JP4778686B2 - Sliding polycarbonate resin composition and molded product thereof - Google Patents

Description

  The present invention relates to a slidable polycarbonate resin composition. More specifically, (i) the resin component is mainly composed of an aromatic polycarbonate resin and a small proportion is an acrylonitrile-styrene copolymer, (ii) mica and talc having a specific particle size as an inorganic filler, and ( iii) a resin composition comprising an organic phosphorus compound as a flame retardant, further comprising (iv) a fluorine-containing compound as an anti-drip agent, and (v) a polyolefin wax as a sliding agent, wherein (a) high rigidity and high strength Further, the present invention relates to a resin composition that can obtain a molded product having high dimensional accuracy, (b) has relatively good flame retardancy and heat resistance, and (c) has good sliding properties. The resin composition of the present invention is suitable for molded products such as chassis and frames to which mechanical parts represented by polyacetal gears, rollers, cams, latches, and the like are attached, and screw molded products for toner stirring. The present invention also relates to these molded articles formed from the resin composition.

  In recent years, for plastic materials used for chassis and frames of devices having optical system units, such as laser beam printers, copiers, and projector devices (hereinafter, these may be simply referred to as “optical unit chassis”). , High rigidity, high strength, high dimensional accuracy (low anisotropy), and good flame retardancy are required.

  The optical unit chassis is often formed with a shaft and a bearing, and mechanical parts such as gears, rollers, cams, and latches formed of a resin having good sliding characteristics represented by polyacetal are attached to such portions. Grease and oil are applied to the shaft and bearing parts in order to make the operation of the mechanical parts smoother and reduce wear of the parts and the mechanical parts. However, depending on the device, the possibility that such grease or oil may adversely affect the device is considered. For the purpose of non-use or significant reduction of grease or oil (hereinafter sometimes referred to as “grease-less”), improvement in the slidability of the shaft and the bearing itself is required. Further, a screw for stirring and transporting toner used in a laser beam printer or a copying machine (referred to herein as a “toner stirring screw”) is required to be as follows. That is, dimensional accuracy (especially there is no warpage in the axial direction), heat resistance (no deformation over time), surface condition (no filler coming off from the molded product surface), and slidability (smooth Smooth rotation and no generation of wear powder) is required.

  As a method for improving the sliding property of the polycarbonate resin, a method of blending a polytetrafluoroethylene resin is known. However, when polytetrafluoroethylene resin is blended with polycarbonate resin, there arises a problem that molding processability and impact strength are lowered. Polytetrafluoroethylene resin is also very expensive. As one method for solving such a problem, a method of blending a polyethylene resin with a polytetrafluoroethylene resin in a polycarbonate resin is known (see Patent Documents 1 and 2). It is known that a resin composition in which polyethylene wax is blended with an alloy of polycarbonate resin and ABS resin, and the resin composition has improved weld strength, impact resistance, and solvent resistance (see Patent Document 3). ). Further, a resin composition in which an alloy of polycarbonate resin and ABS resin is blended with a filler such as talc, a phosphorus flame retardant, and a sliding agent such as polytetrafluoroethylene, polyethylene wax, or silicone oil, and the resin composition It is known that objects have improved flame retardancy, rigidity, and slidability (see Patent Documents 4 and 5). However, in spite of the above knowledge, there are still insufficient materials for the chassis having the greaseless bearing and the toner stirring screw.

  Furthermore, a resin composition comprising a specific ratio of aromatic polycarbonate resin, acrylonitrile-styrene copolymer, mica, talc, and phosphate ester oligomer, and the resin composition has high rigidity, high strength, high dimensional system, good It is well known that it is suitable for chassis molded products that have flame retardancy and low mold wear properties, and particularly where cost reduction is important (see Patent Document 6). Further, according to this document, it is also known that a release agent can be blended in the composition. However, according to this document, the knowledge about the resin composition having excellent sliding properties while maintaining such good characteristics to some extent is not yet sufficiently known.

JP-A-48-40849 Japanese Patent Laid-Open No. 7-228763 JP 58-45251 JP-A-9-279006 JP-A-10-101920 WO03 / 080728 pamphlet

  The object of the present invention is to provide high rigidity, high strength, high dimensional accuracy (low anisotropy), good flame retardancy and heat resistance, particularly suitable for chassis molded products having greaseless bearings and screw molded products for toner stirring. Another object of the present invention is to provide a slidable polycarbonate resin composition that satisfies both the sliding characteristics and the balanced characteristics.

  As a result of intensive studies to achieve the above object, the present inventor, as a result, an aromatic polycarbonate resin and a specific proportion of acrylonitrile-styrene copolymer (AS resin) as a resin component, a mica having a specific particle diameter as an inorganic filler, More preferably, a resin composition comprising a combination of specific ratios of the mica and talc, an organic phosphorus compound as a flame retardant, a fluorine-containing anti-dripping agent, and a specific ratio of a polyolefin wax having a specific molecular weight has excellent sliding properties. As a result, it has been found that a molded product that can achieve the above-described problems can be obtained, and the present invention has been completed. As a result, a suitable composition of the present invention is a composition in which an appropriate amount of polyolefin wax as a sliding agent is blended with the resin composition described in Patent Document 6 above. As described in this document, mica having a specific particle size effectively contributes to rigidity and strength, and talc effectively acts on low mold wear and flame retardancy. However, it was surprising that the resin composition has a better sliding property than expected by blending the polyolefin wax into the resin composition.

