JP2017132913A - Antibacterial polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial polycarbonate resin composition excellent in antibacterial properties, impact resistance, and hue.SOLUTION: A antibacterial polycarbonate resin composition comprises, based on (A) polycarbonate resin (A component) 100 pts.wt., (B) at least one thermoplastic resin (B component) selected from rubber-reinforced styrenic resin (B-1 component), aromatic polyester resin (B-2 component) and polyolefin resin (B-3 components) of 0-100 pts.wt., and (C) an antibacterial agent (C component) selected from zinc-based glass antibacterial agent (C-1 component) and silver-based zirconium phosphate antibacterial agent (C-2 component) of 0.3-5 pts.wt., with a weight ratio (C-1:C-2) between C-1 component and C-2 component of 50:50-95:5.SELECTED DRAWING: None

Description

  The present invention relates to a composition comprising a polycarbonate-based resin, a zinc-based glass antibacterial agent and a silver-based zirconium phosphate antibacterial agent, and relates to an antibacterial polycarbonate resin composition having excellent antibacterial properties, impact resistance and hue.

  Polycarbonate resin compositions generally have excellent heat resistance and impact resistance, and are widely used in electronic devices, office machines, machines, automobiles and the like. In addition, when such a resin alone does not exhibit sufficient properties, an aromatic polyester resin represented by polyethylene naphthalate or polybutylene naphthalate, a polyolefin resin such as polypropylene resin, an ABS resin, an AS resin, an MBS resin, or the like By using a resin composition blended with a styrene-based resin or the like represented by the above, chemical resistance and moldability, which are disadvantages of a polycarbonate resin, are imparted and used in a wider range of fields. In recent years, from the viewpoints of hygiene and cleanliness, ATMs (POS), POS terminals, mobile phones installed in housing equipment such as toilets, home appliances such as refrigerators and air conditioners, medical equipment, and convenience stores Materials that have antibacterial performance added to the exterior of phones and smartphones are required. As a method for imparting antibacterial properties to polycarbonate resin, various antibacterial agents (for example, those in which antibacterial metal ions such as silver, copper, and zinc are supported on calcium phosphate, zeolite, zirconium phosphate, etc.) , A method of adding an antioxidant such as phenol, a heat stabilizer, an acid-modified olefin wax (see Patent Documents 1 to 3), a method of adding an antibacterial agent containing glass that elutes silver ions (Patent Document 4), A method of adding an inorganic composite containing zinc as an essential component as an antibacterial component (Patent Document 5) has been proposed, but it cannot be said to have sufficient antibacterial properties. As a method for improving antibacterial properties, a method of blending a polyester fiber with an easily soluble metal ion-carrying inorganic antibacterial agent and a hard-to-elute metal ion-carrying inorganic antibacterial agent in a specific ratio (Patent Document 6), silver-based and A method using a zinc-based antibacterial agent in combination (Patent Document 7) has been proposed, but the characteristics when added to a polycarbonate resin composition were not sufficient.

JP-A-6-240125 Japanese Patent Laid-Open No. 10-168294 JP-A-11-323117 JP 2011-137068 A JP 2005-239904 A JP 2004-190197 A JP 2007-217300 A

  An object of the present invention is to provide an antibacterial polycarbonate resin composition having excellent antibacterial properties, impact resistance and hue.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has obtained antibacterial properties, impact resistance and good properties by blending a zinc-based glass antibacterial agent and a silver-based zirconium phosphate antibacterial agent at a specific ratio in a polycarbonate resin. The present inventors have found a method for obtaining an antibacterial polycarbonate resin composition having a proper hue and have completed the present invention.

  According to the present invention, the above-mentioned problem is (B) rubber-reinforced styrene resin (B-1 component), aromatic polyester resin (B-2 component) with respect to 100 parts by weight of (A) polycarbonate resin (A component). And at least one thermoplastic resin (component B) selected from polyolefin resin (component B-3) and (C) zinc-based glass antibacterial agent (component C-1) and silver-based phosphoric acid It contains 0.3 to 5 parts by weight of an antibacterial agent (C component) made of zirconium antibacterial agent (C-2 component), and the weight ratio of C-1 component to C-2 component (C-1: C-2) is It is achieved by an antibacterial polycarbonate resin composition that is 50:50 to 95: 5. Details of the present invention will be described below.

(A component: polycarbonate resin)
The polycarbonate resin used 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 impact resistance, and is widely used.

In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols 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) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate in which TMC 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 the aromatic polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Carbonate resin, copolymer polycarbonate resin copolymerized with bifunctional alcohol (including alicyclic), and polyester carbonate resin copolymerized with such bifunctional carboxylic acid and bifunctional alcohol are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  The branched polycarbonate resin can impart anti-drip performance and the like to the resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 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, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. It is 0.01-1 mol%, More preferably, it is 0.05-0.9 mol%, More preferably, it is 0.05-0.8 mol%.

  In particular, in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction, and the amount of the branched structural unit is preferably 100% by mole in total with the structural unit derived from dihydric phenol. The content is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and still more preferably 0.01 to 0.8 mol%. In addition, about the ratio of this branched structure, it is possible to calculate by 1H-NMR measurement.

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

Reaction formats such as interfacial polymerization, melt transesterification, carbonate prepolymer solid phase transesterification, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate-based 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-based resin is not particularly limited, but is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.4 × 10. ^{4 to} 3 × 10 ⁴ , more preferably 1.4 × 10 ^{4 to} 2.4 × 10 ⁴ .
With a polycarbonate resin having a viscosity average molecular weight of less than 1 × 10 ⁴ , good mechanical properties cannot be obtained. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ is inferior in versatility in that it is inferior in fluidity during injection molding.

