JP6373201B2 - Resin molded body for toilet equipment obtained by molding flame retardant polycarbonate resin composition - Google Patents

Description

  The present invention relates to a resin molded body for a toilet device obtained by molding a flame retardant polycarbonate resin composition. More specifically, a polycarbonate resin and a polypropylene resin are graft copolymerized with a styrene thermoplastic elastomer, and a butadiene rubber polymer core with an aromatic vinyl monomer and a (meth) acrylate monomer. Addition of core-shell type graft copolymer, halogenated carbonate compound, antimony oxide compound, and polytetrafluoroethylene-based mixture consisting of polytetrafluoroethylene particles and organic polymer, mechanical properties, chemical resistance, flame retardant The present invention relates to a resin molded body for a toilet device obtained by molding a flame retardant polycarbonate resin composition having improved properties, workability, and appearance.

  In general, an ABS resin or a polypropylene resin (PP resin) is used as a resin composition of a resin molded body for a toilet device. ABS resin has processability because it has a small molding shrinkage and dimensional tolerance, but has a problem that it has poor chemical resistance, particularly chemical resistance to household or commercial detergents. Therefore, it is used as a resin molded body of a member that does not require much chemical resistance in the toilet apparatus. Polypropylene resins, on the other hand, have chemical resistance, particularly chemical resistance to household or commercial detergents, but have a drawback of poor workability due to large molding shrinkage and dimensional tolerances. Therefore, it is used as a resin molded body of a member that requires high chemical resistance in a toilet device. Therefore, in recent years, as a resin composition of a resin molded body for a toilet device, a resin composition having a small molding shrinkage ratio, small dimensional tolerance, processability, chemical resistance, and mechanical properties. It has been demanded.

  Polycarbonate resins have excellent mechanical and thermal properties, and are therefore widely used in various fields such as the OA equipment field, the electronic and electrical equipment field, and the automobile field. However, polycarbonate resin has poor workability due to its high melt viscosity, and since it is an amorphous resin, it has difficulty in chemical resistance, particularly for household or commercial detergents. For this reason, it is known to add a polyolefin resin to compensate for these drawbacks, but simple addition has low compatibility between the polycarbonate resin and the polyolefin resin, resulting in delamination and the like, and sufficient mechanical properties. Since it is difficult to obtain, it is in a poor state of practical use.

  Accordingly, various resin compositions have been proposed in order to enhance the compatibility of the polycarbonate resin and the polyolefin resin and to provide practical mechanical properties.

  For example, a method in which an elastomer graft-modified with a hydroxyl group-containing vinyl monomer is added as a compatibilizing agent (see Patent Documents 1 and 2), or a polypropylene modified with a hydroxyl group-containing vinyl monomer is used as a compatibilizing agent. A method using an ethylene-α-olefin copolymer composed of the above α-olefin as an impact resistance agent (see Patent Documents 3 and 4), a method using a terminal carboxylated polycarbonate resin and an epoxidized polypropylene resin (see Patent Document 5) ), A method using a terminal carboxylated polycarbonate resin and a maleic anhydride-modified polypropylene resin (see Patent Document 6), a method of adding a styrene-ethylene-butylene-styrene block copolymer as a compatibilizing agent (see Patent Document 7) Styrene-ethylene / propylene-styrene copolymer Although there is a method of adding it (see Patent Document 8), none of them has achieved both chemical resistance that exceeds the practical range of polycarbonate and mechanical properties that can withstand practical use comparable to PC / ABS.

  In addition, regarding flame retardant formulations, many flame retardant formulations for polycarbonate resins and polypropylene resins have been reported, but flame retardant for resin compositions containing both polycarbonate resins and polypropylene resins. There are few examples to give. Among them, a method of adding a phosphorus-based flame retardant and a fluorine-containing polymer has been proposed (see Patent Document 9), but the present situation is that the chemical resistance and mechanical properties at a high level have not been achieved at the same time.

JP-A-7-330972 JP-A-8-134277 JP 2005-132937 A JP 54-53162 A JP-A-63-215750 Japanese Unexamined Patent Publication No. 63-215752 Japanese Patent Laid-Open No. 5-17633 JP 2000-17120 A JP 2012-41415 A

  In view of the above, an object of the present invention is a resin for a toilet device obtained by molding a flame retardant polycarbonate resin composition that satisfies excellent mechanical properties, chemical resistance, processability, flame retardancy and appearance at a high level. It is to provide a molded body.

  As a result of intensive studies to solve the above problems, the present inventors have found a method for obtaining a flame retardant polycarbonate resin composition satisfying the above problems at a high level, and have completed the present invention.