The present invention provides (1) (A) aromatic polycarbonate resin (component A)
(B) Acrylonitrile-styrene copolymer (component B)
(C) Inorganic filler (C component)
(D) Organophosphorus compound flame retardant (D component)
(E) Fluorine-containing anti-dripping agent (E component)
(F) A slidable polycarbonate resin composition comprising a polyolefin wax (F component) having a molecular weight of 1,000 to 10,000 and satisfying the conditions (i) to (iii). It is such a thing.
(I) The total of the A component and the B component is 50 to 84% by weight, the B component is 1 to 20% by weight, the C component is 15 to 35% by weight, and the D component is 100% by weight in total of the A component to the D component. 1 to 15% by weight, and E component is 0.02 to 2 parts by weight and F component is 0.5 to 5 parts by weight per 100 parts by weight of A component to D component.
(Ii) A component is 75 to 95 parts by weight and B component is 5 to 25 parts by weight per 100 parts by weight of the total of A component and B component.
(Iii) C component is composed of mica (C-1 component) having an average particle size of 30 to 300 μm, or the mica (C-1 component) and talc (C-2 component), and a total of 100 of A component to D component The C-1 component per 10% by weight is 10 to 30% by weight and the C-2 component is 0 to 15% by weight, and the C-1 component is 50 to 50% per 100 parts by weight in total of the C-1 component and the C-2 component. 100 parts by weight.

  According to this configuration (1), a slidable polycarbonate resin composition in which the above problems are solved is provided.

  According to the present invention, there is further provided a slidable mechanism component comprising such a slidable polycarbonate resin composition, and the slidable mechanism component preferably comprises a shaft or bearing to which a mechanism component comprising polyacetal is attached. A chassis molded product having a toner, or a screw molded product for stirring a toner.

  According to the present invention, it has been found that particularly excellent sliding properties can be obtained when the average particle size of mica is small. Therefore, the more preferable average particle diameter of mica is 30 to 100 μm, more preferably 35 to 80 μm, and still more preferably 35 to 50 μm. On the other hand, when rigidity and impact strength are important, mica having an average particle diameter of 100 to 260 μm can be preferably selected. Furthermore, according to the present invention, it has been found that better slidability can be obtained when no rubber component is contained. Therefore, it is preferable that the resin composition of the present invention does not substantially contain a rubber component.

  Next, the resin composition of the present invention will be described in more detail. First, each component constituting the resin composition will be described.

<About resin components>
In the resin composition of the present invention, the resin component consists essentially of an aromatic polycarbonate resin (component A) and an acrylonitrile-styrene copolymer (component B). The B component acrylonitrile-styrene copolymer is generally referred to as an AS resin.

<About component A>
The A component aromatic polycarbonate resin (hereinafter sometimes simply referred to as “aromatic polycarbonate”) is a per se known one that has been conventionally used for various molded articles. That is, it is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  The aromatic polycarbonate resin may be various polycarbonate resins having a high heat resistance or a low water absorption rate, which are polymerized using other dihydric phenols, in addition to the commonly used bisphenol A type polycarbonate. The polycarbonate resin may be produced by any production method, and in the case of interfacial polycondensation, a terminal stopper of a monohydric phenol is usually used. The polycarbonate resin may also be a branched polycarbonate resin obtained by polymerizing trifunctional phenols, and further a copolymer obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a divalent aliphatic or alicyclic alcohol. Polycarbonate may be used. However, an aromatic polycarbonate resin made of a homopolymer of bisphenol A is particularly preferable in terms of excellent impact resistance. Details of the aromatic polycarbonate resin of the present invention are described in the pamphlet of WO 03/080728.

  Specific examples of the aromatic polycarbonate resin having a high heat resistance or a low water absorption rate, polymerized using other dihydric phenols, are preferably exemplified below.

(1) In 100 mol% of the dihydric phenol component constituting the polycarbonate, 4,4 '-(m-phenylenediisopropylidene) diphenol (hereinafter abbreviated as "BPM") component is 20 to 80 mol% (more preferable) 40 to 75 mol%, more preferably 45 to 65 mol%), and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as "BCF") component is 20 to 20 mol. Copolycarbonate which is 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the bisphenol A component is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%), And a BCF component in an amount of 5 to 90 mol% (more preferably 10 to 50 mol%, and still more preferably 15 to 40 mol%).
(3) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and The 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane component is 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%). Copolycarbonate.

  These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.

  The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

  As the A component aromatic polycarbonate resin of the present invention, not only virgin raw materials but also polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins can be used. Used products include soundproof walls, glass windows, translucent roofing materials, various glazing materials represented by automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, and optical recording media Etc. are preferred. These do not contain a large amount of additives or other resins, and the desired quality is easily obtained stably. In particular, an automotive headlamp lens, an optical recording medium, and the like are preferred as preferred embodiments because they satisfy the more preferable conditions of the viscosity average molecular weight. In addition, said virgin raw material is a raw material which is not yet used in the market after the manufacture.

  The viscosity average molecular weight of the A component aromatic polycarbonate resin is preferably in the range of 15,000 to 50,000. When the viscosity average molecular weight of the aromatic polycarbonate is less than 15,000, impact strength, flame retardancy and the like are likely to be lowered. On the other hand, if it exceeds 50,000, the fluidity is lowered, which is not preferable in the present invention. The lower limit of the viscosity average molecular weight is more preferably 16,000, still more preferably 17,000, and most preferably 18,000. The upper limit of the viscosity average molecular weight is more preferably 26,000, still more preferably 25,000, and most preferably 23,000. The aromatic polycarbonate having a viscosity average molecular weight in the above preferred range is excellent in balance between fluidity, strength, and heat resistance.

  The viscosity average molecular weight may be satisfied as the whole component A, and includes those satisfying such a range by a mixture of two or more kinds having different molecular weights. In particular, mixing of an aromatic polycarbonate having a viscosity average molecular weight exceeding 50,000 (more preferably 80,000 or more, more preferably 100,000 or more) may be advantageous in terms of increasing entropy elasticity at the time of melting. For example, it is effective for reducing jetting, gas injection molding, foam molding (including supercritical fluid), injection press molding, and improvement of drawdown. Therefore, the mixing of aromatic polycarbonates having a viscosity average molecular weight exceeding 50,000 is one of the preferred choices when these improvements are required and when these molding methods are applied. Such an effect becomes more prominent as the molecular weight of the aromatic polycarbonate is higher, but the upper limit of the molecular weight is practically 2 million, preferably 300,000, more preferably 200,000. It is preferable that the high molecular weight component is mixed in such an amount that the molecular weight distribution of two or more peaks can be observed in a measuring method such as GPC (gel permeation chromatography).