In addition, the said polycarbonate-type resin may be obtained by mixing that whose viscosity average molecular weight is outside the said range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above range (5 × 10 ⁴ ) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding which may be used when molding a reinforced resin material into a structural member. Such improvement in moldability is even better than that of the branched polycarbonate. As a more preferable aspect, the A component has a viscosity average molecular weight of 7 × 10 ^{4 to} 3 × 10 ⁵ polycarbonate resin A-1-1-1 component), and the viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ . Polycarbonate resin (A-1-1 component) consisting of an aromatic polycarbonate resin (A-1-1-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ , Sometimes referred to as “high molecular weight component-containing polycarbonate resin”).

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

  The high molecular weight component-containing polycarbonate resin (A-1-1 component) is a mixture of the A-1-1-1 component and the A-1-1-2 component in various proportions so as to satisfy a predetermined molecular weight range. It can be obtained by adjusting. Preferably, in 100% by weight of the A-1-1 component, the A-1-1-1 component is 2 to 40% by weight, and more preferably, the A-1-1-1 component is 3 to 30% by weight. More preferably, the A-1-1-1 component is 4 to 20% by weight, and particularly preferably the A-1-1-1 component is 5 to 20% by weight.

  Moreover, as a preparation method of A-1-1 component, (1) The method of superposing | polymerizing each A-1-1-1 component and A-1-1-2 component independently, and mixing these, (2 ) A method for producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method represented by the method disclosed in Japanese Patent Application Laid-Open No. 5-306336 in the same system. And (3) an aromatic polycarbonate resin obtained by the production method (production method (2)) and A separately produced A. Examples thereof include a method of mixing the 1-1-1 component and / or the A-1-1-2 component.

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 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 viscosity average molecular weight of the polycarbonate resin in the antibacterial polycarbonate resin composition of the present invention is calculated 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.

  A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate-based resin (component A) of the present invention. The polycarbonate-polydiorganosiloxane copolymer resin is a copolymer prepared by copolymerizing a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3). A resin is preferred.

[In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2). . ]

[In the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and A group selected from the group consisting of carboxyl groups is represented, and when there are a plurality thereof, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7. ]

[In General Formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number of 10 to 300. X is a C2-C8 divalent aliphatic group. ]

  Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropyl) Phenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2, -Bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2- Bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) Fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4 ′ -Dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldi Enyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4 '-Dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'- Dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydro Xylphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1, 3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the like.

  Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis { 2- (4-hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4 Hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

As the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula (3), for example, the following compounds are preferably used.

  The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol. It is easily produced by hydrosilylation reaction at the end of a polysiloxane chain having a degree of polymerization of. Of these, (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane, particularly (2-methoxy-4) -Allylphenol) -terminated polydimethylsiloxane is preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less. The molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less, in order to develop further excellent low outgassing properties and low temperature impact properties during high temperature molding. When the upper limit of such a suitable range is exceeded, the amount of outgas generated during high temperature molding is large, and the low temperature impact property may be inferior.

  In order to achieve high impact resistance, the diorganosiloxane polymerization degree (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The degree of diorganosiloxane polymerization (p + q) is preferably 10 to 200, more preferably 12 to 150, and still more preferably 14 to 100. If the amount is less than the lower limit of the preferable range, the impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is not effectively exhibited. If the upper limit of the preferable range is exceeded, poor appearance appears.

  The polydiorganosiloxane content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in the component A is preferably 0.1 to 50% by weight. The polydiorganosiloxane component content is more preferably 0.5 to 30% by weight, still more preferably 1 to 20% by weight. Above the lower limit of the preferred range, the impact resistance and flame retardancy are excellent, and below the upper limit of the preferred range, a stable appearance that is hardly affected by the molding conditions is easily obtained. Such polydiorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by 1H-NMR measurement.

In the present invention, hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.
Further, within the range not hindering the present invention, other comonomer other than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is within a range of 10% by weight or less based on the total weight of the copolymer. It can also be used together.

In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by a reaction of a dihydric phenol (I) and a carbonate-forming compound in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution. To do.
In producing the oligomer of the dihydric phenol (I), the whole amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at one time, or a part of the dihydric phenol (I) is used as a post-added monomer at the latter stage interface. You may add to a polycondensation reaction as a reaction raw material. The post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.

Although the method of this oligomer production | generation reaction is not specifically limited, Usually, the method performed in a solvent in presence of an acid binder is suitable.
The use ratio of the carbonate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using gaseous carbonate ester-forming compounds, such as phosgene, the method of blowing this into a reaction system can be employ | adopted suitably.

  Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. The use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, it is preferable to use 2 equivalents or slightly more acid binder than the number of moles of dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents). .

  As said solvent, what is necessary is just to use a solvent inert to various reaction, such as what is used for manufacture of a well-known polycarbonate, individually or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

  The reaction pressure for oligomer formation is not particularly limited, and any of normal pressure, pressurization, and reduced pressure may be used, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours. The pH range of the oligomer formation reaction is the same as the known interfacial reaction conditions, and the pH is always adjusted to 10 or more.

  In the present invention, after obtaining a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group in this way, the molecular weight distribution (Mw / Mn) is up to 3 while stirring the mixed solution. A highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (4) is added to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation. As a result, a polycarbonate-polydiorganosiloxane copolymer is obtained.

In (the general formula ^{(4), R 3, R} 4, R 5, R 6, R 7 and ^{R 8} are each independently a hydrogen atom, substituted 6-12 alkyl group carbon atoms or from 1 to 12 carbon atoms Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, p + q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

  In performing the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the dihydric phenol (I) as described above is added as a post-added monomer to this reaction stage, It is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles of monovalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

The polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.
In such a polymerization reaction, a terminal terminator or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monohydric phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols, aliphatic carboxylic acids Examples include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, alkyl ether phenol and the like. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, based on 100 mol of all dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. is there.

