JP2008033147A - Toner case - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner case improved in molding workability, heat conductiveness and heat radiation performance, and also, presenting heat conductivity and heat emissivity showing nearly an intermediate value between those of a metal and general-purpose resin, consequently, with less heat retention, and suitable to radiate the heat generated with stirring and heat of the toner. <P>SOLUTION: The heat radiation type toner case is composed of a heat conductive resin composition constituted of a thermoplastic resin [A] and specific heat conductive filler [B], wherein the blending amount of the heat conductive filler [B] to 100 parts by mass of the thermoplastic resin [A] is 10 to 1,000 parts by mass. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner case, and more particularly to a heat dissipation type toner case capable of efficiently removing heat from the inside of the case.

  Conventionally, as a toner case, for example, a toner case having a stirring mechanism for toner stored inside is known (for example, Patent Documents 1 to 3). By the way, in such a toner case, it is desired to remove the heat generated by stirring or the heat of the toner itself from the viewpoint of maintaining the quality of the toner, but conventionally, such a function has been actively provided. No heat dissipation type toner case has been proposed. On the other hand, in the field of electronic components, various heat conductive resin compositions have been proposed as part of heat dissipation measures for products including heat generating components.

  For example, a resin composition including a thermoplastic resin such as PBT or PEEK, inorganic fibers such as aluminum nitride, and inorganic powder has been proposed (Patent Document 4). Moreover, a resin composition containing a specific block copolymer or hydrogenated block copolymer, a rubber softener, and a heat conductive material such as magnesium hydroxide has been proposed (Patent Document 5). Further, fillers made of aluminum nitride sintered powder or the like are dispersed in the matrix resin, and the fillers are mutually connected via a metal network formed in a network by a low melting point metal or eutectic alloy having a melting point of 500 ° C. There has been proposed a high thermal conductive composite that is continuously welded to (Patent Document 6).

  Other materials that impart thermal conductivity include powdery substances such as graphite powder, fibrous substances, etc., and conductive compositions containing non-spherical massive graphite particles and a resin have been proposed. (Patent Document 7). Furthermore, a conductive resin composition including a thermoplastic resin and graphite powder having an aspect ratio of 70% or more of particles of 3 or less has been proposed (Patent Document 8).

JP-A-2005-43524 JP-A-2005-77572 JP 2006-119549 A JP-A-8-283456 JP 2001-106865 A Japanese Patent Laid-Open No. 6-196684 JP 2003-253127 A JP 2001-60413 A

  Therefore, it is conceivable to use the above heat conductive resin composition as a molding material for the toner case, but the heat dissipation of the above heat conductive resin composition is not necessarily sufficient.

  The present invention has been made in view of such circumstances, and its purpose is excellent in molding processability, thermal conductivity, and heat dissipation, and it has a thermal conductivity and thermal radiation of approximately intermediate values between metal and general-purpose resin. Therefore, it is an object of the present invention to provide a toner case suitable for releasing heat generated by stirring and heat of the toner itself.

  As a result of intensive studies, the present inventors have obtained the knowledge that the above-mentioned problems can be solved by a resin composition containing a specific heat conductive filler, and have completed the present invention.

  That is, the gist of the present invention consists of a thermoplastic resin [A] and any one or more heat conductive fillers [B] defined in the following (1) to (3), and the thermoplastic resin [A] 100: The heat dissipating toner case is composed of a heat conductive resin composition having a heat conductive filler [B] content of 10 to 1,000 parts by weight with respect to parts by weight.

(1) Graphite particles having an aspect ratio of 10 to 20, a weight average particle diameter of 10 to 200 μm, and a fixed carbon content of 98% by mass or more.

(2) The purity is 95.0% by mass or more, the BET specific surface area is 5.0 m ² / g or less, the volume average particle size (Dv) is 0.5 to 60 μm, and the volume average particle size (Dv) Magnesium oxide particles having a ratio Dv / Dn of 10 to 55 with the number average particle diameter (Dn).

(3) Boron nitride particles having a BET specific surface area of 0.05 to 10 m ² / g, a weight average particle diameter of 1 to 200 μm, and a scaly shape.

  Since the toner case of the present invention is composed of a specific heat conductive resin composition, the toner case is less likely to heat up and can efficiently dissipate heat generated by stirring and heat of the toner itself.

  Hereinafter, the present invention will be described in detail. In the following description, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acryl and methacryl.

  FIG. 1 is an external view of an example of a toner case having a conventionally known stirring mechanism, and the illustrated toner case has a structure similar to that of the toner replenishing device described in Japanese Patent Laid-Open No. 2005-77572. . That is, the toner case (11) includes a container main body (13) having a lid (12), an agitating blade and a conveying screw (none of which are shown) disposed therein, and a gear (14) for driving them. The shutter (15) is opened, and the toner is supplied into the copying apparatus by the operation of the conveying screw. The toner case of the present invention is not limited to the above illustrated one, and the shape and structure thereof are not limited as long as the stirring mechanism is provided.

<Thermal conductive resin composition>
The thermally conductive resin composition used in the present invention (hereinafter also referred to as “the composition of the present invention”) includes a thermoplastic resin [A] (hereinafter also referred to as “component [A]”) and a specific heat. It consists of conductive filler [B] (hereinafter also referred to as “component [B]”), and the amount of [thermal conductive filler [B] is 10 to 1,000 parts by mass with respect to 100 parts by mass of thermoplastic resin [A]. It is.

(Component [A])
The component [A] is not particularly limited as long as it is a polymer having thermoplasticity. Polystyrene, styrene / acrylonitrile copolymer, styrene / maleic anhydride copolymer, (meth) acrylic acid ester / styrene copolymer Styrenic (co) polymers such as; rubber-reinforced resins such as ABS resins, AES resins, and ASA resins; at least one α-olefin having 2 to 10 carbon atoms such as polyethylene, polypropylene, and ethylene / propylene copolymer Olefin resins such as α-olefin (co) polymers and modified polymers thereof (such as chlorinated polyethylene) and cyclic olefin copolymers; ionomers, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers Ethylene copolymers such as polyvinyl chloride, ethylene / vinyl chloride polymer, polychlorinated Vinyl chloride resins such as vinylidene; Acrylic resins such as (co) polymers using one or more (meth) acrylates such as polymethyl methacrylate (PMMA); Polyamide 6, Polyamide 6, 6, Polyamide Polyamide resins (PA) such as 6, 12; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate; polyacetal resin (POM); polycarbonate resin (PC); polyarylate resin; Polyphenylene ether; Polyphenylene sulfide; Fluororesin such as polytetrafluoroethylene and polyvinylidene fluoride; Liquid crystal polymer; Imide resin such as polyimide, polyamideimide, and polyetherimide; Polyetherketone, polyetherether Ketone resins such as ketones; Sulfone resins such as polysulfone and polyethersulfone; Urethane resins; Polyvinyl acetate; Polyethylene oxide; Polyvinyl alcohol; Polyvinyl ether; Polyvinyl butyral; Phenoxy resins; Photosensitive resins; Is mentioned. These can be used in combination of two or more. Among these, rubber reinforced resins, polycarbonate resins and alloys thereof, olefin resins, polyamide resins and polyester resins are preferable.

  The rubber reinforced resin is a rubber reinforced vinyl resin (A1) obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of a rubbery polymer (a) or the rubber reinforced resin. It consists of a mixture of a vinyl resin (A1) and a (co) polymer (A2) of vinyl monomers.

  The rubbery polymer (a) may be a homopolymer or a copolymer as long as it is rubbery at room temperature, but it may be a diene polymer (diene rubbery polymer) and a non-polymer. A diene polymer (non-diene rubber polymer) is preferred. Further, the rubber polymer (a) may be a non-crosslinked polymer or a crosslinked polymer. These can be used in combination of two or more.

  Examples of the diene polymer (diene rubber polymer) include homopolymers such as polybutadiene, polyisoprene, and polychloroprene; styrene / butadiene copolymer, styrene / butadiene / styrene copolymer, acrylonitrile / styrene / Styrene / butadiene copolymer rubber such as butadiene copolymer; Styrene / isoprene copolymer rubber such as styrene / isoprene copolymer, styrene / isoprene / styrene copolymer, acrylonitrile / styrene / isoprene copolymer; Examples include natural rubber. Each of these copolymers may be a block copolymer or a random copolymer. Said diene polymer can be used in combination of 2 or more types.

