alcohols (methanol, ethanol, etc.). Only one type of aqueous medium may be used, or two or more types may be used.
• the amount of the aqueous medium used may be any appropriate amount within the range that does not impair the effects of the present invention.
• the amount of such an aqueous medium used is typically an amount that allows the reaction to proceed appropriately in a suspension polymerization reaction in which an oil phase is added to an aqueous phase and suspended therein, and is preferably 100 to 5,000 parts by weight, and more preferably 150 to 2,000 parts by weight, relative to 100 parts by weight of the total amount of the oil phase.
• the aqueous phase may contain any appropriate component as long as it does not impair the effects of the present invention.
• a representative example of such a component is a dispersion stabilizer.
• the dispersion stabilizer may be of only one type, or of two or more types.
• the amount of dispersion stabilizer is preferably 0.5 to 10 parts by weight per 100 parts by weight of the aqueous medium.
• Dispersion stabilizers include, for example, inorganic water-soluble polymeric compounds such as polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinylpyrrolidone, and sodium tripolyphosphate.
• inorganic water-soluble polymeric compounds such as polyvinyl alcohol, polycarboxylic acid, celluloses (hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinylpyrrolidone, and sodium tripolyphosphate.
• dispersion stabilizers include phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, and zinc pyrophosphate; and poorly water-soluble inorganic compounds such as calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, and colloidal silica.
• magnesium pyrophosphate is preferred because it is relatively easy to remove from the lubricant-containing resin particles and is unlikely to remain on the surface of the lubricant-containing resin particles.
• the resin composition according to an embodiment of the present invention includes the lubricant-containing resin particles according to an embodiment of the present invention and a base resin.
• the base resin may be one type or two or more types.
• base resins include thermoplastic resins such as polyolefins, ethylene-vinyl acetate copolymers (EVA), polyvinyl chloride (PVC), acrylic resins, urethane resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), polystyrene (PS), (meth)acrylate-styrene copolymers, polyamide resins (nylon 6, nylon 66, etc.), modified polyamides, polycarbonates, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacetal (POM), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified polyphenylene ether, and fluororesins; olefin-based elastomers, styrene-based elastomers, and urethane-
• Thermoplastic elastomers such as polyester-based elastomers, polyamide-based elastomers, and fluorine-based elastomers; ionomer resins such as ethylene-based ionomers, urethane-based ionomers, styrene-based ionomers, and fluorine-based ionomers; thermosetting resins such as epoxy resins, phenolic resins, unsaturated polyester resins, polyimides, and polyamideimides; rubbers such as natural rubber, isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), butyl rubber, silicone rubber, acrylic rubber, urethane rubber, fluororubber, polyether rubber, ethylene-propylene rubber (EPM), and ethylene-propylene-diene rubber (EPDM); and bioplastics such as polylactic acid (
• the lubricant-containing resin particles according to an embodiment of the present invention have excellent heat resistance and excellent impact resistance, so even if a resin composition using a heat-resistant resin with a high melting point, such as a polyamide resin, as the base resin is kneaded and extruded at high temperatures in an extruder, the resin particles are unlikely to melt, crack or chip, and a molded article that exhibits sliding properties can be provided.
• a resin composition using a heat-resistant resin with a high melting point, such as a polyamide resin, as the base resin is kneaded and extruded at high temperatures in an extruder, the resin particles are unlikely to melt, crack or chip, and a molded article that exhibits sliding properties can be provided.
• the content ratio of the lubricant-containing resin particles in the resin composition according to an embodiment of the present invention may be any appropriate content ratio depending on the purpose, as long as the effect of the present invention is not impaired.
• the content ratio is preferably 0.01 to 1000 parts by weight, more preferably 0.1 to 500 parts by weight, even more preferably 1 to 100 parts by weight, and particularly preferably 5 to 50 parts by weight, in terms of the amount of the lubricant-containing resin particles per 100 parts by weight of the base resin.