In order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.
The reaction time of such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

  A branching agent can be used in combination with the above dihydric phenol compound to form a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucin, phloroglucid, or 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, 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and the like Lisphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone Examples thereof include tetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are included. 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. The ratio of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0 in the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. 0.9 mol%, more preferably 0.01 to 0.8 mol%, particularly preferably 0.05 to 0.4 mol%. Such a branched structure amount can be calculated by 1H-NMR measurement.

The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure. Usually, it can be suitably carried out at normal pressure or about the pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but it is usually performed in 0.5 to 10 hours.
In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [η _SP / c].
The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purity) after various post-treatments such as a known separation and purification method.

  The average size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. The average size is more preferably 1 to 30 nm, still more preferably 5 to 25 nm. If it is less than the lower limit of such a suitable range, the impact resistance and flame retardancy are not sufficiently exhibited, and if it exceeds the upper limit of such a suitable range, the impact resistance may not be stably exhibited. Thereby, a polycarbonate resin composition excellent in impact resistance and appearance is provided.

  The average domain size and normalized dispersion of the polydiorganosiloxane domain of the polycarbonate-polydiorganosiloxane copolymer resin molded product in the present invention were evaluated by a small angle X-ray scattering method (SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering / diffraction generated in a small-angle region within a scattering angle (2θ) <10 °. In this small-angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in the substance, the X-ray diffuse scattering is measured by the difference in electron density. The particle diameter of the measurement object is obtained based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which a polydiorganosiloxane domain is dispersed in a polycarbonate polymer matrix, X-ray diffuse scattering occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 ° is measured, the small-angle X-ray scattering profile is measured, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. Assuming that there is a particle size, a simulation is performed using a commercially available analysis software from the temporary particle size and the temporary particle size distribution model to obtain the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size and particle size distribution of the polydiorganosiloxane domain dispersed in the polycarbonate polymer matrix, which cannot be accurately measured by observation with a transmission electron microscope, can be accurately, simply, and reproducibly reproduced. Can be measured. The average domain size means the number average of individual domain sizes. Normalized dispersion means a parameter in which the spread of the particle size distribution is normalized by the average size. Specifically, it is a value obtained by normalizing the dispersion of the polydiorganosiloxane domain size with the average domain size, and is represented by the following formula (1).

  In the above formula (1), δ is the standard deviation of the polydiorganosiloxane domain size, and Dav is the average domain size.

  The terms “average domain size” and “normalized dispersion” used in connection with the present invention are the measurement of the 1.0 mm thickness of the three-stage plate produced by the method described in the Examples by the small angle X-ray scattering method. The measured values obtained by In addition, the analysis was performed using an isolated particle model that does not take into account the interparticle interaction (interparticle interference).

(B component: at least one thermoplastic resin selected from rubber-reinforced styrene resin, aromatic polyester resin and polyolefin resin)
The rubber-reinforced styrene resin used in the present invention is a copolymer obtained by copolymerizing an aromatic vinyl compound and one or more selected from other vinyl monomers and rubbery polymers. Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, Examples thereof include dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable.

  Preferable examples of the other vinyl monomer copolymerizable with the aromatic vinyl compound include a vinyl cyanide compound and a (meth) acrylic acid ester compound. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.

  Specific examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned. The notation of (meth) acrylate indicates that both methacrylate and acrylate are included, and the notation of (meth) acrylic acid ester indicates that both methacrylic acid ester and acrylic acid ester are included. Particularly preferred (meth) acrylic acid ester compounds include methyl methacrylate.

  Other vinyl monomers copolymerizable with aromatic vinyl compounds other than vinyl cyanide compounds and (meth) acrylic acid ester compounds include epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide, N-methylmaleimide, Examples thereof include maleimide monomers such as N-phenylmaleimide, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid, and anhydrides thereof.

  Examples of the rubber polymer include polybutadiene, polyisoprene, and diene copolymers (for example, random copolymers and block copolymers of styrene / butadiene, acrylonitrile / butadiene copolymers, and (meth) acrylic acid alkyl esters. Copolymer of ethylene and α-olefin (eg, ethylene / propylene random copolymer and block copolymer, ethylene / butene random copolymer and block copolymer, etc.) , Copolymers of ethylene and unsaturated carboxylic acid esters (for example, ethylene / methacrylate copolymers and ethylene / butyl acrylate copolymers), copolymers of ethylene and aliphatic vinyl (for example, ethylene / vinyl acetate) Copolymer), ethylene and propylene Non-conjugated diene terpolymers (eg, ethylene / propylene / hexadiene copolymers), acrylic rubbers (eg, polybutyl acrylate, poly (2-ethylhexyl acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate Etc.), as well as silicone rubber (eg, polyorganosiloxane rubber, IPN type rubber composed of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component; that is, the two rubber components are entangled with each other so that they cannot be separated. And rubber having a structure, and an IPN type rubber composed of a polyorganosiloxane rubber component and a polyisobutylene rubber component). Of these, polybutadiene, polyisoprene, or diene-based copolymers that are more likely to exhibit the effect are more preferable, and polybutadiene is particularly preferable.

Specific examples of rubber-reinforced styrene resins include HIPS resin, ABS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin, SIS resin (styrene-isoprene-styrene), and SEPS resin (styrene-ethylene). -Propylene-styrene) and SBS resin (styrene-butadiene-styrene) etc. are mentioned, and all are easily available. Among these, HIPS resin, ABS resin, AES resin, ASA resin, and MBS resin are more preferable.
Among these, ABS resin and MBS resin are particularly preferable. ABS resin has excellent moldability for thin-walled molded products, and also has good impact resistance. MBS resin also has good impact resistance to thin molded articles. In particular, favorable characteristics are exhibited in combination with an aromatic polycarbonate resin.