  According to the present invention, the above-mentioned problem is (A) 60 to 90 parts by weight of polycarbonate resin (component A) and (B) 10 to 40 parts by weight of polypropylene resin (component B), C) 3-15 parts by weight of a styrene-based thermoplastic elastomer (component C), (D) graft copolymerization of an aromatic vinyl monomer and a (meth) acrylate monomer on a butadiene-based rubber-like polymer core 1 to 10 parts by weight of a core-shell type graft copolymer (D component), (E) 1 to 20 parts by weight of a halogenated carbonate compound (E component), (F) 0.5 to 10 parts by weight of an antimony oxide compound (F component) Part and (G) a polytetrafluoroethylene mixture (G component) comprising 0.01 to 3 parts by weight of a polytetrafluoroethylene-based mixture composed of polytetrafluoroethylene particles and an organic polymer It is achieved by the toilet apparatus resin molded body obtained by molding the fat composition.

Details of the present invention will be described below.
(A component: polycarbonate resin)
The polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization 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.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of excellent toughness and deformation characteristics, and is widely used.

  In the present invention, in addition to the general-purpose polycarbonate bisphenol A-based polycarbonate, a special polycarbonate produced using other dihydric phenols can be used as the A component.

  For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
(1) 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 A copolymeric polycarbonate in which the BCF component is 20 to 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 BPA component is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%), and A copolymeric polycarbonate in which the BCF component is 5 to 90 mol% (more preferably 10 to 50 mol%, 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 Copolymer polycarbonate in which the Bis-TMC component is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

  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.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

  Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

  As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing a polycarbonate resin by interfacial polymerization of the above dihydric phenol and carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc., as necessary. May be used. The polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. And a copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  The branched polycarbonate resin increases the melt tension of the resin composition of the present invention, and can improve the molding processability in extrusion molding, foam molding and blow molding based on such properties. As a result, a molded product by these molding methods, which is superior in dimensional accuracy, is obtained. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2,4,6- Trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1 , 1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4- {4- [1,1- Trisphenol such as bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol is preferably exemplified. Other polyfunctional aromatic compounds include phloroglucin, phloroglucid, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene. And trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4- Hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is preferably in a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. Is 0.03 to 1 mol%, more preferably 0.07 to 0.7 mol%, particularly preferably 0.1 to 0.4 mol%.

Further, such a branched structural unit is not only derived from a polyfunctional aromatic compound but also derived without using a polyfunctional aromatic compound, such as a side reaction during a melt transesterification reaction. Also good. The ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

  The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and linear saturated aliphatic dicarboxylic acids such as icosanedioic acid, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as acids. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

  Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  The reaction forms such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymer, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are various documents and patent publications. This is a well-known method.

In producing the resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.4 × 10 ^4. a to 3 × 10 ^4, more preferably from ^{1.4 × 10 4 ~2.4 × 10 4} . A polycarbonate resin having a viscosity average molecular weight of less than 1 × 10 ⁴ may not provide practically sufficient toughness and crack resistance. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ generally has a low versatility because a high molding temperature is required or a special molding method is required. A high molding process temperature tends to cause deterioration of deformation characteristics and rheological characteristics of the resin composition.

The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above value (5 × 10 ⁴ ) increases the melt tension of the resin composition of the present invention, and molding in extrusion molding, foam molding and blow molding based on such characteristics. Processability can be improved. Such an improvement effect is even better than the branched polycarbonate. As a more suitable aspect, the A component is a polycarbonate resin (A-3-1 component) having a viscosity average molecular weight of 7 × 10 ⁴ to 2 × 10 ^{6, and} a polycarbonate resin having a viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ Polycarbonate resin (A-3 component) consisting of (A-3-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ (hereinafter, “high molecular weight component-containing polycarbonate resin”) May also be used).

In such a high molecular weight component-containing polycarbonate resin (A-3 component), the molecular weight of the A-3-1 component is preferably 7 × 10 ^{4 to} 3 × 10 ⁵ , more preferably 8 × 10 ⁴ to 2 × 10 ⁵ , preferably ^{1 × 10 5 ~2 × 10 5} , particularly preferably ^{1 × 10 5 ~1.6 × 10 5} . The molecular weight of the A-3-2 component is preferably 1 × 10 ^{4 to} 2.5 × 10 ⁴ , more preferably 1.1 × 10 ^{4 to} 2.4 × 10 ⁴ , and still more preferably 1.2 × 10 ^4. to 2.4 × 10 ^4, particularly preferably ^{1.2 × 10 4 ~2.3 × 10 4} .

  The high molecular weight component-containing polycarbonate resin (component A-3) can be obtained by mixing the components A-3-1 and A-3-2 in various proportions and adjusting them so as to satisfy a predetermined molecular weight range. . Preferably, in 100% by weight of the A-3 component, the A-3-1 component is 2 to 40% by weight and the A-3-2 component is 60 to 98% by weight, more preferably the A-3-1 component is 5 to 20% by weight and the A-3-2 component is 80 to 95% by weight. Usually, the molecular weight distribution of the polycarbonate resin is in the range of 2-3. Therefore, it is preferable that the A-3-1 component and the A-3-2 component of the present invention satisfy the molecular weight distribution range. The molecular weight distribution is represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated by GPC (gel permeation chromatography) measurement. And Mw is based on standard polystyrene conversion.