• the total content ratio of the base resin and the lubricant-containing resin particles in the resin composition according to an embodiment of the present invention may be any appropriate content ratio depending on the purpose, as long as the effect of the present invention is not impaired.
• a content ratio is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even more preferably 90% by weight to 100% by weight, and particularly preferably 95% by weight to 100% by weight.
• the resin composition according to an embodiment of the present invention may contain any other appropriate components in addition to the base resin and the lubricant-containing resin particles.
• examples of such other components include antioxidants, UV absorbers, light stabilizers, fillers, flame retardants, plasticizers, pigments, inorganic powders, organic powders, and antistatic agents.
• the resin composition according to an embodiment of the present invention may be produced by any appropriate method as long as the effects of the present invention are not impaired.
• a method may include, for example, a method in which the base resin, the lubricant-containing resin particles, and, if necessary, other components are mixed by any appropriate mixing method.
• mixing methods include mixing by a mixing stirrer, mixer, Henschel mixer, super mixer, ribbon mixer, ribbon blender, kneader, roll, mixing roll, single-shaft kneader, twin-shaft kneader, multi-shaft kneader, etc.
• the molded article according to the embodiment of the present invention is obtained by molding the resin composition according to the embodiment of the present invention.
• the molded article according to the embodiment of the present invention is obtained by molding the resin composition according to the embodiment of the present invention by any suitable method depending on the purpose.
• a molding method a molding method generally known in the art can be used, for example, extrusion molding, injection molding, vacuum molding, blow molding, compression molding, press molding, transfer molding, RIM molding, and cast molding.
• the sliding member according to the embodiment of the present invention may be formed from the resin composition according to the embodiment of the present invention, or may be formed from the molded article according to the embodiment of the present invention.
• the sliding member according to the embodiment of the present invention may include a resin composition according to the embodiment of the present invention, or may include a molded body according to the embodiment of the present invention.
• volume average particle size of the particles was measured by the Coulter method as follows.
• the volume average particle size of the particles was measured using a Coulter Multisizer (registered trademark) 4e (measuring device manufactured by Beckman Coulter, Inc.).
• the measurement was performed using an aperture calibrated according to the Multisizer 4e User's Manual published by Beckman Coulter, Inc.
• the aperture used in the measurement was appropriately selected according to the volume average particle size of the particles to be measured.
• an aperture having a size of 10 ⁇ m was selected
• an aperture having a size of 20 ⁇ m was selected
• an aperture having a size of 100 ⁇ m was selected.
• the measurement sample was prepared by dispersing 0.1 g of particles in 10 ml of a 0.1 wt % aqueous solution of a nonionic surfactant using a touch mixer (manufactured by Yamato Scientific Co., Ltd., "TOUCHMIXER MT-31”) and an ultrasonic cleaner (manufactured by Vervoclear Co., Ltd., "ULTRASONIC CLEANER VS-150") to prepare a dispersion. During the measurement, the beaker was gently stirred to prevent air bubbles from being introduced, and the measurement was terminated when 100,000 particles were measured. The volume average particle size of the particles was taken as the arithmetic average of the particle size distribution based on the volume of 100,000 particles.
• TG-DTA ⁇ Measurement of the difference between the weight residual ratio at 250° C. and the weight residual ratio at 400° C. when the temperature is increased at 10° C./min in a nitrogen atmosphere in TG-DTA>>
• the weight residual rate was measured using a simultaneous differential thermal and thermogravimetric analyzer "TG/DTA6200, AST-2" manufactured by SII NanoTechnology Inc.
• the sampling method and temperature conditions were as follows. The sample was filled to the bottom of a platinum measuring container with 10.5 ⁇ 0.5 mg of sample without leaving any gaps, and used as a sample for measurement.
• the TG/DTA curve was obtained by heating the sample from 30°C to 800°C at a heating rate of 10°C/min.