Here, AES resin is a copolymer resin mainly composed of acrylonitrile, ethylene-propylene rubber, and styrene, ASA resin is a copolymer resin mainly composed of acrylonitrile, styrene, and acrylic rubber, and MABS resin is methyl methacrylate, acrylonitrile, Copolymer resin mainly composed of butadiene and styrene, and MAS resin represent copolymer resin mainly composed of methyl methacrylate, acrylic rubber, and styrene. Styrenic thermoplastic elastomers such as SIS resin, SEPS resin, and SBS resin are preferably block copolymers 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 rubber-reinforced styrene resin can be used alone or in combination of two or more. For example, a combination of ABS resin and MBS resin is also preferably used in the present invention.

In the ABS resin used in the present invention, the proportion of the diene rubber component is preferably 5 to 80% by weight in 100% by weight of the ABS resin component (that is, in the total of 100% by weight of the ABS polymer and the AS polymer). The amount is preferably 7 to 70% by weight, particularly preferably 10 to 60% by weight.
In the ABS resin, the rubber particle diameter is preferably 0.05 to 5 [mu] m, more preferably 0.1 to 2.0 [mu] m, and still more preferably 0.1 to 1.5 [mu] m in terms of weight average particle diameter. The rubber particle size distribution can be either a single distribution (monodisperse type) or a compound having two or more ridges (polydisperse type), and the rubber also has a morphology. Even if the particles form a single phase, they may have a salami structure by containing an occluded phase around the rubber particles.

Further, it is well known that an ABS resin contains a copolymer of a vinyl cyanide compound and an aromatic vinyl compound that are not grafted to a diene rubber component. The ABS resin of the present invention may contain a free polymer component generated during such polymerization as described above, and a vinyl compound heavy polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound. A blended blend may be used.
Thus, the rubber-reinforced styrene-based resin of the present invention includes a mode in which a rubber component-containing copolymer and a rubber component-free polymer obtained by polymerizing separately are blended. Such blending may be performed when the resin composition of the present invention is produced, or may be performed prior to blending.

  Examples of the thermoplastic copolymer (AS copolymer) obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound include those described above as the vinyl cyanide compound, and acrylonitrile is particularly preferably used. Examples of the aromatic vinyl compound include those described above, and styrene and α-methylstyrene are preferable. The proportion of each component in the AS copolymer is 5 to 50% by weight, preferably 15 to 35% by weight, and 95 to 50% by weight of the aromatic vinyl compound when the whole is 100% by weight. %, Preferably 85 to 65% by weight. Further, these vinyl compounds may be copolymerized with the above-mentioned other copolymerizable vinyl compounds, and the content is preferably 15% by weight or less in the AS copolymer. Moreover, conventionally well-known various things can be used for the initiator, chain transfer agent, etc. which are used by reaction as needed.

Such an AS copolymer may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, suspension bulk polymerization, and emulsion polymerization, but is preferably based on bulk polymerization. The copolymerization method may be either one-stage copolymerization or multistage copolymerization. The reduced viscosity of the AS copolymer is such that the reduced viscosity (30 ° C.) determined by the method described below is 0.2 to 1.0 dl / g, more preferably 0.3 to 0.7 dl / g. It is.
The reduced viscosity is a value obtained by precisely weighing 0.25 g of AS copolymer and measuring a solution dissolved in 50 ml of dimethylformamide over 2 hours in an environment of 30 ° C. using an Ubbelohde viscometer. A viscometer having a solvent flow time of 20 to 100 seconds is used. The reduced viscosity is determined from the following formula from the solvent flow down seconds (t ₀ ) and the solution flow down seconds (t).
Reduced viscosity (η _sp / C) = {(t / t ₀ ) −1} /0.5

The ratio of the free AS copolymer can be obtained by dissolving the ABS copolymer in a good solvent for the AS copolymer such as acetone and collecting the soluble AS copolymer. On the other hand, the insoluble matter (gel) becomes a net ABS copolymer.
The ratio of the vinyl cyanide compound and aromatic vinyl compound grafted to the diene rubber component in the ABS copolymer (the ratio of the weight of the graft component to the weight of the diene rubber component), that is, the graft ratio (wt%) is 20 -200% is preferable, More preferably, it is 20-80%.

  Such ABS resin may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. More preferred is an ABS resin produced by a bulk polymerization method. Further, as such bulk polymerization method, the continuous bulk polymerization method (so-called Toray method) described in Chemical Engineering Vol. 48, No. 6, page 415 (1984) and Chemical Engineering Vol. 53, No. 6, page 423 (1989) are typical. ) Is a continuous bulk polymerization method (so-called Mitsui Toatsu method). Any ABS resin is preferably used as the ABS resin of the present invention. Further, the copolymerization may be carried out in one step or in multiple steps.

In the MBS resin used in the present invention, the proportion of the diene rubber component is preferably 30 to 90% by weight, more preferably 40 to 85% by weight, and particularly preferably 50 to 80% by weight in 100% by weight of the MBS resin component. %.
In the MBS resin, the rubber particle diameter is preferably 0.05 to 2 [mu] m, more preferably 0.1 to 1.0 [mu] m, still more preferably 0.1 to 0.5 [mu] m in terms of weight average particle diameter. The rubber particle size distribution may be a single distribution or a rubber particle having a plurality of peaks of two or more. As such MBS resin, those produced by emulsion polymerization can be preferably used.

  The aromatic polyester resin used in the present invention is preferably a polyester resin in which 70 mol% or more of 100 mol% of the dicarboxylic acid component among the dicarboxylic acid component and diol component forming the polyester is an aromatic dicarboxylic acid, more preferably. Is a polyester resin in which 90 mol% or more, most preferably 99 mol% or more is an aromatic dicarboxylic acid.

  Examples of this dicarboxylic acid include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid. Acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane Examples thereof include dicarboxylic acid, 5-Na sulfoisophthalic acid, and ethylene-bis-p-benzoic acid. These dicarboxylic acids can be used alone or in admixture of two or more. In addition to the above aromatic dicarboxylic acid, the polyester resin of the present invention can be copolymerized with an aliphatic dicarboxylic acid component of less than 30 mol%. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like.

  Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2, 4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3 -Cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether) and the like. These can be used alone or in admixture of two or more. In addition, it is preferable that the dihydric phenol in a diol component is 30 mol% or less.

  Specific polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2- In addition to bis (phenoxy) ethane-4,4′-dicarboxylate, there may be mentioned copolymer polyester resins such as polyethylene isophthalate / terephthalate copolymer, polybutylene terephthalate / isophthalate copolymer, and the like.

  In addition, the terminal group structure of the polyester resin used in the present invention is not particularly limited, and even when the ratio of the hydroxyl group and the carboxyl group in the terminal group is substantially the same, Good. Moreover, those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.

  For the production method of the polyester resin used in the present invention, in accordance with a conventional method, in the presence of a polycondensation catalyst containing titanium, germanium, antimony and the like, the dicarboxylic acid component and the diol component are polymerized while heating, By discharging water or lower alcohol produced as a by-product out of the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, and the like. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. Can be illustrated. Further, in the present invention, compounds such as manganese, zinc, calcium, magnesium, etc., which are used in a transesterification reaction that is a prior stage of a conventionally known polycondensation, can be used in combination, and phosphoric acid or phosphorous after completion of the transesterification reaction. Such a catalyst can be deactivated and polycondensed with an acid compound or the like. Furthermore, the production method of the polyester resin can be either batch type or continuous polymerization type.

  Furthermore, polyethylene terephthalate is particularly suitable among the polyester resins. The polyethylene terephthalate of the present invention is a polymer obtained by polycondensation reaction from terephthalic acid or a derivative thereof and 1,4-ethanediol or a derivative thereof, but as described above, other dicarboxylic acid components and other alkylene glycols. Includes copolymerized components.

  The terminal group structure of polyethylene terephthalate is not particularly limited as described above, but more preferably the terminal carboxyl group is less than the terminal hydroxyl group. Moreover, although the said various methods can be taken also about a manufacturing method, the thing of continuous polymerization type is preferable. This is because the quality stability is high and the cost is advantageous. Further, an organic titanium compound is preferably used as the polymerization catalyst. This is because the influence on the transesterification reaction tends to be small.

Preferred examples of such organic titanium compounds include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitic acid, a reaction product of tetrabutyl titanate and trimellitic anhydride, and the like. be able to. The amount of the organic titanium compound used is preferably such that the titanium atom is 3 to 12 mg atom% with respect to the acid component constituting polyethylene terephthalate.
The molecular weight of the polyester resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 35 ° C. using o-chlorophenol as a solvent is preferably 0.5 to 1.5, particularly preferably 0.6 to 1. .2.

  The polyolefin resin used in the present invention is a synthetic resin obtained by polymerizing or copolymerizing an olefin monomer having a radical polymerizable double bond. The olefin-based monomer is not particularly limited, and examples thereof include α- such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 4-methyl-1-pentene. Examples thereof include olefins and conjugated dienes such as butadiene and isoprene. Olefinic monomers may be used alone or in combination of two or more. The polyolefin-based resin is not particularly limited. For example, a homopolymer of ethylene, a copolymer of ethylene and an α-olefin other than ethylene, a homopolymer of propylene, and a copolymer of propylene and an α-olefin other than propylene. Examples include polymers, butene homopolymers, homopolymers or copolymers of conjugated dienes such as butadiene and isoprene, and propylene homopolymers and copolymers of propylene and α-olefins other than propylene are preferred. . More preferred is a homopolymer of propylene. Polyolefin resins may be used alone or in combination of two or more.

  In the present invention, a polypropylene resin is more preferably used from the viewpoint of versatility and rigidity. 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 polyolefin resin in the present invention is preferably 1 to 200 g / 10 min. The melt flow rate is also called “MFR”. MFR was measured according to ISO1133.

In this invention, the polyolefin resin modified | denatured as polyolefin resin is used independently, or the example in which polyolefin resin and modified polyolefin resin are used together is also included. The modified polyolefin resin is a modified polyolefin resin having a polar group. The polar group to be modified includes acid groups such as epoxy groups, glycidyl groups, and carboxyl groups, and acid groups such as acid anhydride groups. It is at least one functional group selected from the group consisting of derivatives. Specifically, a copolymer obtained by copolymerizing a monomer containing a polar group such as an epoxy group, a carboxyl group, and an acid anhydride group with the above-described polyolefin resin can be preferably used. What was made can be used more preferably. Examples of the monomer containing an epoxy group include glycidyl methacrylate, butyl glycidyl malate, butyl glycidyl fumarate, propyl glycidyl fumarate, glycidyl acrylate, N- (4- (2,3-epoxy) -3,5-dimethyl) Preferred is acrylamide. Examples of the monomer containing a carboxyl group include acrylic acid, methacrylic acid, and maleic acid. Examples of the monomer containing an acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Among the above-mentioned monomers having a polar group, acrylic acid and maleic anhydride are preferable from the viewpoint of reactivity and availability. The melt flow rate (190 ° C., 2.16 kg) of the modified polyolefin resin is preferably 50 g / 10 min or more, more preferably 100 g / 10 min or more, and particularly preferably 150 g / 10 min or more.
The ratio of these B components is 0-100 weight part with respect to 100 weight part of A component, Preferably it is 1-85 weight part, More preferably, it is 2-80 weight part. When the content of the component B exceeds 100 parts by weight, the hue change due to molding retention is large, and a large amount of flame retardant is required for flame retardancy, so the impact strength decreases.

(C component: antibacterial agent comprising zinc-based glass antibacterial agent (C-1 component) and silver-based zirconium phosphate antibacterial agent (C-2 component))
The resin composition of the present invention contains an antibacterial agent comprising a zinc-based glass antibacterial agent and a silver-based zirconium phosphate antibacterial agent.