  In addition, as a method for preparing the A-3 component, (1) a method in which the A-3-1 component and the A-3-2 component are independently polymerized and mixed, and (2) JP-A-5-306336. The method of producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method, represented by the method shown in Japanese Patent Publication No. Gazette, in the same system, the aromatic polycarbonate resin of the present invention A- Examples include a method for producing a component satisfying the conditions of one component, a method for mixing a polytetrafluoroethylene-based mixture resin with a separately produced A-3-1 component and / or A-3-2 component, and the like. Can do.

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 polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C., with a specific viscosity (η _SP ) 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 viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.

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
The calculation of the viscosity average molecular weight in the resin composition of the present invention is performed as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

(B component: polypropylene resin)
The resin composition of the present invention contains a polypropylene resin as the B component. Polypropylene resin is a polymer of propylene, but in the present invention, it also includes copolymers with other monomers. Examples of the polypropylene resin of the present invention include a homopolypropylene resin, a block copolymer of propylene, ethylene, and an α-olefin having 4 to 10 carbon atoms (also referred to as “block polypropylene”), propylene, ethylene, and 4 to 4 carbon atoms. 10 random copolymers with α-olefin (also referred to as “random polypropylene”). “Block polypropylene” and “random polypropylene” are also collectively referred to as “polypropylene copolymer”.

  In the present invention, one or more of the above-mentioned homopolypropylene resin, block polypropylene, and random polypropylene may be used as the polypropylene resin, and among them, homopolypropylene and block polypropylene are preferable.

  Examples of the α-olefin having 4 to 10 carbon atoms used for the polypropylene copolymer include 1-butene, 1-pentene, isobutylene, 3-methyl-1-butene, 1-hexene, and 3,4-dimethyl-1. -Butene, 1-heptene, 3-methyl-1-hexene are included.

  The content of ethylene in the polypropylene copolymer is preferably 5% by mass or less in all monomers. The content of the α-olefin having 4 to 10 carbon atoms in the polypropylene copolymer is preferably 20% by mass or less in all monomers.

  The polypropylene copolymer is preferably a copolymer of propylene and ethylene or a copolymer of propylene and 1-butene, and particularly preferably a copolymer of propylene and ethylene.

  The melt flow rate (230 ° C., 2.16 kg) of the polypropylene resin in the present invention is preferably 0.1 to 5 g / 10 min, more preferably 0.2 to 4 g / 10 min, and 0.3 to 3 g / 10 min is particularly preferable. If the melt flow rate of the polypropylene resin is less than 0.1 g / 10 min, the moldability is inferior due to high viscosity, and if it exceeds 5 g / 10 min, sufficient toughness may not be exhibited. The melt flow rate is also called “MFR”. In addition, MFR was measured based on ISO1133.

  The composition ratio of the polycarbonate-based resin (component A) and the polypropylene-based resin (component B) in the resin composition of the present invention is 100 parts by weight in total, and the component A is 60 to 90 parts by weight, preferably 62. 0.5 to 80 parts by weight, more preferably 65 to 75 parts by weight, and B component is 10 to 40 parts by weight, preferably 20 to 37.5 parts by weight, more preferably 25 to 35 parts by weight. When the component A is less than 60 parts by weight, strength and rigidity are not sufficiently exhibited, and further, dimensional tolerance and molding shrinkage ratio are increased, and workability is lowered. On the other hand, when it exceeds 90 parts by weight, the chemical resistance is deteriorated and the density is also increased.

(C component: Styrenic thermoplastic elastomer)
The resin composition of the present invention contains a styrenic thermoplastic elastomer as the C component. The styrenic thermoplastic elastomer used in the present invention is preferably a block copolymer represented by the following formula (I) or (II).
X- (Y-X) n (I)
(XY) n (II)
X in the general formulas (I) and (II) is an aromatic vinyl polymer block, and in the formula (I), the degree of polymerization may be the same or different at both ends of the molecular chain. Y represents a butadiene polymer block, an isoprene polymer block, a butadiene / isoprene copolymer block, a hydrogenated butadiene polymer block, a hydrogenated isoprene polymer block, a hydrogenated butadiene / isoprene copolymer. It is at least one selected from a polymer block, a partially hydrogenated butadiene polymer block, a partially hydrogenated isoprene polymer block, and a partially hydrogenated butadiene / isoprene copolymer block. N is an integer of 1 or more.

  Specific examples include styrene-ethylene / butylene-styrene copolymers, styrene-ethylene / propylene / styrene copolymers, styrene / ethylene / ethylene / propylene / styrene copolymers, and styrene / butadiene / butene / styrene copolymers. Styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-hydrogenated butadiene diblock copolymer, styrene-hydrogenated isoprene block copolymer, styrene-butadiene diblock copolymer, Examples include styrene-isoprene diblock copolymers, among which styrene-ethylene / butylene-styrene copolymers, styrene-ethylene / propylene / styrene copolymers, styrene / ethylene / ethylene / propylene / styrene copolymers, Styrene-Butaji Down - butene - styrene copolymer are most preferred.