  The non-diene polymer (non-diene rubbery polymer) is an ethylene / α-olefin copolymer rubber containing an ethylene unit and a unit composed of an α-olefin having 3 or more carbon atoms; Examples include urethane rubbers; acrylic rubbers; silicone rubbers; silicone / acrylic IPN rubbers; polymers obtained by hydrogenating (co) polymers containing units composed of conjugated diene compounds. Each of these copolymers may be a block copolymer or a random copolymer. Said non-diene polymer can be used in combination of 2 or more types. The non-diene polymer is preferably a polymer obtained by hydrogenating an ethylene / α-olefin copolymer rubber and a (co) polymer containing a unit composed of a conjugated diene compound.

  The shape of the rubber-like polymer (a) used for forming the rubber-reinforced vinyl resin (A1) is not particularly limited. And when it is a particulate form, the weight average particle diameter is 50-3,000 nm normally, Preferably it is 100-2,000 nm, More preferably, it is 120-800 nm. When the weight average particle diameter is less than 50 nm, the impact resistance of the composition of the present invention tends to be inferior, and when it exceeds 3,000 nm, the surface appearance of the toner case tends to be inferior. The weight average particle diameter can be measured by a laser diffraction method, a light scattering method, or the like.

  When the rubbery polymer (a) is in the form of particles, as long as the weight average particle diameter is within the above range, for example, JP-A-61-233010, JP-A-59-93701, JP-A-56. What was enlarged by the well-known method described in 167704 gazette etc. can also be used.

  As a method for producing the rubbery polymer (a), emulsion polymerization is preferred in consideration of adjustment of the average particle diameter and the like. In this case, the average particle size can be adjusted by selecting production conditions such as the type of emulsifier and the amount used, the type and amount of initiator used, the polymerization time, the polymerization temperature, and the stirring conditions. Moreover, as another adjustment method of said average particle diameter (particle diameter distribution), the method of blending 2 or more types of the rubber-like polymer (a) which has a different particle diameter may be sufficient.

  The vinyl monomer (b) used for forming the rubber-reinforced vinyl resin (A1) only needs to contain an aromatic vinyl compound. Otherwise, for example, a vinyl cyanide compound, (meth) acrylic acid A compound copolymerizable with the aromatic vinyl compound such as an ester compound, a maleimide compound, and an acid anhydride can be used in combination. Two or more kinds can be used in combination. Accordingly, the vinyl monomer (b) includes at least one aromatic vinyl compound, or at least one aromatic vinyl compound, and at least one compound copolymerizable with the aromatic vinyl compound. The monomer which combined these can be used.

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, Examples thereof include p-methylstyrene, vinyltoluene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinylxylene, vinylnaphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, and fluorostyrene. These can be used in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Moreover, these can be used in combination of 2 or more types. Examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, and the like. These can be used in combination of two or more.

  Examples of the maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide, and the like. Is mentioned. These can be used in combination of two or more. In addition, as another method for introducing a unit composed of a maleimide compound, for example, a method in which maleic anhydride is copolymerized and then imidized may be used. Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used in combination of two or more.

  In addition to the above compounds, a vinyl compound having a functional group such as a hydroxyl group, an amino group, an epoxy group, an amide group, a carboxyl group, or an oxazoline group can be used as necessary. Examples of such vinyl compounds include 2-hydroxyethyl (meth) acrylate, hydroxystyrene, N, N-dimethylaminomethyl (meth) acrylate, N, N-diethyl-p-aminomethylstyrene, (meth ) Glycidyl acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, methallyl glycidyl ether, allyl glycidyl ether, methacrylamide, acrylamide, (meth) acrylic acid, vinyl oxazoline and the like. These can be used in combination of two or more.

  The vinyl monomer (b) contains an aromatic vinyl compound. In this case, the polymerization ratio between the aromatic vinyl compound (b1) and the other vinyl monomer (b2) is as follows. When the total is 100% by mass, it is usually (2-95)% by mass / (98-5)% by mass, preferably (10-90)% by mass / (90-10)% by mass. If the amount of the aromatic vinyl compound (b1) used is too small, the moldability tends to be inferior. If it is too large, the toner case of the present invention may not have sufficient chemical resistance, heat resistance and the like.

  The vinyl monomer (b) used for forming the rubber-reinforced vinyl resin (A1) is preferably used in the following combinations. By using a vinyl cyanide compound, the physical property balance of chemical resistance and discoloration resistance is improved.

(1) Aromatic vinyl compound and vinyl cyanide compound (2) Aromatic vinyl compound, vinyl cyanide compound and other compounds

  The rubber-reinforced vinyl resin (A1) is obtained by polymerizing the vinyl monomer (b) in the presence of the rubber polymer (a). The rubber-reinforced vinyl resin (A1) may be one or more of rubber-reinforced vinyl resins (i) obtained using only an aromatic vinyl compound as the vinyl monomer (b). It may be one or more rubber-reinforced vinyl resins (ii) obtained by using the monomer (1) as the monomer (b), and the vinyl monomer (b) as described above. One or more rubber-reinforced vinyl resins (iii) obtained using the monomer (2) may be used. Furthermore, these may be combined appropriately.

  As described above, when a rubber reinforced resin is used as the component [A], the rubber reinforced resin may be only the rubber reinforced vinyl resin (A1), the rubber reinforced vinyl resin (A1), It may be a mixture with the (co) polymer (A2) obtained by polymerization of a vinyl monomer. Examples of the vinyl monomer include compounds used for forming the rubber-reinforced vinyl resin (A1), that is, aromatic vinyl compounds, cyanide vinyl compounds, (meth) acrylic acid ester compounds, maleimide compounds, acids. One or more selected from an anhydride and a compound having a functional group can be used. Therefore, the (co) polymer (A2) is a polymer obtained by polymerizing components having exactly the same composition as the vinyl monomer (b) used for forming the rubber-reinforced vinyl resin (A1). Alternatively, it may be a polymer obtained by polymerizing the same type of monomer with different compositions, or may be a polymer obtained by polymerizing different types of monomers with different compositions. May be. Two or more of these polymers may be contained.

  The (co) polymer (A2) is a homopolymer or copolymer obtained by polymerization of a vinyl monomer, and is exemplified by the following (3) to (8). In addition, each monomer can apply the compound used for formation of rubber reinforced vinyl-type resin (A1), and its preferable compound is also the same.

(3) One or more types of (co) polymers obtained by polymerizing only aromatic vinyl compounds (4) One type of (co) polymers obtained by polymerizing only (meth) acrylic acid ester compounds (5) One or more types of copolymers obtained by polymerizing aromatic vinyl compounds and vinyl cyanide compounds (6) Copolymers obtained by polymerizing aromatic vinyl compounds and (meth) acrylic acid ester compounds One or more types of polymers (7) One or more types of copolymers obtained by polymerizing aromatic vinyl compounds, vinyl cyanide compounds and other compounds (8) Aromatic vinyl compounds and vinyl cyanide compounds One or more types of copolymers obtained by polymerizing with other compounds

  These can be used in combination of two or more.

  Accordingly, specific examples of the (co) polymer (A2) include acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, styrene / methyl methacrylate copolymer. Examples thereof include a polymer and an acrylonitrile / styrene / N-phenylmaleimide copolymer.

  Next, a method for producing the rubber-reinforced vinyl resin (A1) and the (co) polymer (A2) will be described.

  The rubber-reinforced vinyl resin (A1) can be produced by polymerizing the vinyl monomer (b) in the presence of the rubber polymer (a). As the polymerization method, emulsion polymerization, solution polymerization or bulk polymerization is suitable.

  In the production of the rubber-reinforced vinyl resin (A1), the rubber polymer (a) and the vinyl monomer (b) are present in the reaction system in the presence of the total amount of the rubber polymer (a). In addition, the vinyl-based monomer (b) may be added all at once, or dividedly or continuously. Moreover, the method which combined these may be used. Furthermore, polymerization may be carried out by adding the whole or part of the rubbery polymer (a) during the polymerization.

  When producing 100 parts by mass of the rubber-reinforced vinyl resin (A1), the amount of the rubbery polymer (a) used is usually 5 to 80 parts by mass, preferably 10 to 70 parts by mass, and more preferably 15 to 60 parts by mass. Part. Moreover, about the usage-amount of a vinyl-type monomer (b), it is 25-1,900 mass parts normally with respect to 100 mass parts of rubber-like polymers (a), Preferably it is 60-560 mass parts.