(Zinc glass antibacterial agent)
Zinc glass antimicrobial agents are generally material formulation glass _{(ZnO, B 2 O 3,} Al 2 O 3, N a 2O, any combination such as SiO ₂ and _P 2 _{O 5) 1000~2000} After melting at 0 ° C., the melt is rapidly cooled to prepare glass, and then the resulting bulk glass is a powdery glass having an arbitrary particle size obtained by wet grinding with a ball mill. The average particle size (D50) measured by a laser diffraction / scattering method of a zinc-based glass antibacterial agent is preferably 1 to 10 μm. 2-7 micrometers is more preferable. If the average particle size is less than 1 μm, the antibacterial property is low, which is not preferable. If the average particle diameter exceeds 10 μm, the appearance of the surface of the molded product is poor, and the impact strength may be lowered, which is not preferable.

(Silver-based zirconium phosphate antibacterial agent)
The silver-based zirconium phosphate antibacterial agent is obtained by acid-treating lithium in crystalline lithium zirconium phosphate obtained by hydrothermal synthesis described in JP-A-2002-53756, substituting it with protons, and further converting protons into silver ions. After substitution, it can be dried and baked at a high temperature. Such silver-based zirconium phosphate antibacterial agents are commercially available from Toagosei Co., Ltd. under the trade names Novalon AG100, AG300, and AG1100, and are easily available. The average particle size (D50) measured by a laser diffraction / scattering method of a silver-based zirconium phosphate antibacterial agent is preferably 0.5 to 2 μm. 0.8-1.5 micrometers is more preferable. If the average particle size is less than 0.5 μm, the antibacterial property is low, which is not preferable. When the average particle diameter exceeds 2 μm, the appearance of the surface of the molded product is poor, and the impact strength may be lowered.

The weight ratio (C-1: C-2) of the zinc-based glass antibacterial agent (C-1 component) and the silver-based zirconium phosphate antibacterial agent (C-2 component) is 50:50 to 95: 5, 50: It is preferable that it is 50-85: 15, and it is more preferable that it is 65: 35-75: 25. By setting the weight ratio within the above range, antibacterial properties can be efficiently expressed without reducing the impact strength. When the C-1 component is less than 50% by weight in the C component, the hue at the time of molding deteriorates, and when it exceeds 95% by weight, the antibacterial properties and impact strength are lowered. In addition, as the C component, a product obtained by previously blending the C-1 component and the C-2 component can be used, and the product name (C-1 component: C-2 component) named Novalon VFA701 (manufactured by Toagosei Co., Ltd.). = 70:30).
Content of C component is 0.3-5 weight part with respect to 100 weight part of A component, 0.5-3 weight part is preferable, and 0.8-2.5 weight part is more preferable. When the proportion of component C is less than 0.3 parts by weight, antibacterial properties do not develop, and when it exceeds 5 parts by weight, the mechanical strength decreases and the hue also deteriorates.

(D component: phosphorus stabilizer and / or phenol stabilizer)
The resin composition of the present invention can contain a phosphorus stabilizer and / or a phenol stabilizer as component D.

(Phosphorus stabilizer)
Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.
Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, dis Allyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is 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.
Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula (5) are preferable.

（式（５）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In Formula (5), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.)

As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and both can be used.
Among the above formulas (5), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

  Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgafos126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are also available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Further, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is produced by ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Manufactured by Dober Chemical Co.) and any of them can be used.

(Phenolic stabilizer)
As the phenol stabilizer, a hindered phenol compound is generally used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodie Renbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2 {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy Examples include -5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferably used.

  The content of component D is preferably 0.01 to 1.0 part by weight per 100 parts by weight of component A, more preferably 0.03 to 0.8 part by weight, still more preferably 0.05 to 0. .5 parts by weight. If the content is less than 0.01 part by weight, the effect of suppressing thermal decomposition during processing may not be exhibited, and the mechanical characteristics may not be deteriorated. If the content exceeds 1.0 part by weight, the mechanical characteristics may be deteriorated. .

(Other additives)
Moreover, you may add the various additive as described in Unexamined-Japanese-Patent No. 2015-203098 and Unexamined-Japanese-Patent No. 2007-269821 to the composition of this invention as needed. Various flame retardants and flame retardant aids including brominated phosphate ester flame retardants (bromine, phosphazene, metal salt, antimony oxide, etc.), fluorine-containing anti-dripping agents, mold release agents, UV absorbers, Known substances such as additives such as antistatic agents, titanium oxide, dyes and pigments, and inorganic fillers typified by talc and glass fibers can be added. As a ratio to be added, 0.01 to 25 parts by weight of the flame retardant / flame retardant aid, 0.01 to 5 parts by weight of the release agent, the ultraviolet absorber and the antistatic agent with respect to 100 parts by weight of the component A Parts and dyes are preferably 0.01 to 5 parts by weight, and the inorganic filler is preferably 0.1 to 50 parts by weight.

(Manufacture of antibacterial polycarbonate resin composition)
In order to produce the antibacterial polycarbonate resin composition of the present invention, any method is adopted. For example, the components A to C and optionally the component D and 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 the like. A method of granulating such a premix by an extrusion granulator 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.

(About a molded article made of the resin composition of the present invention)
The resin composition in the present invention can usually produce various products by injection molding the pellets obtained by the above-described method. 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 product 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 molded products, 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 also 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 product by rotational molding, blow molding or the like.

  The antibacterial polycarbonate resin composition of the present invention is extremely useful for various industrial applications including the field of housing equipment, the field of office automation equipment, the field of electrical and electronic equipment such as various information terminals, and the field of automobiles. The antibacterial polycarbonate resin composition of the present invention is useful for a wide variety of other applications, specifically, toilets, vanity-related plastic parts, tablets, notebook computers, smartphones, digital cameras, medical monitors, POS, Office machine, printer, TV, etc., iron, hair dryer, rice cooker, microwave oven, air conditioner, air cleaner, negative ion generator, various plastic parts related to vehicles, antibacterial polycarbonate resin composition A resin product formed from a product can be used. As is clear from the above, the industrial effect exhibited by the present invention is extremely great.