  The content of the X component in the block copolymer is 20 to 80% by weight, preferably 30 to 75% by weight, more preferably 40 to 70% by weight. If this amount is less than 20% by weight, the rigidity and impact strength of the resin composition are lowered, and if it exceeds 80% by weight, the impact strength may be lowered.

  The weight average molecular weight of the styrenic thermoplastic elastomer is preferably 250,000 or less, more preferably 200,000 or less, and further preferably 150,000 or less. When the weight average molecular weight exceeds 250,000, the moldability is lowered, and the dispersibility in the polycarbonate resin composition may be deteriorated. The lower limit of the weight average molecular weight is not particularly limited, but is preferably 40,000 or more, more preferably 50,000 or more. The weight average molecular weight was measured by the following method. That is, the molecular weight was measured in terms of polystyrene by gel permeation chromatography, and the weight average molecular weight was calculated. The melt flow rate (230 ° C., 2.16 kg) of the styrenic thermoplastic elastomer in the present invention is preferably 0.1 to 10 g / 10 min, more preferably 0.15 to 9 g / 10 min, 0 It is particularly preferably 2 to 8 g / 10 min. If the melt flow rate of the styrenic thermoplastic elastomer is less than 0.1 g / 10 min and exceeds 10 g / 10 min, sufficient toughness may not be exhibited. MFR was measured at 230 ° C. and 2.16 kg load according to ISO1133.

  Content of C component is 3-15 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 4-14 weight part, More preferably, it is 5-13 weight part. When the content is less than 3 parts by weight, impact strength and chemical resistance are deteriorated and appearance of the molded product is deteriorated. When the content exceeds 15 parts by weight, rigidity and flame retardancy are deteriorated.

(D component: core-shell type graft copolymer obtained by graft copolymerization of aromatic vinyl monomer and (meth) acrylic acid ester monomer to butadiene rubber polymer core)
The resin composition of the present invention contains a core-shell type graft copolymer obtained by graft copolymerizing an aromatic vinyl monomer and a (meth) acrylic acid ester monomer to a butadiene rubber-like polymer core as a D component. To do. The graft copolymer that can be used in the present invention is a core-shell type graft copolymer obtained by graft copolymerizing an aromatic vinyl monomer and a (meth) acrylic acid ester monomer to a butadiene rubber-like polymer core. If it is, it will not restrict | limit in particular, For example, the graft copolymer manufactured by well-known methods, such as an emulsion polymerization method, a micro suspension polymerization method, a miniemulsion polymerization method, can be used. Among these, a graft copolymer produced by an emulsion polymerization method can be suitably used because the structure can be easily controlled. The butadiene rubber-like polymer in the graft copolymer is a copolymer of a polybutadiene rubber polymer or a butadiene monomer and a vinyl monomer or monomer mixture copolymerizable therewith. Although it will not be restrict | limited especially if it is a copolymer, It is preferable that the ratio of the butadiene in a butadiene-type rubber-like polymer is 50 weight% or more from a viewpoint of the impact strength provision of a composition. The aromatic vinyl monomer and (meth) acrylic acid ester monomer used for forming the shell in the graft copolymer are introduced into the polymerization system all at once or graft-polymerized according to a known method. Just do it. When two or more aromatic vinyl monomers and (meth) acrylic acid ester monomers are used, they may be added separately or in advance according to a known method. Examples of the aromatic vinyl monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene, but are not limited thereto. Absent. In addition, these can be used suitably individually or in combination of 2 or more types. Examples of the (meth) acrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethyl methacrylate. Examples include, but are not limited to, methacrylic acid alkyl esters such as hexyl, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate and the like. Is not to be done. These may be used alone or in combination of two or more. In the present invention, (meth) acryl means acryl and / or methacryl unless otherwise specified. After polymerization of the graft copolymer, a phenol-based, sulfur-based, hindered amine-based antioxidant or the like can be used as necessary. Such polymers are commercially available and can be easily obtained. Kaneace M series (M-701, M-721, etc.) manufactured by Kaneka Co., Ltd., and Metabrene C series (C) manufactured by Mitsubishi Rayon Co., Ltd. -223A, etc.) and E series (E-860A, etc.).

  The content of component D is 1 to 10 parts by weight, preferably 1.5 to 7.5 parts by weight, more preferably 2 to 6 parts by weight, based on 100 parts by weight of the total of component A and component B. is there. When the content is less than 1 part by weight, mechanical properties and chemical resistance are lowered, and when it exceeds 10 parts by weight, rigidity and flame retardancy are lowered.