In the aromatic polycarbonate resin (component A) of the present invention, the amount of phenolic hydroxyl group is preferably 30 eq / ton or less, more preferably 25 eq / ton or less, and further preferably 20 eq / ton or less. Such a value can be substantially 0 eq / ton by sufficiently reacting the terminal terminator. The amount of the phenolic hydroxyl group is determined by performing ¹ H-NMR measurement, and calculating the molar ratio of the dihydric phenol unit having a carbonate bond, the divalent phenol unit having a phenolic hydroxyl group, and the terminal terminator unit. It is calculated | required by converting into the amount of phenolic hydroxyl groups per polymer weight based.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of aromatic polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C., and the specific viscosity calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

<About B component>
In the resin composition of the present invention, the B component, which is a resin component together with the A component, is an acrylonitrile-styrene copolymer, which is a resin usually called an AS resin. The proportion of each component (monomer) in this B component copolymer (AS resin) is 5 to 50% by weight, preferably 15 to 35% by weight, with respect to 100% by weight of the entire resin. The styrene is 95 to 50% by weight, preferably 85 to 65% by weight. The B component copolymer may be copolymerized with a small proportion of other copolymerizable vinyl compounds in addition to acrylonitrile and styrene. The copolymerization ratio of other vinyl compounds is 15% by weight or less, preferably 10% by weight or less in the component B. As the polymerization initiator or chain transfer agent used for the polymerization reaction of the component B, conventionally known ones can be used as necessary.

  Such component B (AS resin) may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, but is preferably produced by bulk polymerization or suspension polymerization. Most preferably, it is produced by a bulk polymerization method, and the polymerization method is the most common in the industry. The copolymerization method may be either one-stage copolymerization or multistage copolymerization. Moreover, as for the weight average molecular weight of this B component (AS resin), 40,000-200,000 are preferable in standard polystyrene conversion by GPC measurement. The lower limit is more preferably 50,000, and even more preferably 70,000. The upper limit is more preferably 160,000, further preferably 150,000.

<About component C>
The resin composition of the present invention is characterized by the use of mica having a specific particle size as an inorganic filler (component C), particularly by using a combination of the two types of mica and talc. ing.

  The average particle diameter of mica (C-1 component) in the inorganic filler is a number average particle diameter calculated by a total number of 1,000 indiscriminately observed with a scanning electron microscope. The number average particle diameter is 30 to 300 μm, preferably 30 to 100 μm, more preferably 35 to 80 μm, and still more preferably 35 to 50 μm. When importance is attached to rigidity and impact strength, mica having an average particle diameter of 100 to 260 μm can be selected. When the number average particle size is less than 30 μm, the impact strength is lowered. When the number average particle size is more than 300 μm, the impact strength is improved, but the sliding characteristics are deteriorated.

  As the thickness of mica, one having a thickness measured by electron microscope observation of 0.01 to 10 μm, preferably 0.1 to 5 μm can be used. An aspect ratio of 5 to 200, preferably 10 to 100 can be used. The mica used (C-1 component) is preferably mascobite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite, and solves the problems of the present invention at a higher level.

  In addition, as a method for pulverizing mica, a dry pulverization method of pulverizing raw mica ore with a dry pulverizer, and coarsely pulverizing mica rough ore with a dry pulverizer, followed by adding a grinding aid such as water in a slurry state There is a wet pulverization method in which main pulverization is performed by a wet pulverizer, followed by dehydration and drying. The mica of the present invention can be produced by any pulverization method, but the dry pulverization method is generally lower in cost. On the other hand, the wet pulverization method is effective for pulverizing mica more thinly and finely, but is expensive. Mica may be surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes, and further granulated with sizing agents such as various resins, higher fatty acid esters, and waxes to form granules. May be.

Talc (component C-2) used as an inorganic filler is a scaly particle having a layered structure, which is hydrous magnesium silicate in terms of chemical composition, and generally has a chemical formula of 4SiO ₂ .3MgO. It is represented by 2H ₂ O and is usually composed of about 56 to 65% by weight of SiO ₂ , 28 to 35% by weight of MgO, and about 5% by weight of H ₂ O. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less, the specific gravity is about 2.7, and the Mohs hardness is 1. The average particle diameter of talc is preferably 0.5 to 30 μm. The average particle size is a particle size at a 50% stacking rate obtained from the particle size distribution measured by the Andreazen pipette method measured according to JIS M8016. The particle diameter of talc is preferably 2 to 30 μm, more preferably 2 to 20 μm. Good flame retardancy is achieved in the range of 0.5 to 30 μm.

  In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).

  Further, talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.

<About D component>
The resin composition of the present invention contains an organic phosphorus compound-based flame retardant (component D) as a flame retardant. By using an organic phosphorus compound-based flame retardant (component D), not only good flame retardancy of a molded product can be achieved by a relatively small blending ratio, but also rigidity (flexural modulus) can be improved, Further, the specific gravity can be reduced as compared with the halogen-based flame retardant. In addition, the low melt viscosity of the resin composition based on the plasticizing effect also has the effect of reducing the wear of the mold surface, and the good surface smoothness achieved as a result contributes to the improvement of the sliding characteristics.

  Examples of the organic phosphorus compound-based flame retardant of component D of the present invention include one or more phosphate compounds represented by the following general formula (i).

上記式中のＸは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトン、ビス（４−ヒドロキシフェニル）サルファイドから誘導される二価の基であり、ｎは０〜５の整数であり、またはｎ数の異なるリン酸エステルの混合物の場合は０〜５の平均値であり、Ｒ^１１、Ｒ^１２、Ｒ^１３、およびＲ^１４はそれぞれ独立して１個以上のハロゲン原子を置換したもしくは置換していないフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノール、ｐ−クミルフェノールから誘導される一価の基である。

X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4 -Hydroxyphenyl) divalent group derived from sulfide, n is an integer of 0-5, or an average value of 0-5 in the case of a mixture of phosphoric acid esters with different numbers of n, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol substituted or unsubstituted with one or more halogen atoms. Is a valent group.