  When the rubber-reinforced vinyl resin (A1) is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water, and the like are used.

  As the polymerization initiator, an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide and a reducing agent such as a sugar-containing pyrophosphate formulation and a sulfoxylate formulation are combined. Redox initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used in combination of two or more. Furthermore, the above polymerization initiator can be added to the reaction system all at once or continuously. Moreover, the usage-amount of said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b) whole quantity, Preferably it is 0.2-0.7 mass%.

  As the chain transfer agent, mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan, terpinolene, Examples include α-methylstyrene dimers. These can be used in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the vinyl monomer (b).

  As an emulsifier used in the case of emulsion polymerization, sulfates of higher alcohols, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, higher aliphatic carboxylates, phosphates, etc. And anionic surfactants such as polyethylene glycol alkyl ester type and alkyl ether type nonionic surfactants. These can be used in combination of two or more. The usage-amount of said emulsifier is 0.3-5.0 mass% normally with respect to vinyl-type monomer (b) whole quantity.

  The latex obtained by emulsion polymerization is usually purified by coagulation with a coagulant to make the polymer component into powder, and then washing and drying. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid. In addition, in the case of using a plurality of rubber-reinforced vinyl resins (A1) in combination, they may be mixed after isolation, but as another method, they are mixed after producing a latex containing each resin, Then, it can be set as the mixed rubber reinforced vinyl resin (A1) by solidifying or the like.

  A known method can be applied to the method for producing the rubber-reinforced vinyl resin (A1) by solution polymerization and bulk polymerization.

  The graft ratio of the rubber-reinforced vinyl resin (A1) is usually 10 to 200% by mass, preferably 15 to 150% by mass, and more preferably 20 to 100% by mass. When the graft ratio is less than 10% by mass, the surface appearance and impact resistance of the toner case of the present invention may be deteriorated. On the other hand, if it exceeds 200%, the moldability is inferior.

  Here, the graft ratio is x gram of rubber component in 1 gram of rubber reinforced vinyl resin (A1), and y gram of insoluble content when 1 gram of rubber reinforced vinyl resin (A1) is dissolved in acetone. Is a value obtained by the following equation. However, acetonitrile is used when the rubbery polymer (a) is an acrylic rubber.

  In addition, the intrinsic viscosity [η] (in methyl ethyl ketone) of the soluble component by acetone of the rubber-reinforced vinyl resin (A1) (however, acetonitrile is used when the rubbery polymer (a) is an acrylic rubber). , Measured at 30 ° C.) is usually 0.1 to 1.0 dl / g, preferably 0.2 to 0.9 dl / g, more preferably 0.3 to 0.7 dl / g. By setting it within this range, the moldability is excellent, and the impact resistance of the toner case of the present invention is also excellent.

  The above-mentioned graft ratio and intrinsic viscosity [η] are the types and amounts of polymerization initiator, chain transfer agent, emulsifier, solvent, etc. when producing the rubber-reinforced vinyl resin (A1), and the polymerization time. It can be easily controlled by adjusting the polymerization temperature and the like.

  The (co) polymer (A2) can be produced by polymerizing monomer components using a polymerization initiator or the like applied to the production of the rubber-reinforced vinyl resin (A1). As the polymerization method, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like, thermal polymerization without using a polymerization initiator, and combinations of these polymerization methods can be employed.

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the (co) polymer (A2) is usually 0.1 to 1.0 dl / g, preferably 0.15 to 0.7 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent. The intrinsic viscosity [η] of this (co) polymer (A2) can be controlled by adjusting the production conditions, as in the case of the rubber-reinforced vinyl resin (A1).

  Intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the above-mentioned rubber-reinforced resin by acetone (but acetonitrile is used when the rubbery polymer (a) is an acrylic rubber). ) Is usually 0.1 to 0.8 dl / g, preferably 0.15 to 0.7 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent.

  As the component [A], a rubber reinforced resin is used, and when the rubber reinforced resin is a rubber reinforced vinyl resin (A1), and by polymerization of the rubber reinforced vinyl resin (A1) and a vinyl monomer. In any case of the mixture with the obtained (co) polymer (A2), the content of the rubbery polymer (a) in the composition of the present invention is usually 1 to 50% by mass, preferably It is 3-40 mass%, More preferably, it is 3-35 mass%, Most preferably, it is 5-35 mass%. When the content of the rubbery polymer (a) is in the above range, the moldability is excellent, and the toner case of the present invention is excellent in impact resistance, surface appearance, rigidity, and heat resistance.

  When a rubber reinforced resin is used as the component [A], various compositions can be obtained by selecting the type of the rubber reinforced vinyl resin (A1). For example, a composition combining a diene rubber-reinforced vinyl resin using a diene polymer as a rubber polymer (a) and a polycarbonate resin, and a non-diene polymer as a rubber polymer (a). The composition is a combination of a non-diene rubber-reinforced vinyl resin used and an olefin resin.

  The polycarbonate resin is not particularly limited as long as it has a carbonate bond in the main chain, and may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, you may use combining these. In the present invention, an aromatic polycarbonate is preferable from the viewpoint of impact resistance, heat resistance, and the like. The polycarbonate resin may have a terminal modified with an R—CO— group or an R′—O—CO— group (R and R ′ each represents an organic group). This polycarbonate resin can be used in combination of two or more.

  Examples of the aromatic polycarbonate include those obtained by melt transesterification (transesterification reaction) of an aromatic dihydroxy compound and a carbonic acid diester, those obtained by an interfacial polycondensation method using phosgene, pyridine and phosgene, Those obtained by the pyridine method using the above reaction product can be used.

  The aromatic dihydroxy compound may be any compound having two hydroxyl groups in the molecule, such as dihydroxybenzene such as hydroquinone and resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane ( Hereinafter, referred to as “bisphenol A”), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis ( -Hydroxyphenyl) pentane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 1,1-bis (p-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (p-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 1,1-bis (p-hydroxyphenyl) -1-phenylethane, 9,9-bis (p-hydroxyphenyl) fluorene, 9,9-bis (p-hydroxy-3-methyl) Phenyl) fluorene, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) diphenol, bis (p-hydroxyphenyl) oxide, bis (p-hydroxy) Phenyl) ketone, bis (p-hydroxyphenyl) ether, bis (p-hydroxy) Phenyl) ester, bis (p-hydroxyphenyl) sulfide, bis (p-hydroxy-3-methylphenyl) sulfide, bis (p-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, Examples thereof include bis (p-hydroxyphenyl) sulfoxide. These can be used in combination of two or more.

  Of the above-mentioned aromatic dihydroxy compounds, compounds having a hydrocarbon group between two benzene rings are preferred. In this compound, the hydrocarbon group may be a halogen-substituted hydrocarbon group. Further, the benzene ring may be one in which a hydrogen atom contained in the benzene ring is substituted with a halogen atom. Therefore, the above compounds include bisphenol A, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2, 2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (P-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane and the like can be mentioned. Of these, bisphenol A is particularly preferred.

  Examples of the carbonic acid diester used for obtaining the aromatic polycarbonate by transesterification include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, and ditolyl carbonate. These can be used in combination of two or more.

  The viscosity average molecular weight of the polycarbonate resin is usually 15,000 to 40,000, preferably 17,000 to 30,000, and more preferably 18,000 to 28,000. As the viscosity average molecular weight is higher, the fluidity is not sufficient and the moldability tends to be lowered. The polycarbonate resin may be used by mixing two or more polycarbonate resins having different viscosity average molecular weights as long as the overall viscosity average molecular weight falls within the above range.

  The polycarbonate resin is an acrylonitrile / styrene copolymer, an acrylonitrile / α-methylstyrene copolymer, an acrylonitrile / styrene / methyl methacrylate copolymer exemplified as the rubber-reinforced resin or the (co) polymer (A2). It can be used as component [A] together with a copolymer such as As described above, the rubber reinforced resin preferably includes a rubber reinforced vinyl resin (diene rubber reinforced vinyl resin) using a diene polymer as the rubber polymer (a).

  When a polycarbonate resin and a rubber reinforced resin are used in combination as the component [A], these use ratios are usually 30 to 90% by mass and 70 to 10%, respectively, assuming that the total of the polycarbonate resin and the rubber reinforced resin is 100% by mass. It is 40 mass%, Preferably it is 40-85 mass% and 60-15 mass%, More preferably, it is 50-80 mass% and 50-20 mass%. However, the total of the polycarbonate resin and the rubber reinforced resin is 100% by mass. In addition, in the composition using a polycarbonate resin and a rubber reinforced resin as the component [A], the content of the rubbery polymer (a) is usually 1 to 50% by mass, preferably 3 to 40% by mass, and more preferably. Is 3 to 35% by mass, particularly preferably 5 to 35% by mass.