• the weight residual ratios at 250°C and 400°C were measured from the obtained curve using the analysis software attached to the device, with alumina as the reference material, under a nitrogen gas flow rate of 230 mL/min.
• the long-term sliding properties of the molded bodies to be evaluated were evaluated by measuring the change in friction coefficient over time using a ring-on-disk method using a high-load, high-speed friction and wear tester (Model EFM-3-H, manufactured by A&D Co., Ltd.).
• the test conditions were a load of 200 N, a measurement speed of 0.5 m/sec, and a measurement time of 1 hour (Example 11, Comparative Examples 8 and 9) or 2 hours (Example 12).
• a high carbon chromium bearing steel material (SUJ2) was used as the mating material.
• Example 1 An oil phase was prepared by mixing 1.75 g of a compound having an ether structure represented by formula (1) (trade name "Noryl (registered trademark) SA9000-111 resin", manufactured by SABIC Corporation), 3.00 g of divinylbenzene (DVB) 810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., 81% content, 19% is ethylvinylbenzene (EVB)), 0.25 g of styrene, 2.50 g of heptane, 2.50 g of liquid paraffin, 0.075 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 0.03 g of "KAYAMER (registered trademark) PM-21” (manufactured by Nippon Kayaku Co., Ltd.) as a radical polymerizable monomer having a phosphoric acid
• the oil phase was added to 30 g of a 2 wt % aqueous dispersion of magnesium pyrophosphate as the aqueous phase, and the mixture was stirred at 7000 rpm for 2 minutes using a Polytron homogenizer "PT10-35" (manufactured by Central Scientific Trading Co., Ltd.) to prepare a suspension.
• the resulting suspension was heated at 55°C for 16 hours to complete the polymerization reaction.
• Hydrochloric acid was added to the resulting slurry to decompose the magnesium pyrophosphate, and the solid content was separated by dehydration through filtration, purified by repeated washing with water, and then dried at 80°C for 24 hours to obtain particles (1).
• An external photograph of the obtained particle (1) is shown in Fig.
• Fig. 2 a cross-sectional photograph is shown in Fig. 2. From Fig. 1, Fig. 2, and a weight comparison between the obtained particle and its raw material, it was confirmed that the obtained particle (1) was a lubricant-encapsulating resin particle having a shell and a hollow portion.
• the volume average particle size of the obtained particles (1) was 17.9 ⁇ m.
• the weight residual ratio of the obtained particles (1) at 250° C. and 400° C. when heated at 10° C./min in a nitrogen atmosphere by TG/DTA was 94.3% and 65.0%, respectively, and the difference was 29.3%.
• Table 1 The results are shown in Table 1.
• Example 2 Particles (2) were obtained in the same manner as in Example 1, except that the amount of the compound having an ether structure represented by formula (1) was 1.25 g, the amount of divinylbenzene (DVB) 810 was 3.50 g, and 0.05 g of 1-octanethiol was added.
• An external photograph of the obtained particle (2) is shown in Fig. 3, and a cross-sectional photograph is shown in Fig. 4. From Fig. 3, Fig. 4, and a weight comparison between the obtained particle and its raw material, it was confirmed that the obtained particle (2) was a lubricant-encapsulating resin particle having a shell and a hollow portion.
• the volume average particle size of the obtained particles (2) was 17.2 ⁇ m.
• the weight residual ratio of the obtained particles (2) at 250°C when heated at 10°C/min in a nitrogen atmosphere by TG/DTA was 94.2% and at 400°C was 66.4%, the difference being 27.8%.
• the results are shown in Table 1.
• Example 3 Particles (3) were obtained in the same manner as in Example 1, except that the amount of the compound having an ether structure represented by formula (1) was 2.00 g, the amount of divinylbenzene (DVB) 810 was 1.2 g, the amount of styrene was 0.80 g, the amount of 1-octanethiol was 0.04 g, the amount of heptane was 2.00 g, the amount of liquid paraffin was 2.00 g, the amount of 2,2'-azobis(2,4-dimethylvaleronitrile) was 0.061 g, the amount of KAYAMER PM-21 was 0.024 g, and the amount of 2 wt % aqueous dispersion of magnesium pyrophosphate in the aqueous phase was 32 g.