More preferably, X in the above formula is a divalent group derived from hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, j, k, l and m are each 1 and n is 1 In the case of a blend of phosphoric acid esters having different numbers of n as a main component, and R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently 1 It is a monovalent group derived from phenol, cresol or xylenol which is substituted or more preferably substituted with at least one halogen atom.

  The D component organophosphorus compound has a 5% weight loss temperature of 280 ° C. or higher when the temperature is raised from 23 ° C. in a nitrogen gas atmosphere to 600 ° C. at a rate of temperature increase of 20 ° C./min. Those are preferred. The weight reduction temperature is more preferably 320 ° C. or higher, further preferably 330 ° C. or higher, and particularly preferably 340 ° C. or higher. The upper limit of the weight reduction temperature is generally 380 ° C. or lower and is generally available, and 370 ° C. or lower is more appropriate. An organophosphorus compound having a relatively high weight reduction temperature as described above is preferred in that it can impart good heat resistance (such as good deflection temperature under load) to the resin composition as the melt viscosity of the resin composition decreases.

  Among the phosphoric acid esters of the above formula, phosphoric acid ester oligomers mainly composed of resorcinol bis (dixylenyl phosphate), phosphoric acid ester oligomers mainly composed of 4,4-dihydroxydiphenyl bis (dixylenyl phosphate), and bisphenol A phosphoric acid ester oligomer mainly composed of A bis (diphenyl phosphate) is preferable (here, the main component means that it may contain a small amount of other components having different degrees of polymerization, and more preferably the above formula (i ) In which n = 1 is contained in an amount of 80% by weight or more, more preferably 85% by weight or more, and still more preferably 90% by weight or more.

  Furthermore, from the same point, as component D, phosphazene polymers represented by phenoxyphosphazene oligomers and cyclic phenoxyphosphazene oligomers can also be preferably used.

<About E component>
The resin composition of the present invention contains a fluorine-containing anti-dripping agent (E component). By including this fluorine-containing anti-dripping agent (E component), good flame retardancy can be achieved without impairing the physical properties of the molded product.

  Examples of the fluorine-containing anti-drip agent for component E include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoro). Propylene copolymer, etc.), partially fluorinated polymers as disclosed in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

  PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.

  Examples of commercially available PTFE having such fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L from Daikin Industries, Ltd. Commercially available PTFE aqueous dispersions include Asahi IC Fluoropolymers' full-on AD-1, AD-936, Daikin Kogyo's full-on D-1 and D-2, Mitsui Dupont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation.

  As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and a vinyl monomer is further polymerized in the mixture dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Examples of commercially available PTFE in a mixed form include “Metablene A3000” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

  As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved. In addition, the ratio of the said E component shows the quantity of a net fluorine-containing dripping inhibitor, and in the case of mixed form PTFE, it shows a net PTFE quantity.

<About F component>
The polyolefin wax (F component) used in the present invention is an ethylene homopolymer having a molecular weight of 1,000 to 10,000, a homopolymer or copolymer of an α-olefin having 3 to 60 carbon atoms, or It is a copolymer of ethylene and an α-olefin having 3 to 60 carbon atoms. Such molecular weight is a number average molecular weight measured by GPC (gel hermization chromatography) method. The upper limit of the number average molecular weight of the F component of the present invention is more preferably 6,000, and still more preferably 3,000. If the molecular weight is less than 1,000, the properties of the wax are insufficient. On the other hand, if the molecular weight exceeds 10,000, it is difficult to move to the surface of the molded product, and thus the slidability tends to be insufficient. Further, when the molecular weight exceeds 10,000, the appearance is likely to deteriorate. A molded article having excellent appearance, impact strength and weld strength can be obtained by the polyolefin wax having the molecular weight range.

  Such GPC measurement was performed in a clean air environment at a temperature of 23 ° C. and a relative humidity of 50%, Shodex AC800P and (Shodex K-805L × 2) as a column, chloroform as a mobile phase, standard polystyrene as a standard substance, and a detector. As a measurement method, a GPC measurement apparatus comprising a differential refractometer is used, chloroform is used as a developing solvent, and the column temperature is 40 ° C. and the flow rate is 1 ml / min.

  The carbon number of the α-olefin component in the F component is preferably 60 or less, more preferably 40 or less. More preferred specific examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. A more preferable F component of the present invention is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 60 carbon atoms. Here, the proportion of the α-olefin having 3 to 60 carbon atoms in the polymer is preferably 20 mol% or less, more preferably 10 mol% or less, based on 100 mol% of all the structural units of the polymer. It is. What is marketed as what is called a polyethylene wax can be used suitably as F component of this invention.

Moreover, in F component, the molecular weight distribution as shown by weight average molecular weight / number average molecular weight is preferably in the range of 1 to 10, more preferably 1.2 to 5, and still more preferably 1.5 to 4. If the molecular weight distribution is too wide, low molecular weight components tend to cause defects such as stickiness on the surface of the molded product. The density is preferably in the range of 0.880 to 0.965 g / cm ³ . The lower limit is preferably 0.890, more preferably 0.920. Higher density tends to be advantageous in terms of sliding characteristics at high loads. The melting point is preferably in the range of 80 to 135 ° C, more preferably in the range of 100 to 130 ° C. The degree of branching of the F component is not particularly limited. The polyolefin wax of the F component may be a mixture of two or more kinds, and a polar group such as an acidic functional group, an ester bond-containing functional group, and an epoxy group may be introduced. A preferable level of such an introduction amount is, for example, an acidic functional group, an acid value (JIS K5902) of 20 mgKOH / g or less (more preferably 10 mgKOH / g or less, and further preferably 2 mgKOH / g or less). It is preferable that other functional groups have the same content.

  The polyolefin wax of component F can be produced by a known method, and is produced by a polymerization method such as solution polymerization, slurry polymerization, and gas phase polymerization using a known Ziegler catalyst, Phillips catalyst, or metallocene catalyst. be able to. Further, the F component can also be produced by thermally decomposing a high molecular weight polyolefin produced by such a production method, or by separating and purifying the low molecular weight component.