  The olefin-based resin is an α-olefin-based (co) polymer, a cyclic olefin copolymer, or the like containing at least one unit composed of an α-olefin having 2 to 10 carbon atoms that is non-rubber at room temperature. These modified polymers are also included.

  Examples of the α-olefin having 2 to 10 carbon atoms include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylhexene-1, and the like. It is done. These can be used in combination of two or more. Of these, ethylene, propylene, butene-1, 3-methylbutene-1 and 4-methylpentene-1 are preferred.

  When said olefin resin is a homopolymer, polyethylene, polypropylene, etc. are mentioned. These can be used in combination of two or more.

  When the olefin resin is a copolymer, a copolymer comprising two or more of the α-olefins, such as an ethylene / propylene copolymer and an ethylene / 1-butene copolymer, Co-weight consisting of α-olefin and non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene Examples include coalescence. These can be used in combination of two or more. When the olefin resin is a copolymer, it may be a random copolymer or a block (type) copolymer.

  As said olefin resin, polyethylene and the (co) polymer containing a propylene unit are preferable. The content of propylene units constituting the (co) polymer containing propylene units is usually 40 to 100% by mass, preferably 55 to 100% by mass, more preferably 70 to 100% by mass, based on the total amount of all units. It is.

  When the olefin resin is a polypropylene homopolymer (homotype), the bending modulus and hardness tend to be excellent, and when the block type copolymer is used, the impact resistance and flexibility tend to be excellent.

  In addition, the olefin resin is an acid anhydride group-modified olefin resin or carboxyl group-modified olefin resin obtained by modifying the α-olefin (co) polymer with an acid anhydride such as maleic anhydride. Further, it may be a modified polymer such as chlorinated polyethylene.

  The crystallinity of the olefin resin is not limited, but the crystallinity by X-ray diffraction is preferably 20% or more at room temperature. Moreover, it is preferable that melting | fusing point measured based on JISK7121 is 40 degreeC or more. Moreover, the melt flow rate (based on JIS K7210) of said olefin resin is 0.01-500 g / 10min normally, Preferably it is 0.05-100 g / 10min.

  When an olefin resin is used as the component [A], it is excellent in releasability when a toner case is molded using a mold. Further, the obtained toner case is excellent in impact resistance. The olefin resin can be used as the component [A] together with the rubber reinforced resin.

  When the component [A] is an olefin resin, it is excellent in moldability, mold release, impact resistance and bending modulus as compared with the case of a conventional diene rubber reinforced vinyl resin. Heat resistance tends to decrease and bending strain tends to increase. However, by combining an olefin resin and a rubber reinforced resin, a toner case having an excellent balance of impact resistance, bending modulus, bending strain and hardness can be obtained.

  As described above, the rubber-reinforced resin includes a rubber-reinforced vinyl resin (non-diene rubber-reinforced vinyl resin) using a non-diene polymer as the rubbery polymer (a). preferable.

  The polyamide-based resin is not particularly limited as long as it is a polymer having an acid amide bond (—CO—NH—) in the main chain. This polyamide resin is usually produced by a known method such as ring-opening polymerization of a lactam compound having a ring structure, polymerization of an aminocarboxylic acid, condensation polymerization of a dicarboxylic acid and a diamine compound. Therefore, the polyamide-based resin is used as a homopolyamide, a copolyamide or the like.

  Examples of the lactam compound used in the ring-opening polymerization include ε-caprolactam and ω-laurolactam. Examples of the aminocarboxylic acid include aminocaproic acid, aminoenanoic acid, aminocaprylic acid, aminobergonic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, and 12-aminododecanoic acid.

  Examples of the dicarboxylic acid used for polycondensation of dicarboxylic acid and diamine compound include adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, 2-methylterephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. An acid etc. are mentioned. Examples of the diamine compound include ethylene diamine, tetramethylene diamine, hexamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,3,4-trimethylhexamethylene diamine, 2,4,4. -Trimethylhexamethylenediamine, bis (p-aminocyclohexyl) methane, m-xylylenediamine, p-xylylenediamine, paraphenylenediamine, metaphenylenediamine and the like.

  As said polyamide-type resin, nylon 4, 6, 7, 8, 11, 12, 6, 6, 6, 9, 6, 10, 6, 11, 6, 12, 6T, 6/6, 6, 6 / 12, 6 / 6T, 6T / 6I, etc. can be used. In addition, the terminal of this polyamide component may be sealed with carboxylic acid, amine or the like. Examples of the carboxylic acid include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of the amine include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine.

  When a polyamide resin is used as component [A], the resulting toner case is excellent in heat resistance.

  The polyester resin may be any of aliphatic polyester, alicyclic polyester, and aromatic polyester. This polyester resin is usually produced by a reaction between an acid component containing dicarboxylic acid and / or an ester-forming derivative of dicarboxylic acid and a diol component containing a diol compound and / or an ester-forming derivative of a diol compound. Therefore, the above polyester resins can be used as homopolyesters, copolyesters, and the like. In addition, the crystallinity of said polyester-type resin is not specifically limited.

  Among the above acid components, dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4 Aromatic dicarboxylic acids such as' -diphenylmethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, and 4,4'-diphenylisopropylidenedicarboxylic acid are listed. These substitution products (alkyl group substitution products such as methyl isophthalic acid) and derivatives (alkyl ester compounds such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate) can also be used. Furthermore, oxyacids and their ester-forming derivatives such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid can also be used. The above acid components can be used in combination of two or more.

  Examples of the diol component include aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and neopentyl glycol; and alicyclic glycols such as 1,4-cyclohexanedimethanol. In addition, these substitution bodies and derivatives can also be used. Moreover, cyclic ester compounds, such as (epsilon) -caprolactone, can also be used. Furthermore, a long-chain diol compound (polyethylene glycol, polytetramethylene glycol, etc.), an alkylene oxide addition polymer of bisphenols (such as an ethylene oxide addition polymer of bisphenol A), or the like can be used as necessary. The above diol components can be used in combination of two or more.

  Examples of the polyester resin include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, polyneopentyl terephthalate, polyethylene isophthalate, polyethylene naphthalate. Phthalate, polybutylene naphthalate, polyhexamethylene naphthalate, or the like can be used. Also, a copolyester can be used. These can be used in combination of two or more.

  When a polyester resin is used as component [A], the resulting toner case is excellent in heat resistance.

(Component [B])
The component [B] is a heat conductive filler having specific physical properties, and is one or more of three types and components [B1] to [B3] described below.

(Component [B1])
Component [B1] is graphite particles having specific physical properties. That is, the graphite particles have an aspect ratio of 10 to 20, a weight average particle diameter of 10 to 200 μm, and a fixed carbon amount of 98% by mass or more. The aspect ratio is preferably 12 to 18, the weight average particle diameter is preferably 15 to 180 μm, and the fixed carbon amount is preferably 98.5% by mass or more, and more preferably 99% by mass or more. When each physical property is in the above range, the thermal conductivity is further improved.

The above aspect ratio can be calculated by measuring the length and width by an electron microscope or the like. The weight average particle diameter can be measured by a laser diffraction method, a light scattering method, or the like. The “weight average particle diameter” according to the present invention means a particle diameter (D ₅₀ ) obtained by measuring the particle size distribution when the cumulative weight is 50%. The amount of fixed carbon can be measured according to JIS M8511.

Further, component [B1] is the cumulative weight obtained by measuring the particle size distribution, respectively, the ratio _D 80 _{/ D 20} of the particle diameter _{D 20} and _{D 80} when 20% and 80% 2-12 It is preferable that More preferably, it is 2.5-10. When the ratio D ₈₀ / D ₂₀ is less than 2, the thermal conductivity tends to decrease, and the composition may be difficult to produce. On the other hand, when the ratio D ₈₀ / D ₂₀ exceeds 12, impact resistance and molding appearance tend to be lowered.

Component [B1] may be either α-graphite or β-graphite. Moreover, you may combine these. Furthermore, any of natural graphite and artificial graphite may be used. Moreover, you may combine these. The natural graphite is not particularly limited as long as no band is observed at a wavelength around 1360 cm ⁻¹ by laser Raman measurement, and examples thereof include flaky graphite, massive graphite, and earthy graphite. Of these, scaly graphite is preferred.