• the amount of the compound having an ether structure represented by formula (1) was 2.00 g
• the amount of divinylbenzene (DVB) 810 was 1.2 g
• the amount of styrene was
• the obtained particles (3) were lubricant-encapsulated resin particles having a shell and a hollow portion.
• the volume average particle size of the obtained particles (3) was 18.6 ⁇ m.
• the weight residual ratio of the obtained particles (3) when heated at 10° C./min in a nitrogen atmosphere by TG/DTA was 94.4% at 250° C. and 78.1% at 400° C., the difference being 16.3%.
• Table 1 The results are shown in Table 1.
• Example 4 Particles (4) were obtained in the same manner as in Example 1, except that the amount of the compound having an ether structure represented by formula (1) was 1.50 g, the amount of divinylbenzene (DVB) 810 was 3.00 g, and the amount of styrene was 0.50 g. From the SEM image of the obtained particles (4) and a weight comparison between the obtained particles and their raw materials, it was confirmed that the obtained particles (4) were lubricant-encapsulated resin particles having a shell and a hollow portion. The volume average particle size of the obtained particles (4) was 18.5 ⁇ m. The weight residual ratio of the obtained particles (4) at 250° C. and 400° C. was 94.4% and 65.6%, respectively, when the temperature of the particles (4) was increased at 10° C./min in a nitrogen atmosphere by TG/DTA, respectively, and the difference therebetween was 28.8%. The results are shown in Table 1.
• Example 5 Particles (5) were obtained in the same manner as in Example 1, except that the amount of the compound having an ether structure represented by formula (1) was 1.12 g, the amount of divinylbenzene (DVB) 810 was 1.92 g, the amount of styrene was 0.16 g, the amount of 1-octanethiol was 0.032 g, the amount of heptane was 2.40 g, the amount of liquid paraffin was 2.40 g, the amount of 2,2'-azobis(2,4-dimethylvaleronitrile) was 0.048 g, the amount of KAYAMER PM-21 was 0.024 g, and the amount of 2 wt % aqueous dispersion of magnesium pyrophosphate in the aqueous phase was 32 g.
• the amount of the compound having an ether structure represented by formula (1) was 1.12 g
• the amount of divinylbenzene (DVB) 810 was 1.92 g
• Example 6 Particles (6) were obtained in the same manner as in Example 4, except that the amount of heptane was 3.75 g, the amount of liquid paraffin was 1.25 g, and 0.05 g of 1-octanethiol was added. From an SEM image of the obtained particles (6) and a weight comparison between the obtained particles and their raw materials, it was confirmed that the obtained particles (6) were lubricant-encapsulated resin particles having a shell and a hollow portion. The volume average particle size of the obtained particles (6) was 18.7 ⁇ m. The weight residual ratio of the obtained particles (6) when heated at 10° C./min in a nitrogen atmosphere by TG/DTA was 94.7% at 250° C. and 77.9% at 400° C., the difference being 16.8%. The results are shown in Table 1.
• An external photograph of the obtained particle (7) is shown in Fig. 5, and a cross-sectional photograph is shown in Fig. 6. From Fig. 5 and Fig. 6 and a weight comparison between the obtained particle and its raw material, it was confirmed that the obtained particle (7) was a lubricant-encapsulating resin particle having a shell and a hollow portion.
• the volume average particle size of the obtained particles (7) was 4.0 ⁇ m.
• the weight residual ratio of the obtained particles (7) when heated at 10° C./min in a nitrogen atmosphere by TG/DTA was 96.1% at 250° C. and 64.1% at 400° C., the difference being 32.0%.
• the results are shown in Table 1.