(E component: halogenated carbonate compound)
The resin composition of the present invention contains a halogenated carbonate compound as the E component. As the halogenated carbonate compound, a halogenated carbonate compound having a structural unit represented by the following formula (1) of at least 60 mol% of all structural units and a specific viscosity of 0.015 to 0.1 is preferably used.

In Expression (1), X is a bromine atom, R represents an alkylene group having 1 to 4 carbon atoms, an alkylidene group or -SO ₂ 1 to 4 carbon atoms - a. ]
In the formula (1), R preferably represents a methylene group, an ethylene group, an isopropylidene group, —SO ₂ —, and particularly preferably an isopropylidene group.

  The brominated polycarbonate has a small number of remaining chloroformate groups and preferably has a terminal chlorine content of 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine is determined by dissolving a sample in methylene chloride, adding 4- (p-nitrobenzyl) pyridine and allowing it to react with terminal chlorine (terminal chloroformate). -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition becomes better, and molding at a higher temperature becomes possible, and as a result, a resin composition having better molding processability is provided.

  The brominated polycarbonate preferably has a small number of remaining hydroxyl terminals. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less with respect to 1 mol of the structural unit of brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving a sample in deuterated chloroform and measuring it by 1H-NMR method. Such a terminal hydroxyl group amount is preferable because the thermal stability of the polycarbonate resin composition is further improved.

  The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the above-described specific viscosity calculation formula used for calculating the viscosity average molecular weight of the polycarbonate resin which is the component A of the present invention.

  Such halogenated carbonate compounds are commercially available, and examples thereof include tetrabromobisphenol A carbonate oligomers (trade names FG-7000 and FG-8500) manufactured by Teijin Limited, and these can be used in the present invention. it can.

  Content of E component is 1-20 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 5-20 weight part, More preferably, it is 5-15 weight part. When the content of the E component is less than 1 part by weight, sufficient flame retardancy cannot be obtained, and when it exceeds 20 parts by weight, the mechanical properties, chemical resistance, and the like are greatly reduced.

(F component: antimony oxide compound)
The resin composition of the present invention contains an antimony oxide compound as the F component. The antimony oxide compound functions to increase the flame retardancy of the composition by a synergistic effect with the halogenated carbonate compound (E component). Examples of the antimony oxide compound include antimony trioxide, antimony tetraoxide, antimony pentoxide represented by (NaO) p · (Sb ₂ O ₅ ) · qH ₂ O (p = 0 to 1, q = 0 to 4), and Sodium antimonate can be used. The antimony oxide compound is preferably used as particles having a particle size of 0.02 to 5 μm.
The content of the component F is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the total of the component A and the component B. When the content is less than 0.5 parts by weight, the flame retarding effect of the composition due to the synergistic action with the halogenated carbonate compound (component E) is small, and when it exceeds 10 parts by weight, the mechanical properties of the composition are deteriorated.