  The compounding amount of component [B1] is 10 to 1,000 parts by mass with respect to 100 parts by mass of component [A], and can be appropriately determined according to the required performance of the toner case. When the blending amount of the component [B1] is less than 10 parts by mass, the thermal conductivity and the electromagnetic shielding properties are not sufficient. On the other hand, when it exceeds 1,000 parts by mass, the moldability may not be sufficient.

  When it is set as the resin composition with which the compounding quantity of component [B1] is a small amount, the compounding quantity of component [B1] is 10-100 mass parts normally, Preferably it is 25-82 mass parts, More preferably, it is 42-82 mass parts. It is. Moreover, when it is set as the resin composition with a compounding quantity of component [B1], the compounding quantity of component [B1] is 100-1,000 mass parts normally, Preferably it is 150-900 mass parts, More preferably, it is 230. -570 parts by mass.

  The component [B1] contained in the composition of the present invention or the toner case mainly containing the components [A] and [B1] can be obtained by observing a test piece prepared by a known method with an electron microscope or the like. The aspect ratio and the average particle diameter (more specifically, the number average particle diameter) can be determined. The above aspect ratio and average particle diameter are usually the same as the aspect ratio and weight average particle diameter of the component [B1] before blending, respectively.

(Component [B2])
Component [B2] is magnesium oxide particles having specific physical properties. That is, the purity is 95.0% by mass or more, the BET specific surface area is 5.0 m ² / g or less, the volume average particle size (Dv) is 0.5 to 60 μm, and the volume average particle size (Dv) and number are Magnesium oxide particles having a ratio Dv / Dn of 10 to 55 with the average particle diameter (Dn). In particular, it is preferable that 100 parts by mass of magnesium oxide particles are heat-treated with 0.1 to 10 parts by mass of an organosilicon compound.

  The kind of magnesium oxide is not particularly limited, and lightly burned magnesia obtained by firing carbonate (magnesite), nitrate, hydroxide, etc. at 1,400 ° C. or lower, a temperature higher than the above temperature (for example, Hard calcined magnesia (also referred to as “high temperature calcined magnesia clinker”) obtained by sintering at 1800 ° C. or higher) and natural magnesite or seawater magnesia are melted in an electric arc furnace, made into an ingot, and then crushed. The obtained electrofused magnesia is mentioned. These can be used in combination of two or more. In the present invention, electrofused magnesia is preferred.

  The purity of component [B2] is preferably 96.0 to 100% by mass, more preferably 98.0 to 100% by mass, particularly preferably 98.5 to 100% by mass, and even more preferably 99.0 to 100% by mass. %. If the purity is too low, water resistance and thermal conductivity may not be sufficient when a toner case is obtained. The purity can be measured according to JIS K6224.

BET specific surface area of the component [B2] is preferably 0.1~3.5m ² / g, more preferably 0.15~3m ² / g, particularly preferably 0.2~2m ² / g, more preferably 0.2 to 0.8 m ² / g. If the BET specific surface area is too high, water resistance may not be sufficient when a toner case is formed. The BET specific surface area can be measured using a commercially available apparatus.

  Dv of component [B2] is preferably 2 to 50 μm, more preferably 5 to 35 μm. If this Dv is too large, the desired thermal conductivity may not be obtained in the case of a resin composition, and the appearance and mechanical properties of the toner case may deteriorate. On the other hand, if Dv is too small, water resistance and thermal conductivity may not be sufficient when a toner case is used.

  Moreover, ratio Dv / Dn becomes like this. Preferably it is 12-50, More preferably, it is 15-40. If this ratio is too large, the water resistance may not be sufficient when a toner case is used. On the other hand, if it is too small, the desired thermal conductivity may not be obtained. The above Dv and Dn can be measured by a laser diffraction scattering method, a dynamic light scattering method, or the like.

  Component [B2] may be a combination of two or more of them in any proportion as long as the above physical properties fall within the above ranges.

  Examples of the organosilicon compound used for modifying magnesium oxide include silicone oil, silane coupling agents, alkoxysilane compounds, and silylating agents. Of these, silicone oil and silane coupling agent are preferable, and silicone oil is particularly preferable.

  As the silicone oil, any of unmodified silicone oil and modified silicone oil may be used, or a combination thereof may be used. Non-modified silicone oils include dimethyl silicone oil whose polysiloxane side chains and terminals are all methyl groups, methyl phenyl silicone oil whose polysiloxane side chains are partially phenyl groups, and part of polysiloxane side chains. Methyl hydrogen silicone oil in which is a hydrogen atom. The modified silicone oil includes alkoxy modification, amino modification, carboxyl modification, epoxy modification, silazane modification, phenol modification, carbinol modification, methacryl modification, mercapto modification, polyether modification, methylstyryl modification, alkyl modification, higher fatty acid ester. Modification, fluorine modification, hydrophilic special modification and the like can be mentioned, but the presence or absence of reactivity is not particularly limited. Of these, alkoxy-modified silicone oil and methyl hydrogen silicone oil are preferable, and alkoxy-modified silicone oil is particularly preferable. The silicone oils can be used in combination of two or more.

  The kinematic viscosity (25 ° C.) of the silicone oil is usually 0.5 to 10,000 cSt, preferably 1 to 5,000 cSt, and more preferably 1.5 to 3,000 cSt. If the viscosity is too high, the water resistance may not be improved. On the other hand, if the viscosity is too low, it may be difficult to prepare the mixture before the heating step, and the water resistance may not be improved. The viscosity of the silicone oil can be measured by the Ostwald method or the like.

  As silane coupling agents, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (methacryloxypropyl) trimethoxysilane, γ-aminopropyltriethoxysilane, N -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Dimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldichlorosilane, 3-chloropropylmethyldiethoxy Silane, 3-chloropropyl methyl dimethoxy silane, 3-chloropropyl triethoxysilane, and the like. Two or more of the above silane coupling agents can be used in combination.

  Examples of the alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, and methyltriethoxysilane. The above alkoxysilane compounds can be used in combination of two or more. Examples of the silylating agent include trimethylchlorosilane and hexamethyldisilazane. The above silylating agents can be used in combination of two or more.

  In addition, the above silicone oil, silane coupling agent, alkoxysilane compound, silylating agent and the like may be used in combination.

  The usage-amount of an organosilicon compound is 0.5-7 mass parts normally with respect to 100 mass parts of magnesium oxides, Preferably it is 1-3 mass parts. If the amount of the organosilicon compound used is too small, the improved effect of water resistance by the modified magnesium oxide may not be sufficient. On the other hand, if the amount is too large, the thermal conductivity may not be improved.

  The method for preparing the mixture containing magnesium oxide and the organosilicon compound is not particularly limited, and a known charging method, stirring method, or the like can be applied in a known container. By stirring, the entire surface of the magnesium oxide is coated with the organosilicon compound.

  The mixture is heated using an industrial furnace such as an electric furnace or a gas furnace, usually at a temperature in the range of 100 to 800 ° C, preferably 200 to 600 ° C, more preferably 250 to 400 ° C. The heating time at that time is usually 10 minutes to 5 hours, preferably 30 minutes to 4 hours, and more preferably 30 minutes to 3 hours. In both cases where the heating temperature is too low and the heating time is too short, the water resistance improvement effect by the modified magnesium oxide tends to be insufficient. On the other hand, when the temperature is too high and the heating time is too long, the water resistance tends to decrease. In particular, when silicone oil is used as the organosilicon compound, the adhesiveness between the silicone oil and magnesium oxide and the hydrophobicity that develops with the temperature and time conditions at which the silicone oil is completely decomposed tend to decrease.

  Component [B2] may be obtained by the heating step described above, and may be a surface of a phosphate ester, a higher fatty acid and its metal salt, a higher fatty acid ester, a higher fatty acid amide, a higher alcohol, a hardened oil, or the like. What was processed with the processing agent may be used. By using these surface treatment agents, the water resistance may be further improved, and the dispersibility in the thermoplastic resin may be further improved.