<About the amount of each component>
Next, the amount of the A component to the F component constituting the resin composition of the present invention will be described. In the resin composition of the present invention, the total amount of aromatic polycarbonate resin (A component) and acrylonitrile-styrene copolymer (B component; AS resin), which are resin components, is the A component, B component, C component, and D component. The total amount is 50% by weight or more, preferably 60% by weight or more per 100% by weight. The upper limit of the total amount of the component A and the component B is 84% by weight, preferably 80% by weight, more preferably 76% by weight. The ratio of both the A component and the B component is 75 to 95 parts by weight of the A component and 5 to 25 parts by weight of the B component per 100 parts by weight of the total of the A and B components. It is -92 weight part and B component is 8-22 weight part.

  Inorganic filler (component C), that is, the total content of component C-1 and component C-2 is 15 to 35% by weight, preferably 20 to 30% by weight per 100% by weight of components A to D %. In such a total ratio, the C-1 component is 10 to 30% by weight (preferably 15 to 25% by weight) and the C-2 component is 0 to 15% by weight per 100% by weight of the total of the A component to the D component. Preferably, it is 2 to 10% by weight. Further, among these contents, in relation to the C-1 component and the C-2 component, the C-1 component is 50 to 100 parts by weight per 100 parts by weight of the total of the C-1 component and the C-2 component. It is necessary to satisfy that (preferably 60 to 92 parts by weight).

  The organophosphorus compound (D component) is 1 to 15% by weight, preferably 3 to 10% by weight, and more preferably 3 to 8% by weight per 100% by weight of the total of the A component to D component. The fluorine-containing anti-dripping agent (component E) is 0.02 to 2 parts by weight, preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight, per 100 parts by weight of component A to component D. More preferably, it is 0.15-0.8 weight part. The polyolefin wax (F component) for imparting slidability is preferably 0.5 to 3 parts by weight, more preferably 1 to 3 parts by weight per 100 parts by weight in total of the A component to the D component.

  If the amount of the resin is less than the lower limit of the A component and the B component, or the amount of the filler or flame retardant is larger than the upper limit of the C component or D component, the strength of the resin composition is insufficient. To come. On the other hand, when the amount exceeds the upper limit of the A component and B component, or exceeds the upper limit of the C component and D component and the amount of the filler or flame retardant is small, rigidity and dimensional accuracy (when there are few inorganic fillers), Alternatively, either the thermal stability during molding or the flame retardancy (when the phosphorus compound is small) becomes insufficient. When the fluorine-containing anti-dripping agent is insufficient, the flame retardancy is insufficient, and when it exceeds the above range, the weld strength and moldability are adversely affected. Furthermore, when the polyolefin wax is less than the above range, the effect of improving the slidability is insufficient, and when too much exceeds the above range, the flame retardancy and weld strength are adversely affected. . Furthermore, in the inorganic filler, a suitable resin molded product in which mica and talc having a specific particle size are combined in the above relationship is excellent in rigidity, strength, dimensional accuracy, flame retardancy, and slidability. It becomes like this.

  The resin component of the resin composition of the present invention substantially comprises an A component and a B component. However, as long as the object of the present invention is not impaired, a small amount of other resins may be contained. Such other resin is suitably 5 parts by weight or less, more preferably 3 parts by weight or less, per 100 parts by weight of the total of components A to D. Examples of the thermoplastic resin other than the A component and the B component include, for example, a polyethylene resin and a polypropylene resin (excluding the resin of the F component), a polyalkyl methacrylate resin, a polyacetal resin, a polyalkylene terephthalate resin, a polyamide resin, and a cyclic polyolefin resin. , Polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate), various thermoplastic polyimides represented by polyetheretherketone, polyetherimide, polyamideimide, polysulfone, polyethersulfone, polyphenylene sulfide, etc. be able to.

  Furthermore, the slidable polycarbonate resin composition of the present invention can contain a small amount of a rubbery polymer. The ratio is suitably 1.5 parts by weight or less, more preferably 1.3 parts by weight or less, still more preferably 1 part by weight or less with respect to 100 parts by weight of the total of the A component to D component. . Such a rubbery polymer is a polymer composed of a rubber component having a glass transition temperature of 10 ° C. or less, preferably −10 ° C. or less, more preferably −30 ° C. or less, and a polymer composed of the rubber component and other polymers. A copolymer formed by bonding polymer chains. Such a copolymer formed by combining other polymer chains is a more preferable rubbery polymer.

More specifically, as the rubbery polymer, SB (styrene-butadiene) polymer, ABS (
Acrylonitrile-butadiene-styrene polymer, MBS (methyl methacrylate-butadiene-styrene) polymer, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) polymer, MB (methyl methacrylate-butadiene) polymer, ASA (acrylonitrile-styrene) -Acrylic rubber) polymer, AES (acrylonitrile-ethylene propylene rubber-styrene) polymer, MA (methyl methacrylate-acrylic rubber) polymer, MAS (methyl methacrylate-acrylic rubber-styrene) polymer, methyl methacrylate-acrylic butadiene Examples include rubber copolymers, methyl methacrylate-acrylic / butadiene rubber-styrene copolymers, and methyl methacrylate- (acrylic / silicone IPN rubber) polymers. Rukoto can. Any of these polymers is preferably a core-shell type graft copolymer in which a polymer chain composed of the above monomer is bonded to a polymer core composed of a rubber component.

  The rubbery polymer of the present invention may be in a form contained in other components. Examples of such a rubbery polymer include an ABS copolymer contained in the ABS resin (the other polymer contained in the ABS resin is an AS copolymer, that is, the B component).

  Examples of the flame retardant other than the organic phosphorus compound of component D in the present invention include a red phosphorus flame retardant, a halogen flame retardant, a silicone flame retardant, and a metal salt flame retardant. However, in the present invention, those containing substantially only the D component as the flame retardant are suitable.