• Example 8 Particles (8) were obtained in the same manner as in Example 7, except that the amount of the compound having an ether structure represented by formula (1) was 0.50 g, the amount of styrene was 1.50 g, 2.50 g of cyclohexane was used instead of 2.50 g of heptane, and 2.50 g of dimethylpolysiloxane (KF-96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 2.50 g of liquid paraffin.
• An external view of the obtained particle (8) is shown in Fig. 7, and a cross-sectional view is shown in Fig. 8. From Fig. 7 and Fig.
• the obtained particle (8) was a lubricant-encapsulating resin particle having a shell and a hollow portion.
• the volume average particle size of the obtained particles (8) was 4.0 ⁇ m.
• the weight residual rate of the obtained particles (8) when heated at 10° C./min in a nitrogen atmosphere by TG/DTA was 99.8% at 250° C. and 95.0% at 400° C., the difference being 4.8%.
• the results are shown in Table 1.
• Example 9 Particles (9) were obtained in the same manner as in Example 8, except that the amount of cyclohexane was 1.00 g and the amount of dimethylpolysiloxane was 4.00 g.
• An external photograph of the obtained particle (9) is shown in Fig. 9, and a cross-sectional photograph is shown in Fig. 10. From Fig. 9 and Fig. 10 and a comparison of the weight of the obtained particle and its raw material, it was confirmed that the obtained particle (8) was a lubricant-encapsulating resin particle having a shell and a hollow portion.
• the volume average particle size of the obtained particles (9) was 3.8 ⁇ m.
• the weight residual rate of the obtained particles (9) when heated at 10° C./min in a nitrogen atmosphere by TG/DTA was 99.7% at 250° C. and 94.9% at 400° C., the difference being 4.8%.
• Table 1 The results are shown in Table 1.
• Example 10 Particles (10) were obtained in the same manner as in Example 8, except that 2.50 g of dimethylpolysiloxane (KF-96-500cs, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 2.50 g of dimethylpolysiloxane (KF-96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.).
• An external photograph of the obtained particle (10) is shown in Fig. 11, and a cross-sectional photograph is shown in Fig. 12. From Fig. 11 and Fig. 12 and a comparison of the weight of the obtained particle and its raw material, it was confirmed that the obtained particle (8) was a lubricant-encapsulating resin particle having a shell and a hollow portion.
• the volume average particle size of the obtained particles (10) was 3.9 ⁇ m.
• the weight residual rate of the obtained particles (10) at 250° C. and 400° C. when heated at 10° C./min in a nitrogen atmosphere by TG/DTA was 99.8% and 95.9%, respectively, and the difference was 3.9%.
• the results are shown in Table 1.
• Comparative Example 1 10 g of the particles (1) obtained in Example 1 was stirred and washed in 100 g of hexane for 24 hours to extract the encapsulated lubricant, thereby obtaining resin particles (C1) not encapsulating any lubricant.
• the volume average particle diameter of the obtained particles (C1) was 10.1 ⁇ m.
• the weight residual ratio of the obtained particles (C1) at 250°C when heated at 10°C/min in a nitrogen atmosphere by TG/DTA was 95.6% and at 400°C was 79.0%, the difference being 16.6%.
• Table 1 The results are shown in Table 1.
• Comparative Example 2 The same procedure as in Example 1 was carried out except that heptane was not used. As a result, the resin component did not dissolve in the liquid paraffin, suspension polymerization could not be carried out, and lubricant-containing resin particles could not be obtained.
• Comparative Example 3 Particles (C3) were obtained in the same manner as in Example 1, except that heptane was changed to ethyl acetate. An external photograph of the obtained particle (C3) is shown in Fig. 13, and a cross-sectional photograph is shown in Fig. 14. From Fig. 13 and Fig. 14, it was confirmed that the obtained particle (C3) had chipping and an internal porous structure. The volume average particle diameter of the obtained particles (C3) was 15.2 ⁇ m. The weight residual ratio of the obtained particles (C3) when heated at 10°C/min in a nitrogen atmosphere by TG/DTA was 95.8% at 250°C and 67.3% at 400°C, the difference being 28.5%. The results are shown in Table 1.