  Although the usage-amount of a surface treating agent is not specifically limited, It is 0.05-5 mass parts normally with respect to 100 mass parts of magnesium oxides, Preferably it is 0.1-4 mass parts, More preferably, it is 0.2-3 mass parts. It is. In the treatment with the surface treatment agent, a desired amount of the surface treatment agent is added to the magnesium oxide, and the mixture is stirred and mixed while heating to a temperature above which it melts, for example, usually 50 to 150 ° C., preferably 80 to 130 ° C. Can be done. The heating time is usually 5 minutes to 3 hours, preferably 10 minutes to 1 hour.

  Component [B2] can have a water absorption of 1% by mass or less, preferably 0.5% by mass or less, after standing for 8 days in an atmosphere at a temperature of 60 ° C. and a relative humidity of 90%. .

  The amount of component [B2] is 10 to 1,000 parts by mass per 100 parts by mass of component [A], and can be determined as appropriate according to the required performance of the toner case. The amount of component [B2] is preferably 15 to 800 parts by mass, more preferably 20 to 600 parts by mass, and particularly preferably 25 to 400 parts by mass. When the blending amount of component [B1] is less than 10 parts by mass, the thermal conductivity is not sufficient. On the other hand, when it exceeds 1,000 parts by mass, the moldability, the appearance of the toner case and the impact resistance are reduced. There is.

(Component [B3])
Component [B3] is boron nitride particles having specific physical properties. That is, the boron nitride particles have a BET specific surface area of 0.05 to 10 m ² / g, a weight average particle diameter of 1 to 200 μm, and a scaly shape. The boron nitride particles may be subjected to various surface treatments as in the case of the component [B2]. The compounding quantity of component [B3] is the same as the compounding quantity of component [B2].

(Ingredient [C])
The composition of this invention can mix | blend another heat conductive filler (component [C]). The weight average particle diameter of component [C] is usually 0.1 to 500 μm, preferably 1 to 300 μm. Further, those having a high aspect ratio are preferred, and scale-like (plate-like), needle-like and the like are preferred, but those having an aspect ratio close to 1 such as a sphere and a cube can also be used. In particular, mixing with a material having a high aspect ratio may be preferable because it exhibits thermal conductivity regardless of the direction of resin flow during molding. Either conductive or insulating can be used. However, if a problem such as a short circuit occurs due to electrical connection depending on the application, an insulating filler can be used. Specific examples of the component [C] include those described in the following (1) to (4).

(1) Examples of the carbon-based heat conductive filler include graphite (artificial graphite, natural graphite), carbon fiber (PAN-based, pitch-based), carbon nanotube (multi-walled carbon nanotube, single-walled carbon nanotube, carbon nanocoil) and the like. It is done.

(2) Examples of the insulating heat conductive filler include crystalline silica, fused silica, silicon carbide, alumina, zinc oxide, titanium oxide, aluminum nitride, silicon nitride, and beryllia.

(3) Examples of the metal-based heat conductive filler include stainless steel, copper, silver, zinc, iron, aluminum, nickel, and the like.

(4) Examples of other heat conductive fillers include carbon fibers, glass fibers, aramid fibers, and the like, and those having a metal coating on the surface of the flakes.

  Component [C] can be surface treated in the same manner as component [B2]. By performing the surface treatment, effects such as improving the affinity with the resin, preventing thermal decomposition of the resin, and preventing water absorption of the filler can be obtained.

(Component [D])
The composition of the present invention can contain an impact resistance improver (component [D]). Component [D] is a polymer component (soft resin, rubber and elastomer) that improves impact resistance in the toner case of the present invention. Specifically, a conjugated diene polymer, an ethylene / α-olefin copolymer, an ethylene / (meth) acrylate copolymer, and an acid having an unsaturated bond in the presence of these polymers. Acid anhydride grafted polymer obtained by reacting anhydride and its metal salt, ethylene / (meth) acrylic acid copolymer, ethylene / glycidyl ether copolymer, nylon 12 / polytrimethylene glycol copolymer Nylon 12 / polytetramethylene glycol copolymer, polybutylene terephthalate / polytrimethylene glycol copolymer, polybutylene terephthalate / polytetramethylene glycol copolymer, and the like. These can be used in combination of two or more. Of these, conjugated diene polymers, ethylene / α-olefin copolymers, ethylene / (meth) acrylate copolymers, and unsaturated bonds in the presence of these polymers. An acid anhydride grafted polymer obtained by reacting an acid anhydride and a metal salt thereof are preferred. Component [D] may be a non-crosslinked polymer or a crosslinked polymer.

  Component [D] is an acid anhydride having an unsaturated bond in the presence of the conjugated diene polymer, ethylene / α-olefin copolymer or ethylene / (meth) acrylate copolymer. An acid anhydride grafted polymer obtained by reacting one or more kinds can also be used. Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and crotonic anhydride.

  As the above-mentioned acid anhydride grafted polymer, unhydrogenated or hydrogenated styrene / butadiene / styrene block copolymer-g-maleic anhydride copolymer (“g” represents a graft. The same applies hereinafter. Unhydrogenated or hydrogenated styrene / isoprene / styrene block copolymer-g-maleic anhydride copolymer, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g -Maleic anhydride copolymer, ethylene / propylene / 1,4-hexadiene-g-maleic anhydride copolymer, ethylene / propylene / dicyclopentadiene-g-maleic anhydride copolymer, ethylene / propylene / 2, 5-norbornadiene-g-maleic anhydride copolymer, ethylene / methyl (meth) acrylate-g-maleic anhydride copolymer, ethylene (Meth) acrylic acid ethyl -g- maleic anhydride copolymer.

  In the above acid anhydride grafted polymer, the amount of acid anhydride grafted (also referred to as “acid-modified amount”) is usually 0.3 to 0.7 mass based on the acid anhydride grafted copolymer. %, Preferably 0.35 to 0.65 mass%, more preferably 0.4 to 0.6 mass%. If it is this range, sufficient impact resistance will be acquired and the fall of thermal stability can be suppressed.

  The amount of component [D] is usually 1 to 50 parts by weight, preferably 3 to 45 parts by weight, and more preferably 5 to 40 parts by weight with respect to 100 parts by weight as a total of components [A] and [D]. . If it is this range, sufficient impact resistance can be obtained. In addition, when there are too many compounding quantities of component [D], moldability may fall.

(Additive)
The composition of this invention can mix | blend an additive according to the objective, a use, etc. Examples of the additive include fillers, heat stabilizers, antioxidants, ultraviolet absorbers, flame retardants, anti-aging agents, plasticizers, antibacterial agents, and coloring agents.

  The above fillers include heavy calcium carbonate, light calcium carbonate, ultrafine activated calcium carbonate, special calcium carbonate, basic magnesium carbonate, kaolin clay, calcined clay, pyrophyllite clay, silane-treated clay, synthetic silica. Calcium oxide, synthetic magnesium silicate, synthetic aluminum silicate, magnesium carbonate, magnesium hydroxide, kaolin, sericite, talc, fine talc, wollastonite, zeolite, zonotlite, asbestos, PMF (Processed Mineral Fiber), cucumber powder, sepiolite, Potassium titanate, elastadite, gypsum fiber, glass balun, silica balun, hydrotalcite, fly ash balun, shirasu balun, carbon balun, barium sulfate, aluminum sulfate, sulfuric acid Examples include calcium and molybdenum disulfide. These can be used in combination of two or more. The blending amount of the filler is usually 1 to 30 parts by mass, preferably 2 to 25 parts by mass, and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the component [A].

  Examples of the heat stabilizer include phosphites, hindered phenols, and thioethers. These can be used in combination of two or more. The compounding quantity of said heat stabilizer is 0.01-5 mass parts normally with respect to 100 mass parts of component [A].

  Examples of the antioxidant include phosphites, hindered amines, hydroquinones, hindered phenols, and sulfur-containing compounds. These can be used in combination of two or more. The amount of the above antioxidant is usually 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the component [A]. is there.

  Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, and metal complex salts. These can be used in combination of two or more. The blending amount of the ultraviolet absorber is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component [A]. is there.

  Examples of the flame retardant include organic flame retardants, inorganic flame retardants, and reactive flame retardants. These can be used in combination of two or more.

  Organic flame retardants include brominated epoxy compounds, brominated alkyltriazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene resins Halogenated flame retardants such as brominated bisphenol cyanurate resin, brominated polyphenylene ether, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, toki Hexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate Phosphate esters such as phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, compounds modified with these substituents, various condensed types Phosphorus ester compounds, phosphorus-based flame retardants such as phosphazene derivatives containing phosphorus and nitrogen elements; polytetrafluoroethylene and the like. These can be used in combination of two or more.

  Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium-based, molybdenum-based, zinc stannate, guanidine salt, silicone-based, and phosphazene-based compounds. These can be used in combination of two or more. Reactive flame retardants include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl polyacrylate) , Chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether and the like. These can be used in combination of two or more.

  The amount of the flame retardant is usually 1 to 30 parts by mass, preferably 3 to 25 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the component [A].

  In addition, when making the composition of this invention contain a flame retardant, it is preferable to use a flame retardant adjuvant. This flame retardant aid includes antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony tartrate and other antimony compounds, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, polyphosphorus Examples thereof include ammonium acid, tin oxide, and iron oxide. These can be used in combination of two or more. Moreover, in order to improve a flame retardance, a silicone oil can be mix | blended.

  Examples of the anti-aging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, and polyphenol compounds. Examples thereof include a compound, a thiobisphenol compound, a hindered phenol compound, a phosphite compound, an imidazole compound, a nickel dithiocarbamate salt compound, and a phosphate compound. These can be used in combination of two or more.

  The blending amount of the anti-aging agent is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the component [A]. is there.

  Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, and diisodecyl phthalate; Adipate, diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di -Fatty acid esters such as (2-ethylhexyl) sebacate and diisooctyl sebacate; trimellitic acid isodecyl ester, trimellitic acid oct Esters, trimellitic acid esters such as trimellitic acid n-octyl ester, trimellitic acid isononyl ester; di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinolate, trilauryl phosphate, tristearyl phosphate , Tri- (2-ethylhexyl) phosphate, epoxidized soybean oil, polyether ester and the like. These can be used in combination of two or more.

  The compounding amount of the plasticizer is usually 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component [A].

  Examples of the antibacterial agent include zeolite antibacterial agents such as silver zeolite and silver-zinc zeolite, silica gel antibacterial agents such as complexed silver-silica gel, glass antibacterial agents, calcium phosphate antibacterial agents, and zirconium phosphate antibacterial agents. Silicate antibacterial agents such as silver-magnesium aluminate, titanium oxide antibacterial agents, ceramic antibacterial agents, whisker antibacterial agents, etc .; formaldehyde releasing agents, halogenated aromatic compounds, Organic antibacterial agents such as road propargyl derivatives, thiocyanate compounds, isothiazolinone derivatives, trihalomethylthio compounds, quaternary ammonium salts, biguanide compounds, aldehydes, phenols, pyridine oxide, carbanilide, diphenyl ether, carboxylic acid, organometallic compounds; Organic hybrid antibacterial agent; Such as a natural antibacterial agent, and the like. These can be used in combination of two or more.

  The amount of the antibacterial agent is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component [A]. .

  Examples of the colorant include organic dyes, inorganic pigments, and organic pigments, and these can be used in combination of two or more.

  The composition of the present invention can be produced by charging the above raw material components at a predetermined ratio into an extruder, a Banbury mixer, a kneader, a roll, a feeder ruder, etc., and then kneading. The method of using the raw material components is not particularly limited, and the components may be mixed and then kneaded, or may be kneaded after being divided and mixed in multiple stages. The kneading temperature is selected according to the type of component [A].

  The composition of the present invention is excellent in thermal conductivity, and the thermal conductivity measured by the method described in the following test examples is usually 1 W / m · K or more, preferably 1 to 50 W / m · K, more preferably Is 3 to 45 W / m · K, particularly preferably 7 to 40 W / m · K. In addition, the composition of the present invention is excellent in radioactivity, and the emissivity measured by the method described in the following test examples is usually 0.65 to 0.99, preferably 0.70 to 0.98, more preferably. Is 0.75 to 0.97. Further, the composition of the present invention is excellent in electromagnetic shielding properties, and the electromagnetic shielding effect at a frequency of 100 MHz is usually 15 dB or more, preferably 15 to 60 dB, more preferably 20 to 55 dB.

<Toner case>
The toner case of the present invention is obtained by forming a box shape using the composition of the present invention, but it is not necessary to use the composition of the present invention on the entire surface of the toner case, and one surface of the toner case is made of another material. It may be configured. Furthermore, you may laminate | stack metal, such as aluminum and copper; General-purpose resin, such as other ABS resin, olefin resin, polycarbonate resin, polyamide resin, and polyester resin. The thickness of the toner case is not particularly limited, but is usually 1 to 7 mm, preferably about 2 to 5 mm. Examples of the toner case molding method include injection molding, extrusion molding (sheet extrusion, profile extrusion), two-color molding, hollow molding, compression molding, vacuum molding, foam molding, and blow molding.

  The molding temperature and the mold temperature are selected depending on the type of the component [A]. When the component [A] contains the rubber-reinforced vinyl resin (A1), the cylinder temperature at the time of molding is usually 220 to 300 ° C, preferably 230 to 280 ° C. The mold temperature is usually 70 to 90 ° C. When component [A] contains an olefin resin, the cylinder temperature during molding is usually 200 to 280 ° C, preferably 210 to 250 ° C. The mold temperature is usually 30 to 50 ° C. When component [A] contains a polyamide-based resin, the cylinder temperature during molding is usually 230 to 300 ° C, preferably 250 to 280 ° C. The mold temperature is usually 70 to 90 ° C. When component [A] contains a polyester resin, the cylinder temperature at the time of molding is usually 230 to 300 ° C, preferably 250 to 280 ° C. The mold temperature is usually 70 to 90 ° C. When the toner case is large, it is generally manufactured with the cylinder temperature set high.

  The present invention is carried out as described above, and the evaluation results for the composition of the present invention, which is a characteristic part of the present invention, are shown below. In addition, this invention is not limited to the following test examples, unless the summary is exceeded. In the following, parts and% are based on mass unless otherwise specified.

1. Raw material components of the heat conductive resin composition:
The raw material component used for manufacture of a heat conductive resin composition is shown below. The weight average particle diameter of the rubbery polymer; the ratio D ₈₀ / D ₂₀ of the particle diameters D ₂₀ and D ₈₀ when the weight average particle diameter and cumulative weight of the graphite particles are 20% and 80%, respectively. Was measured using a Nikkiso Co., Ltd. microtrack particle size distribution measuring apparatus “FRA type”. The aspect ratio of the graphite particles was calculated from an image obtained by an electron microscope (SEM) using the average values of the longest diameter and the shortest diameter of 100 particles. Further, the fixed carbon content of the graphite particles was measured according to JIS M8511.

<Thermoplastic resin (1): Diene rubber reinforced vinyl resin>
41.5% polybutadiene rubber obtained by emulsion polymerization of styrene and acrylonitrile in the presence of a latex containing polybutadiene rubber particles having a weight average particle diameter of 280 nm and a toluene insoluble content of 80% as a diene rubber polymer. A diene rubber-reinforced vinyl resin composed of 42.7% styrene unit and 15.8% acrylonitrile unit was used. The graft ratio of this resin is 55%, and the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the acetone-soluble component is 0.45 dl / g.

<Thermoplastic resin (2): Acrylonitrile styrene resin>
A copolymer having a styrene unit amount of 74.5% and an acrylonitrile unit amount of 25.5% was used. The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) is 0.60 dl / g.

<Thermoplastic resin (3): Polycarbonate resin>
“NOVAREX 7022PJ” (trade name) manufactured by Mitsubishi Engineering Plastics was used. The viscosity average molecular weight by GPC is 22,000.

<Thermoplastic resin (4): Block type polypropylene>
“NOVATEC BC6C” (trade name) manufactured by Nippon Polypro was used.

<Thermoplastic resin (5): polybutylene terephthalate>
“NOVADURAN 5007” (trade name) manufactured by Mitsubishi Engineering Plastics was used.

<Thermoplastic resin (6): Polyamide resin>
“NOVAMID 1013J” (trade name) manufactured by Mitsubishi Engineering Plastics was used.

<Elastomer: Maleic anhydride-modified ethylene / propylene copolymer>
“T7741P” (trade name) manufactured by JSR Corporation was used. The amount of acid modification by infrared spectroscopy is 0.5%, the density is 0.86 g / cm 3, and the MFR (temperature 23 ° C., load 2.16 kg) according to JIS K7210 is 1.0 g / 10 min.

<Graphite particles>
“HF-150A” (trade name) manufactured by Chuetsu Graphite Industries Co., Ltd. was used. The shape is scaly, the aspect ratio is 16, the weight average particle diameter is 161 μm, and the fixed carbon content is 99.8%. _{Further, D} 80 _/ D ₂₀ is 2.7.