  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. Evaluation was carried out by the following method.

(Evaluation of antibacterial polycarbonate resin composition)
(I) Antibacterial properties According to JIS Z2801 of the JIS standard, a part of a 150 mm × 150 mm × 2 mmt test piece obtained by the following method was cut and used, and the test was performed under the following conditions.
* Bacterial fluid concentration: 1 / 500NB
(NB: Nutrient Borth liquid basal medium)
* Bacteria droplet amount: 0.4ml
* Storage temperature: 35 ± 1 ℃
* Storage humidity: 90% or more * Storage time: 24 ± 1 hour * Bacteria used: Staphylococcus aureus (NBRC12732), Escherichia coli (NBRC3972)
* Purification treatment method: UV irradiation for 10 minutes [Evaluation criteria for antibacterial properties]
The antibacterial activity value was used as an antibacterial evaluation standard.
Antibacterial activity value = Log (viable count of unprocessed sample)-Log (viable count of antimicrobial processed sample)
A: Antibacterial activity value = 2 or more (There is antibacterial effect compared with unprocessed product)
B: Antibacterial activity value = 1 or more and less than 2 (may have antibacterial effect compared to unprocessed product)
C: Antibacterial activity value = 0 to less than 1 (no antibacterial effect)
(Ii) Deflection temperature under load In accordance with ISO75-1 and 2, the deflection temperature under load was measured at a load of 1.80 MPa using an ISO bending test piece obtained by the following method.
(Iii) Charpy impact strength According to ISO 179, the Charpy impact strength (test piece thickness 4 mm) with a notch was measured using the ISO bending test piece obtained by the following method.
(Iv) Flexural modulus The flexural modulus was measured according to ISO 178 using the ISO bending specimen obtained by the following method.
(V) Hue (ΔE = color difference between antibacterial agent-free composition and antibacterial agent-added composition)
Using the compositions described in Examples and Comparative Examples and compositions obtained by removing antibacterial agents from these compositions, square plates of 150 mm × 150 mm × 2 mmt were prepared by the following method, and each hue was measured with a color difference meter (Tokyo Denki) The color difference (ΔE) of Hunter color coordinates was determined by a reflection method using a color analyzer TC-1800MK-II manufactured by Color Industry Co., Ltd. It shows that the discoloration by antibacterial agent addition is so large that (DELTA) E is large. A composition having ΔE of less than 2 was evaluated as ◯, and a composition having Δ2 or more was evaluated as x.
(Vi) Flame retardancy Regarding the composition containing a flame retardant, a V (vertical combustion test) test at 1.5 mm and 2.0 mm in thickness was performed according to UL94, using a UL test piece obtained by the following method. .

[Examples 1 to 18, Comparative Examples 1 to 7]
In the compositions shown in Tables 1 and 2, a mixture of components excluding the liquid flame retardant was supplied from the first supply port of the extruder. Such a mixture was obtained by mixing with a V-type blender. The liquid flame retardant was supplied using a liquid injection device from between the first supply port and the second supply port. 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 260-270 degreeC from the 1st supply port to the die part.

  A part of the obtained pellets were dried in a hot air circulation dryer at 100 ° C. for 6 hours, and then used in Examples 1 to 9 using an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.). 15 and 17 and Comparative Examples 1 to 5 have a cylinder temperature of 260 ° C. and a mold temperature of 70 ° C., Examples 13, 14 and 16 and Comparative Example 6 have a cylinder temperature of 240 ° C., a mold temperature of 60 ° C. and Examples 10 to 12 18 and Comparative Example 7 are a tensile dumbbell piece for evaluation (based on ISO 527-1 and 2), an ISO bending test piece (based on ISO 178 and ISO 179)) and an ISO Charpy impact test at a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. A piece (based on ISO179), a square plate for antibacterial / hue evaluation (150 mm × 150 mm × 2 mmt), and a UL test piece were molded.

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 19,700 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX (product name) manufactured by Teijin Ltd.)
A-2: Aromatic polycarbonate resin (polycarbonate resin pellets having a viscosity average molecular weight of 22,400 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP (product name) manufactured by Teijin Ltd.)
A-3: Aromatic polycarbonate resin (polycarbonate resin pellets having a viscosity average molecular weight of 25,100 made from bisphenol A and phosgene by a conventional method, Panlite L-1250WQ (product name) manufactured by Teijin Ltd.)

(B component)
B-1-1: MBS resin (manufactured by Mitsubishi Rayon Co., Ltd .; Methbrene E-870A (product name)) The core is 70 wt% mainly composed of butadiene rubber, and the shell is 30 wt% mainly composed of methyl methacrylate and styrene. Impact-modifying resin having a core-shell structure, rubber average particle size: about 270 nm (polydispersed type having peaks at around 100 nm and 300 nm), and the amount of residual metal by ICP-AES is Ca: 700 p. p. m. , K: 10 p. p. m. , Na: 5 p. p. m.
B-1-2: ABS resin (manufactured by Nippon A & L Co., Ltd .; Clarastic SXH-330 (product name)) butadiene rubber amount: about 17.5%, rubber average particle size: about 400 nm, MFR: 53 g / 10 min ( 220 ° C., 10 kg load: according to ISO 1133)
B-1-3: SEBS resin (manufactured by Kraton Polymers; G1651EU (product name)) Styrene content: 33 wt%, MFR: 1 or less / 10 min (230 ° C., 5 kg load)
B-1-4: SEPS resin (manufactured by Kuraray Co., Ltd .; Septon 2104 (product name)) Styrene content: 65 wt%, MFR: 0.4 g / 10 min (230 ° C., 2.16 kg load)
B-2-1: PET resin (manufactured by Teijin Limited; TRN-8550FF (product name)) Ti catalyst PET resin, intrinsic viscosity (IV value) 0.77 measured at 35 ° C. using o-chlorophenol as a solvent
B-2-2: PBT resin: (manufactured by Changchun Artificial Resin Co., Ltd .; 1100-211MD (product name)) IV value 0.96
B-3-1: PE resin (manufactured by Prime Polymer Co., Ltd .; Hi-Zex 2100JP (product name)) High-density polyethylene resin (HDPE), MFR: 6 g / 10 min (230 ° C., 2.16 kg load), specific gravity: 0.00. 953, melting point: 127 ° C.
B-3-2: PP resin (manufactured by Sun Allomer; PL400A (product name)) MFR: 2 g / 10 min (230 ° C., 2.16 kg load)