• Comparative Example 4 Particles (C4) were obtained in the same manner as in Example 1, except that the amount of the compound having an ether structure represented by formula (1) was 2.00 g and styrene was not used. An external photograph of the obtained particle (C4) is shown in Fig. 15, and a cross-sectional photograph is shown in Fig. 16. From Fig. 15 and Fig. 16, it was confirmed that the obtained particle (C4) was cracked. The volume average particle diameter of the obtained particles (C4) was 24.6 ⁇ m. The weight residual ratio of the obtained particles (C4) at 250°C when heated at 10°C/min in a nitrogen atmosphere by TG/DTA was 94.9% and at 400°C was 67.7%, the difference being 27.2%. The results are shown in Table 1.
• Comparative Example 5 Particles (C5) were obtained in the same manner as in Example 1, except that the amount of heptane was 4.75 g and the amount of liquid paraffin was 0.250 g. From the SEM image of the obtained particles (C5), it was confirmed that the obtained particles (C5) were cracked. The volume average particle diameter of the obtained particles (C5) was 14.7 ⁇ m. The weight residual ratio of the obtained particles (C5) at 250°C and 400°C when heated at 10°C/min in a nitrogen atmosphere by TG/DTA was 96.6% and 90.5%, respectively, and the difference was 6.1%. The results are shown in Table 1.
• Comparative Example 6 The same procedure as in Example 1 was performed except that the amount of heptane was 0.50 g and the amount of liquid paraffin was 4.50 g. However, the resin component did not dissolve in the liquid paraffin, suspension polymerization could not be performed, and lubricant-encapsulated resin particles were not obtained.
• Comparative Example 7 An oil phase was prepared by mixing 7 g of methyl methacrylate (MMA), 0.1 g of ethylene glycol dimethacrylate (EGDMA), 0.08 g of dilauroyl peroxide (LPO), and 3.15 g of dimethylpolysiloxane (silicone KF-96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.).
• MMA methyl methacrylate
• ELDMA ethylene glycol dimethacrylate
• LPO dilauroyl peroxide
• sicone KF-96-100cs silicone KF-96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.
• As the aqueous phase 27.5 g of ion-exchanged water, 5.5 g of sodium chloride, 0.04 g of polyvinylpyrrolidone, and 3.0 g of colloidal silica containing 20% by weight of active ingredient were added, and the pH was adjusted to
• the oil phase was added thereto, and dispersed for 2 minutes at 7000 rpm using a Polytron homogenizer "PT10-35" to prepare a suspension.
• the resulting suspension was heated at 70°C for 6 hours to complete the polymerization reaction.
• the resulting slurry was dehydrated by filtration to separate the solid content, and purified by repeated washing with water, and then dried at 80°C for 24 hours to obtain particles (C7).
• the volume average particle diameter of the obtained particles (C7) was 12.2 ⁇ m.
• the weight residual ratio of the obtained particles (C7) at 250°C when heated at 10°C/min in a nitrogen atmosphere by TG/DTA was 92.7% and that at 400°C was 36.5%, the difference being 56.2%.
• Table 1 The results are shown in Table 1.
• the obtained polyamide resin composition (1) was dried at 110° C. for 6 hours or more.
• the dried polyamide resin composition (1) was placed in a tablet-shaped mold and hot-pressed for 5 minutes at a set temperature of 250°C using a Lab Press 10T (manufactured by Toyo Seiki Seisakusho, model P1-10T) to produce a tablet-shaped molded product (1) having a diameter of 35 mm and a thickness of 2 ⁇ 5% mm.