  The resin composition of the present invention includes heat stabilizers, antioxidants, ultraviolet absorbers, mold release agents (other than the F component), antistatic agents, foaming agents, dyes and pigments (especially carbon black, titanium oxide, etc.) ) Etc. can also be blended.

(I) Heat stabilizer It is preferable that various heat stabilizers are further blended mainly for the purpose of improving the heat stability during the molding process of the resin composition of the present invention, and phosphorus stabilizers are used as such heat stabilizers. Is preferred. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Such phosphorus stabilizers can be used alone or in combination of two or more.

  Specifically, as the phosphite compound, for example, a trialkyl phosphite such as tridecyl phosphite, a dialkyl monoaryl phosphite such as didecyl monophenyl phosphite, a monoalkyl diaryl phosphite such as monobutyl diphenyl phosphite, Triaryl phosphites such as triphenyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol Such as diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Intererythritol phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite and 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4- Examples include cyclic phosphites such as (di-tert-butylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, and diisopropyl phosphate. Triphenyl phosphate and trimethyl phosphate.

  Preferred examples of the phosphonite compound include tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite. Tetrakis (2,4-di-tert More preferred are -butylphenyl) -biphenylene diphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
An example of the tertiary phosphine is triphenylphosphine.

  The blending amount of the phosphorus stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and more preferably 0.002 to 100 parts by weight based on a total of 100 parts by weight of component A to component D 0.3 parts by weight is more preferable.

(Ii) Antioxidant An antioxidant may be blended mainly for the purpose of improving the thermal stability and heat aging resistance during molding of the slidable polycarbonate resin composition of the present invention. Such an antioxidant is preferably a hindered phenol stabilizer. Examples of the hindered phenol stabilizer include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3′-tert-butyl-5 ′). -Methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl) -4-hydroxy-5-methylphenyl) propionate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl } -2,4,8,10-tetraoxaspiro [5,5] undecane, N, N′-hexamethylenebis- (3,5 Di-tert-butyl-4-hydroxyhydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and tetrakis [ And methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane. All of these are readily available. Of these, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferably used. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types. The blending amount of these antioxidants is preferably 0.0001 to 0.05 parts by weight with respect to 100 parts by weight of the total of A component to D component.

(Iii) Ultraviolet Absorber Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, cyclic imino ester compounds, and cyanoacrylate compounds known as ultraviolet absorbers. More specifically, for example, 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl) Butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl ] -4-methyl-6-tert-butylphenol, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2,2′-p-phenylenebis (3,1-benzoxazine-4 − ), And 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane Is exemplified. Further, hindered amine light stabilizers typified by bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and the like Can also be used. As for the compounding quantity of this ultraviolet absorber and light stabilizer, 0.01-5 weight part is preferable with respect to a total of 100 weight part of A component-D component.

(Iv) Antistatic agent Examples of the antistatic agent include polyether ester amide, glycerin monostearate, naphthalenesulfonic acid formaldehyde highly condensate alkali (earth) metal salt, dodecylbenzenesulfonic acid alkali (earth) metal salt, Examples include dodecylbenzenesulfonic acid ammonium salt, dodecylbenzenesulfonic acid phosphonium salt, maleic anhydride monoglyceride, and maleic anhydride diglyceride. The blending amount of the antistatic agent is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight as a total of the A component to the D component.

  In the slidable polycarbonate resin composition of the present invention, the above-mentioned components are mixed simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, and extruder. Can be manufactured. Preferably, melt kneading with a twin-screw extruder is preferred, and at that time, the C component is preferably fed into the molten resin component from the second feed port using an apparatus such as a side feeder. Usually, the strand extruded from the extruder die is cooled through a water tank, and the cooled strand is cut with a pelletizer to obtain pellets made of the resin composition. Examples of means used for premixing the raw materials include premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. Extrusion granulators, briquetting machines, and the like as necessary Granulation of the pre-mixture obtained by the above can be performed.

  The composition thus obtained can be easily molded by a known method such as injection molding, extrusion molding, compression molding, or rotational molding, and in particular, a high-precision chassis such as a precision instrument can be molded by injection molding. Is possible. At that time, in order to achieve higher accuracy, it is possible to combine injection compression molding and molding with a heat insulating mold, etc., and also use gas assist molding etc. in combination for weight reduction and distortion reduction. Is possible.

  As described above, according to the present invention, there is provided a slidable polycarbonate resin composition having excellent rigidity, dimensional accuracy, and strength, and having sliding characteristics. The slidable polycarbonate resin composition of the present invention is suitable for a molded product such as a chassis or a frame to which mechanical parts represented by polyacetal gears, rollers, cams, latches and the like are attached. Such a molded article comprising the resin composition is provided. Such chassis include OA-related equipment such as laser beam printers, copiers, and projector devices, precision equipment such as mobile phones and cameras, medical equipment such as massage machines and high oxygen therapy equipment, image recorders (so-called DVD recorders, etc.) ), Household appliances such as audio equipment and electronic musical instruments, gaming machines such as pachinko machines and slot machines, and chassis and frames of household robots equipped with precision sensors. Furthermore, the resin composition of the present invention is suitable for a toner stirring screw. Since the resin composition of the present invention has high rigidity, the screw is hardly twisted during stirring, and the toner can be reliably stirred and transported. Furthermore, it has excellent dimensional accuracy and little warpage, so it has excellent shaft center accuracy and achieves smooth rotation of the screw. Further, since the sliding characteristics and the surface characteristics are good, it is possible to suppress as much as possible the mixing of the scraped powder and the falling powder of the filler from the surface into the toner along with the smooth rotation. Furthermore, since the heat resistance is also excellent, the above-mentioned characteristics are maintained without deformation of the screw during long-term use. Therefore, according to the present invention, there is provided a toner agitation screw molded product comprising the slidable polycarbonate resin composition of the present invention and having excellent properties as described above.