<Magnesium oxide: Fused magnesia>
Water-resistant magnesium oxide (trade name “A-10”) manufactured by Kamishima Chemical Co., Ltd. (spherical, average particle size: 10 μm, BET specific surface area: 1.2 m ^{2 /} g, Dv: 14.2, Dv / Dn: 31.0)

<Boron nitride>
Showa Denko (trade name “UHP-EX”) (scale-like, average particle size: 50 μm)

<Antioxidant (1)>
Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenylpropionate) methane “Adekastab AO-60” (trade name) manufactured by Asahi Denka Kogyo Co., Ltd. was used.

<Antioxidant (1)>
Cyclic neopentanetetraylbis (2,6-di-tert-butyl-4-methylphenyl) phosphite “ADK STAB PEP-36” (trade name) manufactured by Asahi Denka Kogyo Co., Ltd. was used.

2. Evaluation items for thermally conductive resin composition:

(1) Moldability:
Molding workability was determined according to the criteria shown in Table 1 below, from the molding conditions of 55 mm long, 80 mm wide and 2.4 mm thick plate-shaped test pieces using an injection molding machine “NN30B type” manufactured by Niigata Iron Works. . The molding conditions of the test piece are as follows: when the thermoplastic resin (1) is used as the component [A], the cylinder temperature is 280 ° C., the mold temperature is 70 ° C., the injection pressure is 80%, and the thermoplastic resin (4 ), The cylinder temperature is 250 ° C., the mold temperature is 50 ° C., the injection pressure is 20%, and when the thermoplastic resins (5) and (6) are used, the cylinder temperature is 280 ° C. and the mold temperature is 70 ° C., injection pressure is 80%.

(2) Thermal conductivity:
The thermal conductivity is a value measured with respect to the flow direction of the composition at the time of molding the test piece. The thermal conductivity at 25 ° C. is measured using a laser flash method thermal constant measuring device “TR-7000R type” manufactured by ULVAC-RIKO. The rate was measured. The test piece is a disc having an inner diameter of 10 mm and a thickness of 1.5 mm.

(3) Emissivity:
It was measured at an ambient temperature of 25 ° C. by a reflection energy measurement method by infrared detection using a thermo spot sensor “TSS-5X type” manufactured by Japan Sensor. The test piece is a flat plate of 150 mm × 150 mm × 3 mm.

(4) Electromagnetic shielding properties:
Using the spectrum analyzers “R3361A type” and “TR17301 type” manufactured by Advantest Corporation, the electromagnetic wave reflectivity was measured at a frequency of 100 MHz, and the electromagnetic shielding property was evaluated. The test piece is a flat plate of 150 mm × 150 mm × 3 mm.

(5) Surface resistivity:
Depending on the resistance value, three types of resistivity meters shown in Table 2 below were used for measurement. The test piece is a disc having an inner diameter of 100 mm and a thickness of 2 mm, and the unit of resistance value is Ω.

(6) Charpy impact resistance:
Charpy impact strength (notched) was measured according to ISO 179. The unit is kJ / m ² .

(7) Bending modulus and bending strain:
In accordance with ISO178, using a precision universal testing machine “Autograph AG-10kNI type” manufactured by Shimadzu Corporation, the specimen was measured by a three-point bending strength measurement method with a span interval of 64 mm and a bending speed of 1 mm / min. . The size of the test piece is 127 mm × 10 mm × 4 mm.

(8) Hardness:
Rockwell hardness (R scale) was measured according to ISO 2039.

(9) Thermal deformation temperature:
It measured according to ISO75. The load is 1.80 MPa.

(10) Heating test:
In order to prevent the influence of convection in a room at a room temperature of 25 ° C., an acrylic resin cover having a height of 1 m and a width of 1 m is installed, and a polycarbonate (PC) frame member (as shown in FIG. Cubic boxes were formed by charging flat plates (2) (150 mm × 150 mm × 3 mm) to be used for evaluation on four surfaces (bottom surface, top surface, and both side surfaces) of the frame body configured in 1). Note that the front and rear surfaces of the cubic box are made of PC wall surfaces. Then, a silicon rubber heater (3) (100 mm × 100 mm × 1.7 mm) is installed at the center of the bottom of the cubic box, and the silicon rubber heater (3) is energized at a voltage of 40 V (32 W). The temperature at each measurement point on the four surfaces was measured. The measurement points are as shown in Table 3 below.

Test Examples 1-18 and Comparative Test Examples 1-4:
Each said raw material component was mixed by the Henschel mixer with the mixture ratio of Tables 4-7. Then, it melt-kneaded (cylinder temperature 240-280 degreeC) using the twin-screw extruder, and manufactured the pellet (heat conductive resin composition). Thereafter, the pellets are supplied to an injection molding machine “J100E type” manufactured by Nippon Steel Co., Ltd. under the conditions of a cylinder temperature of 240 to 280 ° C., a mold temperature of 70 ° C., an injection speed of 60 mm / second, and a holding pressure of 70 MPa. Test pieces for evaluation having a predetermined shape and size according to the evaluation items were prepared and subjected to various evaluations. The results are shown in Tables 5-8.

  From the comparison between the test examples and comparative test examples shown in Tables 4 to 7, the following is clear. That is, in Comparative Test Example 1 in which the heat conductive filler (B) specified in the present invention is not blended, the temperature of T2 is low because of low heat conductivity, and as a result, the surface temperature T3 of the silicon rubber heater is high. ing. Further, Comparative Test Examples 2 and 3 using aluminum and copper, respectively, have a high atmospheric temperature represented by T5 to T8, unlike the test examples using the heat conductive resin composition defined in the present invention. Comparative Test Example 4 using aluminum oxide is inferior in moldability.

External view of an example of a toner case provided with a conventionally known stirring mechanism Longitudinal cross-sectional explanatory diagram of the heat distortion test device

Explanation of symbols

1: Frame member made of polycarbonate (PC) 2: Flat plate for evaluation 3: Silicon rubber heater 11: Toner case 12: Lid 13: Container body 14: Gear 15: Shutter

Claims (8)

It consists of a thermoplastic resin [A] and any one or more heat conductive fillers [B] specified in the following (1) to (3), and a heat conductive filler [B] for 100 parts by mass of the thermoplastic resin [A]. The heat-dissipating toner case is characterized in that it is composed of a thermally conductive resin composition having a blending amount of 10 to 1,000 parts by mass.
(1) Graphite particles having an aspect ratio of 10 to 20, a weight average particle diameter of 10 to 200 μm, and a fixed carbon content of 98% by mass or more.
(2) The purity is 95.0% by mass or more, the BET specific surface area is 5.0 m ² / g or less, the volume average particle size (Dv) is 0.5 to 60 μm, and the volume average particle size (Dv) Magnesium oxide particles having a ratio Dv / Dn of 10 to 55 with the number average particle diameter (Dn).
(3) Boron nitride particles having a BET specific surface area of 0.05 to 10 m ² / g, a weight average particle diameter of 1 to 200 μm, and a scaly shape.   The toner case according to claim 1, wherein the graphite particles according to the above (1) have a scaly shape. The ratio D ₈₀ / D ₂₀ of the particle diameters D ₂₀ and D ₈₀ when the cumulative weights obtained by measuring the particle size distribution of the graphite particles described in (1) are 20% and 80%, respectively, is The toner case according to claim 1, wherein the toner case is 2 to 12.   The toner case according to any one of claims 1 to 3, wherein the magnesium oxide particles according to (2) are fused magnesia.   The toner case according to any one of claims 1 to 4, wherein 100 parts by mass of the magnesium oxide particles according to (2) are heat-treated with 0.1 to 10 parts by mass of an organosilicon compound.   The toner case according to claim 1, wherein the organosilicon compound is silicone oil.   7. The toner according to claim 1, wherein the magnesium oxide particles according to (2) have a water absorption of 1% by mass or less after being left for 8 days in an atmosphere having a temperature of 60 ° C. and a relative humidity of 90%. Case.   The thermoplastic resin [A] is a rubber-reinforced vinyl resin (A1) obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of the rubber polymer (a) or Selected from the group of rubber reinforced resin, polycarbonate resin, olefin resin, polyamide resin and polyester resin comprising a mixture of rubber reinforced vinyl resin (A1) and vinyl monomer (co) polymer (A2) The toner case according to claim 1, wherein the toner case is at least one kind of resin.