(C component)
C-1A: (Toagosei Co., Ltd. Novalon VZ100 (product name)) Average particle diameter: 5 μm, specific gravity: 3.6
C-1B: (Novaron VZF101 (product name) manufactured by Toagosei Co., Ltd.) Average particle size: 1 μm, specific gravity: 3.6
C-1C: (Novaron VZ600 (product name) manufactured by Toagosei Co., Ltd.) Average particle size: 9 μm, specific gravity: 3.1
C-2A: (Novaron AG1100 (product name) manufactured by Toagosei Co., Ltd.) Average particle size: 1 μm, specific gravity: 3.0
CA: Toagosei Co., Ltd. product NOVALON VFA701 (product name), C-1 component / C-2 component mixture (weight ratio (C-1: C-2) = 70/30)), average particle diameter : 1.2 μm, specific gravity: 3.4

(D component)
D-1: Phosphorus stabilizer (manufactured by ADEKA Corporation; Adekastab 2112) Tris (2,4-di-tert-butylphenyl) phosphite D-2: Phosphorus stabilizer (Daihachi Chemical Industry Co., Ltd.) TMP (product name)) Trimethyl phosphate D-3: Phenolic stabilizer (manufactured by ADEKA; Adeka Stab AO-50) Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate

(Other ingredients)
FR-1: Phosphate ester flame retardant (CR-841 (product name) manufactured by Daihachi Chemical Industry Co., Ltd.)
FR-2: Halogenated carbonate compound (brominated carbonate oligomer having a bisphenol A skeleton, Teijin Limited Fireguard FG-7000 (product name))
FR-3: antimony oxide compound (antimony trioxide, PATOX-K (product name) manufactured by Nippon Seiko Co., Ltd.) Average particle size: 1.2 μm
PTFE-1: Polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., Polyflon MPA FA500H (product name))
PTFE-2: 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))
TALC: Talc (manufactured by Katsumiyama Mining Co., Ltd .; Victorylite TK-RC (product name), average particle size (D50) measured by laser diffraction / scattering method: 4.7 μm) Talc with a bulk density of 0.7 to Talc degassed and compressed to 0.8 g / cm ³ , whiteness: 92%, Ig.Loss (ignition loss ratio: conforming to JIS M8855): 5.83%, pH = 9.5)
RW-1: Mixture of triglyceride (30 wt%) and fatty acid ester (70 wt%) (Rikenmar SL900 (product name) manufactured by Riken Vitamin Co., Ltd.)
RW-2: Pentaerythritol tetrastearate (Unistar H-476-S (product name) manufactured by NOF Corporation)
RW-3: Olefin-based wax by copolymerization of α-olefin and maleic anhydride (Licolub CE-2 FINE GRAIN, manufactured by Clariant Co., Ltd.)
AD-1: UV absorber (manufactured by BASF Japan Ltd. Tinuvin 234)
AD-2: UV absorber (manufactured by BASF Japan Ltd. Tinuvin 1577)
AD-3: Light stabilizer (manufactured by BASF Japan Ltd., Tinuvin 622SF (product name)) polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (N- R type)
AD-4: Light stabilizer (manufactured by BASF Japan Ltd. TinuvinPA144 (product name) bis (1,2,2,6,6-pentamethyl-4-piperidyl [[3,5-bis (1,1-dimethylethyl ) -4-Hydroxyphenyl] methyl] butyl malonate (NR type)
TiO2-1: Titanium dioxide (Ishihara Sangyo Co., Ltd. Typek PC-3 (product name), average particle size 0.21 μm
TiO2-2: Titanium dioxide (TIOXIDE R-TC30 (product name), manufactured by HUNSUMAN), average particle size 0.21 μm

  It can be seen from Tables 1 and 2 that an antibacterial polycarbonate resin composition excellent in antibacterial properties, impact resistance, and hue can be obtained by blending the present invention.

Claims (3)

  (A) 100 parts by weight of polycarbonate resin (component A), (B) rubber-reinforced styrene resin (component B-1), aromatic polyester resin (component B-2) and polyolefin resin (component B-3) From 0 to 100 parts by weight of at least one thermoplastic resin (component B) selected from: and (C) a zinc-based glass antibacterial agent (C-1 component) and a silver-based zirconium phosphate antibacterial agent (C-2 component) An antibacterial agent containing 0.3 to 5 parts by weight of an antibacterial agent (C component) and having a weight ratio of C-1 component to C-2 component (C-1: C-2) of 50:50 to 95: 5 Polycarbonate resin composition.   2. The antibacterial polycarbonate resin composition according to claim 1, wherein an average particle size (D50) measured by a laser diffraction / scattering method of component C-1 is 2 to 7 [mu] m.   The antibacterial according to claim 1 or 2, wherein (D) 0.01 to 1 part by weight of a phosphorus stabilizer and / or a phenol stabilizer (D component) is contained with respect to 100 parts by weight of component A. Polycarbonate resin composition.