  From the above, the slidable polycarbonate resin composition of the present invention is useful for various applications such as various electronic / electric equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, transport containers, playground equipment, and miscellaneous goods, Its industrial effect is exceptional.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

The following examples further illustrate the present invention.
[Examples 1 to 5 and Comparative Examples 1 to 3]
Among the components listed in Table 1, components other than inorganic fillers (C-1 component, C-2 component and comparative inorganic filler) were mixed in a V-type blender to prepare a mixture. In addition, the E component is prepared by putting a preliminary mixture with the A component (PC) whose content is 10% by weight into a polyethylene bag, shaking the bag and stirring, Mixed. Using a bent type twin screw extruder (Nippon Steel Works TEX-30XSST) with a screw diameter of 30 mm, the mixture mixed in the V-type blender was fed from the first input port at the end, and also with an inorganic filler (C- 1 component, C-2 component and comparative inorganic filler) are supplied from the second supply port in the middle of the cylinder at a predetermined ratio using a side feeder, and a vacuum pump is used. Under a vacuum of 3 kPa, the mixture was melt-extruded at a cylinder temperature of 270 ° C. and pelletized. However, the D component (FR-2) of Examples 1 to 3 and Comparative Example 3 was heated in the middle of the cylinder using a liquid injection device (HYM-JS-08 manufactured by Fuji Techno Industry Co., Ltd.) while being heated to 80 ° C. (Between the first supply port and the second supply port) was supplied to the extruder at a predetermined ratio.

  The obtained pellets were dried with a hot air circulation dryer at 100 ° C. for 6 hours, and unless otherwise specified in the description of the following evaluation items, an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.). The test piece for evaluation was created at a cylinder temperature of 260 ° C. and a mold temperature of 70 ° C., and evaluated by the following evaluation method.

(1) Mechanical properties of slidable polycarbonate resin composition (i) Rigidity: Flexural modulus was measured according to ASTM D-790 (test piece dimensions: length 127 mm × width 12.7 mm × thickness 6.4 mm).
(Ii) Heat resistance: The deflection temperature under load was measured at 1.82 MPa load according to ASTM D-648 (test piece dimensions: length 127 mm × width 12.7 mm × thickness 6.4 mm).
(Iii) Flammability: A combustion test was performed in accordance with UL standard 94V. (Test specimen thickness 1.6mm)
(Iv) Sliding property: A reciprocating friction and wear tester AFT-15M manufactured by Orientec Co., Ltd. was used as an evaluation device. A pin-shaped test piece shown in FIG. 2 was prepared by injection molding from a polyacetal resin (“TENAC LD755” (trade name) manufactured by Asahi Kasei Corporation). Such a test piece was mounted on a fixed test piece holder of the testing machine. On the other hand, a flat test piece having a length of 150 mm, a width of 150 mm, and a thickness of 2 mm was prepared from the resin compositions of Examples and Comparative Examples (a gate is a fin gate having a width of 40 mm and a thickness of 1 mm from one end of the side) by injection molding. The part was cut into a length of 50 mm and a width of 100 mm, and the cut specimen was fixed on a pedestal that reciprocated.

  The molding conditions for the flat specimen are as follows. That is, injection molding machine: SG-150U manufactured by Sumitomo Heavy Industries, Ltd., cylinder temperature: 260 ° C., mold temperature: 40 ° C. (temperature applied by the refrigerant through the chiller unit), filling time: 1.0 second The holding pressure was 58.8 MPa, the holding pressure time was 3 seconds, and the cooling time was 12 seconds. Such a flat test piece uses a surface roughness meter Surfcom 1400A manufactured by Tokyo Seimitsu Co., Ltd. before evaluation of sliding surface properties, and the surface roughness (Ra value: center plane average value) of the flat test piece before measurement. Was 1.5 μm or less.

  The cylindrical surface of the pin-shaped test piece and the plane normal direction of the flat test piece are parallel to the flat surface portion of the cutting test piece of the flat test piece. In this state, contact was made with a load of 9.8 N applied. Under such a contact state, a distance of 25 mm one way was reciprocated 1,000 times on a straight line in a plane at a rate of 2 seconds per reciprocation in an atmosphere of 23 ° C. and relative humidity 50% RH. Furthermore, the friction force was measured by applying a load to a load cell having a capacity of 49 N connected to the pin-shaped test piece side. The coefficient of dynamic friction after 1000 operations was determined from the friction force after 1000 operations.

  Further, after the test, the wear cross section of the pin-shaped test piece was observed with a video microscope (manufactured by Keyence Corporation) capable of image analysis, and the radius (μm) of the circular cross section caused by the wear was measured and used as an index of the wear amount.

(2) Composition component of slidable polycarbonate resin composition Symbols indicating each component described in Table 1 are as follows.
(A component)
PC-1: aromatic polycarbonate resin (aromatic polycarbonate resin powder having a viscosity average molecular weight of 19,700 made from bisphenol A and phosgene by a conventional method, “Panlite L-1225WX” (trade name) manufactured by Teijin Chemicals Ltd.) )
PC-2: Aromatic polycarbonate resin (Aromatic polycarbonate resin powder having a viscosity average molecular weight of 15,400 made from bisphenol A and phosgene by a conventional method, “Panlite CM-1000” (trade name) manufactured by Teijin Chemicals Ltd.) )

(B component)
AS-1: Acrylonitrile-styrene copolymer ("STAREX HF5670 (trade name)" manufactured by Daiichi Kori Co., Ltd., weight average molecular weight in terms of standard polystyrene by GPC measurement: 95,000, acrylonitrile component content: 28.5 (Wt%, styrene component content: 71.5 wt%)
AS-2: Acrylonitrile-styrene copolymer ("Litac-A BS-218" (trade name) manufactured by Nippon A & L Co., Ltd.), weight average molecular weight in terms of standard polystyrene by GPC measurement: 78,000, acrylonitrile component content: 26 wt%, styrene component content: 74 wt%)

(C component)
MICA-1: Mascobite with an average particle size of about 250 μm (“MC-40” (trade name) manufactured by Hayashi Kasei Co., Ltd.)
MICA-2: Mascobite with an average particle size of about 40 μm (“Kuralite Mica 300D” (trade name) manufactured by Kuraray Co., Ltd.)
TALC: Talc (Katsumiyama Mining Company “Victorylite SG-A” (trade name), stacking ratio 50%, particle size: 15.2 μm, Hunter whiteness measured according to JIS M8016: 90.2%, pH: 9.8 and Mohs hardness: 1)
(Comparative component with C component)
GF: Glass fiber (“ECS T-511” (trade name) manufactured by Nippon Electric Glass Co., Ltd.)