• the tablet-like molded product (1) thus obtained was subjected to an evaluation of the effect of maintaining the slidability for a long time in a sliding state (evaluation based on the presence or absence of a change in the coefficient of friction) and the results are shown in Fig. 17. As shown in Fig. 17, the coefficient of friction hardly increased from the initial stage of sliding until one hour later, which indicates that the slidability can be maintained for a long time in a sliding state.
• polyamide 6 manufactured by Unitika Ltd., product name "A1030BRT
• the dried polyamide resin composition (8) was placed in a tablet-shaped mold and hot-pressed for 5 minutes at a set temperature of 250°C using a Lab Press 10T (manufactured by Toyo Seiki Seisakusho, model P1-10T) to produce a tablet-shaped molded product (8) having a diameter of 35 mm and a thickness of 2 ⁇ 5% mm.
• the tablet-like molded product (8) thus obtained was subjected to an evaluation of the effect of maintaining the slidability for a long time in a sliding state (evaluation based on the presence or absence of a change in the coefficient of friction), and the results are shown in Fig. 18.
• the coefficient of friction hardly increased from the initial stage of sliding until two hours later, which indicates that the slidability can be maintained for a long time in a sliding state.
• Comparative Example 8 The procedure of Example 7 was repeated, except that 21 parts by weight of the particles (C1) obtained in Comparative Example 1 were used instead of the particles (1) obtained in Example 1, to obtain a polyamide resin composition (C1).
• the obtained polyamide resin composition (C1) was dried at 110° C. for 6 hours or more.
• the dried polyamide resin composition (C1) was placed in a tablet-shaped mold and hot-pressed for 5 minutes at a set temperature of 250°C using a Lab Press 10T (manufactured by Toyo Seiki Seisakusho, model P1-10T) to produce a tablet-shaped molded product (C1) having a diameter of 35 mm and a thickness of 2 ⁇ 5% mm.
• the tablet-shaped molded body (C1) thus obtained was evaluated for the long-term effect of slidability in a sliding state (evaluated based on the presence or absence of a change in the friction coefficient), and the results are shown in FIG. 19.
• the friction coefficient increased from the beginning of the sliding.
• the friction coefficient increased with the passage of the measurement time, and 8 minutes after the start of the measurement, the sliding effect was not obtained and the resin melted due to frictional heat. This showed that the slidability in a sliding state could not be maintained for a long time.
• Comparative Example 9 The procedure of Example 7 was repeated, except that 10 parts by weight of the particles (C7) obtained in Comparative Example 7 was used instead of the particles (1) obtained in Example 1, to obtain a polyamide resin composition (C7).
• the obtained polyamide resin composition (C7) was dried at 110° C. for 6 hours or more.
• the dried polyamide resin composition (C7) was placed in a tablet-shaped mold and hot-pressed for 5 minutes at a set temperature of 250°C using a Lab Press 10T (manufactured by Toyo Seiki Seisakusho, model P1-10T) to produce a tablet-shaped molded product (C7) having a diameter of 35 mm and a thickness of 2 ⁇ 5% mm.
• the tablet-shaped molded body (C7) thus obtained was evaluated for the long-term effect of slidability in a sliding state (evaluated based on the presence or absence of a change in the friction coefficient), and the results are shown in FIG. 20.
• the friction coefficient increased from the beginning of the sliding.
• the friction coefficient increased with the passage of the measurement time, and at 41 minutes from the start of the measurement, the sliding effect was not obtained and the resin melted due to frictional heat. This showed that the slidability in a sliding state could not be maintained for a long time.
• the lubricant-containing resin particles according to the embodiment of the present invention and the lubricant-containing resin particles obtained by the manufacturing method according to the embodiment of the present invention can exhibit excellent heat resistance, excellent impact resistance, and long-lasting sliding properties in a sliding state, so that a resin composition containing such lubricant-containing resin particles and a molded body obtained by molding such a resin composition can be suitably used as a sliding member.

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  • 2024-02-15 JP JP2025501217A patent/JPWO2024172129A1/ja active Pending
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