(G component: polytetrafluoroethylene mixture comprising polytetrafluoroethylene particles and organic polymer)
The resin composition of the present invention contains a polytetrafluoroethylene mixture composed of polytetrafluoroethylene particles and an organic polymer as a G component. By including the polytetrafluoroethylene mixture composed of the polytetrafluoroethylene particles and the organic polymer, good flame retardancy can be achieved without impairing the physical properties of the molded product. The polytetrafluoroethylene-based mixture used in the present invention has a particle diameter of 10 μm or less, specifically, polytetrafluoroethylene particles and organic system in which the polytetrafluoroethylene is not an aggregate having a particle diameter exceeding 10 μm. It preferably consists of a polymer. Furthermore, from the viewpoint of dispersibility when blended with a thermoplastic resin, an aqueous polytetrafluoroethylene particle dispersion (G1) having a particle diameter of 0.05 to 1.0 μm and an aqueous organic polymer particle dispersion (G2) It is preferable to use a polymer obtained by polymerizing the vinyl monomer (g2) and then pulverizing it by coagulation or spray drying. The aqueous polytetrafluoroethylene particle dispersion (G1) having a particle size of 0.05 to 1.0 μm used for obtaining the polytetrafluoroethylene-based mixture according to the present invention is obtained by emulsion polymerization using a fluorine-containing surfactant. It is obtained by polymerizing a fluoroethylene monomer. Fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkyl vinyl ether as copolymerization components in the emulsion polymerization of polytetrafluoroethylene particles as long as the properties of polytetrafluoroethylene are not impaired. Fluorine-containing alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate can be used. The content of the copolymer component is preferably 10% by weight or less with respect to tetrafluoroethylene. Commercially available raw materials for the polytetrafluoroethylene particle dispersion (G1) include: Fullon AD-1 and AD-936 manufactured by Asahi Glass Fluoropolymer, Polyflon D-1 and D-2 manufactured by Daikin Industries, Ltd., and Mitsui DuPont Fluorochemical A typical example is Teflon (registered trademark) 30J. The organic polymer particle aqueous dispersion (G2) used for obtaining the polytetrafluoroethylene-based mixture according to the present invention is obtained by polymerizing the vinyl monomer (g1) by a known method such as emulsion polymerization. be able to. The vinyl monomer (g1) and the vinyl monomer (g2) may be the same or different, and are not particularly limited, but are dispersed when blended with the polycarbonate resin (component A). From the viewpoint of properties, it is preferable that the affinity with the polycarbonate resin (component A) is high. Specific examples of these vinyl monomers (g1) and (g2) include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, p-chlorostyrene, Aromatic vinyl monomers such as o-chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, methacryl Ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, acrylic Acid cyclohexyl (Meth) acrylic acid ester monomers such as cyclohexyl methacrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as maleic anhydride; N-phenylmaleimide, N- Maleimide monomers such as methylmaleimide and N-cyclohexylmaleimide; Epoxy group-containing monomers such as glycidyl methacrylate; Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; Carboxylic acids such as vinyl acetate and vinyl butyrate Examples include vinyl monomers; α-olefin monomers such as ethylene, propylene, and isobutylene; and diene monomers such as butadiene, isoprene, and dimethylbutadiene. These monomers can be used alone or in admixture of two or more. Among these monomers, one or more selected from the group consisting of an aromatic vinyl monomer and a vinyl cyanide monomer is preferable from the viewpoint of affinity with the polycarbonate resin (component A). And a monomer containing 30% by weight or more of the above monomer. Particularly preferred are one or more monomers selected from the group consisting of styrene and acrylonitrile, and even more preferred are monomers containing 30% by weight or more of acrylonitrile. The content of polytetrafluoroethylene in the polytetrafluoroethylene-based mixture used in the present invention is preferably 1% by weight to 70% by weight, more preferably 5% by weight to 60% by weight, Most preferred is 20% to 55% by weight. If it is less than 1% by weight, the flame retardancy improving effect becomes insufficient, and if it exceeds 70% by weight, the surface appearance may be adversely affected. The polytetrafluoroethylene-based mixture used in the present invention is prepared by pouring the aqueous dispersion into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salting out, solidifying, and drying. It can also be converted. While ordinary polytetrafluoroethylene fine powder becomes an aggregate of 100 μm or more in the process of recovering as a powder from the state of a particle dispersion, it is difficult to uniformly disperse it in a thermoplastic resin. The polytetrafluoroethylene mixture used in the present invention is extremely excellent in dispersibility with respect to the polycarbonate resin (component A) because the polytetrafluoroethylene alone does not form a domain having a particle diameter exceeding 10 μm. . As a result, in the polycarbonate resin composition of the present invention, polytetrafluoroethylene is efficiently made into fine fibers in the polycarbonate, and the flame retardancy is excellent, and the surface properties and impact characteristics are also excellent. A polytetrafluoroethylene-based mixture composed of such polytetrafluoroethylene particles and an organic polymer is commercially available and can be easily obtained. [For example, “Metablene A3800” and “Metablene A3750” (trade name) of Mitsubishi Rayon Co., Ltd.]

  Content of G component is 0.01-3 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 0.05-1 weight part, More preferably, it is 0.2-1. Parts by weight. If the G component exceeds the above range and is too small, the flame retardancy becomes insufficient. On the other hand, when the G component exceeds the above range and is too much, polytetrafluoroethylene is deposited on the surface of the molded product, resulting in poor appearance as well as an increase in the cost of the resin composition.

(Other additives)
Moreover, the composition of this invention can add various well-known additives as needed, and as a ratio of various additives, it is inorganic filling with respect to a total of 100 weight part of A component and B component. Agent, organic filler is 1-50 parts by weight, antioxidant, heat stabilizer, light stabilizer, lubricant, antistatic agent is 0.1-5 parts by weight, inorganic or organic colorant (titanium oxide, Carbon black) is 0.01 to 5 parts by weight.

(Manufacture of thermoplastic resin composition)
Arbitrary methods are employ | adopted in order to manufacture the thermoplastic resin composition of this invention. For example, the A component to the G component and optionally other additives are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, an extrusion mixer, and then extruded granulated as necessary. There is a method of granulating such a premixed mixture using a vessel or a briquetting machine, then melt-kneading with a melt-kneader represented by a vent type twin screw extruder, and then pelletizing with a pelletizer.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method of premixing components other than the component A in advance and then mixing the components with the thermoplastic resin of the component A or supplying them directly to the extruder. As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

  As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

  Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

(Regarding the resin molded body for toilet apparatus obtained by molding the resin composition of the present invention)
The resin composition in the present invention can be produced by injection molding the pellets obtained by the above-described method, and producing various types of resin moldings for toilet devices. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded body can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, the resin composition in this invention can also be used in the form of various profile extrusion molding, a sheet | seat, a film, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can be formed into a molded body by rotational molding, blow molding, vacuum molding, or the like.

  The resin molded body for toilet apparatus of the present invention satisfies excellent mechanical properties, chemical resistance, processability, flame retardancy and appearance at a high level. Since these characteristics are not present in the prior art, the industrial effects exerted are extremely great.