(D component)
FR-1: resorcinol bis (dixylenyl phosphate) (Adeka Stub FP-500 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd., TGA 5% weight reduction temperature = 351.0 ° C.)
FR-2: phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (“CR-741” (trade name) manufactured by Daihachi Chemical Industry Co., Ltd., TGA 5% weight reduction temperature = 335.9 ° C.)

(E component)
PTFE: Polytetrafluoroethylene having a fibril forming ability (“Polyflon MPA FA500” (trade name) manufactured by Daikin Industries, Ltd.)

(F component)
PE: Polyolefin wax having a number average molecular weight of 1,510 (“High Wax 310MP” (trade name) manufactured by Mitsui Chemicals, Inc., weight average molecular weight / number average molecular weight = 3.36, density = 0.94)
(Ingredient for comparison with F component)
WE: Montanic acid ethylene glycol ester (manufactured by Clariant Japan KK; Licolub WE-1 (trade name))

(Other ingredients)
ABS: acrylonitrile-styrene-butadiene copolymer (“Clarastic S-3710” (trade name) manufactured by Nippon A & L Co., Ltd., polybutadiene content 50% by weight)
CB: Carbon Black Master (“ROYALBLACK904S” (trade name) manufactured by Koshigaya Kasei Co., Ltd., polystyrene resin master containing 40% carbon black)

  As is apparent from the above table, the slidable polycarbonate resin composition of the present invention has high rigidity, high strength, high dimensional accuracy, good flame retardancy, and excellent sliding characteristics. . Further, in the resin compositions of Examples 1 to 5, a chassis molded product having a bearing portion (the polyacetal and the bearing portion are in direct contact) for attaching a polyacetal roller is molded, and the operation of the roller is good. A chassis molded product was obtained. Further, a toner agitation screw molded product shown in FIG. 1 was molded from the resin compositions of Examples 1 to 5 and the resin composition of Comparative Example 2. Although a good screw molded product was obtained from the resin composition of the example, the screw molded product manufactured from the resin composition of the comparative example was warped in the axial direction, and a good product was not obtained.

  The slidable polycarbonate resin composition of the present invention is suitable for molded products such as chassis and frames to which mechanical parts represented by polyacetal gears, rollers, cams, latches, etc. are attached, and screw molded products for toner stirring. is there. However, the resin composition of the present invention can be used in various ways by taking advantage of its properties in addition to such uses and the uses described above. For example, it is useful for products having a long shape such as a guide for a sash window and having a sliding portion, and products requiring high dimensional accuracy and sliding resistance such as a compressor rotor and screws.

The toner stirring screw molded product molded in the examples is shown (partially omitted). The gate is a one-point gate at the left end of the drawing. [2-A] It is a top view which shows the shape of the pin-shaped test piece for sliding surface property evaluation used for evaluation. [2-B] It is a front view which shows the shape of the pin-shaped test piece for sliding surface property evaluation used for evaluation. The hemispherical portion at the tip comes into contact with the opposing flat test piece.

Explanation of symbols

11 Screw molded product body (450mm)
12 Flight part (mountain diameter 10mm, valley diameter 6mm, pitch 6mm)
13 Shaft portion 21 Pin-shaped test piece body 22 for evaluating sliding surface property Pin-shaped test piece pin portion (tip diameter 5 mmφ hemisphere)
23 A base for wearing the wear tester holder 24 Notch for wearing the wear tester holder 25 Pin-shaped test piece pin diameter (5mm)
26 Base diameter (10mm)
27 Gate (width 1mm, length 1.5mm)
28 Pin-shaped specimen pin height (5mm)
29 Pedestal height (14.5mm)
30 Notch length (10mm)
31 Notch allowance (0.5mm)
32 Chamfering at the bottom (C1.0)

Claims (4)

(A) Aromatic polycarbonate resin (component A)
(B) Acrylonitrile-styrene copolymer (component B)
(C) Inorganic filler (C component)
(D) Organophosphorus compound flame retardant (D component)
(E) Fluorine-containing anti-dripping agent (E component)
(F) a polyolefin wax (F component) having a molecular weight of 1,000 to 10,000, and
A slidable polycarbonate resin composition comprising a rubber polymer and these components satisfy the conditions (i) to (iii).
(I) The total of component A and component B is 50 to 84% by weight, component C is 15 to 35% by weight, component D is 1 to 15% by weight per 100% by weight of the total of component A to component D, and E component is 0.02 to 2 parts by weight per 100 parts by weight of A component to D component, F component is 0.5 to 5 parts by weight , and rubbery polymer is 0.5 parts by weight or less .
(Ii) A component is 75 to 95 parts by weight and B component is 5 to 25 parts by weight per 100 parts by weight of the total of A component and B component.
(Iii) C component is composed of mica (C-1 component) having an average particle size of 30 to 300 μm, or the mica (C-1 component) and talc (C-2 component), and a total of 100 of A component to D component The C-1 component per 10% by weight is 10 to 30% by weight and the C-2 component is 0 to 15% by weight, and the C-1 component is 50 to 50% per 100 parts by weight in total of the C-1 component and the C-2 component. 100 parts by weight.   A slidable mechanism component comprising the slidable polycarbonate resin composition according to claim 1.   The slidable mechanism part according to claim 2, wherein the slidable mechanism part is a chassis molded product having a shaft or a bearing to which a mechanism part made of polyacetal is attached.   The slidable mechanism component according to claim 2, wherein the slidable mechanism component is a toner agitated screw molded product.

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