It is the schematic of the toilet seat which is the resin molding for toilet apparatuses created in the Example.

  The form of the invention that the present inventor considers to be the best is an aggregation 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. Unless otherwise specified, parts in the examples are parts by weight, and% is% by weight. Evaluation was carried out by the following method.
(Evaluation of polycarbonate resin composition)
(I) Appearance The appearance of ISO tensile test pieces and UL test pieces obtained by the following method was visually evaluated. The evaluation was performed according to the following criteria.
◎: Appearance is particularly good ○: Appearance failure is not seen △: Flow mark from the gate side is slightly generated ×: Appearance failure such as flow mark from the gate side is strongly generated (Ii) Chemical resistance After applying 1% strain by the three-point bending test method using the ISO tensile test piece obtained by the following method, bath magiclin and toilet magiclin (all Kao Corporation )) And a fabric impregnated with the product), and allowed to stand at 23 ° C. for 96 hours. The evaluation was performed according to the following criteria.
○: No change in appearance Δ: Some occurrence of fine cracks ×: Large cracks leading to breakage (iii) Flexural modulus ISO bending test obtained by the following method The flexural modulus was measured according to ISO 178 using the piece.

(Iv) Charpy impact strength According to ISO 179, the Charpy impact strength with a notch was measured according to ISO 179 using the ISO bending test piece obtained by the following method.
(V) Flame retardancy Using the UL test piece obtained by the following method, a V test was performed according to UL94.
(Vi) Mold Shrinkage The test specimen for molding shrinkage obtained by the following method was left for 24 hours in an atmosphere of 23 ° C. and 50% relative humidity. The dimension of the square plate after standing was measured with a three-dimensional measuring machine (manufactured by Mitutoyo Corporation), and the molding shrinkage in the direction perpendicular to the flow (TD) and the flow (TD) of the resin was calculated by the following formula.
Mold shrinkage (%) = {(die size−square plate size) / die size)} × 100
(Vii) Dimensional tolerance Dimensional tolerances of the overall length (431.5 mm), full width (365 mm), and hinge height (75.05 mm) of the toilet seat (FIG. 1), which is a resin molded body for a toilet device obtained by the following method. Measurements were performed.

[Examples 1-18, Comparative Examples 1-15]
The mixture which consists of a component except the polypropylene resin of B component with the composition shown in Comparative Examples 1-13 of Table 1 and Table 2 was supplied from the 1st supply port of the extruder. Such a mixture was obtained by mixing with a V-type blender. B component polypropylene resin was supplied from the second supply port using a side feeder. Extrusion is performed using a vent type twin screw extruder (Nippon Steel Works TEX30α-38.5BW-3V) with a diameter of 30 mmφ and melt kneading at a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vacuum degree of the vent of 3 kPa. Pellets were obtained. In addition, about extrusion temperature, it implemented at 270 degreeC from the 1st supply port to the die part.

Further, as the flame retardant ABS resin (ABS resin) shown in Comparative Examples 14 and 15 in Table 2, F5450W manufactured by Technopolymer Co., Ltd. and flame retardant polypropylene resin (PP resin) 8803R manufactured by Idemitsu Lion Composite Co., Ltd. were used.
Part of the pellets obtained in the compositions shown in Comparative Examples 1 to 13 in Table 1 and Table 2 were dried in a hot air circulation dryer at 90 to 100 ° C. for 6 hours, and then using an injection molding machine. Test pieces for evaluation at a cylinder temperature of 260 ° C. and a mold temperature of 70 ° C. (ISO tensile test pieces (conforming to ISO527-1 and ISO527-2), ISO bending test pieces (conforming to ISO178 and ISO179)), UL test pieces, molding A test piece for shrinkage evaluation (width 50 mm × length 100 mm × thickness 2 mm (molded using a mold cavity having a thickness 1.5 mm film gate at one end in the length direction)) and a resin molded body for a toilet device A toilet seat (FIG. 1) was molded.

  The pellets of ABS resin and PP resin shown in Comparative Examples 14 and 15 in Table 2 were dried in a hot air circulation dryer at 80 ° C. for 4 hours, and then cylinder temperature 200 ° C. and mold temperature using an injection molding machine. Test piece for evaluation at 50 ° C. (ISO tensile test piece (ISO527-1 and ISO527-2 compliant), ISO bending test piece (ISO178 and ISO179 compliant)), UL test piece, molding shrinkage evaluation test piece (width) 50 mm × length 100 mm × thickness 2 mm (molded using a mold cavity having a thickness 1.5 mm film gate at one end in the length direction) and a toilet seat (FIG. 1), which is a resin molded body for a toilet device .

In addition, each component of the symbol description in Table 1 and Table 2 is as follows.
(A component)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 23,900 made from bisphenol A and phosgene by a conventional method, Panlite L-1250WP (product name) manufactured by Teijin Ltd.)
(B component)
B-1: Polypropylene resin (homopolymer, MFR: 2.0 g / 10 min, manufactured by Sun Allomer, Sun Allomer PL400A (product name))
B-2: Polypropylene resin (homopolymer, MFR: 0.5 g / 10 min, Sun Allomer VS200A (product name) manufactured by Sun Allomer Co., Ltd.)
(C component)
C-1: Styrene-ethylene-propylene-styrene block copolymer (styrene content: 65 wt%, MFR: 0.4 g / 10 min, Kuraray Co., Ltd. Septon 2104 (product name))
C-2: Styrene-ethylene-propylene-styrene block copolymer (styrene content: 30 wt%, MFR: 70 g / 10 min, Kuraray Co., Ltd. Septon 2002 (product name))
C-3: Styrene-ethylene-butylene-styrene block copolymer (styrene content: 67 wt%, MFR: 2.0 g / 10 min, Tuftec H1043 (product name) manufactured by Asahi Kasei Chemicals Corporation)
C-4: Styrene-butadiene-butylene-styrene block copolymer (styrene content: 67 wt%, MFR: 28 g / 10 min, manufactured by Asahi Kasei Chemicals Corporation Tuftec P2000 (product name))
(D component)
D-1: butadiene-based core-shell type graft polymer (core is 70 wt% containing butadiene-based rubber as a main component, shell is a methyl methacrylate, butyl acrylate and styrene graft copolymer, Kaneka Corporation Kane Ace M-701 ( product name))
(E component)
E-1: Halogenated carbonate compound (brominated carbonate oligomer having a bisphenol A skeleton, Teijin Limited Fireguard FG-7000 (product name))
(F component)
F-1: Antimony oxide compound (antimony trioxide, PATOX-K (product name) manufactured by Nippon Seiko Co., Ltd.) Average particle size: 1.2 μm
(G component)
G-1: polytetrafluoroethylene-based mixture (polytetrafluoroethylene coated with methyl methacrylate and butyl acrylate copolymer (polytetrafluoroethylene content: 50% by weight), METABLEN A3750 manufactured by Mitsubishi Rayon Co., Ltd. (Product name))
(Comparative example of G component)
G-2: Polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., Polyflon MPA FA500H (trade name))
(Other ingredients)
Thermal stabilizer: Phenol stabilizer (octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, molecular weight 531, Irganox 1076 (product name) manufactured by BASF Japan Ltd.)
Colorant: Carbon Black Master (Koshigaya Kasei Kogyo Co., Ltd. 50% carbon black containing polystyrene resin master, ROYAL BLACK RB90003S (product name))

  From Tables 1 and 2 above, the flame retardant polycarbonate resin satisfying mechanical properties, chemical resistance, processability, flame retardancy, and appearance at a higher level than conventional ABS resins and polypropylene resins by the blending of the present invention. It turns out that the resin molding for toilet devices obtained by shape | molding a composition is obtained.

Claims (7)

  (C) Styrenic thermoplastic elastomer (C component) with respect to a total of 100 parts by weight of (A) polycarbonate resin (component A) 60 to 90 parts by weight and (B) polypropylene resin (component B) 10 to 40 parts by weight 3) to 15 parts by weight, (D) a core-shell type graft copolymer obtained by graft copolymerizing an aromatic vinyl monomer and a (meth) acrylic acid ester monomer to a butadiene rubber-like polymer core (component D) 1) to 10 parts by weight, (E) halogenated carbonate compound (component E) 1 to 20 parts by weight, (F) antimony oxide compound (component F) 0.5 to 10 parts by weight, and (G) polytetrafluoroethylene particles And obtained by molding a flame retardant polycarbonate resin composition containing 0.01 to 3 parts by weight of a polytetrafluoroethylene-based mixture (G component) composed of an organic polymer and Toilet apparatus resin molded body.   The resin molded body for a toilet device according to claim 1, wherein the content of the styrene unit of the component C is 40 to 70% by weight.   The resin molded body for toilet apparatus according to claim 1 or 2, wherein the hydrogenated polydiene unit in component C is a hydrogenated isoprene unit and is a block copolymer having an ethylene / propylene block unit.   The resin molded body for toilet apparatus according to claim 1 or 2, wherein the hydrogenated polydiene unit in component C is a hydrogenated butadiene unit and is a block copolymer having an ethylene / butylene block unit.   The resin molded body for a toilet device according to claim 1 or 2, wherein the hydrogenated polydiene unit in the component C is a partially hydrogenated butadiene unit and is a block copolymer having a budadiene / butylene block unit.   The resin molded body for a toilet device according to any one of claims 1 to 5, wherein MFR of C component at 230 ° C and a load of 2.16 kg is 0.1 to 10 g / 10 min.   The resin molded body for a toilet device according to any one of claims 1 to 6, wherein the B component has an MFR of 0.1 to 5 g / 10 min at 230 ° C and a load of 2.16 kg.

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